Search results for: electrocatalytic properties

Authors: Mr. Liju Elias, A. Chitharanjan Hegde

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Ni-W alloy coatings have been developed galvanostatically on copper substrate from tri-sodium citrate bath, using glycerol as the additive. The deposition conditions for production of Ni-W coatings have been optimized for peak performance of their electrocatalytic activity, namely hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The corrosion behavior of the coatings were tested under working conditions of electrocatalysis (1M KOH). Electrocatalytic behaviours were tested by cyclic voltammetry and chrono-potentiometry techniques. Experimental results demonstrated that Ni-W coatings at low and high current densities (c. d.) showing superior performance for OER and HER respectively. The increased electrocatalytic activity for HER with increase of deposition c. d. was attributed to the phase structure, surface morphology and chemical composition of the coatings, confirmed by XRD, SEM and EDX analysis, respectively. The dependency of hardness and thickness of the coatings on HER and OER were examined, and results were discussed.

Keywords: electrocatalytic behavior, HER, Ni-W alloy, OER

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Authors: Chia-Ting Chang, Chia-Yu Lin

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We report on the decisive role of iron phosphate (FePO₄), formed in-situ during the electrochemical characterization, played in the electrocatalytic activity, especially its oxygen tolerance of iron oxides towards H₂O₂ reduction. Iron oxides studied including, Nanorod arrays (NRs) of β-FeOOH, γ-Fe₂O₃, α-Fe₂O₃, α-Fe₂O₃ nanosheets (α-Fe₂O₃NS), α-Fe₂O₃ nanoparticles (α-Fe₂O₃NP), were synthesized using chemical bath deposition. The nanostructure was controlled simply by adjusting the composition of precursor solution and reaction duration for CBD process, whereas the crystal phase was controlled by adjusting the annealing temperature. It was found that iron phosphate (FePO₄) was deposited in-situ onto the surface of this nanostructured α-Fe₂O₃ during the electrochemical pretreatment in the phosphate electrolyte, and both FePO₄ and α-Fe₂O₃ showed the activity in catalysing the electrochemical reduction of H₂O₂. In addition, the interaction/compatibility between deposited FePO₄ and iron oxides has a decisive effect on the overall electrocatalytic activity of the resultant electrodes; FePO₄ only showed synergetic effect on the overall electrocatalytic activity of α-Fe₂O₃NR and α-Fe2O₃NS. Both α-Fe₂O₃NR and α-Fe₂O₃NS showed two reduction peaks in phosphate electrolyte containing H₂O₂, one being pH-dependent and related to the electrocatalytic properties of FePO₄, and the other one being pH-independent and only related to the intrinsic electrocatalytic properties of α-Fe₂O₃NR and α-Fe₂O₃NS. However, all iron oxides showed only one pH-independent reductive peak in non-phosphate electrolyte containing H₂O₂. The synergesitic catalysis exerted by FePO₄ with α-Fe₂O₃NR or α-Fe₂O₃NS providing additional oxygen-insensitive active site for H₂O₂ reduction, which allows their applications to electrochemical detection of H₂O₂ without the interference of O₂ involving in oxidase-catalyzed chemical processes.

Keywords: H₂O₂ reduction, Iron oxide, iron phosphate, O₂ tolerance

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Authors: Sujit Kumar Guchhait, Subir Paul

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One of the major research areas is to find an alternative source of energy to fulfill the energy crisis and environmental problems. The Fuel cell is such kind of energy producing unit. Use of fuel cell to produce renewable energy for commercial purpose is limited by the high cost of Pt based electrode material. Development of high energetic, as well as inexpensive fuel cell electrode materials, is needs of hour to produce clean energy using derive bio-fuel. In this present investigation, inexpensive Cu-Ni-CeO2 electrode material has been synthesized by using pulse current. The surface morphology of the electrode materials is controlled by several deposition parameters to increase the rate of electrochemical oxidation of alcoholic fuel, ethanol. The electrochemical characterization of the developed material was done by Cyclic Voltammetry (CV) and Chronoamperometry (CA) and Electrochemical Impedance Spectroscopy test. It is interesting to find that both these materials have shown high electrocatalytic properties in terms of high exchange current density (I0), low polarization resistance (Rp) and low impedance. It is seen that the addition of CeO2 to Ni-Cu has outperformed Pt as far as high electrocatalytic properties are concerned. The exchange current density on the Cu-Ni-CeO2 electrode surface for ethanol oxidation is about eight times higher than the same on the Pt surface with much lower polarization resistance than the later. The surface morphology of the electrode materials has been revealed by Field Effect Scanning Electron Microscope (FESEM). It is seen that grains are narrow and subspherical with 3D surface containing pores in between two elongated grains. XRD study exhibits the presence of Ni and CeO2 on the Cu surface.

Keywords: electro-catalyst, alcoholic fuel, cyclic voltammetry, potentiodynamic polarization, EIS, XRD, SEM

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Authors: Md. Abdul Aziz

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Sulfide ion is water soluble, highly corrosive, toxic and harmful to the human beings. As a result, knowing the exact concentration of sulfide in water is very important. However, the existing detection and quantification methods have several shortcomings, such as high cost, low sensitivity, and massive instrumentation. Consequently, the development of novel sulfide sensor is relevant. Nevertheless, electrochemical methods gained enormous popularity due to a vast improvement in the technique and instrumentation, portability, low cost, rapid analysis and simplicity of design. Successful field application of electrochemical devices still requires vast improvement, which depends on the physical, chemical and electrochemical aspects of the working electrode. The working electrode made of bulk gold (Au) and platinum (Pt) are quite common, being very robust and endowed with good electrocatalytic properties. High cost, and electrode poisoning, however, have so far hindered their practical application in many industries. To overcome these obstacles, we developed a sulfide sensor based on an indium tin oxide nanoparticle (ITONP)-modified ITO electrode. To prepare ITONP-modified ITO, various methods were tested. Drop-drying of ITONPs (aq.) on aminopropyltrimethoxysilane-functionalized ITO (APTMS/ITO) was found to be the best method on the basis of voltammetric analysis of the sulfide ion. ITONP-modified APTMS/ITO (ITONP/APTMS/ITO) yielded much better electrocatalytic properties toward sulfide electro-οxidation than did bare or APTMS/ITO electrodes. The ITONPs and ITONP-modified ITO were also characterized using transmission electron microscopy and field emission scanning electron microscopy, respectively. Optimization of the type of inert electrolyte and pH yielded an ITONP/APTMS/ITO detector whose amperometrically and chronocoulοmetrically determined limits of detection for sulfide in aqueous solution were 3.0 µM and 0.90 µM, respectively. ITONP/APTMS/ITO electrodes which displayed reproducible performances were highly stable and were not susceptible to interference by common contaminants. Thus, the developed electrode can be considered as a promising tool for sensing sulfide.

Keywords: amperometry, chronocoulometry, electrocatalytic properties, ITO-nanoparticle-modified ITO, sulfide sensor

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Authors: Mohamed H. El-Newehy, Badr M. Thamer, Nasser A. M. Barakat, Mohammad A.Abdelkareem, Salem S. Al-Deyab, Hak Y. Kim

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In this study, the influence of nitrogen doping on the electrocatalytic activity of carbon nanofibers with nickel nanoparticles toward methanol oxidation is introduced. The modified carbon nanofibers have been synthesized from calcination of electrospun nanofiber mats composed of nickel acetate tetrahydrate, poly(vinyl alcohol) and urea in argon atmosphere at 750oC. The utilized physicochemical characterizations indicated that the proposed strategy leads to form carbon nanofibers having nickel nanoparticles and doped by nitrogen. Moreover, due to the high-applied voltage during the electrospinning process, the utilized urea chemically bonds with the polymer matrix, which leads to form nitrogen-doped CNFs after the calcination process. Investigation of the electrocatalytic activity indicated that nitrogen doping NiCNFs strongly enhances the oxidation process of methanol as the current density increases from 52.5 to 198.5 mA/cm2 when the urea content in the original electrospun solution was 4 wt% urea. Moreover, the nanofibrous morphology exhibits distinct impact on the electrocatalytic activity. Also, nitrogen-doping enhanced the stability of the introduced Ni-based electrocatalyst. Overall, the present study introduces effective and simple strategy to modify the electrocatalytic activity of the nickel-based materials.

Keywords: electrospinning, methanol electrooxidation, fuel cells, nitrogen-doping, nickel

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Authors: Mirko Ante, Şeniz Sörgel, Andreas Bund

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Li-S- (Lithium-Sulfur-) battery systems provide very high specific gravimetric energy (2600 Wh/kg) and volumetric energy density (2800Wh/l). Hence, Li-S batteries are one of the key technologies for both the upcoming electromobility and stationary applications. Furthermore, the Li-S battery system is potentially cheap and environmentally benign. However, the technical implementation suffers from cycling stability, low charge and discharge rates and incomplete understanding of the complex polysulfide reaction mechanism. The aim of this work is to develop an effective electrocatalyst for the polysulfide reactions so that the electrode kinetics of the sulfur half-cell will be improved. Accordingly, the overvoltage will be decreased, and the efficiency of the cell will be increased. An enhanced electroactive surface additionally improves the charge and discharge rates. To reach this goal, functionalized electrocatalytic coatings are investigated to accelerate the kinetics of the polysulfide reactions. In order to determine a suitable electrocatalyst, apparent exchange current densities of a variety of materials (Ni, Co, Pt, Cr, Al, Cu, ITO, stainless steel) have been evaluated in a polysulfide containing electrolyte by potentiodynamic measurements and a Butler-Volmer fit including diffusion limitation. The samples have been examined by Scanning Electron Microscopy (SEM) after the potentiodynamic measurements. Up to now, our work shows that cobalt is a promising material with good electrocatalytic properties for the polysulfide reactions and good chemical stability in the system. Furthermore, an electrodeposition from a modified Watt’s nickel electrolyte with a sulfur source seems to provide an autocatalytic effect, but the electrocatalytic behavior decreases after several cycles of the current-potential-curve.

Keywords: electrocatalyst, energy storage, lithium sulfur battery, sulfur electrode materials

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Authors: M. A. Hasnat, M. Amirul Islam, M. A. Rashed, Jamil. Safwan, M. Mahabubul Alam

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Symmetric (Cu–Pt|Nafion|Pt–Cu) and asymmetric(Pt|Nafion|Pt–Cu) assemblies were fabricated to study the nitrate reduction processes at the cathode. The electrocatalytic nitrate reduction reactions were performed in these assemblies in order to investigate the prerequisite for the enhanced catalytic activity, electrochemical cell durability as well as preferable product selectivity resulting from the reduction of nitrate at the cathode. It has been observed for the symmetric assembly that Cu particles were oxidized on the anode surface under an applied potential and the resulting copper ions migrated to the cathode surface through the Nafion membrane, which deposited as copper oxide on the cathode surface. The formation of this copper oxide covering layer on the Pt–Cu cathode surface is attributed as the reason for the deactivation of the cathode that governed the reduced nitrate reduction along with increasing nitrite selectivity. These problems were addressed and resolved with the asymmetric design of the electrocatalytic reactor, where enhanced hydrogen evolution activates the surface by eroding the CuO over layer as well as speeding up the slow rate determining hydrogenation reactions.

Keywords: membrane, nitrate, electrocatalysis, voltammetry, electrolysis

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Authors: Yiying Xiao, Chia Wei Lim, Jinquan Chang, Qixin Yuan, Lei Wang, Ning Yan

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Electrocatalytic reductive amination (ERA) offers an attractive way to make organonitrogen chemicals from renewable feedstock. Here, we report carbon nanotube (CNT) as an effective catalyst for the ERA of biomass-derivable α-keto acids into amino acids using NH₃ as the nitrogen source. Through a facile ball milling (BM) treatment, the intrinsic defects in the CNTs were increased while the electrocatalytic activity of CNTs converting 2-ketoglutaric acid into glutamic acid was enhanced by approximately seven times. A high Faradaic efficiency (FE) of ~90% with a corresponding glutamic acid formation rate up to 180.9 mmol•g⁻¹𝒸ₐₜt•h⁻¹ was achieved, and ~60% molar yield of glutamic acid was obtained after 8 h of electrolysis. Electrokinetic analyses indicate that the BM-CNTs catalysed ERA exhibits first-order dependences on the substrate and NH₃, with a rate-determining step (RDS) involving the first electron transfer. Following this protocol, a number of amino acids were prepared with moderate to high FEs and formation rates. Significantly, we synthesised long carbon chain amino acids, which typically face lower yields using the existing methods.

Keywords: amino acids, carbon nanotubes, electrocatalysis, reductive amination, α-keto acids

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Authors: Yongde Xia, Laicong Deng, Zhuxian Yang

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Developing cost-effective electrocatalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is vital in energy conversion and storage applications. Herein, we report a simple method for the synthesis of graphene-reinforced cobalt sulfide/carbon nanocomposites and the evaluation of their electrocatalytic performance for typical electrocatalytic reactions. Nanocomposites of cobalt sulfide embedded in N, S co-doped porous carbon and graphene (CoS@C/Graphene) were generated via simultaneous sulfurization and carbonization of one-pot synthesized graphite oxide-ZIF-67 precursors. The obtained CoS@C/Graphene nanocomposite was characterized by X-ray diffraction, Raman spectroscopy, Thermogravimetric analysis-Mass spectroscopy, Scanning electronic microscopy, Transmission electronic microscopy, X-ray photoelectron spectroscopy and gas sorption. It was found that cobalt sulfide nanoparticles were homogenously dispersed in the in-situ formed N, S co-doped porous carbon/Graphene matrix. The CoS@C/10Graphene composite not only shows excellent electrocatalytic activity toward ORR with high onset potential of 0.89 V, four-electron pathway and superior durability of maintaining 98% current after continuously running for around 5 hours, but also exhibits good performance for OER and HER, due to the improved electrical conductivity, increased catalytic active sites and connectivity between the electrocatalytic active cobalt sulfide and the carbon matrix. This work offers a new approach for the development of novel multifunctional nanocomposites for the next generation of energy conversion and storage applications.

Keywords: MOF derivative, graphene, electrocatalyst, oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction

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Authors: Nurulasma Zainudin, Mashitah Mohd Yusoff, Kwok Feng Chong

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Functionalized reduced graphene oxide is essential importance for their end applications. Chemical functionalization of reduced graphene oxide with strange atoms is a leading strategy to modify the properties of the materials moreover maintains the inherent properties of reduced graphene oxide. A thionine functionalized reduce graphene oxide electrode was fabricated and was used to electrochemically determine nitrite. The electrochemical behaviour of thionine functionalized reduced graphene oxide towards oxidation of nitrite via cyclic voltammetry was studied and the proposed method exhibited enhanced electrocatalytic behaviour.

Keywords: nitrite, sensor, thionine, reduced graphene oxide

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Authors: Z. Khalifa, K. M. Hassan, M. Abdel Azzem

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Potential strategies for deriving useful forms of renewable high density energy from abundant energy stored in carbohydrates is direct conversion of glucose (GLU) to electrical power. A three novel versatile modified electrodes, synthesized by electrochemical polymerization of organic monomers on glassy carbon electrodes (GC), have been developed for biofuel cells results in stable and long-term power production. Electrocatalytic oxidation of glucose in alkaline solution on conducting polymers electrodes modified by incorporation of Ni nanoparticles (NiNPs) onto poly(1,5-aminonaphthalene) (1,5-PDAN), poly(1,8-diaminonaphthalene) (1,8-PDAN) and poly(1-amino-2-methyl-9,10-anthraquinone) (PAMAQ) was investigated. The electrocatalytic oxidation of glucose at NiNPs-modified 1,5-PDAN/GC, 1,8-PDAN/GC and PAMAQ/GC electrodes has been studied using voltammetry technique. The PDAN electrodes show a slight activity in the potential of interest. The prepared NiNPs/PAMAQ/GC catalyst showed a very interesting catalytic activity that was nicely comparable to the NiNPs/1,5-PDAN/GC, NiNPs/1,8-PDAN/GC modified electrodes. In advance, both shows a significant more catalytic activity compared to the reported data for electrodes for glucose electrocatalytic oxidation.

Keywords: biofuel cells, glucose oxidation, electrocatalysis, nanoparticles and modified electrodes

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Authors: Nimisha Jadon, Rajeev Jain, Swati Sharma

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A chemically modified carbon paste sensor has been developed for the simultaneous determination of amlodipine (AML) and nebivolol (NBV). Carbon paste electrode (CPE) was fabricated by the addition of Gr/PANI-CeO2. Gr/PANI-CeO2/CPE has achieved excellent electrocatalytic activity and sensitivity. AML and NBV exhibited oxidation peaks at 0.70 and 0.90 V respectively on Gr/ PANI-CeO2/CPE. The linearity range of AML and NBV was 0.1 to 1.6 μgmL-1 in BR buffer (pH 8.0). The Limit of detection (LOD) was 20.0 ngmL-1 for AML and 30.0 ngmL-1 for NBV and limit of quantification (LOQ) was 80.0 ngmL-1 for AML and 100 ngmL-1 for NBV respectively. These analyses were also determined in pharmaceutical formulation and human serum and good recovery was obtained for the developed method.

Keywords: amlodipine, nebivolol, square wave voltammetry, carbon paste electrode, simultaneous quantification

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Authors: Zahrah Thamer Althagafi, Mohamed I. Awad

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A simple method for the fabrication of Au (111)-like electrode via controlled reductive desorption of a pre-adsorbed cysteine monolayer onto polycrystalline gold (poly-Au) electrode is introduced. Then, the voltammetric behaviour of dopamine (DA) and ascorbic acid (AA) on the thus modified electrode is investigated. Electrochemical characterization of the modified electrode is achieved using cyclic voltammetry and square wave voltammetry. For the binary mixture of DA and AA, the results showed that Au (111)-like electrode exhibits excellent electrocatalytic activity towards the oxidation of DA and AA. This allows highly selective and simultaneous determination of DA and AA. The effect of various experimental parameters on the voltammetric responses of DA and AA was investigated. The enrichment of the Au (111) facet of the poly-Au electrode is thought to be behind the electrocatalytic activity.

Keywords: gold electrode, electroanalysis, electrocatalysis, monolayers, self-assembly, cysteine, dopamine, ascorbic acid

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Authors: Xin Zhao. Xuerong Zheng. Andrey L. Rogach

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Using single metal atoms has been considered an efficient way to develop new HER and OER catalysts. MXenes, a class of two-dimensional materials, have attracted tremendous interest as promising substrates for single-atom metal catalysts. However, there is still a lack of systematic investigations on the interaction mechanisms between various MXenes substrates and single atoms. Besides, due to the poor interaction between metal atoms and substrates resulting in low loading and stability, dual-atom MXenes-based catalysts have not been successfully synthesized. We summarized the electrocatalytic enhancement mechanism of three MXenes-based single-atom catalysts through experimental and theoretical results demonstrating the stronger hybridization between Co 3d and surface-terminated O 2p orbitals, optimizing the electronic structure of Co single atoms in the composite. This, in turn, lowers the OER and HER energy barriers and accelerates the catalytic kinetics in the case of the Co@V2CTx composite. The poor interaction between single atoms and substrates can be improved by a surface modification to synthesize dual-atom catalysts. The synergistic electronic structure enhances the stability and electrocatalytic activity of the catalyst. Our study provides guidelines for designing single-atom and dual-atom MXene-based electrocatalysts and sheds light on the origins of the catalytic activity of single-atoms on MXene substrates.

Keywords: dual-atom catalyst, single-atom catalyst, MXene substrates, water splitting

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Authors: Alireza Mohadesi, Ashraf Salmanipour

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A chemically modified glassy carbon electrode for electrocatalytic determination of sulfide was developed using multiwalled carbon nanotubes (MWCNTs) covalently immobilized with 2,6-dichlorophenolindophenol (DPIP). The immobilization of 2,6-dichlorophenolindophenol with MWCNTs was performed with a new synthetic strategy and characterized by UV–visible absorption spectroscopy, Fourier transform infrared spectroscopy and cyclic voltammetry. The cyclic voltammetric response of DPIP grafted onto MWCNTs indicated that it promotes the low potential, sensitive and stable determination of sulfide. The dependence of response currents on the concentration of sulfide was examined and was linear in the range of 10 - 1100 µM. The detection limit of sulfide was 5 µM and RSD for 100 and 500 µM sulfides were 1.8 and 1.3 %. Many interfering species had little or no effect on the determination of sulfide. The procedure was applied to determination of sulfide in waters samples.

Keywords: functionalized carbon nanotubes, sulfide, biological samples, 2, 6-dichlorophenolindophenol

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Authors: Y. T. Gebreslassie, Abrha Tadesse, R. C. Saini, Rishi Pal

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Caffeine, known chemically as 3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione, is a naturally occurring alkaloid classified as an N-methyl derivative of xanthine. Given its widespread use in coffee and other caffeine-containing products, it is the most commonly consumed psychoactive substance in everyday human life. This research aimed to develop a cost-effective, sensitive, and easily manufacturable sensor for the detection of caffeine. Antraquinone-modified carbon paste electrode (AQMCPE) was fabricated, and the electrochemical behavior of caffeine on this electrode was investigated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in a solution of 0.1M perchloric acid at pH 0.56. The modified electrode displayed enhanced electrocatalytic activity towards caffeine oxidation, exhibiting a two-fold increase in peak current and an 82 mV shift of the peak potential in the negative direction compared to an unmodified carbon paste electrode (UMCPE). Exploiting the electrocatalytic properties of the modified electrode, SWV was employed for the quantitative determination of caffeine. Under optimized experimental conditions, a linear relationship between peak current and concentration was observed within the range of 2.0 x 10⁻⁶ to 1.0× 10⁻⁴ M, with a correlation coefficient of 0.998 and a detection limit of 1.47× 10⁻⁷ M (signal-to-noise ratio = 3). Finally, the proposed method was successfully applied to the quantitative analysis of caffeine in pharmaceutical formulations, yielding recovery percentages ranging from 95.27% to 106.75%.

Keywords: antraquinone-modified carbon paste electrode, caffeine, detection, electrochemical sensor, quantitative analysis

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Authors: Shiying Fan, Xinyong Li

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The development of highly efficient multifunctional catalytic materials towards HER, ORR and Photo-fuel cell applications in terms of combined electrochemical and photo-electrochemical principles have currently confronted with dire challenges. In this study, novel palladium (Pd) and ruthenium (Ru) Bimetal Quantum Dots (BQDs) co-anchored on Titania nanotube (NTs) arrays electrodes have been successfully constructed by facial two-step electrochemical strategy. Double Schottky junctions with superior performance in electrocatalytic (EC) hydrogen generations and solar fuel cell energy conversions (PE) have been found. Various physicochemical techniques including UV-vis spectroscopy, TEM/EDX/HRTEM, SPV/TRV and electro-chemical strategy including EIS, C-V, I-V, and I-T, etc. were chronically utilized to systematically characterize the crystal-, electronic and micro-interfacial structures of the composites with double Schottky junction, respectively. The characterizations have implied that the marvelous enhancement of separation efficiency of electron-hole pairs generations is mainly caused by the Schottky-barriers within the nanocomposites, which would greatly facilitate the interfacial charge transfer for H₂ generations and solar fuel cell energy conversions. Moreover, the DFT calculations clearly indicated that the oriented growth of Ru and Pd bimetal atoms at the anatase (101) surface is mainly driven by the interaction between Ru/Pd and surface atoms, and the most active site for bimetal Ru and Pd adatoms on the perfect TiO₂ (101) surface is the 2cO-6cTi-3cO bridge sites and the 2cO-bridge sites with the highest adsorption energy of 9.17 eV. Furthermore, the electronic calculations show that in the nanocomposites, the number of impurity (i.e., co-anchored Ru-Pd BQDs) energy levels near Fermi surface increased and some were overlapped with original energy level, promoting electron energy transition and reduces the band gap. Therefore, this work shall provide a deeper insight for the molecular design of Bimetal Quantum Dots (BQDs) assembled onto Tatiana NTs composites with superior performance for electrocatalytic hydrogen productions and solar fuel cell energy conversions (PE) simultaneously.

Keywords: eletrocatalytic, Ru-Pd bimetallic quantum dots, titania nanotube arrays, double Schottky junctions, hydrogen production

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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: Bita Bayatsarmadi, Shi-Zhang Qiao

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The development of ordered mesoporous carbon materials with controllable structures and improved physicochemical properties by doping heteroatoms such as nitrogen into the carbon framework has attracted a lot of attention, especially in relation to energy storage and conversion. Herein, a series of Nitrogen-doped mesoporous carbon spheres (NMC) was synthesized via a facile dual soft-templating procedure by tuning the nitrogen content and carbonization temperature. Various physical and (electro) chemical properties of the NMCs have been comprehensively investigated to pave the way for feasible design of nitrogen-containing porous carbon materials. The optimized sample showed a favorable electrocatalytic activity as evidenced by high kinetic current and positive onset potential for oxygen reduction reaction (ORR) due to its large surface area, high pore volume, good conductivity and high nitrogen content, which make it as a highly efficient ORR metal-free catalyst in alkaline solutions.

Keywords: porous carbon, N-doping, oxygen reduction reaction, soft-template

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Authors: Mandana Amiri, Sima Nouhi, Yashar Azizan-Kalandaragh

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Silver nanostructures have been successfully fabricated by using electrodeposition method onto indium-tin-oxide (ITO) substrate. Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and ultraviolet-visible spectroscopy (UV-Vis) techniques were employed for characterization of silver nanostructures. The results show nanostructures with different morphology and electrochemical properties can be obtained by various the deposition potentials and times. Electrochemical behavior of the nanostructures has been studied by using cyclic voltammetry. Silver nanostructures exhibits good electrocatalytic activity towards the reduction of H₂O₂. The presented electrode can be employed as sensing element for hydrogen peroxide.

Keywords: electrochemical sensor, electrodeposition, hydrogen peroxide, silver nanostructures

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Authors: Sadia Ameen, M. Nazim, Hyumg-Kee Seo, Hyung-Shik Shin

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TiO2 nanotube (NT) arrays were grown on titanium (Ti) foil substrate by electrochemical anodic oxidation and utilized as working electrode to fabricate a highly sensitive and reproducible chemical sensor for the detection of harmful phenyl hydrazine chemical. The fabricated chemical sensor based on TiO2 NT arrays electrode exhibited high sensitivity of ~40.9 µA.mM-1.cm-2 and detection limit of ~0.22 µM with short response time (10s).

Keywords: TiO2 NT, phenyl hydrazine, chemical sensor, sensitivity, electrocatalytic properties

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Authors: Sonali Panigrahy, Manjunatha K., Sudip Barman

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Electrocatalytic reduction methods hold significant promise in addressing the urgent need to mitigate excessive greenhouse gas emissions, particularly carbon dioxide (CO₂). A highly effective catalyst is essential for achieving the conversion of CO₂ into valuable products due to the complex, multi-electron, and multi-product nature of the CO₂ reduction process. The electrochemical reduction of CO₂, driven by renewable energy sources, presents a valuable opportunity for simultaneously reducing CO₂ emissions while generating valuable chemicals and fuels, with syngas being a noteworthy product. Silver-based electrodes have been the focus of extensive research due to their low overpotential and remarkable selectivity in promoting the generation of carbon monoxide (CO) in the electrocatalytic carbon dioxide reduction reaction (CO₂RR). In this study, we delve into the synthesis of carbon-supported silver nanoparticles (Ag/C), which serve as efficient electrocatalysts for the reduction of CO₂. The as-prepared catalyst, Ag/C, is not only cost-effective but also highly proficient in facilitating the conversion of CO₂ and H₂O into syngas, which is a customizable mixture of hydrogen (H₂) and carbon monoxide (CO). The highest faradic efficiency for the production of CO on Ag/C was calculated to be 56.4% at -1.4 V vs Ag/AgCl. The maximum partial current density for the generation of CO was determined to be -9.4 mA cm-2 at a potential of -1.6 V vs Ag/AgCl. This research demonstrates the potential of Ag/C as an electrocatalyst to enable the sustainable production of syngas, contributing to the reduction of CO₂ emissions and the synthesis of valuable chemical precursors and fuels.

Keywords: CO₂, carbon monooxide, electrochemical, silver

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Authors: Ipek Gunay, Efe B. Orman, Metin Ozer, Bekir Salih, Ali R. Ozkaya

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Phthalocyanines with macrocyclic ring containing at least three heteroatoms have nine or more membered structures. Metal-free phthalocyanines react with metal salts to obtain chelate complexes. This is one of the most important features of metal-free phthalocyanine as ligand structure. Although phthalocyanines have very similar properties with porphyrins, they have some advantages such as lower cost, easy to prepare, and chemical and thermal stability. It’s known that Pc compounds have shown one-electron metal-and/or ligand-based reversible or quasi-reversible reduction and oxidation processes. The redox properties of phthalocyanines are critically related to the desirable properties of these compounds in their technological applications. Thus, Pc complexes have also been receiving increasing interest in the area of fuel cells due to their high electrocatalytic activity in dioxygen reduction and fuel cell applications. In this study, novel phthalocyanine complexes coordinated with Fe(II) and Co (II) to be used as catalyst were synthesized. Aiming this goal, a new nitrile ligand was synthesized starting from 4-hydroxy-3,5-dimethoxy benzyl alcohol and 4-nitrophthalonitrile in the presence of K2CO3 as catalyst. After the isolation of the new type of nitrile and metal complexes, the characterization of mentioned compounds was achieved by IR, H-NMR and UV-vis methods. In addition, the electrochemical behaviour of Pc complexes was identified by cyclic voltammetry, square wave voltammetry and in situ spectroelectrochemical measurements. Furthermore, the catalytic performances of Pc complexes for oxygen reduction were tested by dynamic voltammetry measurements, carried out by the combined system of rotating ring-disk electrode and potentiostat, in a medium similar to fuel-cell working conditions.

Keywords: phthalocyanine, electrocatalysis, electrochemistry, in-situ spectroelectrochemistry

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Authors: N. Benkhettoua, Y. Barkata

Abstract:

We present first-principles studies of structural and thermodynamic properties of MnNi According to the calculated total energies, by using an all-electron full-potential linear muffin–tin orbital method (FP-LMTO) within LDA and the quasi-harmonic Debye model implemented in the Gibbs program is used for the temperature effect on structural and calorific properties.

Keywords: magnetic materials, structural properties, thermodynamic properties, metallurgical and materials engineering

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Authors: Álvaro Ramírez Vidal, Martín Muñoz Morales, Francisco Jesús Fernández Morales, Luis Rodríguez Romero, José Villaseñor Camacho, Javier Llanos López

Abstract:

In recent times, environmental problems have led to the extensive use of biological systems to solve them. Among the different types of biological systems, the use of plants such as aquatic macrophytes in constructed wetlands and terrestrial plant species for treating polluted soils and sludge has gained importance. Though the use of constructed wetlands for wastewater treatment is a well-researched domain, the slowness of pollutant degradation and high biomass production pose some challenges. Plants used in CW participate in different mechanisms for the capture and degradation of pollutants that also can retain some pharmaceutical and personal care products (PPCPs) that are very persistent in the environment. Thus, these systems present advantages in line with the guidelines published for the transition towards friendly and ecological procedures as they are environmentally friendly systems, consume low energy, or capture atmospheric CO₂. However, the use of CW presents some drawbacks, as the slowness of pollutant degradation or the production of important amounts of plant biomass, which need to be harvested and managed periodically. Taking this opportunity in mind, it is important to highlight that this residual biomass (of lignocellulosic nature) could be used as the feedstock for the generation of carbonaceous materials using thermochemical transformations such as slow pyrolysis or hydrothermal carbonization to produce high-value biomass-derived carbons through sustainable processes as adsorbents, catalysts…, thereby improving the circular carbon economy. Thus, this work carried out the analysis of some PPCPs commonly found in urban wastewater, as salicylic acid or ibuprofen, to evaluate the remediation carried out for the Phragmites Australis. Then, after the harvesting, this biomass can be used to synthesize electrodes through hydrothermal carbonization (HTC) and produce high-value biomass-derived carbons with electrocatalytic activity to remove heavy metals and persistent pollutants, promoting circular economy concepts. To do this, it was chosen biomass derived from the natural environment in high environmental risk as the Daimiel Wetlands National Park in the center of Spain, and the rest of the biomass developed in a CW specifically designed to remove pollutants. The research emphasizes the impact of the composition of the biomass waste and the synthetic parameters applied during HTC on the electrocatalytic activity. Additionally, this parameter can be related to the physicochemical properties, as porosity, surface functionalization, conductivity, and mass transfer of the electrodes lytic inks. Data revealed that carbon materials synthesized have good surface properties (good conductivities and high specific surface area) that enhance the electro-oxidants generated and promote the removal of PPCPs and the chemical oxygen demand of polluted waters.

Keywords: constructed wetlands, carbon materials, heavy metals, pharmaceutical and personal care products, hydrothermal carbonization

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Authors: Si Yin Tee

Abstract:

Bimetallic nanostructures have received tremendous interests as a new class of nanomaterials which may have better technological usefulness with distinct properties from those of individual atoms and molecules or bulk matter. They excelled over the monometallic counterparts because of their improved electronic, optical and catalytic performances. The properties and the applicability of these bimetallic nanostructures not only depend on their size and shape, but also on the composition and their fine structure. These bimetallic nanostructures are potential candidates for bio-applications such as biosensing, bioimaging, biodiagnostics, drug delivery, targeted therapeutics, and tissue engineering. Herein, gold-incorporated copper (Cu/Au) nanostructures were synthesized through the controlled disproportionation of Cu⁺-oleylamine complex at 220 ºC to form copper nanowires and the subsequent reaction with Au³⁺ at different temperatures of 140, 220 and 300 ºC. This is to achieve their synergistic effect through the combined use of the merits of low-cost transition and high-stability noble metals. Of these Cu/Au nanostructures, Cu/Au nanotubes display the best performance towards electrochemical non-enzymatic glucose sensing, originating from the high conductivity of gold and the high aspect ratio copper nanotubes with high surface area so as to optimise the electroactive sites and facilitate mass transport. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

Keywords: bimetallic, electrochemical sensing, glucose oxidation, gold-incorporated copper nanostructures

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Authors: A. K. M. Kafi, S. N. Nina, Mashitah M. Yusoff

Abstract:

In this work, we have described a new 3-dimensional (3D) network of cross-linked Horseradish Peroxidase/Carbon Nanotube (HRP/CNT) on a thiol-modified Au surface in order to build up the effective electrical wiring of the enzyme units with the electrode. This was achieved by the electropolymerization of aniline-functionalized carbon nanotubes (CNTs) and 4-aminothiophenol -modified-HRP on a 4-aminothiophenol monolayer-modified Au electrode. The synthesized 3D HRP/CNT networks were characterized with cyclic voltammetry and amperometry, resulting the establishment direct electron transfer between the redox active unit of HRP and the Au surface. Electrochemical measurements reveal that the immobilized HRP exhibits high biological activity and stability and a quasi-reversible redox peak of the redox center of HRP was observed at about −0.355 and −0.275 V vs. Ag/AgCl. The electron transfer rate constant, KS and electron transfer co-efficient were found to be 0.57 s-1 and 0.42, respectively. Based on the electrocatalytic process by direct electrochemistry of HRP, a biosensor for detecting H2O2 was developed. The developed biosensor exhibits excellent electrocatalytic activity for the reduction of H2O2. The proposed biosensor modified with HRP/CNT 3D network displays a broader linear range and a lower detection limit for H2O2 determination. The linear range is from 1.0×10−7 to 1.2×10−4M with a detection limit of 2.2.0×10−8M at 3σ. Moreover, this biosensor exhibits very high sensitivity, good reproducibility and long-time stability. In summary, ease of fabrication, a low cost, fast response and high sensitivity are the main advantages of the new biosensor proposed in this study. These obvious advantages would really help for the real analytical applicability of the proposed biosensor.

Keywords: redox enzyme, nanomaterials, biosensors, electrical communication

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Authors: A. K. M. Kafi, S. N. Nina, Mashitah M. Yusoff

Abstract:

In this work, we have described a new 3-dimensional (3D) network of crosslinked Horseradish Peroxidase/Carbon Nanotube (HRP/CNT) on a thiol-modified Au surface in order to build up the effective electrical wiring of the enzyme units with the electrode. This was achieved by the electropolymerization of aniline-functionalized carbon nanotubes (CNTs) and 4-aminothiophenol -modified-HRP on a 4-aminothiophenol monolayer-modified Au electrode. The synthesized 3D HRP/CNT networks were characterized with cyclic voltammetry and amperometry, resulting the establishment direct electron transfer between the redox active unit of HRP and the Au surface. Electrochemical measurements reveal that the immobilized HRP exhibits high biological activity and stability and a quasi-reversible redox peak of the redox center of HRP was observed at about −0.355 and −0.275 V vs. Ag/AgCl. The electron transfer rate constant, KS and electron transfer co-efficient were found to be 0.57 s-1 and 0.42, respectively. Based on the electrocatalytic process by direct electrochemistry of HRP, a biosensor for detecting H2O2 was developed. The developed biosensor exhibits excellent electrocatalytic activity for the reduction of H2O2. The proposed biosensor modified with HRP/CNT 3D network displays a broader linear range and a lower detection limit for H2O2 determination. The linear range is from 1.0×10−7 to 1.2×10−4M with a detection limit of 2.2.0×10−8M at 3σ. Moreover, this biosensor exhibits very high sensitivity, good reproducibility and long-time stability. In summary, ease of fabrication, a low cost, fast response and high sensitivity are the main advantages of the new biosensor proposed in this study. These obvious advantages would really help for the real analytical applicability of the proposed biosensor.

Keywords: biosensor, nanomaterials, redox enzyme, thiol-modified Au surface

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Authors: Mohammed Panthakkal Abdul Muthalif, Shanmugasundaram Kanagaraj, Jumi Park, Hangyu Park, Youngson Choe

Abstract:

The present study reports the incorporation of calcium ions into the CuS counter electrodes (CEs) in order to modify the photovoltaic performance of quantum dot-sensitized solar cells (QDSSCs). Metal ion-doped CuS thin film was prepared by the chemical bath deposition (CBD) method on FTO substrate and used directly as counter electrodes for TiO₂/CdS/CdSe/ZnS photoanodes based QDSSCs. For the Ca-doped CuS thin films, copper nitrate and thioacetamide were used as anionic and cationic precursors. Calcium nitrate tetrahydrate was used as doping material. The surface morphology of Ca-doped CuS CEs indicates that the fragments are uniformly distributed, and the structure is densely packed with high crystallinity. The changes observed in the diffraction patterns suggest that Ca dopant can introduce increased disorder into CuS material structure. EDX analysis was employed to determine the elemental identification, and the results confirmed the presence of Cu, S, and Ca on the FTO glass substrate. The photovoltaic current density – voltage characteristics of Ca-doped CuS CEs shows the specific improvements in open circuit voltage decay (Voc) and short-circuit current density (Jsc). Electrochemical impedance spectroscopy results display that Ca-doped CuS CEs have greater electrocatalytic activity and charge transport capacity than bare CuS. All the experimental results indicate that 20% Ca-doped CuS CE based QDSSCs exhibit high power conversion efficiency (η) of 4.92%, short circuit current density of 15.47 mA cm⁻², open circuit photovoltage of 0.611 V, and fill factor (FF) of 0.521 under illumination of one sun.

Keywords: Ca-doped CuS counter electrodes, surface morphology, chemical bath deposition method, electrocatalytic activity

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Authors: Vishakha Kaim, Mookan Natarajan, Sandeep Kaur-Ghumaan

Abstract:

Hydrogen is one of the most abundant elements present on earth’s crust and considered to be the simplest element in existence. It is not found naturally as a gas on earth and thus has to be manufactured. Hydrogen can be produced from a variety of sources, i.e., water, fossil fuels, or biomass and it is a byproduct of many chemical processes. It is also considered as a secondary source of energy commonly referred to as an energy carrier. Though hydrogen is not widely used as a fuel, it still has the potential for greater use in the future as a clean and renewable source of energy. Electrocatalysis is one of the important source for the production of hydrogen which could contribute to this prominent challenge. Metals such as platinum and palladium are considered efficient for hydrogen production but with limited applications. As a result, a wide variety of metal complexes with earth abundant elements and varied ligand environments have been explored for the electrochemical production of hydrogen. In nature, [FeFe] hydrogenase enzyme present in DesulfoVibrio desulfuricans and Clostridium pasteurianum catalyses the reversible interconversion of protons and electrons into dihydrogen. Since the first structure for the enzyme was reported in 1990s, a range of iron complexes has been synthesized as structural and functional mimics of the enzyme active site. Mn is one of the most desirable element for sustainable catalytic transformations, immediately behind Fe and Ti. Only limited number manganese complexes have been reported in the last two decades as catalysts for proton reduction. Furthermore, redox reactions could be carried out in a facile manner, due to the capability of manganese complexes to be stable at different oxidation states. Herein are reported, four µ2-thiolate bridged manganese complexes [Mn₂(CO)₆(μ-S₂N₄C₁₄H₁₀)] 1, [Mn₂(CO)7(μ- S₂N₄C₁₄H₁₀)] 2, Mn₂(CO)₆(μ-S₄N₂C₁₄H₁₀)] 3 and [Mn₂(CO)(μ- S₄N₂C₁₄H₁₀)] 4 have been synthesized and characterized. The cyclic voltammograms of the complexes displayed irreversible reduction peaks in the range - 0.9 to -1.3 V (vs. Fc⁺/Fc in acetonitrile at 0.1 Vs⁻¹). The complexes were catalytically active towards proton reduction in the presence of trifluoroacetic acid as seen from electrochemical investigations.

Keywords: earth abundant, electrocatalytic, hydrogen, manganese

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