The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide poten...The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide potential window with promising Faradic efficiency(FE) towards BHMF,Cu-based electrode has been in the center of investigation.However,its structure-activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory.In this work,we develop a two-step oxidation-reduction strategy to reconstruct the surface atom arrangement of the Cu foam(CF).By combination of multiple quasi-situ/in-situ techniques and density functional theory(DFT) calculation,the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal:Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF,while Cu(100) facet might trigger the accumulation of the by-product 5,5'-bis(hydroxy methy)hydrofurion(BHH).With the optimized composition of the facets on the reconstructed Cu(OH)_(2)-ER/CF,the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of -0.15 V versus reversible hydrogen electrode(vs.RHE) in 0.1 M KOH solution.This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF,and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.展开更多
Electrocatalytic valorization of biomass derivatives can be powered by electricity generated from renewable sources such as solar and wind energy.A shift from centralized,high-temperature,and energy-intensive processe...Electrocatalytic valorization of biomass derivatives can be powered by electricity generated from renewable sources such as solar and wind energy.A shift from centralized,high-temperature,and energy-intensive processes to decentralized,low-temperature conversions is achieved,which meets the requirement of sustainable energy generation.This approach provides an efficient,green,and additive-free strategy for biomass derivative valorization,in which product selectivity could be easily regulated by the applied potential and electrocatalyst utilized.However,a scale-up application is still far from being completed due to the inability of conversion rates and selectivity to meet the industrialization requirements.A better understanding of the reaction mechanism and the development of highefficiency and high-selectivity electrocatalysts are required to pave the path toward larger industrialization applications.Herein,we summarize the recent research progress in the electrocatalytic oxidation and hydrogenation of platform compounds such as furanic compounds and glycerol.In the literature,these three research areas are integrated to realize the scale-up application of the processes as mentioned above.The investigations of the mechanism are based on in situ techniques,theoretical calculations,and advanced electrocatalyst studies.Finally,the challenges and prospects in this topic are described.We expect that this review will provide the fundamental understanding and design guidelines to achieve efficient and high-selectivity catalysts and further facilitate the scale-up application of the electrocatalytic conversion of biomass derivatives.展开更多
The improvement of hydrogen storage materials is a key issue for storage and delivery of hydrogen energy before its potential can be realized. As hydrogen storage media, rare-earth hydrogen storage materials have been...The improvement of hydrogen storage materials is a key issue for storage and delivery of hydrogen energy before its potential can be realized. As hydrogen storage media, rare-earth hydrogen storage materials have been systematically studied in order to improve storage capacity, kinetics, thermodynamics and electrochemical performance. In this review, we focus on recent research progress of gaseous sorption and electrochemical hydrogen storage properties of rare-earth alloys and highlight their commercial applications including hydrogen storage tanks and nickel metal hydride batteries. Furthermore, development trend and prospective of rare-earth hydrogen storage materials are discussed.展开更多
Replacing conventional fossil resources with renewable raw materials for chemical production and energy generation is crucial for achieving the carbon-neutral goal and alleviating the emerging energy crisis.Biomass ha...Replacing conventional fossil resources with renewable raw materials for chemical production and energy generation is crucial for achieving the carbon-neutral goal and alleviating the emerging energy crisis.Biomass has been considered as one of the most promising candidates for this purpose owing to its great natural abundance and inherent ability to fix CO_(2) in the form of multicarbon compounds.Particularly,biomass conversion through an electrochemical route is intriguing because of its operability near ambient conditions,flexible scalability(suitable for distributed manufacturing and even domestic use)and green generation of oxidative or reductive equivalents instead of wasteful and possibly explosive or flammable reagents.Herein,recent progress in electrochemical transformation of biomass,including hydrogenation and amination,is reviewed with the emphasis on catalysts and strategies for enhancing catalytic efficiency.The advances in mechanistic understanding using in-situ spectroscopy are also briefly discussed.Finally,recommendations for the directions for future development are also provided.展开更多
We first report that photoelectrochemical （PEC） performance of electrochemically hydrogenated TiO2 nanotube arrays （TNTAs） as high-efficiency photoanodes for solar water splitting could be well tuned by designing ...We first report that photoelectrochemical （PEC） performance of electrochemically hydrogenated TiO2 nanotube arrays （TNTAs） as high-efficiency photoanodes for solar water splitting could be well tuned by designing and adjusting the phase structure and composition of TNTAs. Among various TNTAs annealed at different temperature ranging from 300 to 700℃, well-crystallized single anatase （A） phase TNTAs-400 photoanode shows the best photoresponse properties and PEC performance due to the favor- able crystallinity, grain size and tubular structures. After electrochemical hydrogenation （EH）. anatase- rutile （A-R） mixed phase EH-TNTAs-600 photoanode exhibits the highest photoactivity and PEC perfor- mance for solar water splitting. Under simulated solar illumination, EH-TNTAs-600 achieves the best photoconversion efficiency of up to 1.52% and maximum H2 generation rate of 40.4 ~mol h i cm-2, our- stripping other EH-TNTAs photoanodes. Systematic studies reveal that the signigicantly enhanced PEC performance for A-R mixed phaes EH-TNTAs-600 photoanode could be attributed to the synergy of A-R mixed phases and intentionally introduced Ti3~ （oxygen vacancies） which enhances the photoactivity over both UV and visible-light regions, and boosts both charge separation and transfer efficiencies. These findings provide new insight and guidelines for the construction of highly efficient TiO2-based devices for the application of solar water splitting.展开更多
Although TiO_(2)nanotubes is a promising electrode as supercapacitors due to its high energy density,easy synthesis and chemical stability,there are draw backs such as low conductivity and capacitance.Many studies con...Although TiO_(2)nanotubes is a promising electrode as supercapacitors due to its high energy density,easy synthesis and chemical stability,there are draw backs such as low conductivity and capacitance.Many studies concentrated on improving its electrochemical performance itself but little attention was payed to the reason of capacitance differences caused by its different crystal structures.Herein,we prepare amorphous and anatase TiO_(2)nanotubes and hydrogenated them by a simple electrochemical hydrogenation method to improve their conductivity and capacitance.And then study and compare their morphology and structure differences by SEM,TEM,XRD and BET.The results show that the pore size distribution,internal structure order and internal carrier concentration are the main reasons for their electrochemical performance differences.The microporous structure less than 2 nm in amorphous nanotubes act as a trap of electrolyte ions at current density larger than 0.1μA cm^(-2),leading to small charge and discharge capacitance.The long-range ordered crystal structure of anatase is more favorable for the orderly diffusion of carriers,reducing the inelastic scattering of carrier diffusion process and the electron hole-complexing probability,making anatase nanotubes exhibit higher coulomb efficiency and cycle stability than that of amorphous ones.展开更多
基金supported by the National Natural Science Foundation of China (21808035, 21901040)the Natural Science Foundation of Fujian Province (2019J05058, 2021J05216, 2022J01922)+3 种基金the Fujian Provincial Department of Finance (GY-Z220231)the fund of the State Key Laboratory of Catalysis in DICP (N-22-08)the Fujian Fishery Disaster Reduction Center (GY-H-22146)College Student Innovation and Entrepreneurship Training Program (x202110388068)。
文摘The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide potential window with promising Faradic efficiency(FE) towards BHMF,Cu-based electrode has been in the center of investigation.However,its structure-activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory.In this work,we develop a two-step oxidation-reduction strategy to reconstruct the surface atom arrangement of the Cu foam(CF).By combination of multiple quasi-situ/in-situ techniques and density functional theory(DFT) calculation,the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal:Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF,while Cu(100) facet might trigger the accumulation of the by-product 5,5'-bis(hydroxy methy)hydrofurion(BHH).With the optimized composition of the facets on the reconstructed Cu(OH)_(2)-ER/CF,the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of -0.15 V versus reversible hydrogen electrode(vs.RHE) in 0.1 M KOH solution.This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF,and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.
基金supported by the National Key R&D Program of China(2020YFA0710000)the Fundamental Research Funds for the Central Universities(531118010127)+1 种基金the National Natural Science Foundation of China(22122901,21902047,21825201,and U19A2017)the Provincial Natural Science Foundation of Hunan(2020JJ5045,2021RC3054).
文摘Electrocatalytic valorization of biomass derivatives can be powered by electricity generated from renewable sources such as solar and wind energy.A shift from centralized,high-temperature,and energy-intensive processes to decentralized,low-temperature conversions is achieved,which meets the requirement of sustainable energy generation.This approach provides an efficient,green,and additive-free strategy for biomass derivative valorization,in which product selectivity could be easily regulated by the applied potential and electrocatalyst utilized.However,a scale-up application is still far from being completed due to the inability of conversion rates and selectivity to meet the industrialization requirements.A better understanding of the reaction mechanism and the development of highefficiency and high-selectivity electrocatalysts are required to pave the path toward larger industrialization applications.Herein,we summarize the recent research progress in the electrocatalytic oxidation and hydrogenation of platform compounds such as furanic compounds and glycerol.In the literature,these three research areas are integrated to realize the scale-up application of the processes as mentioned above.The investigations of the mechanism are based on in situ techniques,theoretical calculations,and advanced electrocatalyst studies.Finally,the challenges and prospects in this topic are described.We expect that this review will provide the fundamental understanding and design guidelines to achieve efficient and high-selectivity catalysts and further facilitate the scale-up application of the electrocatalytic conversion of biomass derivatives.
基金supported by the National Natural Science Foundation of China(Grant No.21521092)the Major Scientific and Technological Developing Project of Changchun City(Grant No.17SS013)+1 种基金the Scientific and Technological Developing Project of Jilin Province(Grant No.20180201098GX)the Natural Science Foundation of Jiangsu Province(Grant No.BK20141174)
文摘The improvement of hydrogen storage materials is a key issue for storage and delivery of hydrogen energy before its potential can be realized. As hydrogen storage media, rare-earth hydrogen storage materials have been systematically studied in order to improve storage capacity, kinetics, thermodynamics and electrochemical performance. In this review, we focus on recent research progress of gaseous sorption and electrochemical hydrogen storage properties of rare-earth alloys and highlight their commercial applications including hydrogen storage tanks and nickel metal hydride batteries. Furthermore, development trend and prospective of rare-earth hydrogen storage materials are discussed.
基金the Monash-Warwick Alliance for funding support through the Accelerator Fund。
文摘Replacing conventional fossil resources with renewable raw materials for chemical production and energy generation is crucial for achieving the carbon-neutral goal and alleviating the emerging energy crisis.Biomass has been considered as one of the most promising candidates for this purpose owing to its great natural abundance and inherent ability to fix CO_(2) in the form of multicarbon compounds.Particularly,biomass conversion through an electrochemical route is intriguing because of its operability near ambient conditions,flexible scalability(suitable for distributed manufacturing and even domestic use)and green generation of oxidative or reductive equivalents instead of wasteful and possibly explosive or flammable reagents.Herein,recent progress in electrochemical transformation of biomass,including hydrogenation and amination,is reviewed with the emphasis on catalysts and strategies for enhancing catalytic efficiency.The advances in mechanistic understanding using in-situ spectroscopy are also briefly discussed.Finally,recommendations for the directions for future development are also provided.
基金supported by the National Natural Science Foundation of China(51402078,21702041,and 11674354)the National Basic Research Program of China(2014CB660815)the Fundamental Research Funds for the Central Universities(JZ2016HGTB0711,JZ2016HGTB0719,and JZ2017HGPA0167)
文摘We first report that photoelectrochemical （PEC） performance of electrochemically hydrogenated TiO2 nanotube arrays （TNTAs） as high-efficiency photoanodes for solar water splitting could be well tuned by designing and adjusting the phase structure and composition of TNTAs. Among various TNTAs annealed at different temperature ranging from 300 to 700℃, well-crystallized single anatase （A） phase TNTAs-400 photoanode shows the best photoresponse properties and PEC performance due to the favor- able crystallinity, grain size and tubular structures. After electrochemical hydrogenation （EH）. anatase- rutile （A-R） mixed phase EH-TNTAs-600 photoanode exhibits the highest photoactivity and PEC perfor- mance for solar water splitting. Under simulated solar illumination, EH-TNTAs-600 achieves the best photoconversion efficiency of up to 1.52% and maximum H2 generation rate of 40.4 ~mol h i cm-2, our- stripping other EH-TNTAs photoanodes. Systematic studies reveal that the signigicantly enhanced PEC performance for A-R mixed phaes EH-TNTAs-600 photoanode could be attributed to the synergy of A-R mixed phases and intentionally introduced Ti3~ （oxygen vacancies） which enhances the photoactivity over both UV and visible-light regions, and boosts both charge separation and transfer efficiencies. These findings provide new insight and guidelines for the construction of highly efficient TiO2-based devices for the application of solar water splitting.
基金Special Talents Science and Technology Innovation Project of Shanxi Province of China(201705D211007)Shanxi Provincial Natural Science Foundation of China(201801D121099,201801D221140,201903D421081)。
基金support of the National Natural Science Foundation of China(grant no.22075197)support of the Shanxi Provincial Natural Science Foundation of China(201903D421081)+1 种基金Research and Development Project of Key Core and Common Technology of Shanxi Province(20201102018)support of the Shanxi Provincial Natural Science Foundation of China(201801D221140)
文摘Although TiO_(2)nanotubes is a promising electrode as supercapacitors due to its high energy density,easy synthesis and chemical stability,there are draw backs such as low conductivity and capacitance.Many studies concentrated on improving its electrochemical performance itself but little attention was payed to the reason of capacitance differences caused by its different crystal structures.Herein,we prepare amorphous and anatase TiO_(2)nanotubes and hydrogenated them by a simple electrochemical hydrogenation method to improve their conductivity and capacitance.And then study and compare their morphology and structure differences by SEM,TEM,XRD and BET.The results show that the pore size distribution,internal structure order and internal carrier concentration are the main reasons for their electrochemical performance differences.The microporous structure less than 2 nm in amorphous nanotubes act as a trap of electrolyte ions at current density larger than 0.1μA cm^(-2),leading to small charge and discharge capacitance.The long-range ordered crystal structure of anatase is more favorable for the orderly diffusion of carriers,reducing the inelastic scattering of carrier diffusion process and the electron hole-complexing probability,making anatase nanotubes exhibit higher coulomb efficiency and cycle stability than that of amorphous ones.
