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
Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle ...Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle this challenge by introducing n-hexane as an electrolyte additive to weaken LiClO4 ionization,achieving minimized dissociation via squeezed solvation shells with compact ion pairs.Molecular dynamics simulations and experimental characterizations reveal that n-hexane enriches anion coordination around Li+,endowing the electrolyte with robust anti-reduction capability.This suppresses SEI overgrowth,reduces interfacial resistance,and accelerates N2 diffusion.Consequently,a thinner,inorganic-rich SEI is formed,enabling high nitrogen flux and rapid active Li3N generation kinetics.Consequently,the proof-of-concept system achieves unprecedentedly high Faradaic efficiency of 53.8%±8.2%at 10 mA cm^(−2)and NH_(3) yield rate of 88.57±9.5 nmol s^(−1)cm^(−2)under ambient conditions,making a giant step further toward industrializing the electrochemical ammonia production.展开更多
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia,helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network.Ohmic junct...Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia,helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network.Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination,but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes.In this study,density functional theory(DFT) calculations were used to confirm the work function matching between Bi and Bi_(2)Ti_(2)O_(7)(BTO),ensuring the formation of an Ohmic junction.A Bi-Bi_(2)Ti_(2)O_(7)(B-BTO) composite was successfully synthesized via a one-step hydrothermal method,using bismuth nitrate and titanium sulfate as precursors.Compared to pure BTO,the B-BTO heterojunction,driven by dual electron injection from both metal Bi and BTO,significantly increased the ammonia synthesis rate to 686.95 μmol g^(-1)h^(-1),making it the most active nitrogen fixation material among similar pyrochlorebased catalysts to date.The differential charge density calculations,photocurrent(i-t) measurements,and photoluminescence(PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes.This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.展开更多
The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from ...The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from the hydrogen evolution reaction(HER).A new paradigm capable of transcending current selectivity constraints is urgently required to advance eNRR toward industrial implementation.In this work,we propose two practical selectivity descriptors(ΔΔG andΔU)based on a systematic investigation of the potential-dependent competition between eNRR and HER on confined dual-atom catalysts.The descriptorΔΔG(G_(N_(2))-ΔG_(H))identifies the potential range where N_(2)adsorption dominates over H adsorption,whileΔU(U_(cross)-U_(eNRR))specifies the potential range to trigger direct eNRR,offering a quantitative benchmark for rational catalyst design.Ideal catalysts should maintain N_(2)-preferential adsorption across a broad potential window to facilitate direct eNRR.Guided by this insight,we demonstrate that confined dual-atom configurations with optimized interatomic distances can simultaneously achieve both overwhelming N_(2)adsorption and sufficient activation,thereby overcoming the conventional selectivity limitations.This strategy enables ammonia synthesis with industrially relevant production rates and current density even at elevated potentials.Our mechanistic insights not only elucidate the root causes of performance limitations in eNRR but also offer a rational design framework for developing high-performance catalysts across a broad range of electrochemical transformations.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
In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry bet...In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry between corresponding building blocks and linking units in addition to the unmanageable packing of 1D organic chains once formed.Herein,two novel imide-linked 1D COFs with phthalocyanine building blocks,namely NiPc-CZDM-COF and NiPc-CZDL-COF,were fabricated from the hydrothermal synthesis reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(II)(NiPc(COOH)_(8))with 9H-carbazole-3,6-diamine(CZDM)and 4,4′-(9H-carbazole-3,6-diyl)dianiline(CZDL),respectively.Two COFs have high crystallinity on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy.Due to their high ratio of exposed active centers on the edge sites of porous ribbons,both NiPc-CZDM-COF and NiPc-CZDL-COF electrodes display high utilization efficiency of NiPc electroactive sites of 8.0%and 7.5% according to the electrochemical measurement,resulting in their excellent capacity toward electrocatalytic nitrate reduction with the nitrate-to-NH3 Faradaic efficiency of nearly 100%.In particular,NiPc-CZDM-COF electrode exhibits superior electrocatalytic performance with high NH3 partial current density of−246 mA/cm^(2),ammonia yield rate of 19.5 mg cm^(−2) h^(−1),and turnover frequency of 5.8 s^(−1) at−1.2 V in an H-type cell associated with its higher conductivity.This work reveals the good potential of 1D porous crystalline materials in electrocatalysis.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supported by the National Natural Science Foundation of China (Grant No. U21A20332)support from the Collaborative Innovation Center of Suzhou Nano Science and Technology
文摘Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle this challenge by introducing n-hexane as an electrolyte additive to weaken LiClO4 ionization,achieving minimized dissociation via squeezed solvation shells with compact ion pairs.Molecular dynamics simulations and experimental characterizations reveal that n-hexane enriches anion coordination around Li+,endowing the electrolyte with robust anti-reduction capability.This suppresses SEI overgrowth,reduces interfacial resistance,and accelerates N2 diffusion.Consequently,a thinner,inorganic-rich SEI is formed,enabling high nitrogen flux and rapid active Li3N generation kinetics.Consequently,the proof-of-concept system achieves unprecedentedly high Faradaic efficiency of 53.8%±8.2%at 10 mA cm^(−2)and NH_(3) yield rate of 88.57±9.5 nmol s^(−1)cm^(−2)under ambient conditions,making a giant step further toward industrializing the electrochemical ammonia production.
基金supported by the Natural Science Foundation of China (NSFC,No.52372212)。
文摘Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia,helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network.Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination,but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes.In this study,density functional theory(DFT) calculations were used to confirm the work function matching between Bi and Bi_(2)Ti_(2)O_(7)(BTO),ensuring the formation of an Ohmic junction.A Bi-Bi_(2)Ti_(2)O_(7)(B-BTO) composite was successfully synthesized via a one-step hydrothermal method,using bismuth nitrate and titanium sulfate as precursors.Compared to pure BTO,the B-BTO heterojunction,driven by dual electron injection from both metal Bi and BTO,significantly increased the ammonia synthesis rate to 686.95 μmol g^(-1)h^(-1),making it the most active nitrogen fixation material among similar pyrochlorebased catalysts to date.The differential charge density calculations,photocurrent(i-t) measurements,and photoluminescence(PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes.This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
基金supported by the Taishan Scholar Program of Shandong Province(tsqn202507090)Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(CPSF)(GZB20250022)+1 种基金Natural Science Foundation of Shandong Province(ZR2025QC1086)Young Talents Project at Ocean University of China。
文摘The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from the hydrogen evolution reaction(HER).A new paradigm capable of transcending current selectivity constraints is urgently required to advance eNRR toward industrial implementation.In this work,we propose two practical selectivity descriptors(ΔΔG andΔU)based on a systematic investigation of the potential-dependent competition between eNRR and HER on confined dual-atom catalysts.The descriptorΔΔG(G_(N_(2))-ΔG_(H))identifies the potential range where N_(2)adsorption dominates over H adsorption,whileΔU(U_(cross)-U_(eNRR))specifies the potential range to trigger direct eNRR,offering a quantitative benchmark for rational catalyst design.Ideal catalysts should maintain N_(2)-preferential adsorption across a broad potential window to facilitate direct eNRR.Guided by this insight,we demonstrate that confined dual-atom configurations with optimized interatomic distances can simultaneously achieve both overwhelming N_(2)adsorption and sufficient activation,thereby overcoming the conventional selectivity limitations.This strategy enables ammonia synthesis with industrially relevant production rates and current density even at elevated potentials.Our mechanistic insights not only elucidate the root causes of performance limitations in eNRR but also offer a rational design framework for developing high-performance catalysts across a broad range of electrochemical transformations.
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supported by the Natural Science Foundation(NSF)of China(Nos.22205015,22175020,and 22235001)the National Postdoctoral Program for Innovative Talents(No.BX20220032)+2 种基金the China Postdoctoral Science Foundation Funded Project(No.2022BG013)the Fundamental Research Funds for the Central Universities(Nos.00007709,00007770,and FRFBR-23-02B)University of Science and Technology Beijing is gratefully acknowledged.
文摘In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry between corresponding building blocks and linking units in addition to the unmanageable packing of 1D organic chains once formed.Herein,two novel imide-linked 1D COFs with phthalocyanine building blocks,namely NiPc-CZDM-COF and NiPc-CZDL-COF,were fabricated from the hydrothermal synthesis reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(II)(NiPc(COOH)_(8))with 9H-carbazole-3,6-diamine(CZDM)and 4,4′-(9H-carbazole-3,6-diyl)dianiline(CZDL),respectively.Two COFs have high crystallinity on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy.Due to their high ratio of exposed active centers on the edge sites of porous ribbons,both NiPc-CZDM-COF and NiPc-CZDL-COF electrodes display high utilization efficiency of NiPc electroactive sites of 8.0%and 7.5% according to the electrochemical measurement,resulting in their excellent capacity toward electrocatalytic nitrate reduction with the nitrate-to-NH3 Faradaic efficiency of nearly 100%.In particular,NiPc-CZDM-COF electrode exhibits superior electrocatalytic performance with high NH3 partial current density of−246 mA/cm^(2),ammonia yield rate of 19.5 mg cm^(−2) h^(−1),and turnover frequency of 5.8 s^(−1) at−1.2 V in an H-type cell associated with its higher conductivity.This work reveals the good potential of 1D porous crystalline materials in electrocatalysis.
