Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

Intrinsic kinetics of catalytic hydrogenation of 2-nitro-4-acetylamino anisole to 2-amino-4-acetylamino anisole over Raney nickel catalyst

The catalytic hydrogenation of 2-nitro-4-acetylamino anisole(NMA)is a less-polluting and efficient method to produce 2-amino-4-acetamino anisole(AMA).However,the kinetics of catalytic hydrogenation of NMA to AMA remains obscure.In this work,the kinetic models including power-law model and Langmuir-Hinshelwood-Hougen-Watson(LHHW)model of NMA hydrogenation to AMA catalyzed by Raney nickel catalyst were investigated.All experiments were carried out under the elimination of mass transfer resistance within the temperature range of 70–100°C and the hydrogen pressure of 0.8–1.5 MPa.The reaction was found to follow 0.52-order kinetics with respect to the NMA concentration and 1.10-order kinetics in terms of hydrogen pressure.Based on the LHHW model,the dual-site dissociation adsorption of hydrogen was analyzed to be the rate determining step.The research of intrinsic kinetics of NMA to AMA provides the guidance for the reactor design and inspires the catalyst modification.

Recent advances in cobalt phosphide-based materials for electrocatalytic water splitting:From catalytic mechanism and synthesis method to optimization design

Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.

Kinetics insights into size effects of carbon nanotubes'growth and their supported platinum catalysts for 4,6-dinitroresorcinol hydrogenation

Size effects are a well-documented phenomenon in heterogeneous catalysis,typically attributed to alterations in geometric and electronic properties.In this study,we investigate the influence of catalyst size in the preparation of carbon nanotube(CNT)and the hydrogenation of 4,6-dinitroresorcinol(DNR)using Fe_(2)O_(3)and Pt catalysts,respectively.Various Fe_(2)O_(3)/Al_(2)O_(3)catalysts were synthesized for CNT growth through catalytic chemical vapor deposition.Our findings reveal a significant influence of Fe_(2)O_(3)nanoparticle size on the structure and yield of CNT.Specifically,CNT produced with Fe_(2)O_(3)/Al_(2)O_(3)containing 28%(mass)Fe loading exhibits abundant surface defects,an increased area for metal-particle immobilization,and a high carbon yield.This makes it a promising candidate for DNR hydrogenation.Utilizing this catalyst support,we further investigate the size effects of Pt nanoparticles on DNR hydrogenation.Larger Pt catalysts demonstrate a preference for 4,6-diaminoresorcinol generation at(100)sites,whereas smaller Pt catalysts are more susceptible to electronic properties.The kinetics insights obtained from this study have the potential to pave the way for the development of more efficient catalysts for both CNT synthesis and DNR hydrogenation.

Metal organic framework supported niobium pentoxide nanoparticles with exceptional catalytic effect on hydrogen storage behavior of MgH_(2)

Nb_(2)O_(5)nanoparticles with an average particle size of 10 nm supported on a rhombic dodecahedral metal organic framework(MOF)were successfully synthesized by a facile one-pot hydrothermal reaction and subsequent calcination process.Experimental results demonstrated that the prepared catalyst drastically improved the hydrogen storage behavior of MgH_(2).7 wt%Nb_(2)O_(5)@MOF doped MgH_(2)started to desorb hydrogen at 181.9℃and 6.2 wt%hydrogen could be released within 2.6 min and 6.3 min at 275℃and 250℃,respectively.The fully dehydrogenated composite also displayed excellent hydrogenation by decreasing the onset absorption temperature to 25℃and taking up4.9 wt%and 6.5 wt%hydrogen within 6 min at 1750C and 1500C,respectively.Moreover,the corresponding activation energy was calculated to be 75.57±4.16 kJ mol^(-1)for desorption reaction and 51.38±1.09 kJ mol^(-1)for absorption reaction.After 20 cycles,0.5 wt%hydrogen capacity was lost for the MgH_(2)+7 wt%Nb_(2)O_(5)@MOF composite,much lower than 1.5 wt%of the MgH_(2)+7 wt%Nb_(2)O_(5)composite.However,the addition of Nb_(2)O_(5)@MOF had limited effect on reducing the dehydrogenation enthalpy of MgH_(2).Microstructure analysis revealed that Nb_(2)O_(5)particles were uniformly distributed on surface of the MgH_(2)matrix and synergistically improved the hydrogen storage property of MgH_(2)with MOF.

The hydrogen storage performance and catalytic mechanism of theMgH_(2)-MoS_(2)composite

In this work,we synthesized MoS_(2)catalyst via one-step hydrothermal method,and systematically investigated the catalytic effect of MoS_(2)on the hydrogen storage properties of MgH_(2).The MgH_(2)-5MoS_(2)composite milled for 5 h starts to release hydrogen at 259℃.Furthermore,it can desorb 4.0 wt.%hydrogen within 20 min at 280℃,and absorb 4.5 wt.%hydrogen within 5 min at 200℃.Mo and MoS_(2)coexistedin the ball milled sample,whereas only Mo was kept in the sample after dehydrogenation and rehydrogenation,which greatly weakens theMg-H bonds and facilitates the dissociation of MgH_(2)on the surface of Mo(110).The comparative study show that the formed MgS has nocatalytic effect for MgH_(2).We believed that the evolution and the catalytic mechanism of MoS_(2)will provide the theoretical guidance for theapplication of metal sulfide in hydrogen storage materials.

Ammonia borane-enabled hydrogen transfer processes:Insights into catalytic strategies and mechanisms

Transfer hydrogenation(TH) with in situ generated hydrogen donor is of great importance in reduction reactions, and an alternative strategy to traditional hydrogenation processes involving pressurized molecular hydrogen. Ammonia borane(NH3BH3, AB) is a promising material of hydrogen storage, and it has attracted much attention in reductive organic transformations owing to its high activity, good atom economy, nontoxicity, sustainability, and ease of transport and storage. This review focuses on summarizing the recent progress of AB-mediated TH reactions of diverse substrates including nitro compounds, nitriles, imines, alkenes, alkynes, carbonyl compounds(ketones and aldehydes), carbon dioxide,and N-and O-heterocycles. Syntheses protocols(metal-containing and metal-free), the effect of reaction parameters, product distribution, and variation of reactivity are surveyed, and the mechanism of each reaction involving the action mode of AB as well as structure-activity relationships is discussed in detail. Finally, perspectives are presented to highlight the challenges and opportunities for AB-enabled TH reactions of unsaturated compounds.

RuRh Bimetallic Nanoparticles Stabilized by 15-membered Macrocycles-terminated Poly(propylene imine) Dendrimer:Preparation and Catalytic Hydrogenation of Nitrile–Butadiene Rubber

A new fourth-generation poly(propylene imine) dendrimer(G4-M) containing 32 triolefinic 15-membered macrocycles on the surfaces has been synthesized. The bimetallic Ru Rh dendrimer-stabilized nanoparticles(DSNs) were first prepared within G4-M by a co-complexation route. The new G4-M dendrimer has been characterized by 1H nuclear magnetic resonance, infrared radiation, and elemental analysis.The dendrimer-stabilized bimetallic ions and reduction courses were analyzed by UV-vis spectroscopy. Highresolution transmission electron microscopy and energy dispersive spectrometer were used to characterize the bimetallic nanoparticle size, size distribution, and particle morphology. The Ru Rh bimetallic DSNs showed high catalytic activity for the hydrogenation of nitrile-butadiene rubber.

Catalytic hydrogenation performance of ZIF-8 carbide for electrochemical reduction of carbon dioxide

The conversion of CO_(2) electrocatalytic hydrogenation into energy-rich fuel is considered to be the most effective way to carbon recycle.Nitrogen-doping carbonized ZIF-8 is proposed as carrier of the earth-rich Sn catalyst to overcome the limit of electron transfer and CO_(2) adsorption capacity of Sn.Hierarchically porous structure of Sn doped carbonized ZIF-8 is controlled by hydrothermal and carbonization conditions,which induces much higher specific surface area than that of the commercial Sn nanoparticle(1003.174 vs.7.410 m^(2)·g^(-1)).The shift of nitrogen peaks in X-ray Photoelectron Spectroscopy spectra indicates interaction between ZIF-8 and Sn,which induces the shift of electron cloud from Sn to the chemical nitrogen to enhance conductivity and regulate electron transfer from catalyst to CO_(2).Lower mass transfer resistance and Warburg resistance are investigated through EIS,which significantly improves the catalytic activity for CO_(2) reduction reaction(CO_(2)RR).Onset potential of the reaction is reduced from-0.74 V to less than-0.54 V vs.RHE.The total Faraday efficiency of HCOOH and CO reaches 68.9%at-1.14 V vs.RHE,which is much higher than that of the commercial Sn(45.0%)and some other Sn-based catalyst reported in the literature.

Unraveling the catalytically active phase of carbon dioxide hydrogenation to methanol on Zn/Cu alloy: Single atom versus small cluster

Methanol synthesis from CO_(2)hydrogenation catalyzed by Zn/Cu alloy has been widely studied,but there is still debate on its catalytic active phase and whether the Zn can be oxidized during the reaction process.What is more,as Zn atoms could locate on Zn/Cu alloy surface in forms of both single atom and cluster,how Zn surface distribution affects catalytic activity is still not clear.In this work,we performed a systematic theoretical study to compare the mechanistic natures and catalytic pathways between Zn single atom and small cluster on catalyst surface,where the surface oxidation was shown to play the critical role.Before surface oxidation,the Zn single atom/Cu is more active than the Zn small cluster/Cu,but its surface oxidation is difficult to take place.Instead,after the easy surface oxidation by CO_(2)decomposition,the oxidized Zn small cluster/Cu becomes much more active,which even exceeds the hardlyoxidized Zn single atom/Cu to become the active phase.Further analyses show this dramatic promotion of surface oxidation can be ascribed to the following factors:i)The O from surface oxidation could preferably occupy the strongest binding sites on the center of Zn cluster.That makes the O intermediates bind at the Zn/Cu interface,preventing their too tight binding for further hydrogenation;ii)The higher positive charge and work function on the oxidized surface could also promote the hydrogenation of O intermediates.This work provided one more example that under certain condition,the metal cluster can be more active than the single atom in heterogeneous catalysis.

Catalytic Hydrogenation of Nitrobenzene to Aniline by Ag/γ-Fe_2O_3

The Ag/γ-Fe_2O_3 nanocomposite was synthesized by solvothermal reduction method via using ferric nitrate and silver nitrate as raw materials, and ethylene glycol as the reducing agent. The composite was characterized by X-ray powder diffraction, scanning electron microscope, transmission electron microscope, and energy dispersive X-ray. The prepared Ag/γ-Fe_2O_3 was used for the catalytic hydrogenation of nitrobenzene to aniline by hydrazine hydrate. The factors such as the silver content in the catalyst, reaction time, reaction temperature and the regeneration of catalyst were investigated. The results showed that the yield of aniline reached 100% by utilizing the 1%wt（nitrobenzene） Ag/γ-Fe_2O_3 for the catalytic hydrogenation of nitrobenzene for 3 h to obtain aniline at 78 ℃, hydrazine hydrate as the hydrogen source, while the silver content in the catalyst was 3%mol.

Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor

A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction,removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production.For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used.Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogenation method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and signi ficant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.

Catalytic Hydrogenation of Diacetyl Monoxime to Tetramethylpyrazine with the Soluble Transition Metal Catalysts

Catalytic hydrogenation of diacetyl monoxime to tetramethylpyrazine, by the homogeneous catalysts generated in situ from some transition metal chlorides with triphenylphosphine in ethanol under H-2 pressure of 0.6 similar to 4.6 MPa at 100 similar to 150 degrees C, has been studied. The optimum H-2 partial pressure was observed at about 1.3 MPa. The maximum conversion of diacetyl monoxime and yield of tetramethylpyrazine were 97% and 90%, respectively.

Synthesis of Agomelatine by One-pot Catalytic Hydrogenation and Acetylation with NiO

Nano-NiO and bulk NiO were prepared from Ni(AC)_2·4 H_2O by coordination precipitation using aqueous ammonia and by a solid state reaction, respectively. The nickel oxide particles were characterized by X-ray Diffraction(XRD) and scanning electron microscopy(SEM). The results indicate that nano-sized NiO has a crystal phase with a standard face-centered cubic lattice structure, with a mean particle diameter of about 10 nm. The evaluation of the activity of nickel oxide nanoparticles in the catalytic hydrogenation of 7-methoxy-1-naphthylacetonitrile was carried out. The results demonstrate the efficient synthesis of the title compound by a one-pot catalytic hydrogenation and acetylation with NiO. The NiO nanoparticles displayed superior catalytic activity in the synthesis of agomelatine in the one-pot reaction.The total yield of agomelatine is over 81.8% with a purity of 99.2%, as determined by HPLC. The structure of agomelatine was confirmed by IR, MS, and 1 H NMR analysis.

Liquid-Phase Catalytic Hydrogenation of Furfural in Variable Solvent Media

Water is the most abundant compound inherently existing in bio-oils. Thus understanding the role of water within bio-oils upgrading process is essential for future engineering scale-up design. In this study, furfural was chosen as bio-oils model compound, and the catalytic hydrogenation of furfural over commercial 5%, Ru/C catalyst was firstly investigated in a series of gradient variable water/ethanol mixture solvents. Water had a significant effect on the distribution of product yields. The dominant reaction pathways varied with the water contents in the water/ethanol mixture solvents. Typically, when ethanol was used as the solvent, the main products were obtained by the hydrogenation of carbonyl group or furan ring. When pure water was used as the solvent, the rearrangement reaction of furfural to cyclopentanone should be selectively promoted theoretically. However, serious polymerization and resinification were observed herein in catalytic hydrogenation system of pure water. The catalyst surface was modified by the water-insoluble polymers, and consequently, a relative low yield of cyclopentanone was obtained. A plausible multiple competitive reaction mechanism between polymerization reaction and the hydrogenation of furfural was suggested in this study. Characterizations(TG,FT-IR,SEM)were employed to analyze and explain our experiments.

Diastereoselective Catalytic Hydrogenation of Schiff Bases of <i>N</i>-Pyruvoyl-(<i>S</i>)-Proline Esters

Diastereoselective catalytic hydrogenation of pyruvic acid esters, amides, and their Schiff bases has been well studied over a long period to show that proline is one of the most effective chiral auxiliaries. Proline derivatives have been used as auxiliaries in the diastereoselective catalytic hydrogenation of pyruvamide Schiff bases. The diastereoselective hydrogenation resulted in up to a 78% enantiomeric excess of the amino acid derived from the hydrolysis of the dipeptide products. The chelation hypothesis explains the stereochemistry of the catalytic hydrogenation using (S)-proline esters in the amide moiety and the two chiral centers in the amide and Schiff base moieties.

CATALYTIC PERFORMANCE OF MIXED-BIMETALLIC RUTHENIUM CARBONYL CLUSTERDERIVED CATALYSTS IN CO HYDROGENATION

The bimetallic catalysts prepared from SiO_2-supported Ru-Co,Ru- Fe and Ru-Mo carbonyl clusters exhibited high yields and selectivities towards oxygenates such as C_1-C_5 from CO+H_2,in contrast to the catalysts prepared from homometallic and bimetallic Ru,Ru-Ni,Ru-Rh,Ru-Mn,and Ru- Cr carbonyl clusters.The FTIR investigation revealed that the 1584 cm^(-1) species plays an important role in the formation of oxygenates in CO hydrogenation,which is possibly assigned to surface formyl species.

Benzene selective hydrogenation over supported Ni(nano-) particles catalysts: Catalytic and kinetics studies

This report aims to reduce the benzene in a mixture of benzene and toluene as a model reaction using catalytic hydrogenation. In this research, we developed a series of catalysts with different supports such as Ni/HMS, Ni/HZSM-5, Ni/HZSM5-HMS, Ni/Al2O3 and Ni/SiO2. Kinetic of this reaction was investigated under various hydrogen and benzene pressures. For more study, two kinetic models have also been selected and tested to describe the kinetics for this reaction. Both used models, the power law and Langmuir-Hinshelwood, provided a good fit toward the experimental data and allowed to determine the kinetic parameters. Among these catalysts, Ni/Al2O3 showed the maximum benzene conversion （99.19%） at 130℃ for benzene hydrogenation. The lowest toluene conversion was observed for Ni/SiO2. Furthermore, this catalyst presented high selectivity to benzene （75.26%） at 130℃. The catalytic performance （activity, selectivity and stability） and kinetics evaluations were shown that the Ni/SiO2 is an effective catalyst to hydrogenate benzene. It seems that the surface properties particularly pore size are effective parameter compared to other factors such as acidity and metal dispersion in this process.

STUDIES ON THE SYNTHESIS OF BAIMUXINOL BY CATALYTIC HYDROGENATION OF DEHYDROBAIMUXINOL

Baimuxinol, a 4-hydroxymethyl agarofuran isolated from Aquilaria Sinensis, was synthsizd. The stereoselectivity of catalytic hydrogenation of dehydrobaimuxino and its derivatives was studied.