Search results for: catalytic decomposition

Authors: Anicet Dansou

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Textile reinforced concrete (TRC)is increasingly used nowadays in various fields, in particular civil engineering, where it is mainly used for the reinforcement of damaged reinforced concrete structures. TRC is a composite material composed of multi- or uni-axial textile reinforcements coupled with a fine-grained cementitious matrix. The TRC composite is an alternative solution to the traditional Fiber Reinforcement Polymer (FRP) composite. It has good mechanical performance and better temperature stability but also, it makes it possible to meet the criteria of sustainable development better.TRCs are highly anisotropic composite materials with nonlinear hardening behavior; their macroscopic behavior depends on multi-scale mechanisms. The characterization of these materials through numerical simulation has been the subject of many studies. Since TRCs are multiscale material by definition, numerical multi-scale approaches have emerged as one of the most suitable methods for the simulation of TRCs. They aim to incorporate information pertaining to microscale constitute behavior, mesoscale behavior, and macro-scale structure response within a unified model that enables rapid simulation of structures. The computational costs are hence significantly reduced compared to standard simulation at a fine scale. The fine scale information can be implicitly introduced in the macro scale model: approaches of this type are called non-classical. A representative volume element is defined, and the fine scale information are homogenized over it. Analytical and computational homogenization and nested mesh methods belong to these approaches. On the other hand, in classical approaches, the fine scale information are explicitly introduced in the macro scale model. Such approaches pertain to adaptive mesh refinement strategies, sub-modelling, domain decomposition, and multigrid methods This research presents the main principles of numerical multiscale approaches. Advantages and limitations are identified according to several criteria: the assumptions made (fidelity), the number of input parameters required, the calculation costs (efficiency), etc. A bibliographic study of recent results and advances and of the scientific obstacles to be overcome in order to achieve an effective simulation of textile reinforced concrete in civil engineering is presented. A comparative study is further carried out between several methods for the simulation of TRCs used for the structural reinforcement of reinforced concrete structures.

Keywords: composites structures, multiscale methods, numerical modeling, textile reinforced concrete

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Authors: Gaweł Magdalena, Lipkowska Anna, Olbert Magdalena, Frąckiewicz Ewelina, Librowski Tadeusz, Nowak Gabriel, Pilc Andrzej

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Heme oxygenase-1 (HO-1), also known as heat shock protein 32 (HSP32), has been shown to be implicated in cytoprotection in various organs. Its activation plays a significant role in acute and chronic inflammation, protecting cells from oxidative injury and apoptosis. This inducible isoform of HO catalyzes the first and rate-limiting step in heme degradation to produce equimolar quantities of biologically active products: carbon monoxide (CO), free iron and biliverdin. CO has been reported to possess anti-apoptotic properties. Moreover, it inhibits the production of proinflammatory cytokines and stimulates the synthesis of the anti-inflammatory interleukin-10 (IL-10), as well as promotes vasodilatation at sites of inflammation. The second product of catalytic HO-1 activity, free cytotoxic iron, is promptly sequestered into the iron storage protein ferritin, which lowers the pro-oxidant state of the cell. The third product, biliverdin, is subsequently converted by biliverdin reductase into the bile pigment bilirubin, the most potent endogenous antioxidant among the constituents of human serum, which modulates immune effector functions and suppresses inflammatory response. Furthermore, being one of the so-called stress proteins, HO-1 adaptively responds to different stressors, such as reactive oxygen species (ROS), inflammatory cytokines and heavy metals and thus protects cells against such conditions as ischemia, hemorrhagic shock, heat shock or hypoxia. It is suggested that pharmacologic modulation of HO-1 may represent an effective strategy for prevention of stress and drug-induced gastrointestinal toxicity. HO-1 is constitutively expressed in normal gastric, intestinal and colonic mucosa and up-regulated during inflammation. It has been proven that HO-1 up-regulated by hemin, heme and cobalt-protoporphyrin ameliorates experimental colitis. In addition, the up-regulation of HO-1 partially explains the mechanism of action of 5-aminosalicylic acid (5-ASA), which is used clinically as an anti-colitis agent. In 2009 Ueda et al. has reported for the first time that mucosal protection by Polaprezinc, a chelate compound of zinc and L-carnosine used as an anti-ulcer drug in Japan, is also attributed to induction of HO-1 in the stomach. Since then, inducers of HO-1 are desired subject of research, as they may constitute therapeutically effective anti-ulcer drugs.

Keywords: heme oxygenase-1, gastric lesions, gastroprotection, Polaprezinc

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Authors: Barun Chakrabarti, Evangelos Kalamaras, Vladimir Yufit, Xinhua Liu, Billy Wu, Nigel Brandon, C. T. John Low

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In this work, we perform electrophoretic deposition of activated carbon on a number of substrates to prepare symmetrical coin cells for supercapacitor applications. From several recipes that involve the evaluation of a few solvents such as isopropyl alcohol, N-Methyl-2-pyrrolidone (NMP), or acetone to binders such as polyvinylidene fluoride (PVDF) and charging agents such as magnesium chloride, we display a working means for achieving supercapacitors that can achieve 100 F/g in a consistent manner. We then adapt this EPD method to deposit reduced graphene oxide on SGL 10AA carbon paper to achieve cathodic materials for testing in a hydrogen/vanadium flow battery. In addition, a self-supported hierarchical carbon nano-fibre is prepared by means of electrospray deposition of an iron phthalocyanine solution onto a temporary substrate followed by carbonisation to remove heteroatoms. This process also induces a degree of nitrogen doping on the carbon nano-fibres (CNFs), which allows its catalytic performance to improve significantly as detailed in other publications. The CNFs are then used as catalysts by attaching them to graphite felt electrodes facing the membrane inside an all-vanadium flow battery (Scribner cell using serpentine flow distribution channels) and efficiencies as high as 60% is noted at high current densities of 150 mA/cm². About 20 charge and discharge cycling show that the CNF catalysts consistently perform better than pristine graphite felt electrodes. Following this, we also test the CNF as an electro-catalyst in the hydrogen/vanadium flow battery (cathodic side as mentioned briefly in the first paragraph) facing the membrane, based upon past studies from our group. Once again, we note consistently good efficiencies of 85% and above for CNF modified graphite felt electrodes in comparison to 60% for pristine felts at low current density of 50 mA/cm² (this reports 20 charge and discharge cycles of the battery). From this preliminary investigation, we conclude that the CNFs may be used as catalysts for other systems such as vanadium/manganese, manganese/manganese and manganese/hydrogen flow batteries in the future. We are generating data for such systems at present, and further publications are expected.

Keywords: electrospinning, carbon nano-fibres, all-vanadium redox flow battery, hydrogen-vanadium fuel cell, electrocatalysis

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Authors: Fathi Abid, Bilel Kaffel

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The olive tree, the olive harvest during winter season and the production of olive oil better known by professionals under the name of the crushing operation have interested institutional traders such as olive-oil offices and private companies such as food industry refining and extracting pomace olive oil as well as export-import public and private companies specializing in olive oil. The major problem facing producers of olive oil each winter campaign, contrary to what is expected, it is not whether the harvest will be good or not but whether the sale price will allow them to cover production costs and achieve a reasonable margin of profit or not. These questions are entirely legitimate if we judge by the importance of the issue and the heavy complexity of the uncertainty and competition made tougher by a high level of indebtedness and the experience and expertise of speculators and producers whose objectives are sometimes conflicting. The aim of this paper is to study the formation mechanism of olive oil prices in order to learn about speculators’ behavior and expectations in the market, how they contribute by their industry knowledge and their financial alliances and the size the financial challenge that may be involved for them to build private information hoses globally to take advantage. The methodology used in this paper is based on two stages, in the first stage we study econometrically the formation mechanisms of olive oil price in order to understand the market participant behavior by implementing ARMA, SARMA, GARCH and stochastic diffusion processes models, the second stage is devoted to prediction purposes, we use a combined wavelet- ANN approach. Our main findings indicate that olive oil market participants interact with each other in a way that they promote stylized facts formation. The unstable participant’s behaviors create the volatility clustering, non-linearity dependent and cyclicity phenomena. By imitating each other in some periods of the campaign, different participants contribute to the fat tails observed in the olive oil price distribution. The best prediction model for the olive oil price is based on a back propagation artificial neural network approach with input information based on wavelet decomposition and recent past history.

Keywords: olive oil price, stylized facts, ARMA model, SARMA model, GARCH model, combined wavelet-artificial neural network, continuous-time stochastic volatility mode

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Authors: Wee Tong Liaw, Elaine Wong Yee Sing

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The main objective and focus of this study are to establish the significance of a sustained health promoting workplace on stock and portfolio returns focusing on companies listed on the Singapore stock exchange, using a two-factor model comprising of the single factor CAPM and a 'health promoting workplace' factor. The 'health promoting workplace' factor represents the excess returns derived between two portfolios of component stocks that, when combined, would represent a top tier stock market index in Singapore, namely the STI index. The first portfolio represents companies that are independently assessed by the Singapore’s Health Award, SHA, to have a sustained and comprehensive health promoting workplace (SHA-STI portfolio) and the second portfolio represents companies that had not been independently assessed (Non-SHA STI portfolio). Since 2001, many companies in Singapore have voluntarily participated in the bi-annual Singapore HEALTH Award initiated by the Health Promotion Board of Singapore (HPB). The Singapore HEALTH Award (SHA), is an industry-wide award and assessment process. SHA assesses and recognizes employers in Singapore for implementing a comprehensive and sustainable health promotion programme at their workplaces. When using a ten year holding period instead of a one year holding period, excess returns in the SHA-STI portfolio over Non-SHA STI portfolio were consistently being observed over all test periods, during 2001 to 2013. In addition, when applied to the SHA-STI portfolio, results from the Two Factor Model consistently revealed higher explanatory powers across all test periods for the portfolio as well as all the individual component stocks in SHA-STI portfolio, than the single factor CAPM model. However, with respect to attaining higher level of achievement in the Singapore Health Award, this study did not show any incentive for selecting listed companies that have achieved a higher level of award. Results from this study would give further insights to investors and fund managers alike who intend to consider health promoting workplace as a risk factor in their stock or portfolio selection process, in particular for investors who have a preference for STI’s component stocks and with a longer investment horizon. Key micro factors like management abilities, business development strategies and production capabilities that meet the needs of market would create the demand for a company’s product(s) or service(s) and consequently contribute to its top line and profitability. Thereafter, the existence of a sustainable health promoting workplace would be a key catalytic factor in sustaining a productive workforce needed to support the continued success of a profitable business.

Keywords: asset pricing model, company's performance, stock returns, financial risk factor, sustained health promoting workplace

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Authors: Najeh Lakhoua

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Introduction: Scientific developments and techniques for the systemic approach generate several names to the systemic approach: systems analysis, systems analysis, structural analysis. The main purpose of these reflections is to find a multi-disciplinary approach which organizes knowledge, creates universal language design and controls complex sets. In fact, system analysis is structured sequentially by steps: the observation of the system by various observers in various aspects, the analysis of interactions and regulatory chains, the modeling that takes into account the evolution of the system, the simulation and the real tests in order to obtain the consensus. Thus the system approach allows two types of analysis according to the structure and the function of the system. The purpose of this paper is to present an application of system analysis of Unmanned Aerial Vehicle (UAV) components in order to represent the architecture of this system. Method: There are various analysis methods which are proposed, in the literature, in to carry out actions of global analysis and different points of view as SADT method (Structured Analysis and Design Technique), Petri Network. The methodology adopted in order to contribute to the system analysis of an Unmanned Aerial Vehicle has been proposed in this paper and it is based on the use of SADT. In fact, we present a functional analysis based on the SADT method of UAV components Body, power supply and platform, computing, sensors, actuators, software, loop principles, flight controls and communications). Results: In this part, we present the application of SADT method for the functional analysis of the UAV components. This SADT model will be composed exclusively of actigrams. It starts with the main function ‘To analysis of the UAV components’. Then, this function is broken into sub-functions and this process is developed until the last decomposition level has been reached (levels A1, A2, A3 and A4). Recall that SADT techniques are semi-formal; however, for the same subject, different correct models can be built without having to know with certitude which model is the good or, at least, the best. In fact, this kind of model allows users a sufficient freedom in its construction and so the subjective factor introduces a supplementary dimension for its validation. That is why the validation step on the whole necessitates the confrontation of different points of views. Conclusion: In this paper, we presented an application of system analysis of Unmanned Aerial Vehicle components. In fact, this application of system analysis is based on SADT method (Structured Analysis Design Technique). This functional analysis proved the useful use of SADT method and its ability of describing complex dynamic systems.

Keywords: system analysis, unmanned aerial vehicle, functional analysis, architecture

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Authors: Giorgia Zotti

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This research comprehensively investigates the multifaceted interplay determining school performance, individual backgrounds, and regional disparities within the landscape of Italian secondary education. Leveraging data gleaned from the INVALSI 2021-2022 database, the analysis meticulously scrutinizes two fundamental distributions of educational achievements: the standardized Invalsi test scores and official grades in Italian and Mathematics, focusing specifically on final-year secondary school students in Italy. Applying a comprehensive methodology, the study initially employs Data Envelopment Analysis (DEA) to assess school performances. This methodology involves constructing a production function encompassing inputs (hours spent at school) and outputs (Invalsi scores in Italian and Mathematics, along with official grades in Italian and Math). The DEA approach is applied in both of its versions: traditional and conditional. The latter incorporates environmental variables such as school type, size, demographics, technological resources, and socio-economic indicators. Additionally, the analysis delves into regional disparities by leveraging the Theil Index, providing insights into disparities within and between regions. Moreover, in the frame of the inequality of opportunity theory, the study quantifies the inequality of opportunity in students' educational achievements. The methodology applied is the Parametric Approach in the ex-ante version, considering diverse circumstances like parental education and occupation, gender, school region, birthplace, and language spoken at home. Consequently, a Shapley decomposition is applied to understand how much each circumstance affects the outcomes. The outcomes of this comprehensive investigation unveil pivotal determinants of school performance, notably highlighting the influence of school type (Liceo) and socioeconomic status. The research unveils regional disparities, elucidating instances where specific schools outperform others in official grades compared to Invalsi scores, shedding light on the intricate nature of regional educational inequalities. Furthermore, it emphasizes a heightened inequality of opportunity within the distribution of Invalsi test scores in contrast to official grades, underscoring pronounced disparities at the student level. This analysis provides insights for policymakers, educators, and stakeholders, fostering a nuanced understanding of the complexities within Italian secondary education.

Keywords: inequality, education, efficiency, DEA approach

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Authors: Ying Li, Rui Hu, Shizhen Chen, Xin Zhou, Yunhuang Yang

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Prostate cancer is one of the leading causes of cancer-related death among men. Prostate-specific antigen (PSA), a specific product of prostatic epithelial cells, is an important indicator of prostate cancer. Though PSA is not a specific serum biomarker for the screening of prostate cancer, it is recognized as an indicator for prostate cancer recurrence and response to therapy for patient’s post-prostatectomy. Since radical prostatectomy eliminates the source of PSA production, serum PSA levels fall below 50 pg/mL, and may be below the detection limit of clinical immunoassays (current clinical immunoassay lower limit of detection is around 10 pg/mL). Many clinical studies have shown that intervention at low PSA levels was able to improve patient outcomes significantly. Therefore, ultra-sensitive and precise assays that can accurately quantify extremely low levels of PSA (below 1-10 pg/mL) will facilitate the assessment of patients for the possibility of early adjuvant or salvage treatment. Currently, the commercially available ultra-sensitive ELISA kit (not used clinically) can only reach a detection limit of 3-10 pg/mL. Other platforms developed by different research groups could achieve a detection limit as low as 0.33 pg/mL, but they relied on sophisticated instruments to get the final readout. Herein we report a microfluidic platform for point-of-care (POC) detection of PSA with a detection limit of 0.5 pg/mL and without the assistance of any equipment. This platform is based on a previously reported volumetric-bar-chart chip (V-Chip), which applies platinum nanoparticles (PtNPs) as the ELISA probe to convert the biomarker concentration to the volume of oxygen gas that further pushes the red ink to form a visualized bar-chart. The length of each bar is used to quantify the biomarker concentration of each sample. We devised a long reading channel V-Chip (LV-Chip) in this work to achieve a wide detection window. In addition, LV-Chip employed a unique enzyme-free ELISA probe that enriched PtNPs significantly and owned 500-fold enhanced catalytic ability over that of previous V-Chip, resulting in a significantly improved detection limit. LV-Chip is able to complete a PSA assay for five samples in 20 min. The device was applied to detect PSA in 50 patient serum samples, and the on-chip results demonstrated good correlation with conventional immunoassay. In addition, the PSA levels in finger-prick whole blood samples from healthy volunteers were successfully measured on the device. This completely stand-alone LV-Chip platform enables convenient POC testing for patient follow-up in the physician’s office and is also useful in resource-constrained settings.

Keywords: point-of-care detection, microfluidics, PSA, ultra-sensitive

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Authors: Katerina Zaharieva, Vicente Rives, Martin Tsvetkov, Raquel Trujillano, Boris Kunev, Ivan Mitov, Maria Milanova, Zara Cherkezova-Zheleva

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The nanostructured cobalt ferrite-type materials Sample A - Co0.25Fe2.75O4, Sample B - Co0.5Fe2.5O4, and Sample C - CoFe2O4 were prepared by co-precipitation in our previous investigations. The co-precipitated Sample B and Sample C were mechanochemically activated in order to produce Sample D - Co0.5Fe2.5O4 and Sample E- CoFe2O4. The PXRD, Moessbauer and FTIR spectroscopies, specific surface area determination by the BET method, thermal analysis, element chemical analysis and temperature-programmed reduction were used to investigate the prepared nano-sized samples. The changes of the Malachite green dye concentration during reaction of the photocatalytic decolorization using nanostructured cobalt ferrite-type catalysts with different chemical composition are included. The photocatalytic results show that the increase in the degree of incorporation of cobalt ions in the magnetite host structure for co-precipitated cobalt ferrite-type samples results in an increase of the photocatalytic activity: Sample A (4 х10-3 min-1) < Sample B (5 х10-3 min-1) < Sample C (7 х10-3 min-1). Mechanochemically activated photocatalysts showed a higher activity than the co-precipitated ferrite materials: Sample D (16 х10-3 min-1) > Sample E (14 х10-3 min-1) > Sample C (7 х10-3 min-1) > Sample B (5 х10-3 min-1) > Sample A (4 х10-3 min-1). On decreasing the degree of substitution of iron ions by cobalt ones a higher sorption ability of the dye after the dark period for the co-precipitated cobalt ferrite materials was observed: Sample C (72 %) < Sample B (78 %) < Sample A (80 %). Mechanochemically treated ferrite catalysts and co-precipitated Sample B possess similar sorption capacities, Sample D (78 %) ~ Sample E (78 %) ~ Sample B (78 %). The prepared nano-sized cobalt ferrite-type materials demonstrate good photocatalytic and sorption properties. Mechanochemically activated Sample D - Co0.5Fe2.5O4 (16х10-3 min-1) and Sample E-CoFe2O4 (14х10-3 min-1) possess higher photocatalytic activity than that of the most common used UV-light catalyst Degussa P25 (12х10-3 min-1). The dependence of the photo-catalytic activity and sorption properties on the preparation method and different degree of substitution of iron ions by cobalt ions in synthesized cobalt ferrite samples is established. The mechanochemical activation leads to formation of nano-structured cobalt ferrite-type catalysts (Sample D and Sample E) with higher rate constants than those of the ferrite materials (Sample A, Sample B, and Sample C) prepared by the co-precipitation procedure. The increase in the degree of substitution of iron ions by cobalt ones leads to improved photocatalytic properties and lower sorption capacities of the co-precipitated ferrite samples. The good sorption properties between 72 and 80% of the prepared ferrite-type materials show that they could be used as potential cheap absorbents for purification of polluted waters.

Keywords: nanodimensional cobalt ferrites, photocatalyst, synthesis, mechanochemical activation

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Authors: Hamed Kalhori, Lin Ye

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In this study, an inverse method was developed to reconstruct the magnitude and duration of impact forces exerted to a rectangular carbon fibre-epoxy composite honeycomb sandwich panel. The dynamic signals captured by Piezoelectric (PZT) sensors installed on the panel remotely from the impact locations were utilized to reconstruct the impact force generated by an instrumented hammer through an extended deconvolution approach. Two discretized forms of convolution integral are considered; the traditional one with an explicit transfer function and the modified one without an explicit transfer function. Deconvolution, usually applied to reconstruct the time history (e.g. magnitude) of a stochastic force at a defined location, is extended to identify both the location and magnitude of the impact force among a number of potential impact locations. It is assumed that a number of impact forces are simultaneously exerted to all potential locations, but the magnitude of all forces except one is zero, implicating that the impact occurs only at one location. The extended deconvolution is then applied to determine the magnitude as well as location (among the potential ones), incorporating the linear superposition of responses resulted from impact at each potential location. The problem can be categorized into under-determined (the number of sensors is less than that of impact locations), even-determined (the number of sensors equals that of impact locations), or over-determined (the number of sensors is greater than that of impact locations) cases. For an under-determined case, it comprises three potential impact locations and one PZT sensor for the rectangular carbon fibre-epoxy composite honeycomb sandwich panel. Assessments are conducted to evaluate the factors affecting the precision of the reconstructed force. Truncated Singular Value Decomposition (TSVD) and the Tikhonov regularization are independently chosen to regularize the problem to find the most suitable method for this system. The selection of optimal value of the regularization parameter is investigated through L-curve and Generalized Cross Validation (GCV) methods. In addition, the effect of different width of signal windows on the reconstructed force is examined. It is observed that the impact force generated by the instrumented impact hammer is sensitive to the impact locations of the structure, having a shape from a simple half-sine to a complicated one. The accuracy of the reconstructed impact force is evaluated using the correlation co-efficient between the reconstructed force and the actual one. Based on this criterion, it is concluded that the forces reconstructed by using the extended deconvolution without an explicit transfer function together with Tikhonov regularization match well with the actual forces in terms of magnitude and duration.

Keywords: honeycomb composite panel, deconvolution, impact localization, force reconstruction

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Authors: Samira Baghbanbari, A. B. P. Lever, Payam S. Shabestari, Donald Weaver

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Existing signal transmission models, although undoubtedly useful, have proven insufficient to explain the full complexity of information transfer within the central nervous system. The development of transformative models will necessitate a more comprehensive understanding of neuronal lipid membrane electrophysiology. Pursuant to this goal, the role of highly organized interfacial phospholipid-water layers emerges as a promising case study. A series of phospholipids in neural-glial gap junction interfaces as well as cholesterol molecules have been computationally modelled using high-performance density functional theory (DFT) calculations. Subsequent 'charge decomposition analysis' calculations have revealed a net transfer of charge from phospholipid orbitals through the organized interfacial water layer before ultimately finding its way to cholesterol acceptor molecules. The specific pathway of charge transfer from phospholipid via water layers towards cholesterol has been mapped in detail. Cholesterol is an essential membrane component that is overrepresented in neuronal membranes as compared to other mammalian cells; given this relative abundance, its apparent role as an electronic acceptor may prove to be a relevant factor in further signal transmission studies of the central nervous system. The timescales over which this electronic charge transfer occurs have also been evaluated by utilizing a system design that systematically increases the number of water molecules separating lipids and cholesterol. Memory loss through hydrogen-bonded networks in water can occur at femtosecond timescales, whereas existing action potential-based models are limited to micro or nanosecond scales. As such, the development of future models that attempt to explain faster timescale signal transmission in the central nervous system may benefit from our work, which provides additional information regarding fast timescale energy transfer mechanisms occurring through interfacial water. The study possesses a dataset that includes six distinct phospholipids and a collection of cholesterol. Ten optimized geometric characteristics (features) were employed to conduct binary classification through an artificial neural network (ANN), differentiating cholesterol from the various phospholipids. This stems from our understanding that all lipids within the first group function as electronic charge donors, while cholesterol serves as an electronic charge acceptor.

Keywords: charge transfer, signal transmission, phospholipids, water layers, ANN

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Authors: Yanping Liao, Zenan Wu, Ruigang Zhao

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Frequency diverse array (FDA) beamforming is a technology developed in recent years, and its antenna pattern has a unique angle-distance-dependent characteristic. However, the beam is always required to have strong concentration, high resolution and low sidelobe level to form the point-to-point interference in the concentrated set. In order to eliminate the angle-distance coupling of the traditional FDA and to make the beam energy more concentrated, this paper adopts a multi-carrier FDA structure based on proposed power exponential frequency offset to improve the array structure and frequency offset of the traditional FDA. The simulation results show that the beam pattern of the array can form a dot-shape beam with more concentrated energy, and its resolution and sidelobe level performance are improved. However, the covariance matrix of the signal in the traditional adaptive beamforming algorithm is estimated by the finite-time snapshot data. When the number of snapshots is limited, the algorithm has an underestimation problem, which leads to the estimation error of the covariance matrix to cause beam distortion, so that the output pattern cannot form a dot-shape beam. And it also has main lobe deviation and high sidelobe level problems in the case of limited snapshot. Aiming at these problems, an adaptive beamforming technique based on exponential correction for multi-carrier FDA is proposed to improve beamforming robustness. The steps are as follows: first, the beamforming of the multi-carrier FDA is formed under linear constrained minimum variance (LCMV) criteria. Then the eigenvalue decomposition of the covariance matrix is ​​performed to obtain the diagonal matrix composed of the interference subspace, the noise subspace and the corresponding eigenvalues. Finally, the correction index is introduced to exponentially correct the small eigenvalues ​​of the noise subspace, improve the divergence of small eigenvalues ​​in the noise subspace, and improve the performance of beamforming. The theoretical analysis and simulation results show that the proposed algorithm can make the multi-carrier FDA form a dot-shape beam at limited snapshots, reduce the sidelobe level, improve the robustness of beamforming, and have better performance.

Keywords: adaptive beamforming, correction index, limited snapshot, multi-carrier frequency diverse array, robust

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Authors: Sangho Park, Mansoo Kim, Kyujung Chae, Junhyuk Yang

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The International Maritime Organization (IMO) recognized the problem of invasive species invasion and adopted the "International Convention for the Control and Management of Ships' Ballast Water and Sediments" in 2004, which came into force on September 8, 2017. In 2011, the IMO approved the "Guidelines for the Control and Management of Ships' Biofouling to Minimize the Transfer of Invasive Aquatic Species" to minimize the movement of invasive species by hull-attached organisms and required ships to manage the organisms attached to their hulls. Invasive species enter new environments through ships' ballast water and hull attachment. However, several obstacles to implementing these guidelines have been identified, including a lack of underwater cleaning equipment, regulations on underwater cleaning activities in ports, and difficulty accessing crevices in underwater areas. The shipping industry, which is the party responsible for understanding these guidelines, wants to implement them for fuel cost savings resulting from the removal of organisms attached to the hull, but they anticipate significant difficulties in implementing the guidelines due to the obstacles mentioned above. Robots or people remove the organisms attached to the hull underwater, and the resulting wastewater includes various species of organisms and particles of paint and other pollutants. Currently, there is no technology available to sterilize the organisms in the wastewater or stabilize the heavy metals in the paint particles. In this study, we aim to analyze the characteristics of the wastewater generated from the removal of hull-attached organisms and select the optimal treatment technology. The organisms in the wastewater generated from the removal of the attached organisms meet the biological treatment standard (D-2) using the sterilization technology applied in the ships' ballast water treatment system. The heavy metals and other pollutants in the paint particles generated during removal are treated using stabilization technologies such as thermal decomposition. The wastewater generated is treated using a two-step process: 1) development of sterilization technology through pretreatment filtration equipment and electrolytic sterilization treatment and 2) development of technology for removing particle pollutants such as heavy metals and dissolved inorganic substances. Through this study, we will develop a biological removal technology and an environmentally friendly processing system for the waste generated after removal that meets the requirements of the government and the shipping industry and lays the groundwork for future treatment standards.

Keywords: biofouling, ballast water treatment system, filtration, sterilization, wastewater

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Authors: Y. Mateyshina, A.Ulihin, N.Uvarov

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Electrolytes with different type of charge carrier can find widely application in different using, e.g. sensors, electrochemical equipments, batteries and others. One of important components ensuring stable functioning of the equipment is electrolyte. Electrolyte has to be characterized by high conductivity, thermal stability, and wide electrochemical window. In addition to many advantageous characteristic for liquid electrolytes, the solid state electrolytes have good mechanical stability, wide working range of temperature range. Thus search of new system of solid electrolytes with high conductivity is an actual task of solid state chemistry. Families of alkali perchlorates and nitrates have been investigated by us earlier. In literature data about transport properties of alkali nitrites are absent. Nevertheless, alkali nitrites MeNO2 (Me= Li+, Na+, K+, Rb+ and Cs+), except for the lithium salt, have high-temperature phases with crystal structure of the NaCl-type. High-temperature phases of nitrites are orientationally disordered, i.e. non-spherical anions are reoriented over several equivalents directions in the crystal lattice. Pure lithium nitrite LiNO2 is characterized by ionic conductivity near 10-4 S/cm at 180°C and more stable as compared with lithium nitrate and can be used as a component for synthesis of composite electrolytes. In this work composite solid electrolytes in the binary system LiNO2 - A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) were synthesized and their structural, thermodynamic and electrical properties investigated. Alkali nitrite was obtained by exchange reaction from water solutions of barium nitrite and alkali sulfate. The synthesized salt was characterized by X-ray powder diffraction technique using D8 Advance X-Ray Diffractometer with Cu K radiation. Using thermal analysis, the temperatures of dehydration and thermal decomposition of salt were determined.. The conductivity was measured using a two electrode scheme in a forevacuum (6.7 Pa) with an HP 4284A (Precision LCR meter) in a frequency range 20 Hz < ν < 1 MHz. Solid composite electrolytes LiNO2 - A A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) have been synthesized by mixing of preliminary dehydrated components followed by sintering at 250°C. In the series of nitrite of alkaline metals Li+-Cs+, the conductivity varies not monotonically with increasing radius of cation. The minimum conductivity is observed for KNO2; however, with further increase in the radius of cation in the series, the conductivity tends to increase. The work was supported by the Russian Foundation for Basic research, grant #14-03-31442.

Keywords: conductivity, alkali nitrites, composite electrolytes, transport properties

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Authors: Ahmad Kayvani Fard, Gordon Mckay, Muataz Hussien

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Adsorption/sorption is believed to be one of the optimal processes for the removal of heavy metals from water due to its low operational and capital cost as well as its high removal efficiency. Different materials have been reported in literature as adsorbent for heavy metal removal in waste water such as natural sorbents, organic polymers (synthetic) and mineral materials (inorganic). The selection of adsorbents and development of new functional materials that can achieve good removal of heavy metals from water is an important practice and depends on many factors, such as the availability of the material, cost of material, and material safety and etc. In this study we reported the synthesis of doped Activated carbon and Carbon nanotube (CNT) with different loading of metal oxide nanoparticles such as Fe2O3, Fe3O4, Al2O3, TiO2, SiO2 and Ag nanoparticles and their application in removal of heavy metals, hydrocarbon, and organics from waste water. Commercial AC and CNT with different loadings of mentioned nanoparticle were prepared and effect of pH, adsorbent dosage, sorption kinetic, and concentration effects are studied and optimum condition for removal of heavy metals from water is reported. The prepared composite sorbent is characterized using field emission scanning electron microscopy (FE-SEM), high transmission electron microscopy (HR-TEM), thermogravimetric analysis (TGA), X-ray diffractometer (XRD), the Brunauer, Emmett and Teller (BET) nitrogen adsorption technique, and Zeta potential. The composite materials showed higher removal efficiency and superior adsorption capacity compared to commercially available carbon based adsorbent. The specific surface area of AC increased by 50% reaching up to 2000 m2/g while the CNT specific surface area of CNT increased by more than 8 times reaching value of 890 m2/g. The increased surface area is one of the key parameters along with surface charge of the material determining the removal efficiency and removal efficiency. Moreover, the surface charge density of the impregnated CNT and AC have enhanced significantly where can benefit the adsorption process. The nanoparticles also enhance the catalytic activity of material and reduce the agglomeration and aggregation of material which provides more active site for adsorbing the contaminant from water. Some of the results for treating wastewater includes 100% removal of BTEX, arsenic, strontium, barium, phenolic compounds, and oil from water. The results obtained are promising for the use of AC and CNT loaded with metal oxide nanoparticle in treatment and pretreatment of waste water and produced water before desalination process. Adsorption can be very efficient with low energy consumption and economic feasibility.

Keywords: carbon nanotube, activated carbon, adsorption, heavy metal, water treatment

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Authors: Alex Eldo Simon, Abhishek Yadav

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This study aimed to evaluate the utility of postmortem computed tomography (CT) and heart weight measurements in the assessment of cardiomegaly in cases of sudden death due to cardiac origin by comparing the results of these two diagnostic methods. The study retrospectively analyzed postmortem computed tomography (PMCT) data from 54 cases of sudden natural death and compared the findings with those of the autopsy. The study involved measuring the cardiothoracic ratio (CTR) from coronal computed tomography (CT) images and determining the actual cardiac weight by weighing the heart during the autopsy. The inclusion criteria for the study were cases of sudden death suspected to be caused by cardiac pathology, while exclusion criteria included death due to unnatural causes such as trauma or poisoning, diagnosed natural causes of death related to organs other than the heart, and cases of decomposition. Sensitivity, specificity, and diagnostic accuracy were calculated, and to evaluate the accuracy of using the cardiothoracic ratio (CTR) to detect an enlarged heart, the study generated receiver operating characteristic (ROC) curves. The cardiothoracic ratio (CTR) is a radiological tool used to assess cardiomegaly by measuring the maximum cardiac diameter in relation to the maximum transverse diameter of the chest wall. The clinically used criteria for CTR have been modified from 0.50 to 0.57 for use in postmortem settings, where abnormalities can be detected by comparing CTR values to this threshold. A CTR value of 0.57 or higher is suggestive of hypertrophy but not conclusive. Similarly, heart weight is measured during the traditional autopsy, and a cardiac weight greater than 450 grams is defined as hypertrophy. Of the 54 cases evaluated, 22 (40.7%) had a cardiothoracic ratio (CTR) ranging from > 0.50 to equal 0.57, and 12 cases (22.2%) had a CTR greater than 0.57, which was defined as hypertrophy. The mean CTR was calculated as 0.52 ± 0.06. Among the 54 cases evaluated, the weight of the heart was measured, and the mean was calculated as 369.4 ± 99.9 grams. Out of the 54 cases evaluated, 12 were found to have hypertrophy as defined by PMCT, while only 9 cases were identified with hypertrophy in traditional autopsy. The sensitivity and specificity of the test were calculated as 55.56% and 84.44%, respectively. The sensitivity of the hypertrophy test was found to be 55.56% (95% CI: 26.66, 81.12¹), the specificity was 84.44% (95% CI: 71.22, 92.25¹), and the diagnostic accuracy was 79.63% (95% CI: 67.1, 88.23¹). The limitation of the study was a low sample size of only 54 cases, which may limit the generalizability of the findings. The comparison of the cardiothoracic ratio with heart weight in this study suggests that PMCT may serve as a screening tool for medico-legal autopsies when performed by forensic pathologists. However, it should be noted that the low sensitivity of the test (55.5%) may limit its diagnostic accuracy, and therefore, further studies with larger sample sizes and more diverse populations are needed to validate these findings.

Keywords: PMCT, virtopsy, CTR, cardiothoracic ratio

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Authors: Byomakesh Debata, Jitendra Mahakud

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The recent financial crisis has been characterized by massive monetary policy interventions by the Central bank, and it has amplified the importance of liquidity for the stability of the stock market. This paper empirically elucidates the actual impact of monetary policy interventions on stock market liquidity covering all National Stock Exchange (NSE) Stocks, which have been traded continuously from 2002 to 2015. The present study employs a multivariate VAR model along with VAR-granger causality test, impulse response functions, block exogeneity test, and variance decomposition to analyze the direction as well as the magnitude of the relationship between monetary policy and market liquidity. Our analysis posits a unidirectional relationship between monetary policy (call money rate, base money growth rate) and aggregate market liquidity (traded value, turnover ratio, Amihud illiquidity ratio, turnover price impact, high-low spread). The impulse response function analysis clearly depicts the influence of monetary policy on stock liquidity for every unit innovation in monetary policy variables. Our results suggest that an expansionary monetary policy increases aggregate stock market liquidity and the reverse is documented during the tightening of monetary policy. To ascertain whether our findings are consistent across all periods, we divided the period of study as pre-crisis (2002 to 2007) and post-crisis period (2007-2015) and ran the same set of models. Interestingly, all liquidity variables are highly significant in the post-crisis period. However, the pre-crisis period has witnessed a moderate predictability of monetary policy. To check the robustness of our results we ran the same set of VAR models with different monetary policy variables and found the similar results. Unlike previous studies, we found most of the liquidity variables are significant throughout the sample period. This reveals the predictability of monetary policy on aggregate market liquidity. This study contributes to the existing body of literature by documenting a strong predictability of monetary policy on stock liquidity in an emerging economy with an order driven market making system like India. Most of the previous studies have been carried out in developing economies with quote driven or hybrid market making system and their results are ambiguous across different periods. From an eclectic sense, this study may be considered as a baseline study to further find out the macroeconomic determinants of liquidity of stocks at individual as well as aggregate level.

Keywords: market liquidity, monetary policy, order driven market, VAR, vector autoregressive model

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Authors: A. O. Adenaiya, S. F. Curling, O. Y. Ogunsanwo, G . A. Ormondroyd

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Treatment of wood with chemicals in order to prolong its service life may prove difficult in some refractory wood species. This impermeability in wood is usually due to biochemical changes which occur during heartwood formation. Bioincision, which is a short-term, controlled microbial decomposition of wood, is one of the promising approaches capable of improving the amenability of refractory wood to chemical treatments. Gmelina Arborea, a mainstay timber species in Nigeria, has impermeable heartwood due to the excessive tyloses which occlude its vessels. Therefore, the chemical uptake and penetration in Gmelina arborea heartwood bioincised with Inonotus dryophilus fungus was investigated. Five mature Gmelina Arborea trees were harvested at the Departmental plantation in Ajibode, Ibadan, Nigeria and a bolt of 300 cm was obtained from the basal portion of each tree. The heartwood portion of the bolts was extracted and converted into dimensions 20 mm x 20 mm x 60 mm and subsequently conditioned (200C at 65% Relative Humidity). Twenty wood samples each were bioincised with the white-rot fungus Inonotus dryophilus (ID, 999) for 3, 5, 7 and 9 weeks using standard procedure, while a set of sterile control samples were prepared. Ten of each bioincised and control sample were pressure-treated with 5% tanalith preservative, while the other ten of each bioincised and control samples were pressure-treated with a liquid dye for easy traceability of the chemical in the wood, both using a full cell treatment process. The bioincised and control samples were evaluated for their Weight Loss before chemical treatment (WL, %), Preservative Absorption (PA, Kg/m3), Preservative Retention (PR, Kg/m3), Axial Absorption (AA, Kg/m3), Lateral Absorption (LA, Kg/m3), Axial Penetration Depth (APD, mm), Radial Penetration Depth (RPD, mm), and Tangential Penetration Depth (TPD, mm). The data obtained were analyzed using ANOVA at α0.05. Results show that the weight loss was least in the samples bioincised for three weeks (0.09%) and highest after 7 weeks of bioincision (0.48%). The samples bioincised for 3 weeks had the least PA (106.72 Kg/m3) and PR (5.87 Kg/m3), while the highest PA (134.9 Kg/m3) and PR were observed after 7 weeks of bioincision (7.42 Kg/m3). The AA ranged from 27.28 Kg/m3 (3 weeks) to 67.05 Kg/m3 (5 weeks), while the LA was least after 5 weeks of incubation (28.1 Kg/m3) and highest after 9 weeks (71.74 Kg/m3). Significantly lower APD was observed in control samples (6.97 mm) than in the samples bioincised after 9weeks (19.22 mm). The RPD increased from 0.08 mm (control samples) to 3.48 mm (5 weeks), while TPD ranged from 0.38 mm (control samples) to 0.63 mm (9 weeks), implying that liquid flow in the wood was predominantly through the axial pathway. Bioincising G. arborea heartwood with I. dryophilus fungus for 9 weeks is capable of enhancing chemical uptake and deeper penetration of chemicals in the wood through the degradation of the occluding vessel tyloses, which is accompanied by a minimal degradation of the polymeric wood constituents.

Keywords: Bioincision, chemical uptake, penetration depth, refractory wood, tyloses

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Authors: Kuheli Chakrabarty, Animesh Ghosh, Atanu Roy, Gourab Kanti Das

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Aldol reaction is an important class of carbon-carbon bond forming reactions. One of the popular ways to impose asymmetry in aldol reaction is the introduction of chiral auxiliary that binds the approaching reactants and create dissymmetry in the reaction environment, which finally evolves to enantiomeric excess in the aldol products. The last decade witnesses the usage of natural amino acids as chiral auxiliary to control the stereoselectivity in various carbon-carbon bond forming processes. In this context, L-proline was found to be an effective organocatalyst in asymmetric aldol additions. In last few decades the use of water as solvent or co-solvent in asymmetric organocatalytic reaction is increased sharply. Simple amino acids like L-proline does not catalyze asymmetric aldol reaction in aqueous medium not only that, In organic solvent medium high catalytic loading (~30 mol%) is required to achieve moderate to high asymmetric induction. In this context, huge efforts have been made to modify L-proline and 4-hydroxy-L-proline to prepare organocatalyst for aqueous medium asymmetric aldol reaction. Here, we report the result of our DFT calculations on asymmetric aldol reaction of benzaldehyde, p-NO2 benzaldehyde and t-butyraldehyde with a number of ketones using L-proline hydrazide as organocatalyst in wet solvent free condition. Gaussian 09 program package and Gauss View program were used for the present work. Geometry optimizations were performed using B3LYP hybrid functional and 6-31G(d,p) basis set. Transition structures were confirmed by hessian calculation and IRC calculation. As the reactions were carried out in solvent free condition, No solvent effect were studied theoretically. Present study has revealed for the first time, the direct involvement of two water molecules in the aldol transition structures. In the TS, the enamine and the aldehyde is connected through hydrogen bonding by the assistance of two intervening water molecules forming a supramolecular network. Formation of this type of supramolecular assembly is possible due to the presence of protonated -NH2 group in the L-proline hydrazide moiety, which is responsible for the favorable entropy contribution to the aldol reaction. It is also revealed from the present study that, water assisted TS is energetically more favorable than the TS without involving any water molecule. It can be concluded from this study that, insertion of polar group capable of hydrogen bond formation in the L-proline skeleton can lead to a favorable aldol reaction with significantly high enantiomeric excess in wet solvent free condition by reducing the activation barrier of this reaction.

Keywords: aldol reaction, DFT, organocatalysis, transition structure

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However, the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol-gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The as-prepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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Authors: Augustus K. Lebechi, Kenneth I. Ozoemena

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Rechargeable zinc-air batteries (RZABs) have been described as one of the most viable next-generation ‘beyond-the-lithium-ion’ battery technologies with great potential for renewable energy storage. It is safe, with a high specific energy density (1086 Wh/kg), environmentally benign, and low-cost, especially in resource-limited African countries. For widespread commercialization, the sluggish oxygen reaction kinetics pose a major challenge that impedes the reversibility of the system. Hence, there is a need for low-cost and highly active bifunctional electrocatalysts. Manganese oxide catalysts on carbon conducting additives remain the best couple for the realization of such low-cost RZABs. In this work, hausmannite Mn₃O₄ nanoparticles were synthesized through the annealing method from commercial electrolytic manganese dioxide (EMD), multi-walled carbon nanotubes (MWCNTs) were synthesized via the chemical vapor deposition (CVD) method and carbon nanofibers (CNFs) were synthesized via the electrospinning process with subsequent carbonization. Both Mn₃O₄ catalysts and the carbon conducting additives (MWCNT and CNF) were thoroughly characterized using X-ray powder diffraction spectroscopy (XRD), scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and X-ray photoelectron spectroscopy (XPS). Composite electrocatalysts (Mn₃O₄/CNT and Mn₃O₄/CNF) were investigated for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in an alkaline medium. Using the established electrocatalytic modalities for evaluating the electrocatalytic performance of materials (including double layer, electrochemical active surface area, roughness factor, specific current density, and catalytic stability), CNFs proved to be the most efficient conducting additive material for the Mn₃O₄ catalyst. From the DFT calculations, the higher performance of the CNFs over the MWCNTs is related to the ability of the CNFs to allow for a more favorable distribution of the d-electrons of the manganese (Mn) and enhanced synergistic effect with Mn₃O₄ for weaker adsorption energies of the oxygen intermediates (O*, OH* and OOH*). In a proof-of-concept, Mn₃O₄/CNF was investigated as the air cathode for rechargeable zinc-air battery (RZAB) in a micro-3D-printed cell configuration. The RZAB showed good performance in terms of open circuit voltage (1.77 V), maximum power density (177.5 mW cm-2), areal-discharge energy and cycling stability comparable to Pt/C (20 wt%) + IrO2. The findings here provide fresh physicochemical perspectives on the future design and utility of CNFs for developing manganese-based RZABs.

Keywords: bifunctional electrocatalyst, oxygen evolution reaction, oxygen reduction reactions, rechargeable zinc-air batteries.

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Authors: Mehran Nozari-Asbemarz, Italo Pisano, Simin Arshi, Edmond Magner, James J. Leahy

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Integrating electrolytic synthesis with renewable energy makes it feasible to address urgent environmental and energy challenges. Conventional water electrolyzers concurrently produce H₂ and O₂, demanding additional procedures in gas separation to prevent contamination of H₂ with O₂. Moreover, the oxygen evolution reaction (OER), which is sluggish and has a low overall energy conversion efficiency, does not deliver a significant value product on the electrode surface. Compared to conventional water electrolysis, integrating electrolytic hydrogen generation from water with thermodynamically more advantageous aqueous organic oxidation processes can increase energy conversion efficiency and create value-added compounds instead of oxygen at the anode. One strategy is to use renewable and sustainable carbon sources from biomass, which has a large annual production capacity and presents a significant opportunity to supplement carbon sourced from fossil fuels. Numerous catalytic techniques have been researched in order to utilize biomass economically. Because of its safe operating conditions, excellent energy efficiency, and reasonable control over production rate and selectivity using electrochemical parameters, electrocatalytic upgrading stands out as an appealing choice among the numerous biomass refinery technologies. Therefore, we propose a broad framework for coupling H2 generation from water splitting with oxidative biomass upgrading processes. Four representative biomass targets were considered for oxidative upgrading that used a hierarchically porous CoFe-MOF/LDH @ Graphite Paper bifunctional electrocatalyst, including glucose, ethanol, benzyl, furfural, and 5-hydroxymethylfurfural (HMF). The potential required to support 50 mA cm-2 is considerably lower than (~ 380 mV) the potential for OER. All four compounds can be oxidized to yield liquid byproducts with economic benefit. The electrocatalytic oxidation of glucose to the value-added products, gluconic acid, glucuronic acid, and glucaric acid, was examined in detail. The cell potential for combined H₂ production and glucose oxidation was substantially lower than for water splitting (1.44 V(RHE) vs. 1.82 V(RHE) for 50 mA cm-2). In contrast, the oxidation byproduct at the anode was significantly more valuable than O₂, taking advantage of the more favorable glucose oxidation in comparison to the OER. Overall, such a combination of HER and oxidative biomass valorization using electrocatalysts prevents the production of potentially explosive H₂/O₂mixtures and produces high-value products at both electrodes with lower voltage input, thereby increasing the efficiency and activity of electrocatalytic conversion.

Keywords: biomass, electrocatalytic, glucose oxidation, hydrogen evolution

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Authors: Alessio Varotto, Lorenzo Freschi, Umberto Pasqual Laverdura, Anastasia Moschovi, Davide Pumiglia, Iakovos Yakoumis, Marta Feroci, Maria Luisa Grilli

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Dry reforming of Methane (DRM) is considered one of the most valuable technologies for green-house gas valorization thanks to the fact that through this reaction, it is possible to obtain syngas, a mixture of H₂ and CO in an H₂/CO ratio suitable for utilization in the Fischer-Tropsch process of high value-added chemicals and fuels. Challenges of the DRM process are the reduction of costs due to the high temperature of the process and the high cost of precious metals of the catalyst, the metal particles sintering, and carbon deposition on the catalysts’ surface. The aim of this study is to demonstrate the feasibility of the synthesis of catalysts using a leachate solution containing Pt coming directly from the recovery of spent diesel oxidation catalysts (DOCs) without further purification. An unusual perovskite support for DRM, the BaCe₁₋ₓ₋ᵧZrₓGdᵧO₃ (BCZG) perovskite, has been chosen as the catalyst support because of its high thermal stability and capability to produce oxygen vacancies, which suppress the carbon deposition and enhance the catalytic activity of the catalyst. BCZG perovskite has been synthesized by a sol-gel modified Pechini process and calcinated in air at 1100 °C. BCZG supports have been impregnated with a Pt-containing leachate solution of DOC, obtained by a mild hydrometallurgical recovery process, as reported elsewhere by some of the authors of this manuscript. For comparison reasons, a synthetic solution obtained by digesting commercial Pt-black powder in aqua regia was used for BCZG support impregnation. Pt nominal content was 2% in both BCZG-based catalysts formed by real and synthetic solutions. The structure and morphology of catalysts were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Thermogravimetric Analysis (TGA) was used to study the thermal stability of the catalyst’s samples. Brunauer-Emmett-Teller (BET) analysis provided a high surface area of the catalysts. H₂-TPR (Temperature Programmed Reduction) analysis was used to study the consumption of hydrogen for reducibility, and it was associated with H₂-TPD characterization to study the dispersion of Pt on the surface of the support and calculate the number of active sites used by the precious metal. Dry reforming of methane (DRM) reaction, carried out in a fixed bed reactor, showed a high conversion efficiency of CO₂ and CH4. At 850°C, CO₂ and CH₄ conversion were close to 100% for the catalyst obtained with the aqua regia-based solution of commercial Pt-black, and ~70% (for CH₄) and ~80 % (for CO₂) in the case of real HCl-based leachate solution. H₂/CO ratios were ~0.9 and ~0.70 in the first and latter cases, respectively. As far as we know, this is the first pioneering work in which a BCGZ catalyst and a real Pt-containing leachate solution were successfully employed for DRM reaction.

Keywords: dry reforming of methane, perovskite, PGM, recycled Pt, syngas

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Authors: Ana M. Antolín, Sandra Contreras, Francesc Medina, Didier Tichit

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Introduction: High levels of nitrates (> 50 ppm NO3-) in drinking water are potentially risky to human health. In the recent years, the trend of nitrate concentration in groundwater is rising in the EU and other countries. Conventional catalytic nitrate reduction processes into N2 and H2O lead to some toxic intermediates and by-products, such as NO2-, NH4+, and NOx gases. Alternatively, photocatalytic nitrate removal using solar irradiation and heterogeneous catalysts is a very promising and ecofriendly technique. It has been scarcely performed and more research on highly efficient catalysts is still needed. In this work, different nanocatalysts supported on Aeroxide Titania P25 (P25) have been prepared varying: 0.5-4 % wt. Ag); Pt (2, 4 % wt.); Pt precursor (H2PtCl6/K2PtCl6); and impregnation order of both metals. Pt was chosen in order to increase the selectivity to N2 and decrease that to NO2-. Catalysts were characterized by nitrogen physisorption, X-Ray diffraction, UV-visible spectroscopy, TEM and X Ray-Photoelectron Spectroscopy. The aim was to determine the influence of the composition and the preparation method of the catalysts on the conversion and selectivity in the nitrate reduction, as well as going through an overall and better understanding of the process. Nanocatalysts synthesis: For the mono and bimetallic catalysts preparation, wise-drop wetness impregnation of the precursors (AgNO3, H2PtCl6, K2PtCl6) followed by a reduction step (NaBH4) was used to obtain the metal colloids. Results and conclusions: Denitration experiments were performed in a 350 mL PTFE batch reactor under inert standard operational conditions, ultraviolet irradiations (λ=254 nm (UV-C); λ=365 nm (UV-A)), and presence/absence of hydrogen gas as a reducing agent, contrary to most studies using oxalic or formic acid. Samples were analyzed by Ionic Chromatography. Blank experiments using respectively P25 (dark conditions), hydrogen only and UV irradiations without hydrogen demonstrated a clear influence of the presence of hydrogen on nitrate reduction. Also, they demonstrated that UV irradiation increased the selectivity to N2. Interestingly, the best activity was obtained under ultraviolet lamps, especially at a closer wavelength to visible light irradiation (λ = 365 nm) and H2. 2% Ag/P25 leaded to the highest NO3- conversion among the monometallic catalysts. However, nitrite quantities have to be diminished. On the other hand, practically no nitrate conversion was observed with the monometallics based on Pt/P25. Therefore, the amount of 2% Ag was chosen for the bimetallic catalysts. Regarding the bimetallic catalysts, it is observed that the metal impregnation order, amount and Pt precursor highly affects the results. Higher selectivity to the desirable N2 gas is obtained when Pt was firstly added, especially with K2PtCl6 as Pt precursor. This suggests that when Pt is secondly added, it covers the Ag particles, which are the most active in this reaction. It could be concluded that Ag allows the nitrate reduction step to nitrite, and Pt the nitrite reduction step toward the desirable N2 gas.

Keywords: heterogeneous catalysis, hydrogenation, nanocatalyst, nitrate removal, photocatalysis

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Authors: Venkata Ramanaiah, Shabina Khanam

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Enormous potential for saving energy is available in coal-based sponge iron plants as these are associated with the high percentage of energy wastage per unit sponge iron production. An energy integration option is proposed, in the present paper, to a coal based sponge iron plant of 100 tonnes per day production capacity, being operated in India using SL/RN (Stelco-Lurgi/Republic Steel-National Lead) process. It consists of the rotary kiln, rotary cooler, dust settling chamber, after burning chamber, evaporating cooler, electrostatic precipitator (ESP), wet scrapper and chimney as important equipment. Principles of process integration are used in the proposed option. It accounts for preheating kiln inlet streams like kiln feed and slinger coal up to 170ᴼC using waste gas exiting ESP. Further, kiln outlet stream is cooled from 1020ᴼC to 110ᴼC using kiln air. The working areas in the plant where energy is being lost and can be conserved are identified. Detailed material and energy balances are carried out around the sponge iron plant, and a modified model is developed, to find coal requirement of proposed option, based on hot utility, heat of reactions, kiln feed and air preheating, radiation losses, dolomite decomposition, the heat required to vaporize the coal volatiles, etc. As coal is used as utility and process stream, an iterative approach is used in solution methodology to compute coal consumption. Further, water consumption, operating cost, capital investment, waste gas generation, profit, and payback period of the modification are computed. Along with these, operational aspects of the proposed design are also discussed. To recover and integrate waste heat available in the plant, three gas-solid heat exchangers and four insulated ducts with one FD fan for each are installed additionally. Thus, the proposed option requires total capital investment of $0.84 million. Preheating of kiln feed, slinger coal and kiln air streams reduce coal consumption by 24.63% which in turn reduces waste gas generation by 25.2% in comparison to the existing process. Moreover, 96% reduction in water is also observed, which is the added advantage of the modification. Consequently, total profit is found as $2.06 million/year with payback period of 4.97 months only. The energy efficient factor (EEF), which is the % of the maximum energy that can be saved through design, is found to be 56.7%. Results of the proposed option are also compared with literature and found in good agreement.

Keywords: coal consumption, energy conservation, process integration, sponge iron plant

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Authors: Sankha Chakrabortty, Biswajit Ruj, Parimal Pal

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Methanol is one of the most important chemical products and intermediates. It can be used as a solvent, intermediate or raw material for a number of higher valued products, fuels or additives. From the last one decay, the total global demand of methanol has increased drastically which forces the scientists to produce a large amount of methanol from a renewable source to meet the global demand with a sustainable way. Different types of non-renewable based raw materials have been used for the synthesis of methanol on a large scale which makes the process unsustainable. In this circumstances, photocatalytic conversion of CO₂ into methanol under solar/UV excitation becomes a viable approach to give a sustainable production approach which not only meets the environmental crisis by recycling CO₂ to fuels but also reduces CO₂ amount from the atmosphere. Development of such sustainable production approach for CO₂ conversion into methanol still remains a major challenge in the current research comparing with conventional energy expensive processes. In this backdrop, the development of environmentally friendly materials, like photocatalyst has taken a great perspective for methanol synthesis. Scientists in this field are always concerned about finding an improved photocatalyst to enhance the photocatalytic performance. Graphene-based hybrid and composite materials with improved properties could be a better nanomaterial for the selective conversion of CO₂ to methanol under visible light (solar energy) or UV light. The present invention relates to synthesis an improved heterogeneous graphene-based photocatalyst with improved catalytic activity and surface area. Graphene with enhanced surface area is used as coupled material of copper-loaded titanium oxide to improve the electron capture and transport properties which substantially increase the photoinduced charge transfer and extend the lifetime of photogenerated charge carriers. A fast reduction method through H₂ purging has been adopted to synthesis improved graphene whereas ultrasonication based sol-gel method has been applied for the preparation of graphene coupled copper loaded titanium oxide with some enhanced properties. Prepared photocatalysts were exhaustively characterized using different characterization techniques. Effects of catalyst dose, CO₂ flow rate, reaction temperature and stirring time on the efficacy of the system in terms of methanol yield and productivity have been studied in the present study. The study shown that the newly synthesized photocatalyst with an enhanced surface resulting in a sustained productivity and yield of methanol 0.14 g/Lh, and 0.04 g/gcat respectively, after 3 h of illumination under UV (250W) at an optimum catalyst dosage of 10 g/L having 1:2:3 (Graphene: TiO₂: Cu) weight ratio.

Keywords: renewable energy, CO₂ capture, photocatalytic conversion, methanol

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Authors: Paramita Banerjee, K. R. S. Chandrakumar, G. P. Das

Abstract:

Bulk MgH2 has drawn much attention for the purpose of hydrogen storage because of its high hydrogen storage capacity (~7.7 wt %) as well as low cost and abundant availability. However, its practical usage has been hindered because of its high hydrogen desorption enthalpy (~0.8 eV/H2 molecule), which results in an undesirable desorption temperature of 3000C at 1 bar H2 pressure. To surmount the limitations of bulk MgH2 for the purpose of hydrogen storage, a detailed first-principles density functional theory (DFT) based study on the structure and stability of neutral (Mgm) and positively charged (Mgm+) Mg nanoclusters of different sizes (m = 2, 4, 8 and 12), as well as their interaction with molecular hydrogen (H2), is reported here. It has been found that due to the absence of d-electrons within the Mg atoms, hydrogen remained in molecular form even after its interaction with neutral and charged Mg nanoclusters. Interestingly, the H2 molecules do not enter into the interstitial positions of the nanoclusters. Rather, they remain on the surface by ornamenting these nanoclusters and forming new structures with a gravimetric density higher than 15 wt %. Our observation is that the inclusion of Grimme’s DFT-D3 dispersion correction in this weakly interacting system has a significant effect on binding of the H2 molecules with these nanoclusters. The dispersion corrected interaction energy (IE) values (0.1-0.14 eV/H2 molecule) fall in the right energy window, that is ideal for hydrogen storage. These IE values are further verified by using high-level coupled-cluster calculations with non-iterative triples corrections i.e. CCSD(T), (which has been considered to be a highly accurate quantum chemical method) and thereby confirming the accuracy of our ‘dispersion correction’ incorporated DFT calculations. The significance of the polarization and dispersion energy in binding of the H2 molecules are confirmed by performing energy decomposition analysis (EDA). A total of 16, 24, 32 and 36 H2 molecules can be attached to the neutral and charged nanoclusters of size m = 2, 4, 8 and 12 respectively. Ab-initio molecular dynamics (AIMD) simulation shows that the outermost H2 molecules are desorbed at a rather low temperature viz. 150 K (-1230C) which is expected. However, complete dehydrogenation of these nanoclusters occur at around 1000C. Most importantly, the host nanoclusters remain stable up to ~500 K (2270C). All these results on the adsorption and desorption of molecular hydrogen with neutral and charged Mg nanocluster systems indicate towards the possibility of reducing the dehydrogenation temperature of bulk MgH2 by designing new Mg-based nano materials which will be able to adsorb molecular hydrogen via this weak Mg-H2 interaction, rather than the strong Mg-H bonding. Notwithstanding the fact that in practical applications, these interactions will be further complicated by the effect of substrates as well as interactions with other clusters, the present study has implications on our fundamental understanding to this problem.

Keywords: density functional theory, DFT, hydrogen storage, molecular dynamics, molecular hydrogen adsorption, nanoclusters, physisorption

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Authors: Mohsen Bahrami, Banafsheh Nikmehr, Yueqiang Song, Anuradha Koduru, Ayse K. Vuruskan, Hongkun Lu, Tamer M. Yalcinkaya

Abstract:

In recent years, we have witnessed an explosion of studies aimed at using a combination of artificial intelligence (AI) and time-lapse imaging data on embryos to improve IVF outcomes. However, despite promising results, no study has used a matched cohort of transferred embryos which only differ in pregnancy outcome, i.e., embryos from a single clinic which are similar in parameters, such as: morphokinetic condition, patient age, and overall clinic and lab performance. Here, we used time-lapse data on embryos with known pregnancy outcomes to see if the rich spatiotemporal information embedded in this data would allow the prediction of the pregnancy outcome regardless of such critical parameters. Methodology—We did a retrospective analysis of time-lapse data from our IVF clinic utilizing Embryoscope 100% of the time for embryo culture to blastocyst stage with known clinical outcomes, including live birth vs nonpregnant (embryos with spontaneous abortion outcomes were excluded). We used time-lapse data from 200 elective single transfer embryos randomly selected from January 2019 to June 2021. Our sample included 100 embryos in each group with no significant difference in patient age (P=0.9550) and morphokinetic scores (P=0.4032). Data from all patients were combined to make a 4th order tensor, and feature extraction were subsequently carried out by a tensor decomposition methodology. The features were then used in a machine learning classifier to classify the two groups. Major Findings—The performance of the model was evaluated using 100 random subsampling cross validation (train (80%) - test (20%)). The prediction accuracy, averaged across 100 permutations, exceeded 80%. We also did a random grouping analysis, in which labels (live birth, nonpregnant) were randomly assigned to embryos, which yielded 50% accuracy. Conclusion—The high accuracy in the main analysis and the low accuracy in random grouping analysis suggest a consistent spatiotemporal pattern which is associated with pregnancy outcomes, regardless of patient age and embryo morphokinetic condition, and beyond already known parameters, such as: early cleavage or early blastulation. Despite small samples size, this ongoing analysis is the first to show the potential of AI methods in capturing the complex morphokinetic changes embedded in embryo time-lapse data, which contribute to successful pregnancy outcomes, regardless of already known parameters. The results on a larger sample size with complementary analysis on prediction of other key outcomes, such as: euploidy and aneuploidy of embryos will be presented at the meeting.

Keywords: IVF, embryo, machine learning, time-lapse imaging data

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Authors: Anjali Vanpariya, Priyanka Marathey, Sakshum Khanna, Roma Patel, Indrajit Mukhopadhyay

Abstract:

Silicon (Si) is a promising negative electrode material for lithium-ion batteries (LiBs) due to its low cost, non-toxicity, and a high theoretical capacity of 4200 mAhg⁻¹. The primary challenge of the application of Si-based LiBs is large volume expansion (~ 300%) during the charge-discharge process. Incorporation of graphene, carbon nanotubes (CNTs), morphological control, and nanoparticles was utilized as effective strategies to tackle volume expansion issues. However, molten salt methods can resolve the issue, but high-temperature requirement limits its application. For sustainable and practical approach, room temperature (RT) based methods are essentially required. Use of ionic liquids (ILs) for electrodeposition of Si nanostructures can possibly resolve the issue of temperature as well as greener media. In this work, electrodeposition of Si nanoparticles on gold substrate was successfully carried out in the presence of ILs media, 1-butyl-3-methylimidazolium-bis (trifluoromethyl sulfonyl) imide (BMImTf₂N) at room temperature. Cyclic voltammetry (CV) suggests the sequential reduction of Si⁴⁺ to Si²⁺ and then Si nanoparticles (SiNs). The structure and morphology of the electrodeposited SiNs were investigated by FE-SEM and observed interconnected Si nanoparticles of average particle size ⁓100-200 nm. XRD and XPS data confirm the deposition of Si on Au (111). The first discharge-charge capacity of Si anode material has been found to be 1857 and 422 mAhg⁻¹, respectively, at current density 7.8 Ag⁻¹. The irreversible capacity of the first discharge-charge process can be attributed to the solid electrolyte interface (SEI) formation via electrolyte decomposition, and trapped Li⁺ inserted into the inner pores of Si. Pulverization of SiNs results in the creation of a new active site, which facilitates the formation of new SEI in the subsequent cycles leading to fading in a specific capacity. After 20 cycles, charge-discharge profiles have been stabilized, and a reversible capacity of 150 mAhg⁻¹ is retained. Electrochemical impedance spectroscopy (EIS) data shows the decrease in Rct value from 94.7 to 47.6 kΩ after 50 cycles of charge-discharge, which demonstrates the improvements of the interfacial charge transfer kinetics. The decrease in the Warburg impedance after 50 cycles of charge-discharge measurements indicates facile diffusion in fragmented and smaller Si nanoparticles. In summary, Si nanoparticles deposited on gold substrate using ILs as media and characterized well with different analytical techniques. Synthesized material was successfully utilized for LiBs application, which is well supported by CV and EIS data.

Keywords: silicon nanoparticles, ionic liquid, electrodeposition, cyclic voltammetry, Li-ion battery

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Authors: Andrea Dragu, Solen Kinayyigit, Valerie Colliere, Karin Karin Philippot, Camelia Bala, Vasile I. Parvulescu

Abstract:

The production of transportation fuels from biomass has gained a growing attention due to diminishing fossil fuel reserves, rising petroleum prices and increasing concern about global warming. In recent years, renewable hydrocarbons that are completely fungible with fossil fuels have been suggested to be efficiently produced by catalytic deoxygenation of fatty acids and their derivatives viadecarboxylation / decarbonylation. Several triglycerides (tall oil fatty acids) and saturated/unsaturated fatty acids and their corresponding esters were used as feedstocks. Their impact together with the influence of the reaction conditions and the catalyst composition on the nature of the reaction pathways of the deoxygenation of vegetable oils and their derivatives were recently reviewed. Following this state of the art the aim of the present study was the investigation of Pd NPs deposited onto mesoporous carbon supports as active and stable catalysts for the deoxygenation of oleic acid. The catalysts were prepared by the deposition of Pd NPs synthesised following an organometallic route on mesoporous carbons with different characteristics. Experiments were carried out under both batch and flow conditions. They demonstrated that under batch conditions (200 atm; 573K), the extent of the reaction depended, firstly, on the Pd loading and then on the metal dispersion and the oxidation state of palladium, both influenced by the way the support has been treated before the NPs deposition and by the preparation/stabilization methodology of Pd NPs. No aromatic compounds were detected in the reaction products but octadecanol and octadecane were observed in large extents. Under flow conditions (4 atm; 573 K), the conversion of stearic acid was superior to that observed in batch conditions. The product mixture contained over 20% heptadecane. No octadecanol, octadecane, and aromatic compounds were detected. The maxima in performances are obtained after only 0.5 h. After that, the yields in heptadecane suffer from a severe decrease until 3h reaction time. However, at that time, stopping feeding the reactor with oleic acid and flushing the catalyst only with mesitylene recovered the activity and the selectivity of the catalysts. With the complete removal of H2, the analysis revealed the presence of heptadecene in high excess compared to heptadecane (almost 7 to 1), thus suggesting decarbonylation as the main route. ICP-OES measurements indicated no leaching of palladium and simple washing of catalysts with mesitylene allowed recycling without any change in conversion or product distribution. Noteworthy, mesitylene as solvent exhibited no effect in this reaction. In conclusion, this study demonstrates the feasibility of such catalysts for the green production of fuels from biomass.

Keywords: fuels from biomass, green catalyst, Pd nano-particles , recycble catalyst

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