Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances ar...Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances are far from practical needs due to the lack of efficient electrocatalysts.Engineering the lattice of metal-based nanomaterials via phase control has emerged as an effective strategy to modulate their intrinsic electrocatalytic properties.Herein,we realize boron(B)-insertion-induced phase regulation of rhodium(Rh)nanocrystals to obtain amorphous Rh_(4)B nanoparticles(NPs)and hexagonal close-packed(hcp)RhB NPs through a facile wet-chemical method.A high Faradaic efficiency(92.1±1.2%)and NH_(3) yield rate(629.5±11.0μmol h^(−1) cm^(−2))are achieved over hcp RhB NPs,far superior to those of most reported NORR nanocatalysts.In situ spectro-electrochemical analysis and density functional theory simulations reveal that the excellent electrocatalytic performances of hcp RhB NPs are attributed to the upshift of d-band center,enhanced NO adsorption/activation profile,and greatly reduced energy barrier of the rate-determining step.A demonstrative Zn-NO battery is assembled using hcp RhB NPs as the cathode and delivers a peak power density of 4.33 mW cm−2,realizing simultaneous NO removal,NH3 synthesis,and electricity output.展开更多
Green ammonia,produced by harnessing renewable solar energy to split nitrogen,plays a pivotal role in both agricultural practices and forthcoming energy configurations,driving the sustainable development of human soci...Green ammonia,produced by harnessing renewable solar energy to split nitrogen,plays a pivotal role in both agricultural practices and forthcoming energy configurations,driving the sustainable development of human society with zero-carbon emissions.However,nitrogen photoreduction currently faces the challenges of poor activation ability and low yield,and it is still challenging to unravel the intertwined problems in this field and provide direction for its development due to the complex reaction mechanism and multidisciplinary aspects such as photochemistry,catalysis,interface science,and technology.This review focuses on capturing the latest advances in photocatalytic nitrogen-to-ammonia conversion,delving into fundamental principles regarding the process,efficient photocatalysts for practical ammonia synthesis,and well-designed catalytic environments.Besides,this article provides insightful guidelines for analyzing complicated reaction mechanisms and identifying key bottlenecks or specific rate-determining steps,such as reactant activation,interfacial reaction engineering,and hydrogen evolution side reactions.By integrating perspectives from atomic mechanisms,nanoscale photocatalysts,microscale interfacial engineering,and macroscale reaction system design,this review advances the development of nitrogen photoreduction from proof-of-concept discoveries to viable solar-to-chemical conversion technologies,while also providing a valuable entry point for researchers into this burgeoning field.展开更多
Electrocatalytic nitrate reduction reaction(NO3RR)represents a sustainable and environmentally benign route for ammonia(NH3)synthesis.However,NO3RR is still limited by the competition from hydrogen evolution reaction(...Electrocatalytic nitrate reduction reaction(NO3RR)represents a sustainable and environmentally benign route for ammonia(NH3)synthesis.However,NO3RR is still limited by the competition from hydrogen evolution reaction(HER)and the high energy barrier in the hydrogenation step of nitrogen-containing intermediates.Here,we report a selective etching strategy to construct Ru M nanoalloys(M=Fe,Co,Ni,Cu)uniformly dispersed on porous nitrogen-doped carbon substrates for efficient neutral NH3electrosynthesis.Density functional theory calculations confirm that the synergic effect between Ru and transition metal M modulates the electronic structure of the alloy,significantly lowering the energy barrier for the conversion of*NO_(2)to*HNO_(2).Experimentally,the optimized Ru Fe-NC catalyst achieves 100%Faraday efficiency with a high yield rate of 0.83 mg h^(-1)mg^(-1)catat a low potential of-0.1 V vs.RHE,outperforming most reported catalysts.In situ spectroscopic analyses further demonstrate that the Ru M-NC effectively promotes the hydrogenation of nitrogen intermediates while inhibiting the formation of hydrogen radicals,thereby reducing HER competition.The Ru FeNC assembled Zn-NO_(3)^(-)battery achieved a high open-circuit voltage and an outstanding power density and capacity,which drive selective NO_(3)^(-)conversion to NH3.This work provides a powerful synergistic design strategy for efficient NH3electrosynthesis and a general framework for the development of advanced multi-component catalysts for sustainable nitrogen conversion.展开更多
Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate...Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate reduction(eNO_(3)RR)emerges as an attractive strategy to simultaneously enable nitrate removal and decentralized ammo-nia fabrication,restoring the globally perturbed nitrogen cycle.However,complex deoxygenation-hydrogenationprocesses and sluggish proton-electron transfer kinetics significantly hinder practical application of eNO_(3)RR.In this study,we developed carbon-coated Cu-Ni bimetallic catalysts derived from metal-organic frameworks(MOFs)to facilitate eNO_(3)RR.The unique structural features of catalyst promote enhanced synergy between Cuand Ni,effectively addressing critical challenges in nitrate reduction.Comprehensive structural and electrochem-ical analysis demonstrate that electrochemical nitrate-to-nitrite conversion mainly takes place on active Cu sites,the introduction of Ni could efficiently accelerate the generation of aquatic active hydrogen,promoting the hy-drogenation of oxynitrides during eNO_(3)RR.In addition,Ni introduction could push up the d-band center of thecatalyst,thus enhancing the adsorption and activation of nitrate and the corresponding intermediates.Detailedreaction pathways for nitrate-to-ammonia conversion are illuminated by rotating disk electrode(RDE),in-situFourier-transform infrared spectroscopy,in-situ Raman spectrum and electrochemical impedance spectroscopy(EIS).Benefiting from the synergistic effect of Cu and Ni,optimum catalyst exhibited excellent nitrate reductionperformance.This work provides a new idea for elucidating the underlying eNO_(3)RR reaction mechanisms andcontributes a promising strategy for designing efficient bimetallic electrocatalysts.展开更多
基金funding support from General Research Fund[Project No.14300525]from the Research Grants Council(RGC)of Hong Kong SAR,Chinafunding support from Natural Science Foundation of China(NSFC)Young Scientists Fund(Project No.22305203)+2 种基金NSFC Projects Nos.22309123,22422303,22303011,22033002,92261112 and U21A20328support from the Hong Kong Branch of National Precious Metals Material Engineering Research Center(NPMM)at City University of Hong Kongsupport from Young Collaborative Research Grant[Project No.C1003-23Y]support from RGC of Hong Kong SAR,China.
文摘Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances are far from practical needs due to the lack of efficient electrocatalysts.Engineering the lattice of metal-based nanomaterials via phase control has emerged as an effective strategy to modulate their intrinsic electrocatalytic properties.Herein,we realize boron(B)-insertion-induced phase regulation of rhodium(Rh)nanocrystals to obtain amorphous Rh_(4)B nanoparticles(NPs)and hexagonal close-packed(hcp)RhB NPs through a facile wet-chemical method.A high Faradaic efficiency(92.1±1.2%)and NH_(3) yield rate(629.5±11.0μmol h^(−1) cm^(−2))are achieved over hcp RhB NPs,far superior to those of most reported NORR nanocatalysts.In situ spectro-electrochemical analysis and density functional theory simulations reveal that the excellent electrocatalytic performances of hcp RhB NPs are attributed to the upshift of d-band center,enhanced NO adsorption/activation profile,and greatly reduced energy barrier of the rate-determining step.A demonstrative Zn-NO battery is assembled using hcp RhB NPs as the cathode and delivers a peak power density of 4.33 mW cm−2,realizing simultaneous NO removal,NH3 synthesis,and electricity output.
基金financially supported by the National Energy Green Hydrogen Refining Research&Development Center,National Natural Science Foundation of China(No.22476222)Natural Science Funds of Guangdong for Distinguished Young Scholar(No.2022B1515020098).
文摘Green ammonia,produced by harnessing renewable solar energy to split nitrogen,plays a pivotal role in both agricultural practices and forthcoming energy configurations,driving the sustainable development of human society with zero-carbon emissions.However,nitrogen photoreduction currently faces the challenges of poor activation ability and low yield,and it is still challenging to unravel the intertwined problems in this field and provide direction for its development due to the complex reaction mechanism and multidisciplinary aspects such as photochemistry,catalysis,interface science,and technology.This review focuses on capturing the latest advances in photocatalytic nitrogen-to-ammonia conversion,delving into fundamental principles regarding the process,efficient photocatalysts for practical ammonia synthesis,and well-designed catalytic environments.Besides,this article provides insightful guidelines for analyzing complicated reaction mechanisms and identifying key bottlenecks or specific rate-determining steps,such as reactant activation,interfacial reaction engineering,and hydrogen evolution side reactions.By integrating perspectives from atomic mechanisms,nanoscale photocatalysts,microscale interfacial engineering,and macroscale reaction system design,this review advances the development of nitrogen photoreduction from proof-of-concept discoveries to viable solar-to-chemical conversion technologies,while also providing a valuable entry point for researchers into this burgeoning field.
基金financially supported by National Natural Science Foundation of China(22466010)Guizhou Provincial Basic Research Program(Natural Science)ZK[2023]47 and key program ZD[2025]075+6 种基金Innovation and Entrepreneurship Project for overseas Talents in Guizhou Province[2022]02Specific Natural Science Foundation of Guizhou University(X202207)the national undergraduate innovation and entrepreneurship training program(gzugc2023006gzusc2024012)SRT project of Guizhou university(2023SRT0292023SRT024)supported by Shanghai Technical Service Center of Science and Engineering Computing,Shanghai University。
文摘Electrocatalytic nitrate reduction reaction(NO3RR)represents a sustainable and environmentally benign route for ammonia(NH3)synthesis.However,NO3RR is still limited by the competition from hydrogen evolution reaction(HER)and the high energy barrier in the hydrogenation step of nitrogen-containing intermediates.Here,we report a selective etching strategy to construct Ru M nanoalloys(M=Fe,Co,Ni,Cu)uniformly dispersed on porous nitrogen-doped carbon substrates for efficient neutral NH3electrosynthesis.Density functional theory calculations confirm that the synergic effect between Ru and transition metal M modulates the electronic structure of the alloy,significantly lowering the energy barrier for the conversion of*NO_(2)to*HNO_(2).Experimentally,the optimized Ru Fe-NC catalyst achieves 100%Faraday efficiency with a high yield rate of 0.83 mg h^(-1)mg^(-1)catat a low potential of-0.1 V vs.RHE,outperforming most reported catalysts.In situ spectroscopic analyses further demonstrate that the Ru M-NC effectively promotes the hydrogenation of nitrogen intermediates while inhibiting the formation of hydrogen radicals,thereby reducing HER competition.The Ru FeNC assembled Zn-NO_(3)^(-)battery achieved a high open-circuit voltage and an outstanding power density and capacity,which drive selective NO_(3)^(-)conversion to NH3.This work provides a powerful synergistic design strategy for efficient NH3electrosynthesis and a general framework for the development of advanced multi-component catalysts for sustainable nitrogen conversion.
基金supported by the Natural Science Foundation of China(No.52101279)the Key Scientific Research Foundation of Education department of Hunan Province(No.24A0003)the Scientific Research Project of Education Department of Hunan Province(No.21B000)and the Fundamental Research Funds for the Central Universities of Central South University.
文摘Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate reduction(eNO_(3)RR)emerges as an attractive strategy to simultaneously enable nitrate removal and decentralized ammo-nia fabrication,restoring the globally perturbed nitrogen cycle.However,complex deoxygenation-hydrogenationprocesses and sluggish proton-electron transfer kinetics significantly hinder practical application of eNO_(3)RR.In this study,we developed carbon-coated Cu-Ni bimetallic catalysts derived from metal-organic frameworks(MOFs)to facilitate eNO_(3)RR.The unique structural features of catalyst promote enhanced synergy between Cuand Ni,effectively addressing critical challenges in nitrate reduction.Comprehensive structural and electrochem-ical analysis demonstrate that electrochemical nitrate-to-nitrite conversion mainly takes place on active Cu sites,the introduction of Ni could efficiently accelerate the generation of aquatic active hydrogen,promoting the hy-drogenation of oxynitrides during eNO_(3)RR.In addition,Ni introduction could push up the d-band center of thecatalyst,thus enhancing the adsorption and activation of nitrate and the corresponding intermediates.Detailedreaction pathways for nitrate-to-ammonia conversion are illuminated by rotating disk electrode(RDE),in-situFourier-transform infrared spectroscopy,in-situ Raman spectrum and electrochemical impedance spectroscopy(EIS).Benefiting from the synergistic effect of Cu and Ni,optimum catalyst exhibited excellent nitrate reductionperformance.This work provides a new idea for elucidating the underlying eNO_(3)RR reaction mechanisms andcontributes a promising strategy for designing efficient bimetallic electrocatalysts.
