Search results for: isomeric hydrogen bond

Authors: Mohamed Ayoub

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The structures and energetics of various isomeric hydrogen bonded dimers, such as (FH…OC, FH…CO), (FH…CNH, FH…NCH), (FH…N2O, FH…ON2), and (FH…NHCO, FH…OCNH) have been investigated using DFT B3LYP with aug-cc-pVTZ basis set and by natural bond orbital (NBO) analysis. For each isomeric pair we calculated: H-bond energy (ΔEB…H), charge-transfer (QCT), where B is atom bearing lone-pairs in CO, CNH, NCH, N2O, and NHCO, H-bond distances (RB…H), the elongation of HF bond (ΔRHF) and the red-shift of HF stretching frequency (ΔVHF). We conclude that the principle difference in the relative stability between each isomeric pair is attributed to distinctive interaction of carbon and oxygen lone pairs of CO, carbon and nitrogen lone-pairs of CNH and NCH, and nitrogen and oxygen lone pairs of N2O and NHCO into the unfilled antibond on HF (σ*HF).

Keywords: charge transfer, computational chemistry, isomeric hydrogen bond, natural bond orbital

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Authors: Mohamed Ayoub

Abstract:

We perform computational investigation using density functional theory, B3LYP with aug-cc-pVTZ basis set followed by natural bond orbital analysis (NBO), which provides best single “natural Lewis structure” (NLS) representation of chosen wavefunction (Ψ) with natural resonance theory (NRT) to provide an analysis of molecular electron density in terms of resonance structures (RS) and weights (w). We selected for the study a wide range of gas phase dimers (B…HA), with hydrogen bond dissociation energies (ΔEB…H) that span more than two orders of magnitude. We demonstrate that charge transfer from a donor Lewis-type NBO (nB:) to an acceptor non-Lewis-type NBO (σHA*) is the primary cause for H-bonding not classical electrostatic (dipole-dipole or ionic). We provide a variety of structure, and spectroscopic descriptors to support the conclusion, such as IR frequency shift (ΔνHA), H-bond penetration distance (ΔRB..H), bond order (bB..H), charge-transfer (CTB→HA) and the corresponding donor-acceptor stabilization energy (ΔE(2)).

Keywords: natural bond orbital, hydrogen bonding, electron donor, electron acceptor

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Authors: Choukri Lekbir, Mira Mokhtari

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Hydrogen-Materials interaction and mechanisms can be modeled at nano scale by quantum methods. In this work, the effect of hydrogen on the electronic properties of a cluster material model «nickel» has been studied by using of density functional theoretical (DFT) method. Two types of clusters are optimized: Nickel and hydrogen-nickel system. In the case of nickel clusters (n = 1-6) without presence of hydrogen, three types of electronic structures (neutral, cationic and anionic), have been optimized according to three basis sets calculations (B3LYP/LANL2DZ, PW91PW91/DGDZVP2, PBE/DGDZVP2). The comparison of binding energies and bond lengths of the three structures of nickel clusters (neutral, cationic and anionic) obtained by those basis sets, shows that the results of neutral and anionic nickel clusters are in good agreement with the experimental results. In the case of neutral and anionic nickel clusters, comparing energies and bond lengths obtained by the three bases, shows that the basis set PBE/DGDZVP2 is most suitable to experimental results. In the case of anionic nickel clusters (n = 1-6) with presence of hydrogen, the optimization of the hydrogen-nickel (anionic) structures by using of the basis set PBE/DGDZVP2, shows that the binding energies and bond lengths increase compared to those obtained in the case of anionic nickel clusters without the presence of hydrogen, that reveals the armor effect exerted by hydrogen on the electronic structure of nickel, which due to the storing of hydrogen energy within nickel clusters structures. The comparison between the bond lengths for both clusters shows the expansion effect of clusters geometry which due to hydrogen presence.

Keywords: binding energies, bond lengths, density functional theoretical, geometry optimization, hydrogen energy, nickel cluster

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Authors: Setareh Shekarsaraei, Marjan Moridi, Nasser L. Hadipour

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In this study, nuclear magnetic resonance spectroscopy and nuclear quadrupole resonance spectroscopy parameters of 14N (Nitrogen in imidazole ring) in N–H…O hydrogen bonding for Histidine hydrochloride monohydrate were calculated via density functional theory. We considered a five-molecule model system of Histidine hydrochloride monohydrate. Also, we examined the trends of environmental effect on hydrogen bonds as well as cooperativity. The functional used in this research is M06-2X which is a good functional and the obtained results have shown good agreement with experimental data. This functional was applied to calculate the NMR and NQR parameters. Some correlations among NBO parameters, NMR, and NQR parameters have been studied which have shown the existence of strong correlations among them. Furthermore, the geometry optimization has been performed using M062X/6-31++G(d,p) method. In addition, in order to study cooperativity and changes in structural parameters, along with increase in cluster size, natural bond orbitals have been employed.

Keywords: hydrogen bonding, density functional theory (DFT), natural bond orbitals (NBO), cooperativity effect

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Authors: T. Zaki, Fathi S. Soliman

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Desulfurization process is required by most, if not all refineries, to achieve ultra-low sulfur fuel, that contains less than 10 ppm sulfur. A lot of research works and many effective technologies have been studied to achieve deep desulfurization process in moderate reaction environment, such as adsorption desulfurization (ADS), oxidative desulfurization (ODS), biodesulfurization and extraction desulfurization (EDS). Extraction desulfurization using deep eutectic solvents (DESs) is considered as simple, cheap, highly efficient and environmentally friend process. In this work, four DESs were designed and synthesized. Choline chloride (ChCl) was selected as typical hydrogen bond acceptors (HBA), and ethylene glycol (EG), glycerol (Gl), urea (Ur) and thiourea (Tu) were selected as hydrogen bond donors (HBD), from which a series of deep eutectic solvents were synthesized. The experimental data showed that the synthesized DESs showed desulfurization affinities towards the thiophene species in cyclohexane solvent. Ethylene glycol molecules showed more affinity to create hydrogen bond with thiophene instead of choline chloride. Accordingly, ethylene glycol choline chloride DES has the highest extraction efficiency.

Keywords: DES, desulfurization, green solvent, extraction

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Authors: Boris M. Popović, Tatjana Jurić, Bojana Blagojević, Denis Uka, Ružica Ždero Pavlović

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Green solvents are environmentally friendly and greatly improve the sustainability of chemical processes. There is a growing interest in the green extraction of polyphenols from fruits. In this study, we consider three Natural Deep Eutectic Solvents (NADES) systems based on choline chloride as a hydrogen bond acceptor and malic acid, urea, and fructose as hydrogen bond donors. NADES systems were prepared by heating and stirring, ultrasound, and microwave (MW) methods. Sour cherry pomace was used as a natural source of polyphenols. Polyphenol extraction from cherry pomace was performed by ultrasound-assisted extraction and microwave-assisted extraction and compared with conventional heat and stirring method extraction. It was found that MW-assisted preparation of NADES was the fastest, requiring less than 30 s. Also, MW extraction of polyphenols was the most rapid, with less than 5 min necessary for the extract preparation. All three NADES systems were highly efficient for anthocyanin extraction, but the most efficient was the system with malic acid as a hydrogen bond donor (yield of anthocyanin content was enhanced by 62.33% after MW extraction with NADES compared with the conventional solvent).

Keywords: anthocyanins, green extraction, NADES, polyphenols

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Authors: Motonori Tamura

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The hydrogen barrier properties of the coatings of diamond-like carbon (DLC) were evaluated. Using plasma chemical vapor deposition and sputtering, DLC coatings were deposited on Type 316L stainless steels. The hydrogen permeation rate was reduced to 1/1000 or lower by the DLC coatings. The DLC coatings with high hydrogen content had high hydrogen barrier function. For hydrogen diffusion in coatings, the movement of atoms through hydrogen trap sites such as pores in coatings, and crystal defects such as dislocations, is important. The DLC coatings are amorphous, and there are both sp3 and sp2 bonds, and excess hydrogen could be found in the interstitial space and the hydrogen trap sites. In the DLC coatings with high hydrogen content, these hydrogen trap sites are likely already filled with hydrogen atoms, and the movement of new hydrogen atoms could be limited.

Keywords: hydrogen permeation, stainless steels, diamond-like carbon, hydrogen trap sites

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Authors: Mandeep Kaur, Jitendra K. Bera

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The search for atom-economical and green synthetic methods for the synthesis of functionalized molecules has attracted much attention. Metal ligand cooperation (MLC) plays a pivotal role in organometallic catalysis to activate C−H, H−H, O−H, N−H and B−H bonds through reversible bond breaking and bond making process. Towards this goal, a bifunctional N─heterocyclic carbene (NHC) based pyridyl-functionalized amide ligand precursor, and corresponding dearomatized iridium complex was synthesized. The NMR and UV/Vis acid titration study have been done to prove the proton response nature of the iridium complex. Further, the dearomatized iridium complex explored as a catalyst on the platform of MLC via dearomatzation/aromatization mode of action towards atom economical α and β─alkylation of ketones and secondary alcohols by using primary alcohols through hydrogen borrowing methodology. The key features of the catalysis are high turnover frequency (TOF) values, low catalyst loading, low base loading and no waste product. The greener syntheses of quinoline, lactone derivatives and selective alkylation of drug molecules like pregnenolone and testosterone were also achieved successfully. Another structurally similar iridium complex was also synthesized with modified ligand precursor where a pendant amide unit was absent. The inactivity of this analogue iridium complex towards catalysis authenticated the participation of proton responsive imido sidearm of the ligand to accelerate the catalytic reaction. The mechanistic investigation through control experiments, NMR and deuterated labeling study, authenticate the borrowing hydrogen strategy.

Keywords: C-C bond formation, hydrogen borrowing, metal ligand cooperation (MLC), n-heterocyclic carbene

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Authors: Rama Seshu Doguparti

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This paper presents the experimental investigation on the bond behavior of geo polymer concrete. The bond behavior of geo polymer concrete cubes of grade M35 reinforced with 16 mm TMT rod is analyzed. The results indicate that the bond performance of reinforced geo polymer concrete is good and thus proves its application for construction.

Keywords: geo-polymer, concrete, bond strength, behaviour

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Authors: Vijay Kumar Kutala, Addepalli Pavani, M. Amresh Rao, Naushad Sm

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In this study, we evaluated the impact of CYP2C9*2 and CYP2C9*3 variants on binding and hydroxylation of warfarin. In silico data revealed that warfarin forms two hydrogen bonds with protein backbone i.e. I205 and S209, one hydrogen bond with protein side chain i.e. T301 and stacking interaction with F100 in CYP2C9*1. In CYP2C9*2 and CYP2C9*3 variants, two hydrogen bonds with protein backbone are disrupted. In double variant, all the hydrogen bonds are disrupted. The distances between C7 of S-warfarin and Fe-O in CYP2C9*1, CYP2C9*2, CYP2C9*3 and CYP2C9*2/*3 were 5.81A°, 7.02A°, 7.43° and 10.07°, respectively. The glide scores (Kcal/mol) were -7.698, -7.380, -6.821 and -6.986, respectively. Increase in warfarin/7-hydroxy warfarin ratio was observed with increase in variant alleles. To conclude, CYP2C9*2 and CYP2C9*3 variants result in disruption of hydrogen bonding interactions with warfarin and longer distance between C7 and Fe-O thus impairing warfarin 7-hydroxylation due to lower binding affinity of warfarin.

Keywords: warfarin, CYP2C9 polymorphism, personalized medicine, in Silico

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Authors: Xiaohua Jing

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Efficient extraction for separation of V and Cr in the leaching/aqueous solution is essential to the reuse of V and Cr in the V-Cr slag. Trioctylamine, a common tertiary amine extractant, with some good characters (e.g., weak base, insoluble in water and good stability) different from N1923, was investigated in this paper. The separation factor of Cr and V can be reached to 230.71 when initial pH of the aqueous solution is 0.5, so trioctylamine can be used for extracting Cr from the leaching/aqueous solution contained V and Cr. The highest extraction percentages of Cr and V were 98.73% and 90.22% when the initial pH values were 0.5 and 1.5, respectively. Via FT-IR spectra of loaded organic phase and trioctylamine, the hydrogen bond association mechanism of extracting V and Cr was investigated, which was the same with the way of extracting the two metals with primary amine N1923.

Keywords: selective extraction, trioctylamine, V and Cr, separation factor, hydrogen bond association

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Authors: Minhee Son, Kyung Nam Kim

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This study explores the plan of the Korean and Japanese governments to transition into the hydrogen economy. Two motor companies, Hyundai Motor Company from Korea and Toyota from Japan, released the Hydrogen Fuel Cell Vehicle to monopolize the green energy automobile market. Although, they are the main countries which emit greenhouse gas, hydrogen energy can bring from a certain industry places, such as chemical plants and steel mills. Recent, the two countries have been focusing on the hydrogen industry including a fuel cell vehicle, a hydrogen station, a fuel cell plant, a residential fuel cell. The purpose of this paper is to find out the differences of the policies in the two countries to be hydrogen societies. We analyze the behavior of the public and private sectors in Korea and Japan about hydrogen energy and fuel cells for the transition of the hydrogen economy. Finally we show the similarities and differences of both countries in hydrogen fuel cells. And some cities have feature such as Hydrogen cities. Hydrogen energy can make impact environmental sustainability.

Keywords: fuel cell, hydrogen city, hydrogen fuel cell vehicle, hydrogen station, hydrogen energy

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Authors: Yew Mun Yip, Dawei Zhang

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Proteins are the biological machinery that executes specific vital functions in every cell of the human body by folding into their 3D structures. When a protein misfolds from its native structure, the machinery will malfunction and lead to misfolding diseases. Although in vitro experiments are able to conclude that the mutations of the amino acid sequence lead to incorrectly folded protein structures, these experiments are unable to decipher the folding process. Therefore, molecular dynamic (MD) simulations are employed to simulate the folding process so that our improved understanding of the folding process will enable us to contemplate better treatments for misfolding diseases. MD simulations make use of force fields to simulate the folding process of peptides. Secondary structures are formed via the hydrogen bonds formed between the backbone atoms (C, O, N, H). It is important that the hydrogen bond energy computed during the MD simulation is accurate in order to direct the folding process to the native structure. Since the atoms involved in a hydrogen bond possess very dissimilar electronegativities, the more electronegative atom will attract greater electron density from the less electronegative atom towards itself. This is known as the polarization effect. Since the polarization effect changes the electron density of the two atoms in close proximity, the atomic charges of the two atoms should also vary based on the strength of the polarization effect. However, the fixed atomic charge scheme in force fields does not account for the polarization effect. In this study, we introduce the polarized structure-specific backbone charge (PSBC) model. The PSBC model accounts for the polarization effect in MD simulation by updating the atomic charges of the backbone hydrogen bond atoms according to equations derived between the amount of charge transferred to the atom and the length of the hydrogen bond, which are calculated from quantum-mechanical calculations. Compared to other polarizable models, the PSBC model does not require quantum-mechanical calculations of the peptide simulated at every time-step of the simulation and maintains the dynamic update of atomic charges, thereby reducing the computational cost and time while accounting for the polarization effect dynamically at the same time. The PSBC model is applied to two different β-peptides, namely the Beta3s/GS peptide, a de novo designed three-stranded β-sheet whose structure is folded in vitro and studied by NMR, and the trpzip peptides, a double-stranded β-sheet where a correlation is found between the type of amino acids that constitute the β-turn and the β-propensity.

Keywords: hydrogen bond, polarization effect, protein folding, PSBC

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Authors: Qiming Wang

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Dynamic polymer networks (DPNs) crosslinked by dynamic bonds have received intensive attention because of their special crack-healing capability. Diverse DPNs have been synthesized using a number of dynamic bonds, including dynamic covalent bond, hydrogen bond, ionic bond, metal-ligand coordination, hydrophobic interaction, and others. Despite the promising success in the polymer synthesis, the fundamental understanding of their self-healing mechanics is still at the very beginning. Especially, a general analytical model to understand the interfacial self-healing behaviors of DPNs has not been established. Here, we develop polymer-network based analytical theories that can mechanistically model the constitutive behaviors and interfacial self-healing behaviors of DPNs. We consider that the DPN is composed of interpenetrating networks crosslinked by dynamic bonds. bonds obey a force-dependent chemical kinetics. During the self-healing process, we consider the The network chains follow inhomogeneous chain-length distributions and the dynamic polymer chains diffuse across the interface to reform the dynamic bonds, being modeled by a diffusion-reaction theory. The theories can predict the stress-stretch behaviors of original and self-healed DPNs, as well as the healing strength in a function of healing time. We show that the theoretically predicted healing behaviors can consistently match the documented experimental results of DPNs with various dynamic bonds, including dynamic covalent bonds (diarylbibenzofuranone and olefin metathesis), hydrogen bonds, and ionic bonds. We expect our model to be a powerful tool for the self-healing community to invent, design, understand, and optimize self-healing DPNs with various dynamic bonds.

Keywords: self-healing polymers, dynamic covalent bonds, hydrogen bonds, ionic bonds

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Authors: Abbas Vahedian, Rijun Shrestha, Keith Crews

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The bond mechanism between timber and fibre reinforced polymer (FRP) is relatively complex and is influenced by a number of variables including bond thickness, bond width, bond length, material properties, and geometries. This study investigates the influence of bond thickness on the behaviour of interface, failure mode, and bond strength of externally bonded FRP-to-timber interface. In the present study, 106 single shear joint specimens have been investigated. Experiment results showed that higher layers of FRP increase the ultimate load carrying capacity of interface; conversely, such increase led to decrease the slip of interface. Moreover, samples with more layers of FRPs may fail in a brittle manner without noticeable warning that collapse is imminent.

Keywords: fibre reinforced polymer, FRP, single shear test, bond thickness, bond strength

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Authors: Ferid Hammami

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The molecular geometries of the possible conformations of pyruvic acid-water complexes (PA-(H₂O)ₙ = 1- 4) have been fully optimized at DFT/B3LYP/6-311G ++ (d, p) levels of calculation. Among several optimized molecular clusters, the most stable molecular arrangements obtained when one, two, three, and four water molecules are hydrogen-bonded to a central pyruvic acid molecule are presented in this paper. Apposite topological and geometrical parameters are considered as primary indicators of H-bond strength. Atoms in molecules (AIM) analysis shows that pyruvic acid can form a ring structure with water, and the molecular structures are stabilized by both strong O-H...O and C-H...O hydrogen bonds. In large clusters, classical O-H...O hydrogen bonds still exist between water molecules, and a cage-like structure is built around some parts of the central molecule of pyruvic acid. The electrostatic potential energy map (MEP) and the HOMO-LUMO molecular orbital (highest occupied molecular orbital-lowest unoccupied molecular orbital) analysis has been performed for all considered complexes.

Keywords: pyruvic acid, PA-water complex, hydrogen bonding, DFT, AIM, MEP, HOMO-LUMO

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Authors: Osamu Takakuwa, Yuta Mano, Hitoshi Soyama

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This paper reveals the interaction between hydrogen and surface stress in austenitic stainless steel by X-ray diffraction stress measurement and thermal desorption analysis before and after being charged with hydrogen. The surface residual stress was varied by surface finishing using several disc polishing agents. The obtained results show that the residual stress near surface had a significant effect on hydrogen absorption behavior, that is, tensile residual stress promoted the hydrogen absorption and compressive one did opposite. Also, hydrogen induced equi-biaxial stress and this stress has a linear correlation with hydrogen content.

Keywords: hydrogen embrittlement, residual stress, surface finishing, stainless steel

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Authors: Raj Kumari Bahl, Sotirios Sabanis

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In this paper, we are concerned with the valuation of the first Catastrophic Mortality Bond that was launched in the market namely the Swiss Re Mortality Bond 2003. This bond encapsulates the behavior of a well-defined mortality index to generate payoffs for the bondholders. Pricing this bond is a challenging task. We adapt the payoff of the terminal principal of the bond in terms of the payoff of an Asian put option and present an approach to derive model-independent bounds exploiting comonotonic theory. We invoke Jensen’s inequality for the computation of lower bounds and employ Lagrange optimization technique to achieve the upper bound. The success of these bounds is based on the availability of compatible European mortality options in the market. We carry out Monte Carlo simulations to estimate the bond price and illustrate the strength of these bounds across a variety of models. The fact that our bounds are model-independent is a crucial breakthrough in the pricing of catastrophic mortality bonds.

Keywords: mortality bond, Swiss Re Bond, mortality index, comonotonicity

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Authors: Mohammed Auwal Ibrahim, Aminu Mohammed

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Stigmasterol has previously been reported to possess antitrypanosomal activity using in vitro and in vivo models. However, the mechanism of antitrypanosomal activity is yet to be elucidated. In the present study, molecular docking was used to decipher the mode of interaction and binding affinity of stigmasterol to three known antitrypanosomal drug targets viz; adenosine kinase, ornithine decarboxylase and triose phosphate isomerase. Stigmasterol was found to bind to the selected trypanosomal enzymes with minimum binding energy of -4.2, -6.5 and -6.6 kcal/mol for adenosine kinase, ornithine decarboxylase, and triose phosphate isomerase respectively. However, hydrogen bond was not involved in the interaction of stigmasterol with all the three enzymes, but hydrophobic interaction seemed to play a vital role in the binding phenomenon which was predicted to be non-competitive like type of inhibition. It was concluded that binding to the three selected enzymes, especially triose phosphate isomerase, might be involved in the antitrypanosomal activity of stigmasterol but not mediated via a hydrogen bond interaction.

Keywords: antitrypanosomal, in silico, molecular docking, stigmasterol

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Authors: Motonori Tamura

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Ceramics coatings consisting of fine crystal grains, with diameters of about 100 nm or less, provided superior hydrogen-permeation barriers. Applying TiN, TiC or Al₂O₃ coatings on a stainless steel substrate reduced the hydrogen permeation by a factor of about 100 to 5,000 compared with uncoated substrates. Effect of the microstructure of coatings on hydrogen-permeation behavior is studied. The test specimens coated with coatings, with columnar crystals grown vertically on the substrate, tended to exhibit higher hydrogen permeability. The grain boundaries of the coatings became trap sites for hydrogen, and microcrystalline structures with many grain boundaries are expected to provide effective hydrogen-barrier performance.

Keywords: hydrogen permeation, tin coating, microstructure, crystal grain, stainless steel

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Authors: Hunmin Jung, Michael Hawkins, Seongmin Lee

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The exocyclic amines of nucleobases can undergo deamination by various DNA damaging agents such as reactive oxygen species, nitric oxide, and water. The deamination of guanine and adenine generates the promutagenic xanthine and hypoxanthine, respectively. The exocyclic amines of bases in DNA are hydrogen bond donors, while the carbonyl moiety generated by the base deamination acts as hydrogen bond acceptors, which can alter base pairing properties of the purines. Xanthine is known to base pair with both cytosine and thymine, while hypoxanthine predominantly pairs with cytosine to promote A to G mutations. Despite the known promutagenicity of the major deaminated purines, structures of DNA polymerase bypassing these lesions have not been reported. To gain insights into the deaminated-induced mutagenesis, we solved crystal structures of human DNA polymerase η (polη) catalyzing across xanthine and hypoxanthine. In the catalytic site of polη, the deaminated guanine (i.e., xanthine) forms three Watson-Crick-like hydrogen bonds with an incoming dCTP, indicating the O2-enol tautomer of xanthine involves in the base pairing. The formation of the enol tautomer appears to be promoted by the minor groove contact by Gln38 of polη. When hypoxanthine is at the templating position, the deaminated adenine uses its O6-keto tautomer to form two Watson-Crick hydrogen bonds with an incoming dCTP, providing the structural basis for the high promutagenicity of hypoxanthine.

Keywords: DNA damage, DNA polymerase, deamination, mutagenesis, tautomerization, translesion synthesis

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Authors: Vaclav Heral

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Ideas about the mechanism of heterogeneous catalytic hydrogenation are diverse. The Horiuti-Polanyi mechanism is most often referred to, based on the idea of a semi-hydrogenated state. In our opinion, it does not represent a satisfactory explanation of the hydrogenation mechanism, because, for example: (1) It neglects the fact that the bond of atomic hydrogen to the metal surface is strongly polarized, (2) It does not explain why a surface deprived of atomic hydrogen (by thermal desorption or by alkyne) loses isomerization capabilities, but hydrogenation capabilities remain preserved, (3) It was observed that during the hydrogenation of 1-alkenes, the reaction can be of the 0th order to hydrogen and to the alkene at the same time, which is excluded during the competitive adsorption of both reactants on the catalyst surface. We offer an alternative mechanism that satisfactorily explains many of the ambiguities: It is the idea of an independent course of olefin isomerization, catalyzed by acidic atomic hydrogen bonded on the surface of the catalyst, in addition to the hydrogenation itself, in which a two-layer complex appears on the surface of the catalyst: olefin bound to the surface and molecular hydrogen bound to it in the second layer. The rate-determining step of hydrogenation is the conversion of this complex into the final product. We believe that the Horiuti-Polanyi mechanism is flawed and we naturally think that our two-layer theory better describes the experimental findings.

Keywords: acidity of hydrogenation catalyst, Horiuti-Polanyi, hydrogenation, two-layer hydrogenation

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Authors: Hamoud Al-Hadrami, Hossein Emadi, Athar Hussain

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Green hydrogen is quickly emerging as a new source of renewable energy for the world. Hydrogen production using water electrolysis is deemed as an environmentally friendly and safe source of energy for transportation and other industries. However, storing a high volume of hydrogen seems to be a significant challenge. Abandoned hydrocarbon reservoirs are considered as viable hydrogen storage options because of the availability of the required infrastructure such as wells and surface facilities. However, long-term wellbore integrity in these wells could be a serious challenge. Hydrogen reduces the compressive strength of a set cement if it gets in contact with the cement slurry. Also, mixing hydrogen with cement slurry slightly increases its density and rheological properties, which need to be considered to have a successful primary cementing operation.

Keywords: hydrogen, well bore integrity, clean energy, cementing

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Authors: Jee-Sang Kim, Jong Ho Park

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Geopolymer concretes are a new class of construction materials that have emerged as an alternative to Ordinary Portland cement concrete. Considerable researches have been carried out on material development of geopolymer concrete, however, a few studies have been reported on the structural use of them. This paper presents the bond behaviors of reinforcement embedded in fly ash based geopolymer concrete. The development lengths of reinforcement for various compressive strengths of concrete, 20, 30 and 40 MPa, and reinforcement diameters, 10, 16, and 25 mm are investigated. Total 27 specimens were manufactured and pull-out test according to EN 10080 was applied to measure bond strength and slips between concrete and reinforcements. The average bond strengths decreased from 23.06MPa to 17.26 MPa, as the diameters of reinforcements increased from 10mm to 25mm. The compressive strength levels of geopolymer concrete showed no significant influence on bond strengths in this study. Also, the bond-slip relations between geopolymer concrete and reinforcement are derived using non-linear regression analysis for various experimental conditions.

Keywords: bond-slip relation, bond strength, geopolymer concrete, pull-out test

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Authors: Shahriar Ghammamy, Masomeh Shahsavary

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In this paper, the optimized geometries and frequencies of the stationary point and the minimum energy paths of C13H12F7ClN2O are calculated by using the DFT (B3LYP) methods with LANL2DZ basis sets. B3LYP/ LANL2DZ calculation results indicated that some selected bond length and bond angles values for the C13H12F7ClN2O.

Keywords: C13H12F7ClN2O, vatural bond orbital, fluorous compounds, functional calculations

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Authors: Aibek Kukpayev, Dhawal Shah

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Combustion of sour fuels containing high amount of sulfur leads to the formation of sulfur oxides, which adversely harm the environment and has a negative impact on human health. Considering this, several legislations have been imposed to bring down the sulfur content in fuel to less than 10 ppm. In recent years, novel deep eutectic solvents (DESs) have been developed to achieve deep desulfurization, particularly to extract thiophenic compounds from liquid fuels. These novel DESs, considered as analogous to ionic liquids are green, eco-friendly, inexpensive, and sustainable. We herein, using molecular dynamic simulation, analyze the interactions of metal-based DESs with model oil consisting of thiophenic compounds. The DES used consists of polyethylene glycol (PEG-200) as a hydrogen bond donor, choline chloride (ChCl) or tetrabutyl ammonium chloride (TBAC) as a hydrogen bond acceptor, and cobalt chloride (CoCl₂) as metal salt. In particular, the combination of ChCl: PEG-200:CoCl₂ at a ratio 1:2:1 and the combination of TBAC:PEG-200:CoCl₂ at a ratio 1:2:0.25 were simulated, separately, with model oil consisting of octane and thiophenes at 25ᵒC and 1 bar. The results of molecular dynamics simulations were analyzed in terms of interaction energies between different components. The simulations revealed a stronger interaction between DESs/thiophenes as compared with octane/thiophenes, suggestive of an efficient desulfurization process. In addition, our analysis suggests that the choice of hydrogen bond acceptor strongly influences the efficiency of the desulfurization process. Taken together, the results also show the importance of the metal ion, although present in small amount, in the process, and the role of the polymer in desulfurization of the model fuel.

Keywords: deep eutectic solvents, desulfurization, molecular dynamics simulations, thiophenes

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Authors: Viney Dixit, Rohit R. Shahi, Ashish Bhatnagar, P. Jain, T. P. Yadav, O. N. Srivastava

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Carbons are being widely investigated as hydrogen storage material owing to their light weight, fast hydrogen absorption kinetics and low cost. However, these materials suffer from low hydrogen storage capacity at room temperature. The aim of the present study is to synthesize carbon based material which shows moderate hydrogen storage at room temperature. For this purpose, hydrogenation characteristics of natural precursor coconut kernel is studied in this work. The hydrogen storage measurement reveals that the as-synthesized materials have good hydrogen adsorption and desorption capacity with fast kinetics. The synthesized material absorbs 8 wt.% of hydrogen at liquid nitrogen temperature and 2.3 wt.% at room temperature. This could be due to the presence of certain elements (KCl, Mg, Ca) which are confirmed by TEM.

Keywords: coconut kernel, carbonization, hydrogenation, KCl, Mg, Ca

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Authors: Hugo Daneluzzo, Christelle Rabbat, Alan Jean-Marie

Abstract:

Water electrolysis is one of the most advanced technologies for producing hydrogen and can be easily combined with electricity from different sources. Under the influence of electric current, water molecules can be split into oxygen and hydrogen. The production of hydrogen by water electrolysis favors the integration of renewable energy sources into the energy mix by compensating for their intermittence through the storage of the energy produced when production exceeds demand and its release during off-peak production periods. Among the various electrolysis technologies, anion exchange membrane (AEM) electrolyser cells are emerging as a reliable technology for water electrolysis. Modeling and simulation are effective tools to save time, money, and effort during the optimization of operating conditions and the investigation of the design. The modeling and simulation become even more important when dealing with multiphysics dynamic systems. One of those systems is the AEM electrolysis cell involving complex physico-chemical reactions. Once developed, models may be utilized to comprehend the mechanisms to control and detect flaws in the systems. Several modeling methods have been initiated by scientists. These methods can be separated into two main approaches, namely equation-based modeling and graph-based modeling. The former approach is less user-friendly and difficult to update as it is based on ordinary or partial differential equations to represent the systems. However, the latter approach is more user-friendly and allows a clear representation of physical phenomena. In this case, the system is depicted by connecting subsystems, so-called blocks, through ports based on their physical interactions, hence being suitable for multiphysics systems. Among the graphical modelling methods, the bond graph is receiving increasing attention as being domain-independent and relying on the energy exchange between the components of the system. At present, few studies have investigated the modelling of AEM systems. A mathematical model and a bond graph model were used in previous studies to model the electrolysis cell performance. In this study, experimental data from literature were simulated using OpenModelica using bond graphs and mathematical approaches. The polarization curves at different operating conditions obtained by both approaches were compared with experimental ones. It was stated that both models predicted satisfactorily the polarization curves with error margins lower than 2% for equation-based models and lower than 5% for the bond graph model. The activation polarization of hydrogen evolution reactions (HER) and oxygen evolution reactions (OER) were behind the voltage loss in the AEM electrolyzer, whereas ion conduction through the membrane resulted in the ohmic loss. Therefore, highly active electro-catalysts are required for both HER and OER while high-conductivity AEMs are needed for effectively lowering the ohmic losses. The bond graph simulation of the polarisation curve for operating conditions at various temperatures has illustrated that voltage increases with temperature owing to the technology of the membrane. Simulation of the polarisation curve can be tested virtually, hence resulting in reduced cost and time involved due to experimental testing and improved design optimization. Further improvements can be made by implementing the bond graph model in a real power-to-gas-to-power scenario.

Keywords: hydrogen production, anion-exchange membrane, electrolyzer, mathematical modeling, multiphysics modeling

Procedia PDF Downloads 91

Authors: Sung-yong Choi, Woo-tai Jung, Young-hwan Park

Abstract:

This study intends to improve the bond performance of the polypropylene fiber used as reinforcing fiber for concrete by changing its shape into double crimped type through the enhancement its fabrication process. The bond performance of such double crimped fiber is evaluated by applying the JCI SF-8 (dog-bone shape) testing method. The test results reveal that the double crimped fiber develops bond performance improved by more than 19% compared to the conventional crimped type fiber.

Keywords: Bond, Polypropylene, fiber reinforcement, macro fiber, shape change

Procedia PDF Downloads 462

Authors: M. A. Lahmer, K. Guergouri

Abstract:

In this work, Kinetic Monte Carlo (KMC) method was applied to study the thermal stability of hydrogen in ZnO bulk and thin films. Our simulation includes different possible events such as interstitial hydrogen (Hi) jumps, substitutional hydrogen (HO) formation and dissociation, oxygen and zinc vacancies jumps, hydrogen-VZn complexes formation and dissociation, HO-Hi complex formation and hydrogen molecule (H2) formation and dissociation. The obtained results show that the hidden hydrogen formed during thermal annealing or at room temperature is constituted of both hydrogen molecule and substitutional hydrogen. The ratio of this constituants depends on the initial defects concentration as well as the annealing temperature. For annealing temperature below 300°C hidden hydrogen was found to be constituted from both substitutional hydrogen and hydrogen molecule, however, for higher temperature it is composed essentially from HO defects only because H2 was found to be unstable. In the other side, our results show that the remaining hydrogen amount in sample during thermal annealing depend greatly on the oxygen vacancies in the material. H2 molecule was found to be stable for thermal annealing up to 200°C, VZnHn complexes are stable up to 350°C and HO was found to be stable up to 450°C.

Keywords: ZnO, hydrogen, thermal annealing, kinetic Monte Carlo

Procedia PDF Downloads 341