Identifying Noble Metal Catalysts for the Hydrogenation and Dehydrogenation of Dibenzyltoluene: A Combined Theoretical-Experimental Study.

We present a comprehensive theoretical and experimental investigation of the hydrogenation and dehydrogenation of dibenzyltoluene (DBT) using Pd-, Pt-, Ru-, and Rh-supported metal catalysts to identify the optimal catalysts for hydrogen storage and release processes. Our results demonstrated significant variation in the catalytic activity of the metal catalysts. 5 wt % Rh/Al2O3 and 5 wt % Pt/Al2O3 showed the highest activity for hydrogenation and dehydrogenation with the highest selectivity and turnover frequency (TOF), respectively. Conversely, 5 wt % Pd/Al2O3 and 5 wt % Ru/Al2O3 exhibited lower catalytic activity toward full hydrogenation and dehydrogenation. Rh/Al2O3 showed the best catalytic hydrogenation activity with a TOF of 26.49 h-1 and a hydrogenation degree of 92.69% in 2 h, while Pt/Al2O3 exhibited the best catalytic dehydrogenation activity with a released H2 volume of 3755 mL, a dehydrogenation degree of 78.23%, and a TOF of 39.56 h-1 in 2 h. Additionally, we estimated the activation energies for hydrogenation and dehydrogenation to be 67.20 and 82.78 kJ/mol, respectively. Notably, the produced hydrogen gas was of high purity and suitable for use in fuel cells. Density functional theory (DFT) calculations were used to analyze the adsorption structure and reaction energy changes of all intermediate products of DBT on the surface of the chosen catalysts. Our research provides valuable insights into developing efficient catalysts for liquid organic hydrogen carriers.

Palladium Phosphide as a Stable and Efficient Electrocatalyst for Overall Water Splitting.

A palladium phosphide electrocatalyst supported on carbon black (PdP2 @CB) shows efficient water splitting in both alkaline and neutral electrolytes. Significantly lower overpotentials are required for PdP2 @CB (27.5 mV in 0.5 m H2 SO4 ; 35.4 mV in 1 m KOH; 84.6 mV in 1 m PBS) to achieve a HER electrocatalytic current density of 10 mA cm-2 compared to commercial Pt/CB (30.1 mV in 0.5 m H2 SO4 ; 46.6 mV in 1 m KOH; 122.7 mV in 1 m PBS). Moreover, no loss in HER activity is detectable after 5000 potential sweeps. Only 270 mV and 277 mV overpotentials are required to reach a current density of 10 mA cm-2 for PdP2 @CB to catalyze OER in 1 m KOH and 1 m PBS electrolytes, which is better OER activity than the benchmark IrO2 electrocatalyst (301 mV and 313 mV to drive a current density of 10 mA cm-2 ). 1.59 V and 1.72 V are needed for PdP2 @CB to achieve stable water splitting catalytic current density of 10 mA cm-2 in 1 m PBS and 50 mA cm-2 in 1 m KOH for 10 h, respectively.

On the mechanism of catalytic hydrogenation of thiophene on hydrogen tungsten bronze.

Hydrogenation of unsaturated organosulfur compounds is an essential process through which these species are converted into cleaner and more useful compounds. Hydrogen bronze materials have been demonstrated to be efficient catalysts in hydrogenation of simple unsaturated compounds. Herein, we performed density functional theory calculations to investigate hydrogenation of thiophene on hydrogen tungsten bronze. Various reaction pathways were investigated and the most favourable routes were identified. Our results suggest that the reaction proceeds with moderate barriers, and formation of tetrahydrothiophene is facile both thermochemically and kinetically. The present study provides a useful insight into the design of hydrogenation thiophene and its derivatives and effective hydrodesulfurization catalysts.

Density functional theory study on the full ALD process of silicon nitride thin film deposition via BDEAS or BTBAS and NH3.

A detailed reaction mechanism has been proposed for the full ALD cycle of Si3N4 deposition on the ß-Si3N4(0001) surface using bis(diethylamino)silane (BDEAS) or bis(tertiarybutylamino)silane (BTBAS) as a Si precursor with NH3 acting as the nitrogen source. Potential energy landscapes were derived for all elementary steps in the proposed reaction network using a periodic slab surface model in the density functional approximation. Although the dissociative reactivity of BTBAS was slightly better than that of BDEAS, the thermal deposition process was still found to be an inherently high temperature process due to the high activation energies during the dissociative chemisorption of both precursors and the surface re-amination steps. These results underline the need to develop new precursors and alternative nitrogen sources when low temperature thermal silicon nitride films are targeted.

Strategic structure modulation of novel quinoxaline-derived liquid organic hydrogen carriers for enhanced dehydrogenation kinetics.

This study introduces novel Liquid Organic Hydrogen Carriers (LOHCs) derived from quinoxaline. It shows that strategically incorporating N atoms and methyl groups markedly improves the hydrogen release kinetics. This structural modulation optimizes the adsorption properties and enables low-temp C-H bond activation, providing valuable insights for developing efficient LOHCs.

Fabrication of highly transparent and conductive indium-tin oxide thin films with a high figure of merit via solution processing.

Deposition technology of transparent conducting oxide (TCO) thin films is critical for high performance of optoelectronic devices. Solution-based fabrication methods can result in substantial cost reduction and enable broad applicability of the TCO thin films. Here we report a simple and highly effective solution process to fabricate indium-tin oxide (ITO) thin films with high uniformity, reproducibility, and scalability. The ITO films are highly transparent (90.2%) and conductive (ρ = 7.2 × 10(-4) Ω·cm) with the highest figure of merit (1.19 × 10(-2) Ω(-1)) among all the solution-processed ITO films reported to date. The high transparency and figure of merit, low sheet resistance (30 Ω/sq), and roughness (1.14 nm) are comparable with the benchmark properties of dc sputtering and can meet the requirements for most practical applications.

A Brush-like Li-Ion Exchange Polymer as Potential Artificial Solid Electrolyte Interphase for Dendrite-Free Lithium Metal Batteries.

Artificial polymeric solid electrolyte interfaces (APSEIs) are an emerging material that enables use of a lithium metal anode as a lithium metal battery technique with high energy density. However, the poor ionic conductivity, low lithium transference number, and bad compatibity with lithium metal anode lead to a large dissipative loss of energy capacity. Here we report that, by properly constructing a brush-like structure in cellulose nanofibril (CNF) based APSEIs, a good ion-aggregation morphology with interconnected ionic conducting channels can be built, such that the Li-ion conduction in the APSEI layer becomes highly efficient. The optimal approach to constructing such an ionic highway is proved computationally using coarse-grained molecular dynamics (CGMD) simulations and implemented experimentally based on transmission electron microscopy (TEM) and atomic force microscopy (AFM). In addition, Li-ion exchange structures and hydroxyl-abundant structures endow the APSEIs with good ability to suppress dendrite growth and excellent compatibility with the anode surface.

Expeditious diastereoselective construction of a thiochroman skeleton via a cinchona alkaloid-derived catalyst.

An example of diastereoselective and enantioselective synthesis of thiochroman derivatives through a sulfa-Michael-Michael cascade sequence is disclosed. This is a significant complement of the quinine-thiourea catalyzed sulfa-Michael-Michael cascade reaction. The densely functionalized target thiochromans were obtained in high diastereoselectivities, and with high to excellent enantioselectivities.

Force fields for metallic clusters and nanoparticles.

Atomic force fields for simulating copper, silver, and gold clusters and nanoparticles are developed. Potential energy functions are obtained for both monatomic and binary metallic systems using an embedded atom method. Many cluster configurations of varying size and shape are used to constrain the parametrization for each system. Binding energies for these training clusters were computed using density functional theory (DFT) with the Perdew-Wang exchange-correlation functional in the generalized gradients approximation. Extensive testing shows that the many-body potentials are able to reproduce the DFT energies for most of the structures that were included in the training set. The force fields were used to calculate surface energies, bulk structures, and thermodynamic properties. The results are in good agreement with the DFT values and consistent with the available experimental data.

Study of catalytic hydrogenation and dehydrogenation of 2,3-dimethylindole for hydrogen storage application.

2,3-Dimethylindole (2,3-DMID), a candidate with a hydrogen storage capacity of 5.23 wt%, was studied as a new liquid organic hydrogen carrier (LOHC) in detail in this report. Hydrogenation of 2,3-DMID was conducted over 5 wt% Ru/Al2O3 by investigating the influences of temperature and hydrogen pressure. 100% of fully hydrogenated product, 8H-2,3-DMID can be achieved at 190 °C and 7 MPa in 4 h. Dehydrogenation of 8H-2,3-DMID was performed over 5 wt% Pd/Al2O3 at 180-210 °C and 101 kPa. It is found that dehydrogenation of 8H-2,3-DMID followed first order kinetics with an apparent activation energy of 39.6 kJ mol-1. The structures of intermediates produced in the 8H-2,3-DMID dehydrogenation process were analyzed by DFT calculations.

A first principles study of water dissociation on small copper clusters.

Water dissociation on copper is one of the rate-limiting steps in the water-gas-shift (WGS) reaction. Copper atoms dispersed evenly from freshly made catalyst segregate to form clusters under the WGS operating conditions. Using density functional theory, we have examined water adsorption and dissociation on the smallest stable 3-dimensional copper cluster, Cu(7). Water molecules are adsorbed on the cluster sequentially until full saturation at which no direct water-copper contact is sterically possible. The adsorption is driven mainly by the overlap between the p-orbital of O atom occupied by the lone pair and the 3d-orbitals of copper, from which a fractional charge is promoted to the 4s-orbital to accommodate the charge transfer from water. Water dissociation on the Cu(7) cluster was investigated at both low and high water coverage. It was found that water dissociation into OH and H is exothermic but is inherently a high temperature process at low coverage. At high coverage, the reaction becomes more exothermic with fast kinetics. In both cases, water can catalyze the reaction. It was found that direct dissociation of the OH species is endothermic with a significantly higher barrier at both low and high coverage. However, the OH species can readily react with another adjacent hydroxyl group to form an O adatom and water molecule. Our studies indicate that the basic chemical properties of water dissociative chemisorption may not change significantly with the size of small copper clusters. Similarities between water dissociation on copper clusters and on copper crystalline surfaces are discussed.

Understanding the mechanism of the competitive adsorption in 8-methylquinoline hydrogenation over a Ru catalyst.

The competitive adsorption of 8-methylquinoline (8-MQL) and partially hydrogenated product, 4H-8-MQL, was studied by performing a combination of experiments and first-principles calculations over a selected Ru catalyst. A series of hydrogenation reactions were conducted with 8-MQL and 4H-8-MQL as initial reactants, respectively. 8-MQL exhibits stronger adsorption on catalyst surface active sites compared with 4H-8-MQL and the massive adsorption of 8-MQL hampers the further adsorption of 4H-8-MQL. The effects of temperature, pressure and solvent on the selectivity in 8-MQL hydrogenation were investigated as well. Full hydrogenation of 8-MQL to 10H-8-MQL was achieved within 120 min when the catalyst dosage increased from 5 wt% to 7 wt% under 160 °C and a hydrogen pressure of 7 MPa. The electronic charge of the N-heteroatom in 8-MQL and 4H-8-MQL was analyzed and the adsorption geometries of 8-MQL and 4H-8-MQL on the Ru(001) surface were optimized by DFT calculations to explain the competitive adsorption behaviors of 8-MQL and 4H-8-MQL.

Instant Postsynthesis Aqueous Dispersion of Sb-Doped SnO2 Nanocrystals: The Synergy between Small-Molecule Amine and Sb Dopant Ratio.

Direct printing of transparent conducting oxide (TCO) nanocrystal dispersions holds great promise in solution-processed optoelectronics due to its advantages of low material waste and direct patterning on substrates. An essential prerequisite for printable TCO colloidal solutions is the effective stabilization of TCO nanocrystals to prevent their strong aggregation. In situ stabilization uses long-chain ligands to provide interparticle steric repulsion between TCO nanocrystals during the growth of TCO nanocrystals. In sharp contrast, the postsynthesis dispersion of TCO nanocrystals is particularly challenging since the agglomeration already occurs, especially for TCO nanocrystals synthesized without protection by any organic species. Herein, we propose an instant postsynthesis strategy for aqueous colloidal dispersions of Sb-doped SnO2 (ATO) nanocrystals using small-molecule amines of propylamine, ethylenediamine, monoethanolamine, and triethylamine. The average size of ATO secondary particles in aqueous dispersions can be instantly reduced from around 400 to about 25 nm using these amines. The increased Sb dopant ratio also plays a synergistic role in the dispersion effect. The small-molecule amines are found to be preferably adsorbed onto the Sb sites exposed on ATO nanocrystal surface. A higher Sb dopant ratio would facilitate the adsorption of more amines and induce stronger surface charge repulsion that benefits the stable dispersion of ATO nanocrystals. TCO films fabricated with the ATO nanocrystal dispersions have a high transparency of 80.6% and low sheet resistance of 492 Ω/sq, showing promising application in electrochromic devices.

An enhanced hydrogen adsorption enthalpy for fluoride intercalated graphite compounds.

We present a combined theoretical and experimental study on H(2) physisorption in partially fluorinated graphite. This material, first predicted computationally using ab initio molecular dynamics simulation and subsequently synthesized and characterized experimentally, represents a novel class of "acceptor type" graphite intercalated compounds that exhibit significantly higher isosteric heat of adsorption for H(2) at near ambient temperatures than previously demonstrated for commonly available porous carbon-based materials. The unusually strong interaction arises from the semi-ionic nature of the C-F bonds. Although a high H(2) storage capacity (>4 wt %) at room temperature is predicted not to be feasible due to the low heat of adsorption, enhanced storage properties can be envisaged by doping the graphitic host with appropriate species to promote higher levels of charge transfer from graphene to F(-) anions.

Force field for copper clusters and nanoparticles.

An atomic force field for simulating copper clusters and nanoparticles is developed. More than 2000 cluster configurations of varying size and shape are used to constrain the parametrization of the copper force field. Binding energies for these training clusters were computed using density functional theory. Extensive testing shows that the copper force field is fast and reliable for near-equilibrium structures of clusters, ranging from only a few atoms to large nanoparticles that approach bulk structure. Nonequilibrium dissociation and compression structures that are included in the training set are also well described by the force field. Implications for molecular dynamics simulations and extensions to other metallic and covalent systems are discussed.

On reversible bonding of hydrogen molecules on platinum clusters.

The local reactivity of hydrogenated platinum clusters (Pt clusters) has been studied using the regional density functional theory method. We observed that antibond orbitals constitute the preferable binding site for hydrogen molecules H(2). Those sites are characterized by lowered electronic chemical potential and strong directionality and exhibit electrophilic nature. The platinum-dihydrogen (Pt-H(2)) sigma complexes were formed only by occupation of the lowest electronic chemical potential sites associated with Pt-H antibonds (sigma(PtH) ( *)) in saturated platinum clusters. The formation of sigma complexes caused mutual stabilization with the trans Pt-H bond. Such activated H(2) molecules on Pt clusters in a sense resemble heme-oxygen (heme-O(2)) complex with interaction strength greater than physisorption or hydrogen bonding but below chemisorption strength.

Tuning the Catalytic Activity of Pd x Ni y (x + y = 6) Bimetallic Clusters for Hydrogen Dissociative Chemisorption and Desorption.

Density functional theory was used to study dissociative chemisorption and desorption on Pd x Ni y (x + y = 6) bimetallic clusters. The H2 dissociative chemisorption energies and the H desorption energies at full H saturation were computed. It was found that bimetallic clusters tend to have higher chemisorption energy than pure clusters, and the capacity of Pd3Ni3 and Pd2Ni4 clusters to adsorb H atoms is substantially higher than that of other clusters. The H desorption energies of Pd3Ni3 and Pd2Ni4 are also lower than that of the Pd6 cluster and comparable to that of the Ni6 cluster, indicating that it is easier to pull the H atom out of these bimetallic catalysts. This suggests that the catalytic efficiency for specific Pd x Ni y bimetallic clusters may be superior to bare Ni or Pd clusters and that it may be possible to tune bimetallic nanoparticles to obtain better catalytic performance.

Tungsten Carbide Hollow Microspheres with Robust and Stable Electrocatalytic Activity toward Hydrogen Evolution Reaction.

Here, we report a stable tungsten carbide hollow microsphere (W2C-HS) electrocatalyst with robust electrocatalytic activity toward hydrogen evolution reaction fabricated from carburization of tungsten oxides at 700 °C with CH4/H2 flow, which demands overpotentials of 153 and 264 mV to deliver 10 and 100 mA cm-2 ascribing to the hollow structures beneficial for interfacial charge transfer as well as releasing of hydrogen molecular. Meanwhile, the W2C-HS electrocatalyst exhibits undetectable degradation after 20 000 potential cycles indicative of extraordinary durability; in contrast, overpotential@100 mA cm-2 is dramatically increased from 128 to 251 mV after only 2000 potential cycles for benchmark platinum electrocatalyst.

Targeted filling of silica in Nafion by a modified in situ sol-gel method for enhanced fuel cell performance at elevated temperatures and low humidity.

Herein, a modified in situ sol-gel method was applied to prepare the Nafion/silica composite membrane with targeted filling of silica into ionic clusters. The low humidity (20-60% RH) proton conductivity of Nafion was therefore doubled at elevated temperatures (110-120 °C), and the high-temperature fuel cell performance was significantly improved by 45%.

A facile non-solvent induced phase separation process for preparation of highly porous polybenzimidazole separator for lithium metal battery application.

The drawbacks of low porosity, inferior electrolyte wettability, low thermal dimensional stability and permissive lithium dendrite growth of the conventional microporous polyolefin-based separators hinder their widely application in the high power density and safe Lithium ion batteries. Herein, highly porous polybenzimidazole-based separator is prepared by a facile non-solvent induced phase separation process (NIPS) using water, ethanol, chloroform and ethyl acetate as the coagulation bath solvent, respectively. It was found that the ethanol is suitable to fabricate uniform morphology macroporous separator with the porosity of 92%, electrolyte uptake of 594 wt.%, and strong mechanical strength of 15.9 MPa. In addition, the experimental tests (electrochemical analysis and XPS test) and density functional theory calculation suggest that the electron-rich imidazole ring of polybenzimidazle can enhance Li+ mobility electrostatic attraction interaction while the block the PF6- mobility via electrostatic repulsion interaction. Therefore, high Li+ transference number of 0.76 was obtained for the neat polybenzimidazole-based polymer electrolyte. As a proof of concept, the Li/LiFePO4 cell with the polybenzimidazole-based polymer electrolyte/1.0 M LiPF6- ethylene carbonate/dimethyl carbonate (v:v = 1:1) electrolyte exhibits excellent rate capability of >100 mAh g-1 at 6 C (1 C = 170 mA g-1) and superior cycle stability of 1000 cycles.