Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achievin...Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achieving water splitting due to severe charge recombination.Herein,we elucidate an innovative approach involving the incorporation of single Ru atom with a CoFe-LDH cocatalyst(Ru_(0.51)-CoFe-LDH)and integrating it onto the BiVO_(4)semiconductor substrate.The resulting Ru_(0.51)-CoFe-LDH/BiVO_(4)photoanode film demonstrates commendable charge injection efficiency(76%)and charge collection efficiency(100%).Interestingly,the yield of hydrogen and oxygen increases linearly at a stoichiometric ratio of about 2:1,reaching 158.6 and 67.4μmol after140 min of irradiation,respectively.According to experimental characterization and density functional theory calculation,this remarkable performance results from single Ru atoms triggering the electron rearrangement of Ru_(0.51)-CoFe-LDH to engineer active sites and optimize interfacial energetics.Additionally,the negative shift of Ru_(0.51)-CoFe-LDH band edge gives rise to more conspicuous band bending of the n-n junction formed with BiVO_(4),expediting the separation and transfer of photogenerated electron-hole pairs at the interface.This work furnishes a new preparation perspective for PEC water splitting systems to construct single atoms in the semiconductor substrate.展开更多
Carbon dioxide(CO_(2))emission significantly impacts global climate change,emerging as a critical developmental issue for humanity.Carbon cycling has been established as an effective strategy to address this challenge...Carbon dioxide(CO_(2))emission significantly impacts global climate change,emerging as a critical developmental issue for humanity.Carbon cycling has been established as an effective strategy to address this challenge.Consequently,the conversion of atmospheric CO_(2)into commercially valuable carbon via catalytic reaction pathways presents substantial potential.Rare metals exhibit unique properties,including high-temperature resistance,corrosion resistance,substantial hardness,and commendable electrical and thermal conductivity.Research advancements concerning rare metals have substantiated their potential environmental and economic advantages.Herein,we first summarize the fundamental concepts and applications of electrocatalysis,photocatalysis,photoelectrocatalysis,and photothermal catalysis in CO_(2)reduction(CO_(2)R)reactions(CO_(2)RRs).The catalysts are classified at the atomic scale,and the influence of catalysts on CO_(2)RRs at this scale is discussed.Second,we thoroughly examine the relationship between rare metal materials and the selectivity of CO_(2)R products.Third,we provide a comprehensive overview of the latest advancements in the application of rare metals in CO_(2)R,as well as the reaction mechanisms of CO_(2)R catalysts,through the lens of advanced characterization technologies.Finally,we propose potential opportunities and future directions for the development of rare metals in CO_(2)R.展开更多
The oxidative upgrading of organic compounds is essential for synthesizing value-added chemicals that support various industries,including pharmaceuticals,agrochemicals,and materials science.Aerobic oxidation,using mo...The oxidative upgrading of organic compounds is essential for synthesizing value-added chemicals that support various industries,including pharmaceuticals,agrochemicals,and materials science.Aerobic oxidation,using molecular O_(2)(or air)as a green oxidant,offers a more sustainable alternative to traditional oxidation methods that rely on hazardous or strong toxic oxidants.However,conventional thermal aerobic oxidation processes typically require high temperatures,resulting in a significant carbon footprint.In contrast,using green energy sources(e.g.,solar energy and electricity)as driving forces provides a more environmentally friendly approach for aerobic oxidation reactions.In this mini review,we summarize innovative approaches to aerobic oxidation reactions for upgrading organic compounds,including photocatalytic,electrochemical,and photoelectrochemical processes.For each approach,we place particular emphasis on the key design principle,representative oxidation reactions,reaction mechanisms,and notable achievements.Additionally,we discuss the challenges and prospects for promoting these emerging technologies,highlighting their potential to drive advancements toward sustainability in organic oxidation reactions.展开更多
The lower electricity consumption(EC)and higher value-added products are much desired yet still challenging for the development of CO_(2) coupling electrocatalytic systems.Herein,we give insight into the inherent natu...The lower electricity consumption(EC)and higher value-added products are much desired yet still challenging for the development of CO_(2) coupling electrocatalytic systems.Herein,we give insight into the inherent nature of the retrenchment of EC by exploring the photo-assisted co-electrolysis of methanol and CO_(2) system using a kind of hydroxyl-rich covalent organic frameworks(Dha-COF-Co)with well-tuned pore structure and morphology.Specifically,the hydroxyl induced hydrogen bond interaction in Dha-COF-Co enables to simultaneously regulate the pore microenvironment and nanoribbon morphology of COFs for performance boosting.Notably,the obtained Dha-COF-Co nanoribbon exhibits an overall EC retrenchment of~41.2%(highest in porous crystalline materials to date)when replacing the anodic OER with MOR in the photo-electrocatalytic MOR-CO_(2)RR coupling system,as well as superior FEHCOOH(anode,~100%)and FE_(CO)(cathode,>95%)at 1.8 V.Combined theoretical calculations with various characterizations,the vital role of hydroxyl group in both microenvironment and morphology tuning that can facilitate the CO_(2)RR and MOR kinetics to retrench the EC has been intensively discussed.展开更多
基金financially supported by the Hunan Provincial Natural Science Foundation for Distinguished Young Scholars(2025JJ20019)the National Key R&D Program of China(2025YFE0107600)。
文摘Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achieving water splitting due to severe charge recombination.Herein,we elucidate an innovative approach involving the incorporation of single Ru atom with a CoFe-LDH cocatalyst(Ru_(0.51)-CoFe-LDH)and integrating it onto the BiVO_(4)semiconductor substrate.The resulting Ru_(0.51)-CoFe-LDH/BiVO_(4)photoanode film demonstrates commendable charge injection efficiency(76%)and charge collection efficiency(100%).Interestingly,the yield of hydrogen and oxygen increases linearly at a stoichiometric ratio of about 2:1,reaching 158.6 and 67.4μmol after140 min of irradiation,respectively.According to experimental characterization and density functional theory calculation,this remarkable performance results from single Ru atoms triggering the electron rearrangement of Ru_(0.51)-CoFe-LDH to engineer active sites and optimize interfacial energetics.Additionally,the negative shift of Ru_(0.51)-CoFe-LDH band edge gives rise to more conspicuous band bending of the n-n junction formed with BiVO_(4),expediting the separation and transfer of photogenerated electron-hole pairs at the interface.This work furnishes a new preparation perspective for PEC water splitting systems to construct single atoms in the semiconductor substrate.
基金the National Natural Science Foundation of China(No.52172206)Natural Science Foundation of Shandong province(No.ZR2023QB110)+3 种基金Basic Research Projects for the Pilot Project of Integrating Science,Education and Industry of Qilu University of Technology(Shandong Academy of Sciences)(No.2023PX108)the Talent research projects of Qilu University of Technology(Shandong Academy of Sciences)(No.2023RCKY099)Taishan Scholars Projectthe Development Plan of Youth Innovation Team in Colleges and Universities of Shandong Province。
文摘Carbon dioxide(CO_(2))emission significantly impacts global climate change,emerging as a critical developmental issue for humanity.Carbon cycling has been established as an effective strategy to address this challenge.Consequently,the conversion of atmospheric CO_(2)into commercially valuable carbon via catalytic reaction pathways presents substantial potential.Rare metals exhibit unique properties,including high-temperature resistance,corrosion resistance,substantial hardness,and commendable electrical and thermal conductivity.Research advancements concerning rare metals have substantiated their potential environmental and economic advantages.Herein,we first summarize the fundamental concepts and applications of electrocatalysis,photocatalysis,photoelectrocatalysis,and photothermal catalysis in CO_(2)reduction(CO_(2)R)reactions(CO_(2)RRs).The catalysts are classified at the atomic scale,and the influence of catalysts on CO_(2)RRs at this scale is discussed.Second,we thoroughly examine the relationship between rare metal materials and the selectivity of CO_(2)R products.Third,we provide a comprehensive overview of the latest advancements in the application of rare metals in CO_(2)R,as well as the reaction mechanisms of CO_(2)R catalysts,through the lens of advanced characterization technologies.Finally,we propose potential opportunities and future directions for the development of rare metals in CO_(2)R.
基金support from the National Key R&D Program of China(grant no.2023YFA1507201)the National Natural Science Foundation of China(grant nos.22421005,52120105002,52432006,and 22088102)the Chinese Academy of Sciences(CAS)Project for Young Scientists in Basic Research(grant no.YSBR-004).
文摘The oxidative upgrading of organic compounds is essential for synthesizing value-added chemicals that support various industries,including pharmaceuticals,agrochemicals,and materials science.Aerobic oxidation,using molecular O_(2)(or air)as a green oxidant,offers a more sustainable alternative to traditional oxidation methods that rely on hazardous or strong toxic oxidants.However,conventional thermal aerobic oxidation processes typically require high temperatures,resulting in a significant carbon footprint.In contrast,using green energy sources(e.g.,solar energy and electricity)as driving forces provides a more environmentally friendly approach for aerobic oxidation reactions.In this mini review,we summarize innovative approaches to aerobic oxidation reactions for upgrading organic compounds,including photocatalytic,electrochemical,and photoelectrochemical processes.For each approach,we place particular emphasis on the key design principle,representative oxidation reactions,reaction mechanisms,and notable achievements.Additionally,we discuss the challenges and prospects for promoting these emerging technologies,highlighting their potential to drive advancements toward sustainability in organic oxidation reactions.
基金supported by the National Key R&D Program of China(No.2023YFA1507204).The National Natural Science Foundation of China(Nos.22225109,22309054,22171139,22071109,22371080,22201084)China Postdoctoral Science Foundation(Nos.2023M731154,2023M731155,and 2023T160236)+2 种基金China National Postdoctoral Program for Innovative Talents(No.BX20220116)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515013220)Natural Science Foundation of Guangdong Province(No.2023B1515020076).
文摘The lower electricity consumption(EC)and higher value-added products are much desired yet still challenging for the development of CO_(2) coupling electrocatalytic systems.Herein,we give insight into the inherent nature of the retrenchment of EC by exploring the photo-assisted co-electrolysis of methanol and CO_(2) system using a kind of hydroxyl-rich covalent organic frameworks(Dha-COF-Co)with well-tuned pore structure and morphology.Specifically,the hydroxyl induced hydrogen bond interaction in Dha-COF-Co enables to simultaneously regulate the pore microenvironment and nanoribbon morphology of COFs for performance boosting.Notably,the obtained Dha-COF-Co nanoribbon exhibits an overall EC retrenchment of~41.2%(highest in porous crystalline materials to date)when replacing the anodic OER with MOR in the photo-electrocatalytic MOR-CO_(2)RR coupling system,as well as superior FEHCOOH(anode,~100%)and FE_(CO)(cathode,>95%)at 1.8 V.Combined theoretical calculations with various characterizations,the vital role of hydroxyl group in both microenvironment and morphology tuning that can facilitate the CO_(2)RR and MOR kinetics to retrench the EC has been intensively discussed.
