Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechani...Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechanism of catalysts in the market were analyzed.Different types of catalysts were studied to look for green catalysts with high activity,sulfur resistance,water vapor resistance and other advantages.The mechanism of denitration reaction of green catalysts was discussed,and the laws of formation,propagation and consumption of active species in the reaction process were revealed to provide theoretical basis for optimizing catalyst design and improving reaction conditions.Then the research status and problems of new catalysts for flue gas denitrification were described.Finally,the future development direction of green catalysts for flue gas denitration was discussed to improve the performance and stability of catalysts and meet the performance requirements of denitration catalysts in different industries.展开更多
Lithium metal batteries are regarded as prominent contenders to address the pressing needs owing to the high theoretical capacity.Toward the broader implementation,the primary obstacle lies in the intricate multi-elec...Lithium metal batteries are regarded as prominent contenders to address the pressing needs owing to the high theoretical capacity.Toward the broader implementation,the primary obstacle lies in the intricate multi-electron,multi-step redox reaction associated with sluggish conversion kinetics,subsequently giving rise to a cascade of parasitic issues.In order to smooth reaction kinetics,catalysts are widely introduced to accelerate reaction rate via modulating the energy barrier.Over past decades,a large amount of research has been devoted to the catalyst design and catalytic mechanism exploration,and thus the great progress in electrochemical performance has been realized.Therefore,it is necessary to make a comprehensive review toward key progress in catalyst design and future development pathway.In this review,the basic mechanism of lithium metal batteries is provided along with corresponding advantages and existing challenges detailly described.The main catalysts employed to accelerate cathode reaction with emphasis on their catalytic mechanism are summarized as well.Finally,the rational design and innovative direction toward efficient catalysts are suggested for future application in metal-sulfur/gas battery and beyond.This review is expected to drive and benefit future research on rational catalyst design with multi-parameter synergistic impacts on the activity and stability of next-generation metal battery,thus opening new avenue for sustainable solution to climate change,energy and environmental issues,and the potential industrial economy.展开更多
Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design princi...Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design principles by understanding the catalytic mechanisms and identifying the active sites.Distinct from sp2-conjugated graphene and carbon nanotube,fullerene possesses unique characteristics that are growingly being discovered and exploited by the electrocatalysis community.For instance,the well-defined atomic and molecular structures,the good electron affinity to tune the electronic structures of other substances,the intermolecular self-assembly into superlattices,and the on-demand chemical modification have endowed fullerene with incomparable advantages as electrocatalysts that are otherwise not applicable to other carbon ma-terials.As increasing studies are being reported on this intriguing topic,it is necessary to provide a state-of-the-art overview of the recent progress.This review takes such an initiative by summarizing the promises and challenges in the electrocatalytic applications of fullerene and its derivatives.The content is structured according to the composition and structure of fullerene,including intact fullerene(e.g.,fullerene composite and superlattices)and fullerene derivatives(e.g.,doped,endohedral,and disintegrated fullerene).The synthesis,characterization,catalytic mechanisms,and deficiencies of these fullerene-based materials are explicitly elaborated.We conclude it by sharing our perspectives on the key aspects that future efforts shall consider.展开更多
Two major challenges,high cost and short lifespan,have been hindering the commercialization process of lowtemperature fuel cells.Professor Wei's group has been focusing on decreasing cathode Pt loadings without lo...Two major challenges,high cost and short lifespan,have been hindering the commercialization process of lowtemperature fuel cells.Professor Wei's group has been focusing on decreasing cathode Pt loadings without losses of activity and durability,and their research advances in this area over the past three decades are briefly reviewed herein.Regarding the Pt-based catalysts and the low Pt usage,they have firstly tried to clarify the degradation mechanism of Pt/C catalysts,and then demonstrated that the activity and stability could be improved by three strategies:regulating the nanostructures of the active sites,enhancing the effects of support materials,and optimizing structures of the three-phase boundary.For Pt-free catalysts,especialiy carbon-based ones,several strategies that they proposed to enhance the activity of nitrogen-/heteroatom-doped carbon catalysts are firstly presented.Then,an indepth understanding of the degradation mechanism for carbon-based catalysts is discussed,and followed by the corresponding stability enhancement strategies.Also,the carbon-based electrode at the micrometer-scale,faces the challenges such as low active-site density,thick catalytic layer,and the effect of hydrogen peroxide,which require rational structure design for the integral cathodic electrode.This review finally gives a brief conclusion and outlook about the low cost and long lifespan of cathodic oxygen reduction catalysts.展开更多
Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utiliz...Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.展开更多
The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic ...The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.展开更多
Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such ...Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.展开更多
The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,...The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,the roles of individual metals,coordination atoms,and their synergy effect on the electroanalytic performance remain unclear.Therefore,in this work,a series of 2DMOFs with different metals and coordinating atoms are systematically investigated as electrocatalysts for ammonia synthesis using density functional theory calculations.For a specific metal,a proper metal-intermediate atoms p-d orbital hybridization interaction strength is found to be a key indicator for their NRR catalytic activities.The hybridization interaction strength can be quantitatively described with the p-/d-band center energy difference(Δd-p),which is found to be a sufficient descriptor for both the p-d hybridization strength and the NRR performance.The maximum free energy change(ΔG_(max))andΔd-p have a volcanic relationship with OsC_(4)(Se)_(4)located at the apex of the volcanic curve,showing the best NRR performance.The asymmetrical coordination environment could regulate the band structure subtly in terms of band overlap and positions.This work may shed new light on the application of orbital engineering in electrocatalytic NRR activity and especially promotes the rational design for SACs.展开更多
The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application i...The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application in high-pressure solid rocket motors.In this work,the combustion characteristics of AP/HTPB/Al composite propellants containing ferrocene-based catalysts were investigated,including the burning rate,thermal behavior,the local heat transfer,and temperature profile in the range of 7-28 MPa.The results showed that the exponent breaks were still observed in the propellants after the addition of positive catalysts(Ce-Fc-MOF),the burning rate inhibitor((Ferrocenylmethyl)trimethylammonium bromide,Fc Br)and the mixture of Fc Br/catocene(GFP).However,the characteristic pressure has increased,and the exponent decreased from 1.14 to 0.66,0.55,and 0.48 when the addition of Ce-FcMOF,Fc Br and Fc Br/GFP in the propellants.In addition,the temperature in the first decomposition stage was increased by 7.50℃ and 11.40℃ for the AP/Fc Br mixture and the AP/Fc Br/GFP mixture,respectively,compared to the pure AP.On the other hand,the temperature in the second decomposition stage decreased by 48.30℃ and 81.70℃ for AP/Fc Br and AP/Fc Br/GFP mixtures,respectively.It was also found that Fc Br might generate ammonia to cover the AP surface.In this case,a reaction between the methyl in Fc Br and perchloric acid caused more ammonia to appear at the AP surface,resulting in the suppression of ammonia desorption.In addition,the coarse AP particles on the quenched surface were of a concave shape relative to the binder matrix under low and high pressures when the catalysts were added.In the process,the decline at the AP/HTPB interface was only exhibited in the propellant with the addition of Ce-Fc-MOF.The ratio of the gas-phase temperature gradient of the propellants containing catalysts was reduced significantly below and above the characteristic pressure,rather than 3.6 times of the difference in the blank propellant.Overall,the obtained results demonstrated that the pressure exponent could be effectively regulated and controlled by adjusting the propellant local heat and mass transfer under high and low pressures.展开更多
CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet...CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet the industrial demands.Herein,the nanorod-like bimetallic ln_(2)O_(3)/Bi_(2)O_(3)catalysts were successfully synthesized by pyrolysis of bimetallic InBi-MOF precursors.The abundant oxygen vacancies generated from the lattice mismatch of Bi_(2)O_(3)and ln_(2)O_(3)reduced the activation energy of CO_(2)to*CO_(2)·^(-)and improved the selectivity of*CO_(2)·^(-)to formate simultaneously.Meanwhile,the carbon skeleton derived from the pyrolysis of organic framework of InBi-MOF provided a conductive network to accelerate the electrons transmission.The catalyst exhibited an ultra-broad applied potential window of 1200 mV(from-0.4 to-1.6 V vs RHE),relativistic high Faradaic efficiency of formate(99.92%)and satisfactory stability after 30 h.The in situ FT-IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO_(2)molecules,and oxygen vacancy path is dominant pathway.This work provides a convenient method to construct high-performance bimetallic catalysts for the industrial application of CO_(2)RR.展开更多
The exploration of sustainable energy utilization requires the imple-mentation of advanced electrochemical devices for efficient energy conversion and storage,which are enabled by the usage of cost-effective,high-perf...The exploration of sustainable energy utilization requires the imple-mentation of advanced electrochemical devices for efficient energy conversion and storage,which are enabled by the usage of cost-effective,high-performance electro-catalysts.Currently,heterogeneous atomically dispersed catalysts are considered as potential candidates for a wide range of applications.Compared to conventional cata-lysts,atomically dispersed metal atoms in carbon-based catalysts have more unsatu-rated coordination sites,quantum size effect,and strong metal-support interactions,resulting in exceptional catalytic activity.Of these,dual-atomic catalysts(DACs)have attracted extensive attention due to the additional synergistic effect between two adja-cent metal atoms.DACs have the advantages of full active site exposure,high selectiv-ity,theoretical 100%atom utilization,and the ability to break the scaling relationship of adsorption free energy on active sites.In this review,we summarize recent research advancement of DACs,which includes(1)the comprehensive understanding of the synergy between atomic pairs;(2)the synthesis of DACs;(3)characterization meth-ods,especially aberration-corrected scanning transmission electron microscopy and synchrotron spectroscopy;and(4)electrochemical energy-related applications.The last part focuses on great potential for the electrochemical catalysis of energy-related small molecules,such as oxygen reduction reaction,CO_(2) reduction reaction,hydrogen evolution reaction,and N_(2) reduction reaction.The future research challenges and opportunities are also raised in prospective section.展开更多
MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high...MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).展开更多
Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central is...Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.展开更多
Industrial catalyst waste has emerged as a hazardous pollutant that requires safe and proper disposal after the unloading process.Finding a valuable and sustainable strategy for its treatment is a significant challeng...Industrial catalyst waste has emerged as a hazardous pollutant that requires safe and proper disposal after the unloading process.Finding a valuable and sustainable strategy for its treatment is a significant challenge compared to traditional methods.In this study,we present a facile method for the recovery of molybdenum and aluminum contents from spent Mo-Ni/Al_(2)O_(3) hydrogenation catalysts through crystallization separation and coprecipitation.Furthermore,the recovered molybdenum and aluminum are utilized as active metals and carriers for the preparation of new catalysts.Their properties were thoroughly analyzed and investigated using various characterization techniques.The hydrogenation activity of these newly prepared catalysts was evaluated on a fixed-bed small-scale device and compared with a reference catalyst synthesized from commercial raw reagents.Finally,the hydrogenation activity of the catalysts was further assessed by using the entire distillate oil of coal liquefaction as the raw oil,specifically focusing on denitrogenation and aromatic saturation.This work not only offers an effective solution for recycling catalysts but also promotes sustainable development.展开更多
The removal of organic sulfur through catalytic hydrolysis is a significant area of research in the field of desulfurization.This review provides an overview of recent advancements in catalytic hydrolysis technology o...The removal of organic sulfur through catalytic hydrolysis is a significant area of research in the field of desulfurization.This review provides an overview of recent advancements in catalytic hydrolysis technology of organic sulfur,including the activity,stability,and atmosphere effects of hydrolysis catalysts.The emphasis is on strategies for enhancing hydrolysis activity and anti-oxygen poisoning property of catalysts.Surface modification,metal doping and nitrogen doping have been found to improve the activity of catalysts.Alkaline components modification is the most commonly used method,the formation of oxygen vacancies through metal doping and creation of nitrogen basic sites through nitrogen doping also contribute to the hydrolysis of organic sulfur.The strategies for anti-oxygen poisoning are discussed in a systematic manner.The structural regulation of catalysts is beneficial for the desorption and diffusion of hydrogen sulfide(H_(2)S),thereby effectively inhibiting its oxidation.Nitrogen doping and the addition of electronic promoters such as transition metals can protect active sites and decrease the number of active oxygen species.These methods have been proven to enhance the anti-poisoning performance of catalysts.Additionally,this article summarizes how different atmospheres affect the activity of hydrolysis catalysts.The objective of this review is to pave the way for the development of efficient,stable and widely used catalysts for organic sulfur hydrolysis.展开更多
A series of model catalysts were obtained by treating commercial fresh and spent catalysts unloaded from the factory with different methods, including green oil dipping, extraction and high-temperature regeneration;fi...A series of model catalysts were obtained by treating commercial fresh and spent catalysts unloaded from the factory with different methods, including green oil dipping, extraction and high-temperature regeneration;finally, the deactivation behavior of the commercial catalyst for acetylene hydrogenation were studied. The influence of various possible deactivation factors on the catalytic performance was elucidated via detailed structural characterization, surface composition analysis, and activity evaluation.The results showed that green oil, carbon deposit and sintering of active metal were the main reasons for deactivation, among which green oil and carbon deposit led to rapid deactivation, while the activity could be recovered after regeneration by high-temperature calcination. The sintering of active metal components was attributed to the high-temperature regeneration in hydrothermal conditions, which was slow but irreversible and accounted for permanent deactivation. Thus, optimizing the regeneration is expected to extend the service life of the commercial catalyst.展开更多
Porous silica nano-flowers(KCC-1)immobilized Pt-Pd alloy NPs(Pt-Pd/KCC-1)with different mass ratios of Pd and Pt were successfully prepared by a facile in situ one-step reduction,using hydrazinium hydroxide as a reduc...Porous silica nano-flowers(KCC-1)immobilized Pt-Pd alloy NPs(Pt-Pd/KCC-1)with different mass ratios of Pd and Pt were successfully prepared by a facile in situ one-step reduction,using hydrazinium hydroxide as a reducing agent.The as-synthesized silica nanospheres possess radial fibers with a distance of 15 nm,exhibiting a high specific surface area(443.56 m^(2)·g^(-1)).Meanwhile,the obtained Pt-Pd alloy NPs are uniformly dispersed on the silica surface with a metallic particle size of 4-6 nm,which exist as metallic Pd and Pt on the surface of monodisperse KCC-1,showing the transfer of electrons from Pd to Pt.The as-synthesized 2.5%Pt-2.5%Pd/KCC-1 exhibited excellent catalytic activity and stability for the continuous dehydrogenation of 2-methoxycyclohexanol to prepare guaiacol.Compared with Pt or Pd single metal supported catalysts,the obtained 2.5%Pt-2.5%Pd/KCC-1 shows 97.2%conversion rate of 2-methoxycyclohexanol and 76.8%selectivity for guaiacol,which attributed to the significant synergistic effect of bimetallic Pt-Pd alloy NPs.Furthermore,turn over frequency value of the obtained 2.5%Pt-2.5%Pd/KCC-1 NPs achieved 4.36 s^(-1),showing higher catalytic efficiency than other two monometallic catalysts.Reaction pathways of dehydro-aromatization of 2-methoxycyclohexanol over the obtained catalyst are proposed.Consequently,the obtained 2.5%Pt-2.5%Pd/KCC-1 NPs prove their potential in the dehydrogenation of 2-methoxycyclohexanol,while the kinetics and mechanistic study of the dehydrogenation reaction over the catalyst in a continuous fixed-bed reactor may provide valuable information for the development of green,outstanding and powerful synthetic pathway of guaiacol.展开更多
Green hydrogen from electrolysis of water has attracted widespread attention as a renewable power source.Among several hydrogen production methods,it has become the most promising technology.However,there is no large-...Green hydrogen from electrolysis of water has attracted widespread attention as a renewable power source.Among several hydrogen production methods,it has become the most promising technology.However,there is no large-scale renewable hydrogen production system currently that can compete with conventional fossil fuel hydrogen production.Renewable energy electrocatalytic water splitting is an ideal production technology with environmental cleanliness protection and good hydrogen purity,which meet the requirements of future development.This review summarizes and introduces the current status of hydrogen production by water splitting from three aspects:electricity,catalyst and electrolyte.In particular,the present situation and the latest progress of the key sources of power,catalytic materials and electrolyzers for electrocatalytic water splitting are introduced.Finally,the problems of hydrogen generation from electrolytic water splitting and directions of next-generation green hydrogen in the future are discussed and outlooked.It is expected that this review will have an important impact on the field of hydrogen production from water.展开更多
Geometrical configurations play a crucial role in dual-atom catalysts(DACs)for electrocatalytic applications.Significant progress has been made to design DACs electrocatalysts with various geometri-cal configurations,...Geometrical configurations play a crucial role in dual-atom catalysts(DACs)for electrocatalytic applications.Significant progress has been made to design DACs electrocatalysts with various geometri-cal configurations,but in-depth understanding the relationship between geometrical configurations and metal-metal interaction mechanisms for designing targeted DACs is still required.In this review,the recent progress in engineering of geometrical configurations of DACs is systematically summarized.Based on the polarity of geometrical configuration,DACs can be classified into two different types that are homonuclear and heteronuclear DACs.Furthermore,with regard to the geometrical configurations of the active sites,homonuclear DACs are identified into adjacent and bridged configurations,and heteronuclear DACs can be classified into adjacent,bridged,and separated configurations.Subsequently,metal-metal interactions in DACs with different geometrical configurations are introduced.Additionally,the applications of DACs in different electrocatalytic reactions are discussed,including the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),and other catalysis.Finally,the future challenges and perspectives for advancements in DACs are high-lighted.This review aims to provide inspiration for the design of highly effcient DACs towards energy relatedapplications.展开更多
基金Supported by the Interdisciplinary Team Project of Shenyang University of Technology in 2021:Green and Low-carbon(Technology and Evaluation)of Typical Industries of Carbon Peak(2021-70-06)"Double First-class"Construction Project of Liaoning Province in 2020(Scientific Research)(FWDFGD2020041).
文摘Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechanism of catalysts in the market were analyzed.Different types of catalysts were studied to look for green catalysts with high activity,sulfur resistance,water vapor resistance and other advantages.The mechanism of denitration reaction of green catalysts was discussed,and the laws of formation,propagation and consumption of active species in the reaction process were revealed to provide theoretical basis for optimizing catalyst design and improving reaction conditions.Then the research status and problems of new catalysts for flue gas denitrification were described.Finally,the future development direction of green catalysts for flue gas denitration was discussed to improve the performance and stability of catalysts and meet the performance requirements of denitration catalysts in different industries.
基金supported by the National Natural Science Foundation of China(52272194)Liaoning Revitalization Talents Program(XLYC2007155)。
文摘Lithium metal batteries are regarded as prominent contenders to address the pressing needs owing to the high theoretical capacity.Toward the broader implementation,the primary obstacle lies in the intricate multi-electron,multi-step redox reaction associated with sluggish conversion kinetics,subsequently giving rise to a cascade of parasitic issues.In order to smooth reaction kinetics,catalysts are widely introduced to accelerate reaction rate via modulating the energy barrier.Over past decades,a large amount of research has been devoted to the catalyst design and catalytic mechanism exploration,and thus the great progress in electrochemical performance has been realized.Therefore,it is necessary to make a comprehensive review toward key progress in catalyst design and future development pathway.In this review,the basic mechanism of lithium metal batteries is provided along with corresponding advantages and existing challenges detailly described.The main catalysts employed to accelerate cathode reaction with emphasis on their catalytic mechanism are summarized as well.Finally,the rational design and innovative direction toward efficient catalysts are suggested for future application in metal-sulfur/gas battery and beyond.This review is expected to drive and benefit future research on rational catalyst design with multi-parameter synergistic impacts on the activity and stability of next-generation metal battery,thus opening new avenue for sustainable solution to climate change,energy and environmental issues,and the potential industrial economy.
基金This study is supported by the National Natural Science Foundation of China(21925104)the Natural Science Foun-dation of Hubei Province(2021CFA020)the start-up funding of Huazhong University of Science and Technology(3004110178).
文摘Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design principles by understanding the catalytic mechanisms and identifying the active sites.Distinct from sp2-conjugated graphene and carbon nanotube,fullerene possesses unique characteristics that are growingly being discovered and exploited by the electrocatalysis community.For instance,the well-defined atomic and molecular structures,the good electron affinity to tune the electronic structures of other substances,the intermolecular self-assembly into superlattices,and the on-demand chemical modification have endowed fullerene with incomparable advantages as electrocatalysts that are otherwise not applicable to other carbon ma-terials.As increasing studies are being reported on this intriguing topic,it is necessary to provide a state-of-the-art overview of the recent progress.This review takes such an initiative by summarizing the promises and challenges in the electrocatalytic applications of fullerene and its derivatives.The content is structured according to the composition and structure of fullerene,including intact fullerene(e.g.,fullerene composite and superlattices)and fullerene derivatives(e.g.,doped,endohedral,and disintegrated fullerene).The synthesis,characterization,catalytic mechanisms,and deficiencies of these fullerene-based materials are explicitly elaborated.We conclude it by sharing our perspectives on the key aspects that future efforts shall consider.
基金supported by the National Key Research and Development Program of China(No.2020YFB1506002,2019YFB1504503,2016YFB0101202)National 973 Program of China(No.2012CB215501)National Natural Science Foundation of China(No.52021004,22022502(2021),21822803(2019),21576031(2016),51272297(2013),20936008(2010),20676156(2007),20376088(2004),20176066(2002),29976047(2000)).
文摘Two major challenges,high cost and short lifespan,have been hindering the commercialization process of lowtemperature fuel cells.Professor Wei's group has been focusing on decreasing cathode Pt loadings without losses of activity and durability,and their research advances in this area over the past three decades are briefly reviewed herein.Regarding the Pt-based catalysts and the low Pt usage,they have firstly tried to clarify the degradation mechanism of Pt/C catalysts,and then demonstrated that the activity and stability could be improved by three strategies:regulating the nanostructures of the active sites,enhancing the effects of support materials,and optimizing structures of the three-phase boundary.For Pt-free catalysts,especialiy carbon-based ones,several strategies that they proposed to enhance the activity of nitrogen-/heteroatom-doped carbon catalysts are firstly presented.Then,an indepth understanding of the degradation mechanism for carbon-based catalysts is discussed,and followed by the corresponding stability enhancement strategies.Also,the carbon-based electrode at the micrometer-scale,faces the challenges such as low active-site density,thick catalytic layer,and the effect of hydrogen peroxide,which require rational structure design for the integral cathodic electrode.This review finally gives a brief conclusion and outlook about the low cost and long lifespan of cathodic oxygen reduction catalysts.
基金supported by the National Natural Science Foundation of China(22234005,21974070)the Natural Science Foundation of Jiangsu Province(BK20222015)。
文摘Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(NRF,2021R1C1C1013953,2022K1A4A7A04094394,2022K1A4A7A04095890)。
文摘The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.
基金the financial support from by the National Key Research and Development Program of China(No.2022YFB4101800)National Natural Science Foundation of China(No.22278298)Program for Introducing Talents of Discipline to Universities of China(No.BP0618007).
文摘Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.
基金supported by the National Natural Science Foundation of China(21905253,51973200,and 52122308)the Natural Science Foundation of Henan(202300410372)the National Supercomputing Center in Zhengzhou
文摘The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,the roles of individual metals,coordination atoms,and their synergy effect on the electroanalytic performance remain unclear.Therefore,in this work,a series of 2DMOFs with different metals and coordinating atoms are systematically investigated as electrocatalysts for ammonia synthesis using density functional theory calculations.For a specific metal,a proper metal-intermediate atoms p-d orbital hybridization interaction strength is found to be a key indicator for their NRR catalytic activities.The hybridization interaction strength can be quantitatively described with the p-/d-band center energy difference(Δd-p),which is found to be a sufficient descriptor for both the p-d hybridization strength and the NRR performance.The maximum free energy change(ΔG_(max))andΔd-p have a volcanic relationship with OsC_(4)(Se)_(4)located at the apex of the volcanic curve,showing the best NRR performance.The asymmetrical coordination environment could regulate the band structure subtly in terms of band overlap and positions.This work may shed new light on the application of orbital engineering in electrocatalytic NRR activity and especially promotes the rational design for SACs.
基金the support of the National Natural Science Foundation of China grant number 51776175。
文摘The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application in high-pressure solid rocket motors.In this work,the combustion characteristics of AP/HTPB/Al composite propellants containing ferrocene-based catalysts were investigated,including the burning rate,thermal behavior,the local heat transfer,and temperature profile in the range of 7-28 MPa.The results showed that the exponent breaks were still observed in the propellants after the addition of positive catalysts(Ce-Fc-MOF),the burning rate inhibitor((Ferrocenylmethyl)trimethylammonium bromide,Fc Br)and the mixture of Fc Br/catocene(GFP).However,the characteristic pressure has increased,and the exponent decreased from 1.14 to 0.66,0.55,and 0.48 when the addition of Ce-FcMOF,Fc Br and Fc Br/GFP in the propellants.In addition,the temperature in the first decomposition stage was increased by 7.50℃ and 11.40℃ for the AP/Fc Br mixture and the AP/Fc Br/GFP mixture,respectively,compared to the pure AP.On the other hand,the temperature in the second decomposition stage decreased by 48.30℃ and 81.70℃ for AP/Fc Br and AP/Fc Br/GFP mixtures,respectively.It was also found that Fc Br might generate ammonia to cover the AP surface.In this case,a reaction between the methyl in Fc Br and perchloric acid caused more ammonia to appear at the AP surface,resulting in the suppression of ammonia desorption.In addition,the coarse AP particles on the quenched surface were of a concave shape relative to the binder matrix under low and high pressures when the catalysts were added.In the process,the decline at the AP/HTPB interface was only exhibited in the propellant with the addition of Ce-Fc-MOF.The ratio of the gas-phase temperature gradient of the propellants containing catalysts was reduced significantly below and above the characteristic pressure,rather than 3.6 times of the difference in the blank propellant.Overall,the obtained results demonstrated that the pressure exponent could be effectively regulated and controlled by adjusting the propellant local heat and mass transfer under high and low pressures.
基金financially supported by the National Natural Science Foundation of China(52072409)the Major Scientific and Technological Innovation Project of Shandong Province(2020CXGC010403)+1 种基金the Taishan Scholar Project(No.ts201712020)the Natural Science Foundation of Shandong Province(ZR2021QE062)
文摘CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet the industrial demands.Herein,the nanorod-like bimetallic ln_(2)O_(3)/Bi_(2)O_(3)catalysts were successfully synthesized by pyrolysis of bimetallic InBi-MOF precursors.The abundant oxygen vacancies generated from the lattice mismatch of Bi_(2)O_(3)and ln_(2)O_(3)reduced the activation energy of CO_(2)to*CO_(2)·^(-)and improved the selectivity of*CO_(2)·^(-)to formate simultaneously.Meanwhile,the carbon skeleton derived from the pyrolysis of organic framework of InBi-MOF provided a conductive network to accelerate the electrons transmission.The catalyst exhibited an ultra-broad applied potential window of 1200 mV(from-0.4 to-1.6 V vs RHE),relativistic high Faradaic efficiency of formate(99.92%)and satisfactory stability after 30 h.The in situ FT-IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO_(2)molecules,and oxygen vacancy path is dominant pathway.This work provides a convenient method to construct high-performance bimetallic catalysts for the industrial application of CO_(2)RR.
基金This work was financially supported by the National Key Research and Development Program of China(2018YFA0702002)the Beijing Natural Science Foundation(Z210016)+1 种基金the National Natural Science Foundation of China(51967020,21935001)Shanxi Energy Internet Research Institute(SXEI 2023A004).
文摘The exploration of sustainable energy utilization requires the imple-mentation of advanced electrochemical devices for efficient energy conversion and storage,which are enabled by the usage of cost-effective,high-performance electro-catalysts.Currently,heterogeneous atomically dispersed catalysts are considered as potential candidates for a wide range of applications.Compared to conventional cata-lysts,atomically dispersed metal atoms in carbon-based catalysts have more unsatu-rated coordination sites,quantum size effect,and strong metal-support interactions,resulting in exceptional catalytic activity.Of these,dual-atomic catalysts(DACs)have attracted extensive attention due to the additional synergistic effect between two adja-cent metal atoms.DACs have the advantages of full active site exposure,high selectiv-ity,theoretical 100%atom utilization,and the ability to break the scaling relationship of adsorption free energy on active sites.In this review,we summarize recent research advancement of DACs,which includes(1)the comprehensive understanding of the synergy between atomic pairs;(2)the synthesis of DACs;(3)characterization meth-ods,especially aberration-corrected scanning transmission electron microscopy and synchrotron spectroscopy;and(4)electrochemical energy-related applications.The last part focuses on great potential for the electrochemical catalysis of energy-related small molecules,such as oxygen reduction reaction,CO_(2) reduction reaction,hydrogen evolution reaction,and N_(2) reduction reaction.The future research challenges and opportunities are also raised in prospective section.
基金supported by research programs of National Natural Science Foundation of China(52101274,51731002)Natural Science Foundation of Shandong Province(No.ZR2020QE011)Youth Top Talent Foundation of Yantai University(2219008).
文摘MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).
文摘Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.
基金supported by grants from the National Key Research and Development Program of China(2023YE41507601)the National Natural Science Foundation of China(22122807,22378038)+1 种基金the Fundamental Research Funds for the Central Universities(DUT23RC(3)044)State Key Laboratory of Heavy Oil Processing,China University of Petroleum(WX20230149)。
文摘Industrial catalyst waste has emerged as a hazardous pollutant that requires safe and proper disposal after the unloading process.Finding a valuable and sustainable strategy for its treatment is a significant challenge compared to traditional methods.In this study,we present a facile method for the recovery of molybdenum and aluminum contents from spent Mo-Ni/Al_(2)O_(3) hydrogenation catalysts through crystallization separation and coprecipitation.Furthermore,the recovered molybdenum and aluminum are utilized as active metals and carriers for the preparation of new catalysts.Their properties were thoroughly analyzed and investigated using various characterization techniques.The hydrogenation activity of these newly prepared catalysts was evaluated on a fixed-bed small-scale device and compared with a reference catalyst synthesized from commercial raw reagents.Finally,the hydrogenation activity of the catalysts was further assessed by using the entire distillate oil of coal liquefaction as the raw oil,specifically focusing on denitrogenation and aromatic saturation.This work not only offers an effective solution for recycling catalysts but also promotes sustainable development.
基金supported by Fundamental Research Program of Shanxi Province,China(202203021212245)the Science and Technology Achievement Transformation Guidance Special Program of Shanxi Province,China(202104021301052)the Patent Transformation Program of Shanxi Province,China(202306013).
文摘The removal of organic sulfur through catalytic hydrolysis is a significant area of research in the field of desulfurization.This review provides an overview of recent advancements in catalytic hydrolysis technology of organic sulfur,including the activity,stability,and atmosphere effects of hydrolysis catalysts.The emphasis is on strategies for enhancing hydrolysis activity and anti-oxygen poisoning property of catalysts.Surface modification,metal doping and nitrogen doping have been found to improve the activity of catalysts.Alkaline components modification is the most commonly used method,the formation of oxygen vacancies through metal doping and creation of nitrogen basic sites through nitrogen doping also contribute to the hydrolysis of organic sulfur.The strategies for anti-oxygen poisoning are discussed in a systematic manner.The structural regulation of catalysts is beneficial for the desorption and diffusion of hydrogen sulfide(H_(2)S),thereby effectively inhibiting its oxidation.Nitrogen doping and the addition of electronic promoters such as transition metals can protect active sites and decrease the number of active oxygen species.These methods have been proven to enhance the anti-poisoning performance of catalysts.Additionally,this article summarizes how different atmospheres affect the activity of hydrolysis catalysts.The objective of this review is to pave the way for the development of efficient,stable and widely used catalysts for organic sulfur hydrolysis.
基金the financial support from the Sinopec Catalyst Co.Ltd.,China。
文摘A series of model catalysts were obtained by treating commercial fresh and spent catalysts unloaded from the factory with different methods, including green oil dipping, extraction and high-temperature regeneration;finally, the deactivation behavior of the commercial catalyst for acetylene hydrogenation were studied. The influence of various possible deactivation factors on the catalytic performance was elucidated via detailed structural characterization, surface composition analysis, and activity evaluation.The results showed that green oil, carbon deposit and sintering of active metal were the main reasons for deactivation, among which green oil and carbon deposit led to rapid deactivation, while the activity could be recovered after regeneration by high-temperature calcination. The sintering of active metal components was attributed to the high-temperature regeneration in hydrothermal conditions, which was slow but irreversible and accounted for permanent deactivation. Thus, optimizing the regeneration is expected to extend the service life of the commercial catalyst.
基金supported by Natural Science Foundation of Henan Province of China(162300410253)the Open Research Fund of State Key Laboratory of Coking Coal Exploitation and Comprehensive Utilization,China Pingmei Shen-ma Group(41040220181107-8).
文摘Porous silica nano-flowers(KCC-1)immobilized Pt-Pd alloy NPs(Pt-Pd/KCC-1)with different mass ratios of Pd and Pt were successfully prepared by a facile in situ one-step reduction,using hydrazinium hydroxide as a reducing agent.The as-synthesized silica nanospheres possess radial fibers with a distance of 15 nm,exhibiting a high specific surface area(443.56 m^(2)·g^(-1)).Meanwhile,the obtained Pt-Pd alloy NPs are uniformly dispersed on the silica surface with a metallic particle size of 4-6 nm,which exist as metallic Pd and Pt on the surface of monodisperse KCC-1,showing the transfer of electrons from Pd to Pt.The as-synthesized 2.5%Pt-2.5%Pd/KCC-1 exhibited excellent catalytic activity and stability for the continuous dehydrogenation of 2-methoxycyclohexanol to prepare guaiacol.Compared with Pt or Pd single metal supported catalysts,the obtained 2.5%Pt-2.5%Pd/KCC-1 shows 97.2%conversion rate of 2-methoxycyclohexanol and 76.8%selectivity for guaiacol,which attributed to the significant synergistic effect of bimetallic Pt-Pd alloy NPs.Furthermore,turn over frequency value of the obtained 2.5%Pt-2.5%Pd/KCC-1 NPs achieved 4.36 s^(-1),showing higher catalytic efficiency than other two monometallic catalysts.Reaction pathways of dehydro-aromatization of 2-methoxycyclohexanol over the obtained catalyst are proposed.Consequently,the obtained 2.5%Pt-2.5%Pd/KCC-1 NPs prove their potential in the dehydrogenation of 2-methoxycyclohexanol,while the kinetics and mechanistic study of the dehydrogenation reaction over the catalyst in a continuous fixed-bed reactor may provide valuable information for the development of green,outstanding and powerful synthetic pathway of guaiacol.
基金supported by the National Natural Science Foundation of China(U23A20573,U23A20140,22109038)the Starting Research Funds of Hebei University of Science and Technology,Hebei Natural Science Foundation(D2022208001)+1 种基金the S&T Program of Hebei(23314401D)Hebei Pharmaceutical and Chemical Technology Innovation Center(225676121H).
文摘Green hydrogen from electrolysis of water has attracted widespread attention as a renewable power source.Among several hydrogen production methods,it has become the most promising technology.However,there is no large-scale renewable hydrogen production system currently that can compete with conventional fossil fuel hydrogen production.Renewable energy electrocatalytic water splitting is an ideal production technology with environmental cleanliness protection and good hydrogen purity,which meet the requirements of future development.This review summarizes and introduces the current status of hydrogen production by water splitting from three aspects:electricity,catalyst and electrolyte.In particular,the present situation and the latest progress of the key sources of power,catalytic materials and electrolyzers for electrocatalytic water splitting are introduced.Finally,the problems of hydrogen generation from electrolytic water splitting and directions of next-generation green hydrogen in the future are discussed and outlooked.It is expected that this review will have an important impact on the field of hydrogen production from water.
基金supported by the Natural Science Foundation of China (22179062,52125202,and U2004209)the Natural Science Foundation of Jiangsu Province (BK20230035)+1 种基金the Fundamental Research Funds for the Central Universities (30922010303)the Intergovernmental Cooperation Projects in the National Key Research and Development Plan of the Ministry of Science and Technology of PRC (2022YFE0196800)
文摘Geometrical configurations play a crucial role in dual-atom catalysts(DACs)for electrocatalytic applications.Significant progress has been made to design DACs electrocatalysts with various geometri-cal configurations,but in-depth understanding the relationship between geometrical configurations and metal-metal interaction mechanisms for designing targeted DACs is still required.In this review,the recent progress in engineering of geometrical configurations of DACs is systematically summarized.Based on the polarity of geometrical configuration,DACs can be classified into two different types that are homonuclear and heteronuclear DACs.Furthermore,with regard to the geometrical configurations of the active sites,homonuclear DACs are identified into adjacent and bridged configurations,and heteronuclear DACs can be classified into adjacent,bridged,and separated configurations.Subsequently,metal-metal interactions in DACs with different geometrical configurations are introduced.Additionally,the applications of DACs in different electrocatalytic reactions are discussed,including the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),and other catalysis.Finally,the future challenges and perspectives for advancements in DACs are high-lighted.This review aims to provide inspiration for the design of highly effcient DACs towards energy relatedapplications.