The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively red...The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts c...The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.展开更多
Ammonia borane(AB)has received much attention as an environmentally friendly,non-toxic,room temperature stable hydrogen storage material with high hydrogen content of 19.6%.However,its hydrolysis for hydrogen producti...Ammonia borane(AB)has received much attention as an environmentally friendly,non-toxic,room temperature stable hydrogen storage material with high hydrogen content of 19.6%.However,its hydrolysis for hydrogen production at room-temperature is kinetically slow and requires precious metal catalysts.In this work,it is found that the prepared Raney Ni W-r treated with high concentration of NaOH(6.25 mol/L)at 110℃exhibited excellent catalytic performance for AB hydrolysis at room temperature.The Raney Ni W-r can promote the AB complete hydrolysis within 60 s under basic condition at small sized trials,even higher than that of the 20%Pt/C catalyst.Its apparent activation energy at room temperature is only 26.6 kJ/mol and the turnover frequency(TOF)value is as high as 51.42 min-1.Owing to its high density and magnetic properties,the catalyst is very easy for magnetic separation.Furthermore,possible mechanism of the hydrolytic reaction of AB based on experimental results is proposed.As a well-established industrial catalyst,Raney Ni has been prepared on a large scale at low cost.This study provides a promising pathway for the large-scale preparation of low-cost and recyclable catalysts for AB hydrolysis.展开更多
Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as...Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.展开更多
Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous s...Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.展开更多
Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active...Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.展开更多
The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their pot...The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications.However,the unsatisfied cyclic stability and electrochemical activity limit their further application.In this work,nickel-molybdenum(Ni-Mo)alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition,thermal annealing,and electrochemical activation.Owing to the synergistic interaction of molybdenum trinickelide(Ni_(3)Mo)and molybdenum dioxide(MoO_(2))in Ni-Mo alloy,the catalyst display superior overall electrochemical properties.A low overpotential of 86 mV at 10 mA/cm^(2)and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H_(2)SO_(4)solution can be achieved.Notably,remarkable stability with negligible performance degradation even after 100 h could be maintained.This work presents a novel and effective strategy for the design and fabrication of high-performance,non-precious metal electrocatalysts for acidic water electrolysis.展开更多
The semiconductor photocatalysis are considered as one of the most promising candidates in hydrogen energy source and environmental remediation area.In this paper,flower-shaped SnS,is successfully combined on g-C,Ns,a...The semiconductor photocatalysis are considered as one of the most promising candidates in hydrogen energy source and environmental remediation area.In this paper,flower-shaped SnS,is successfully combined on g-C,Ns,and the well matching band structure successfully constitutes a new Type-II heterojunction.As expected,the photocatalytic hydrogen production experiment showed that the quantity of hydrogen produced on 5% SnS_(2)/C_(3)N_(5)was 922.5μmol/(g.h),which is 3.6 times higher than that of pure g-C_(3)N_(5).Meanwhile,in photocatalytic degradation of methylene blue,5%SnS2/C,Ns composite material can degrade 95% of contaminants within 40 min,showing good photocatalytic degradation performance.The mechanism study indicates that SnS_(2)/C_(3)N_(5)heterojunction improves the photogenerated charge migration rate and reduces the electron-hole recombination rate,and effectively improves the photocatalytic performance of g-C_(3)N_(5).This work provides a new idea for designing C,Ns-based heterojunctions with efficient hydrogen production and degradation performance.展开更多
The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques inc...The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.展开更多
Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether ...Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether as the recognized site for H_(2)S.The probe TCF-NS displayed a rapid-response fluorescent against H_(2)S with high sensitivity and selection but had no significant fluorescence response to other biothiols.Furthermore,TCF-NS was applied to sense H_(2)S in living cells successfully with minimized cytotoxicity and a large Stokes shift.展开更多
Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),...Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),x=1.0,2.0,3.0,4.0)was synthesized via solid-phase reaction of sodium citrate(NaCA)and pure CN powder in the Teflon-sealed autoclave under air conditions at 180℃.Surface area of Na/O-CN_(3.0) is measured to be 18.8 m^(2)/g,increasing by 60.7%compared to that of pure CN(11.7 m^(2)/g).Bandgap energy of Na/O-CN_(3.0) is determined to be 2.68 eV,marginally lower than that of pure CN(2.70 eV),thereby enhancing its capacity for sunlight absorption.Meanwhile,the incorporation of Na and O atoms into Na/O-CN_(x) is found to effectively reduce recombination rates of photogenerated electron-hole pairs.As a result,Na/O-CN_(x) samples exhibit markedly enhanced photocatalytic hydrogen evolution activity under visible light irradiation.Notably,the optimal Na/O-CN_(3.0) sample achieves a photocatalytic hydrogen production rate of 103.2μmol·g^(–1)·h^(–1),which is 8.2 times greater than that of pure CN(11.2μmol·g^(–1)·h^(–1)).Furthermore,a series of Na/O-CN_(x)-yO_(2)(y=0,20%,40%,60%,80%,100%)samples were prepared by modulating the oxygen content within reaction atmosphere.The catalytic performance evaluations reveal that the incorporation of both Na and O atoms in Na/O-CN_(3.0) enhances photocatalytic activity.This study also introduces novel methodologies for synthesis of metal atom-doped CN materials at lower temperature,highlighting the synergistic effect of Na and O atoms in photocatalytic hydrogen production of Na/O-CN_(x) samples.展开更多
Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Co...Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.展开更多
Nickel laterite ore is an important nickel-bearing mineral.Research on pre-heating and hydrogen pre-reduction in the pyrometallurgical process of nickel laterite ore is very limited,especially when using fluidized bed...Nickel laterite ore is an important nickel-bearing mineral.Research on pre-heating and hydrogen pre-reduction in the pyrometallurgical process of nickel laterite ore is very limited,especially when using fluidized bed roasting.This study systematically explores the mechanisms of fluidized bed pre-heating treatment and hydrogen pre-reduction in the roasting process of saprolitic nickel laterite ore.According to single-factor experiment results,the appropriate pre-heating and pre-reduction conditions were a pre-heating temperature of 700℃,a pre-heating time of 30 min,a pre-reduction temperature of 700℃,a pre-reduction time of 30 min,and a hydrogen concentration of 80%.Then,the nickel metallization rate and iron metallization rate reached 90.56%and 41.31%,respectively.Various analytical and testing methods were employed to study the changes in phase composition,magnetism,surface element valence states,and microstructure of nickel laterite ore during fluidized pre-heating and pre-reduction.The study shows that hydrogen can achieve nickel reduction at relatively low temperatures.It was also found that pre-heating treatment of nickel laterite ore is beneficial.Pre-heating opens up the mineral structures of serpentine and limonite,allowing the reducing gas and nickel to interact quickly during the reduction process,enhancing the pre-reduction process.展开更多
Hydrogen Civilization (HyCi) doctrine is a novel world outlook, all-embracing vision of the sustainability of the human future: humanity can preclude world climate catastrophe and conserve the biosphere's ability ...Hydrogen Civilization (HyCi) doctrine is a novel world outlook, all-embracing vision of the sustainability of the human future: humanity can preclude world climate catastrophe and conserve the biosphere's ability to maintain the life of humanity by the only way, just by the sustainable movement along the vector "Hydrogen Energy → Hydrogen Economy → Hydrogen Civilization". HyCi doctrine is overcoming boundaries between different sciences, between peoples and nations. Hydrogen civilization is a public ideal ('superattractor') putting in the forefront Shakespeare's Hamlet question on a global scale: "To be or not to be the humankind: that is the question".展开更多
Owing to the merits of high energy density,as well as clean and sustainable properties,hydrogen has been deemed to be a prominent alternative energy to traditional fossil fuels.Electrocatalytic hydrogen evolution reac...Owing to the merits of high energy density,as well as clean and sustainable properties,hydrogen has been deemed to be a prominent alternative energy to traditional fossil fuels.Electrocatalytic hydrogen evolution reaction(HER)has been considered to be mostly promising for achieving green hydrogen production,and has been widely studied in acidic and alkaline solutions.In particular,HER in alkaline media has high potential to achieve large-scale hydrogen production because of the increased durability of electrode materials.However,for the currently most prominent catalyst Pt,its HER kinetics in an alkaline solution is generally 2e3 orders lower than that occurring in an acidic solution because of the low Hþconcentration in alkaline electrolytes.Fortunately,construction of heterostructured electrocatalysts has proved to be an efficient strategy for boosting alkaline HER kinetics because of their various structural merits.The synergistic effect is a unique characteristic of heterostructures,which means that one functional active site serves as a promoter for water dissociation and another one takes a charge of moderate hydrogen adsorption,thus synergistically improving HER performance.In addition,each building block of the heterostructures is tunable,providing moreflexibility and chances to construct optimal catalysts.Furthermore,due to the presence of Fermi energy difference between the two components at the interface,the electronic structure of each component could possibly be rationally modulated,thus much enhanced HER performance in alkaline electrolyte can be ach-ieved.With a deeper understanding of on nanoscience and rapid development of nanotechnology,more sophisticated alternative designing strategies have been explored for constructing high-performance heterostructured electro-catalysts.This review presents an outline of the latest development of heterostructured catalysts toward alkaline HER and the rational design principles for constructing interfacial heterostructures to accelerate alkaline HER kinetics.The basic reaction pathways of HER in alkaline media arefirst described,and then emerging efficient strategies to promote alkaline HER kinetics,including synergistic effect,strain effect,electronic interaction,phase engineering,and ar-chitecture engineering.Finally,current existing challenges and research opportunities that deserve further investi-gation are proposed for the consideration of novel heterostructures towards practical applications.展开更多
Highly active and stable nickel catalyst for dehydrogenation of methane and hydrogenation of benzene is prepared from a precursor with hydrotalcite-like anionic clam structure by coprecipitation. The nickel particles ...Highly active and stable nickel catalyst for dehydrogenation of methane and hydrogenation of benzene is prepared from a precursor with hydrotalcite-like anionic clam structure by coprecipitation. The nickel particles have a narrow size distribution in several nanometers, and have a strong interaction with other components such as Al2O3. This catalyst is highly sensitive to further modification by doping and to reaction condition. On a modified catalyst, benzene hydrogenation to cyclohexane proceeds to complete at 373 K. While on another catalyst, different structured nanocarbons are obtained at moderate temperatures. It is found that the thioresistance of the nickel catalyst in hydrogenation can be improved by doping.展开更多
The diversities of hydrogen sorption properties of Mg2FeH6-based complexes with and without TiO2 were investigated. Mg2FeH6-based complexes with and without TiO2 were synthesized respectively by reactive mechanical al...The diversities of hydrogen sorption properties of Mg2FeH6-based complexes with and without TiO2 were investigated. Mg2FeH6-based complexes with and without TiO2 were synthesized respectively by reactive mechanical alloying,and hydrogen sorption properties of the complexes were examined by Sieverts-type apparatus. The results show that the sample without TiO2 releases 4.43 % (mass fraction) hydrogen in 1.5 ks at 653 K under 0.1 MPa H2 pressure and absorbs 90% of the total 4.43 % (mass fraction) hydrogen absorbed in 85 s at 623 K under 4.0 MPa H2 pressure. But for the sample with TiO2 addition under the same condition,it only needs 400 s to release all of the stored hydrogen and 60 s to absorb 90% of the total hydrogen absorbed. The activation energies for desorption process of the samples with and without TiO2 are determined to be 71.2 and 80.3 kJ/(mol.K),respectively. The improvement in hydrogen sorption rate and and reduction in activation energy can be attributed to the addition of TiO2.展开更多
文摘The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
文摘The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.
基金supported by the National Natural Science Foundation of China(21908135)Natural Science Foundation of Shanxi Datong University(2022K23)+1 种基金Graduate Research Innovation and Practice Innovation Projects of Shanxi Datong University(23CX31)Postgraduate Educational Reform and Research Program of Shanxi Datong University(23JG07)。
文摘Ammonia borane(AB)has received much attention as an environmentally friendly,non-toxic,room temperature stable hydrogen storage material with high hydrogen content of 19.6%.However,its hydrolysis for hydrogen production at room-temperature is kinetically slow and requires precious metal catalysts.In this work,it is found that the prepared Raney Ni W-r treated with high concentration of NaOH(6.25 mol/L)at 110℃exhibited excellent catalytic performance for AB hydrolysis at room temperature.The Raney Ni W-r can promote the AB complete hydrolysis within 60 s under basic condition at small sized trials,even higher than that of the 20%Pt/C catalyst.Its apparent activation energy at room temperature is only 26.6 kJ/mol and the turnover frequency(TOF)value is as high as 51.42 min-1.Owing to its high density and magnetic properties,the catalyst is very easy for magnetic separation.Furthermore,possible mechanism of the hydrolytic reaction of AB based on experimental results is proposed.As a well-established industrial catalyst,Raney Ni has been prepared on a large scale at low cost.This study provides a promising pathway for the large-scale preparation of low-cost and recyclable catalysts for AB hydrolysis.
文摘Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
文摘Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.
基金supported by Research Grant from China Petroleum and Chemical Corp。
文摘Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.
基金supported by the National Natural Science Foundation of China(22179138).
文摘The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications.However,the unsatisfied cyclic stability and electrochemical activity limit their further application.In this work,nickel-molybdenum(Ni-Mo)alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition,thermal annealing,and electrochemical activation.Owing to the synergistic interaction of molybdenum trinickelide(Ni_(3)Mo)and molybdenum dioxide(MoO_(2))in Ni-Mo alloy,the catalyst display superior overall electrochemical properties.A low overpotential of 86 mV at 10 mA/cm^(2)and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H_(2)SO_(4)solution can be achieved.Notably,remarkable stability with negligible performance degradation even after 100 h could be maintained.This work presents a novel and effective strategy for the design and fabrication of high-performance,non-precious metal electrocatalysts for acidic water electrolysis.
基金This project was supported by the Fundamental Research Program of Shanxi Province(202303021221058)。
文摘The semiconductor photocatalysis are considered as one of the most promising candidates in hydrogen energy source and environmental remediation area.In this paper,flower-shaped SnS,is successfully combined on g-C,Ns,and the well matching band structure successfully constitutes a new Type-II heterojunction.As expected,the photocatalytic hydrogen production experiment showed that the quantity of hydrogen produced on 5% SnS_(2)/C_(3)N_(5)was 922.5μmol/(g.h),which is 3.6 times higher than that of pure g-C_(3)N_(5).Meanwhile,in photocatalytic degradation of methylene blue,5%SnS2/C,Ns composite material can degrade 95% of contaminants within 40 min,showing good photocatalytic degradation performance.The mechanism study indicates that SnS_(2)/C_(3)N_(5)heterojunction improves the photogenerated charge migration rate and reduces the electron-hole recombination rate,and effectively improves the photocatalytic performance of g-C_(3)N_(5).This work provides a new idea for designing C,Ns-based heterojunctions with efficient hydrogen production and degradation performance.
文摘The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.
基金financially supported by the Natural Science Foundation of Jiangsu Province(Grant No.BK20241181)the State Key Laboratory of AnalyticalChemistry for Life Science,School of Chemistry and Chemical Engineering,Nanjing University(Grant No.SKLACLS2419)。
文摘Using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran(TCF)as a near-infrared fluorescent chromophore,we designed and synthesized a TCF-based fluorescent probe TCF-NS by introducing 2,4-dinitrophenyl ether as the recognized site for H_(2)S.The probe TCF-NS displayed a rapid-response fluorescent against H_(2)S with high sensitivity and selection but had no significant fluorescence response to other biothiols.Furthermore,TCF-NS was applied to sense H_(2)S in living cells successfully with minimized cytotoxicity and a large Stokes shift.
基金National Natural Science Foundation of China(21806023)Natural Science Foundation of Hunan Province(2021JJ40199)+2 种基金Education Department Foundation of Hunan Province(20C0813)Hunan University of Science and Technology Fundamental Research FundsPostgraduate Scientific Research Innovation Project of Hunan Province(CX20240877)。
文摘Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),x=1.0,2.0,3.0,4.0)was synthesized via solid-phase reaction of sodium citrate(NaCA)and pure CN powder in the Teflon-sealed autoclave under air conditions at 180℃.Surface area of Na/O-CN_(3.0) is measured to be 18.8 m^(2)/g,increasing by 60.7%compared to that of pure CN(11.7 m^(2)/g).Bandgap energy of Na/O-CN_(3.0) is determined to be 2.68 eV,marginally lower than that of pure CN(2.70 eV),thereby enhancing its capacity for sunlight absorption.Meanwhile,the incorporation of Na and O atoms into Na/O-CN_(x) is found to effectively reduce recombination rates of photogenerated electron-hole pairs.As a result,Na/O-CN_(x) samples exhibit markedly enhanced photocatalytic hydrogen evolution activity under visible light irradiation.Notably,the optimal Na/O-CN_(3.0) sample achieves a photocatalytic hydrogen production rate of 103.2μmol·g^(–1)·h^(–1),which is 8.2 times greater than that of pure CN(11.2μmol·g^(–1)·h^(–1)).Furthermore,a series of Na/O-CN_(x)-yO_(2)(y=0,20%,40%,60%,80%,100%)samples were prepared by modulating the oxygen content within reaction atmosphere.The catalytic performance evaluations reveal that the incorporation of both Na and O atoms in Na/O-CN_(3.0) enhances photocatalytic activity.This study also introduces novel methodologies for synthesis of metal atom-doped CN materials at lower temperature,highlighting the synergistic effect of Na and O atoms in photocatalytic hydrogen production of Na/O-CN_(x) samples.
基金supported by the National Natural Science Foundation of China(22302115,22072079)the Fundamental Research Program of Shanxi Province(202303021221056).
文摘Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.
基金Project(2023JH3/10200010)supported by the Excellent Youth Natural Science Foundation of Liaoning Province,ChinaProject(XLYC2203167)supported by the Liaoning Revitalization Talents Program,China+2 种基金Project(RC231175)supported by the Mid-career and Young Scientific and Technological Talents Program of Shenyang,ChinaProject(2023A03003-2)supported by the Key Special Program of Xinjiang,ChinaProject(N2301026)supported by the Fundamental Research Funds for the Central Universities,China。
文摘Nickel laterite ore is an important nickel-bearing mineral.Research on pre-heating and hydrogen pre-reduction in the pyrometallurgical process of nickel laterite ore is very limited,especially when using fluidized bed roasting.This study systematically explores the mechanisms of fluidized bed pre-heating treatment and hydrogen pre-reduction in the roasting process of saprolitic nickel laterite ore.According to single-factor experiment results,the appropriate pre-heating and pre-reduction conditions were a pre-heating temperature of 700℃,a pre-heating time of 30 min,a pre-reduction temperature of 700℃,a pre-reduction time of 30 min,and a hydrogen concentration of 80%.Then,the nickel metallization rate and iron metallization rate reached 90.56%and 41.31%,respectively.Various analytical and testing methods were employed to study the changes in phase composition,magnetism,surface element valence states,and microstructure of nickel laterite ore during fluidized pre-heating and pre-reduction.The study shows that hydrogen can achieve nickel reduction at relatively low temperatures.It was also found that pre-heating treatment of nickel laterite ore is beneficial.Pre-heating opens up the mineral structures of serpentine and limonite,allowing the reducing gas and nickel to interact quickly during the reduction process,enhancing the pre-reduction process.
文摘Hydrogen Civilization (HyCi) doctrine is a novel world outlook, all-embracing vision of the sustainability of the human future: humanity can preclude world climate catastrophe and conserve the biosphere's ability to maintain the life of humanity by the only way, just by the sustainable movement along the vector "Hydrogen Energy → Hydrogen Economy → Hydrogen Civilization". HyCi doctrine is overcoming boundaries between different sciences, between peoples and nations. Hydrogen civilization is a public ideal ('superattractor') putting in the forefront Shakespeare's Hamlet question on a global scale: "To be or not to be the humankind: that is the question".
基金supported by the National Natural Science Foundation of China(No.22179098)。
文摘Owing to the merits of high energy density,as well as clean and sustainable properties,hydrogen has been deemed to be a prominent alternative energy to traditional fossil fuels.Electrocatalytic hydrogen evolution reaction(HER)has been considered to be mostly promising for achieving green hydrogen production,and has been widely studied in acidic and alkaline solutions.In particular,HER in alkaline media has high potential to achieve large-scale hydrogen production because of the increased durability of electrode materials.However,for the currently most prominent catalyst Pt,its HER kinetics in an alkaline solution is generally 2e3 orders lower than that occurring in an acidic solution because of the low Hþconcentration in alkaline electrolytes.Fortunately,construction of heterostructured electrocatalysts has proved to be an efficient strategy for boosting alkaline HER kinetics because of their various structural merits.The synergistic effect is a unique characteristic of heterostructures,which means that one functional active site serves as a promoter for water dissociation and another one takes a charge of moderate hydrogen adsorption,thus synergistically improving HER performance.In addition,each building block of the heterostructures is tunable,providing moreflexibility and chances to construct optimal catalysts.Furthermore,due to the presence of Fermi energy difference between the two components at the interface,the electronic structure of each component could possibly be rationally modulated,thus much enhanced HER performance in alkaline electrolyte can be ach-ieved.With a deeper understanding of on nanoscience and rapid development of nanotechnology,more sophisticated alternative designing strategies have been explored for constructing high-performance heterostructured electro-catalysts.This review presents an outline of the latest development of heterostructured catalysts toward alkaline HER and the rational design principles for constructing interfacial heterostructures to accelerate alkaline HER kinetics.The basic reaction pathways of HER in alkaline media arefirst described,and then emerging efficient strategies to promote alkaline HER kinetics,including synergistic effect,strain effect,electronic interaction,phase engineering,and ar-chitecture engineering.Finally,current existing challenges and research opportunities that deserve further investi-gation are proposed for the consideration of novel heterostructures towards practical applications.
基金Supported by the National Natural Science Foundation of China(No. 29792070-9, 29876032).
文摘Highly active and stable nickel catalyst for dehydrogenation of methane and hydrogenation of benzene is prepared from a precursor with hydrotalcite-like anionic clam structure by coprecipitation. The nickel particles have a narrow size distribution in several nanometers, and have a strong interaction with other components such as Al2O3. This catalyst is highly sensitive to further modification by doping and to reaction condition. On a modified catalyst, benzene hydrogenation to cyclohexane proceeds to complete at 373 K. While on another catalyst, different structured nanocarbons are obtained at moderate temperatures. It is found that the thioresistance of the nickel catalyst in hydrogenation can be improved by doping.
基金Project (50574105) supported by the National Natural Science Foundation of ChinaProject (NCET-06-0683) supported by the Program for the New Century Excellent Talents in University+1 种基金Project (08-030239) supported by the Program for 121 Excellent Talents in Hunan ProvinceProject (07MX21) supported by Mittal Student Innovation Foundation of Central South University
文摘The diversities of hydrogen sorption properties of Mg2FeH6-based complexes with and without TiO2 were investigated. Mg2FeH6-based complexes with and without TiO2 were synthesized respectively by reactive mechanical alloying,and hydrogen sorption properties of the complexes were examined by Sieverts-type apparatus. The results show that the sample without TiO2 releases 4.43 % (mass fraction) hydrogen in 1.5 ks at 653 K under 0.1 MPa H2 pressure and absorbs 90% of the total 4.43 % (mass fraction) hydrogen absorbed in 85 s at 623 K under 4.0 MPa H2 pressure. But for the sample with TiO2 addition under the same condition,it only needs 400 s to release all of the stored hydrogen and 60 s to absorb 90% of the total hydrogen absorbed. The activation energies for desorption process of the samples with and without TiO2 are determined to be 71.2 and 80.3 kJ/(mol.K),respectively. The improvement in hydrogen sorption rate and and reduction in activation energy can be attributed to the addition of TiO2.
