As a promising fuel candidate,ammonia has been successtully used as anode feed in alkaline fuel cells.However,current technology in catalysts for ammonia electro-oxidation reaction(AOR)with respect to both cost and pe...As a promising fuel candidate,ammonia has been successtully used as anode feed in alkaline fuel cells.However,current technology in catalysts for ammonia electro-oxidation reaction(AOR)with respect to both cost and performance is inadequate to ensure large scale commercial application of direct ammonia fuel cells.Recent studies found that alloying Pt with different transition metals and controlling the morphology of catalysts can improve the AOR activity,and thus potentially can solve the cost issue.Herein,(100)-terminated Pt-M nanocubes(M=3d-transition metals Fe,Co,Ni,Zn)are synthesized via wet-chemistry method and their catalytic activities toward AOR are evaluated.The addition of Fe,Co,Ni and Zn elements can enhance the AOR activity due to decrease in oxophilicity of platinum and bifunctional mechanism.Pt-Zn exhibits the maximum mass activity and specific ativity with values of 0.41 A/mgpt and 169 mA/cm2 that are 1.6 and 1.8 times higher than Pt nanocubes,respectively.Pt-Fe,Pt-Co and PI-Ni nanocubes also ilustrate higher mass and specific activities compared to Pt nanocubes.展开更多
Electrocatalytic ammonia oxidation reaction(EAOR)provides an ideal solution for on-board hydrogen supply for fuel cells,while the lack of efficient and durable EAOR catalysts has been a long-standing obstacle for its ...Electrocatalytic ammonia oxidation reaction(EAOR)provides an ideal solution for on-board hydrogen supply for fuel cells,while the lack of efficient and durable EAOR catalysts has been a long-standing obstacle for its practical application.Herein,we reported that the defect engineering via in-situ electrochemically introducing oxygen vacancies(Vo)not only turns the inactive CuO into efficient EAOR catalyst but also achieves a high stability of over 400 h at a high current density of~200 mA·cm^(−2).Theoretical simulation reveals that the presence of Vo on the CuO surface induces a remarkable upshift of the d-band center of active Cu site closer to the Fermi level,which significantly stabilizes the reaction intermediates(*NHx)and efficiently oxidizes NH3 into N2.This Vo-modulated CuO shows a different catalytic mechanism from that on the conventional Pt-based catalysts,paving a new avenue to develop inexpensive,efficient,and robust catalysts,not limited to EAOR.展开更多
It is still a lack of bifunctional catalysts for ammonia oxidation reaction(AOR)and hydrogen evolution reaction(HER)due to their different reaction mechanisms.In this work,P is doped into PtZn alloy by calcination wit...It is still a lack of bifunctional catalysts for ammonia oxidation reaction(AOR)and hydrogen evolution reaction(HER)due to their different reaction mechanisms.In this work,P is doped into PtZn alloy by calcination with NaH_(2)PO_(2) as P source to induce the lattice tensile strain of Pt and the electronic interaction between P and Zn,which optimizes the AOR and HER activity simultaneously.The sample with the optimal P content can drive the AOR peak current density of 293.6 mA·mgPt^(-1),which is almost 2.7 times of Pt.For HER,the overpotential at^(-1)0 mA·cm^(-2) is only 23 mV with Tafel slope of 34.1 mV·dec^(-1).Furthermore,only 0.59 V is needed to obtain 50 mA·mgPt^(-1) for ammonia electrolysis under a two-electrode system.Therefore,this work shows an ingenious method to design bifunctional catalysts for ammonia electrolysis.展开更多
Efficiently utilizing ammonia(carbon-free fuel)via low-temperature fuel cells is severely hindered by the sluggish kinetics of ammonia oxidation reaction(AOR).Herein,platinum-iridium-tungsten nanocubes(PtIrW-NCBs)with...Efficiently utilizing ammonia(carbon-free fuel)via low-temperature fuel cells is severely hindered by the sluggish kinetics of ammonia oxidation reaction(AOR).Herein,platinum-iridium-tungsten nanocubes(PtIrW-NCBs)with exposed{100}-rich facets were synthesized by a glucose-assisted solvent-thermal method,in which alloying W not only can facilitate the formation of such specific nanostructures to expose more active sites for AOR,but also modulate the electronic structure of PtIr to promote the kinetics of AOR.The PtIrW-NCBs featuring the small nanoparticle size of 5.05±0.07 nm exhibit superior AOR performance,wherein the onset potential is down to 0.319 V and the mass activity is 30.15 A g_((PGM=Pt,Ir))^(-1)at 0.50 V vs.RHE,significantly higher than those of reported majority of AOR catalysts and even commercial PtIr/C.Meanwhile,in situ Fourier transform infrared spectroscopy measurement further reveals that AOR on PtIrW-NCBs dominantly undergoes the dimerization path of NH_(x)(1≤x≤2).In addition,the theoretical calculations also identify that alloying W into PtIr can contribute additional electrons to 5d orbitals of PtIr,enabling the d-band center approaching the Femi level,which in turn induces the high-filling of bonding orbitals of N-N bond in^(*)N_(2)H_(4),promoting the dimerization of^(*)NH_(2)to^(*)N_(2)H_(4)and thus leading to high AOR activity of PtIrW.This work provides new insights for designing efficient AOR electrocatalysts.展开更多
Electrochemical nitrogen looping represents a promising carbon-free and sustainable solution for the energy transition,in which electrochemical ammonia oxidation stays at the central position.However,the various nitro...Electrochemical nitrogen looping represents a promising carbon-free and sustainable solution for the energy transition,in which electrochemical ammonia oxidation stays at the central position.However,the various nitrogen-containing intermediates tend to poison and corrode the electrocatalysts,even the state-of-the-art noble-metal ones,which is worsened at a high applied potential.Herein,we present an ultrarapid laser quenching strategy for constructing a corrosion-resistant and nanostructured CuNi alloy metallic glass electrocatalyst.In this material,single-atom Cu species are firmly bonded with the surrounding Ni atoms,endowing exceptional resistance against ammonia corrosion relative of conventional CuNi alloys.Remarkably,a record-high durability for over 300 h is achieved.Ultrarapid quenching also allows a much higher Cu content than typical single-atom alloys,simultaneously yielding a high rate and selectivity for ammonia oxidation reaction(AOR).Consequently,an outstanding ammonia conversion rate of up to 95%is achieved with 91.8%selectivity toward nitrite after 8 h.Theoretical simulations reveal that the structural amorphization of CuNi alloy could effectively modify the electronic configuration and reaction pathway,generating stable singleatom Cu active sites with low kinetic barriers for AOR.This ultrarapid laser quenching strategy thus provides a new avenue for constructing metallic glasses with well-defined nanostructures,presenting feasible opportunities for performance enhancement for AOR and other electrocatalytic processes.展开更多
As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.With...As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.Within this context,the electrocatalytic ammonia oxidation reaction(AOR)is pivotal.Platinum(Pt),recognized as the most efficient AOR catalyst,has undergone extensive development over the years,yielding notable advancements across various domains,ranging from elucidating the reaction mechanism to exploring innovative materials.This review begins by elucidating the mechanism of ammonia oxidation,summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods.Subsequently,it outlines the research progress surrounding different Pt-based catalysts,followed by a discussion on standard protocols for electrochemical ammonia oxidation testing,which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts.Moreover,the review addresses current challenges in ammonia oxidation and outlines potential future directions,providing a comprehensive outlook on the field.展开更多
The oxophilicity of metal oxides is usually utilized to improve the ammonia oxidation reaction(AOR)activity of Pt-based catalysts.But the effect of strong interaction between Pt and metal oxides on AOR is not studied....The oxophilicity of metal oxides is usually utilized to improve the ammonia oxidation reaction(AOR)activity of Pt-based catalysts.But the effect of strong interaction between Pt and metal oxides on AOR is not studied.Herein,experimental and density functional theory calculation results indicate that a strong interaction is built between Pt and reducible CeOx by high-temperature reduction,which induces the electronic interaction due to the difference of work fu nction,then optimizing the competitive adsorption behavior of*OH and*NH_(3)based on hard-soft acid-base principle.Accordingly,the optimal sample achieves an AOR peak current density of 329 mA mg_(Pt)^(-1),which is 2.4 times that of Pt.Meanwhile,it also shows satisfied hydrogen evolution reaction activity with an overpotential of only 24.3 mV at-10 mA cm^(-2)due to the optimization of*H adsorption energy on Pt by CeO_(x).Therefore,this work proposes an AOR activity enhancement mechanism of metal oxides in terms of the strong interaction,and sheds light on developing effective bifunctional catalysts for ammonia electrolysis.展开更多
The ammonia electrolysis is a highly efficient and energy-saving method for ultra-pure hydrogen generation, which highly relies on electrocatalytic performance of electrocatalysts. In this work, high-quality platinum(...The ammonia electrolysis is a highly efficient and energy-saving method for ultra-pure hydrogen generation, which highly relies on electrocatalytic performance of electrocatalysts. In this work, high-quality platinum(Pt) nanocubes(Pt-NCs) with 4.5 nm size are achieved by facile hydrothermal synthesis. The physical morphology and structure of Pt-NCs are exhaustively characterized, revealing that Pt-NCs with special {100} facets have excellent uniformity, good dispersity and high crystallinity. Meanwhile, the electrocatalytic performance of Pt-NCs for ammonia electrolysis are carefully investigated in alkaline solutions, which display outstanding electroactivity and stability for both ammonia electrooxidation reaction(AEOR) and hydrogen evolution reaction(HER) in KOH solution. Furthermore, a symmetric Pt-NCs||Pt-NCs ammonia electrolyzer based on bifunctional Pt-NCs electrocatalyst is constructed, which only requires 0.68 V electrolysis voltage for hydrogen generation. Additionally, the symmetric Pt-NCs||Pt-NCs ammonia electrolyzer has excellent reversible switch capability for AEOR at anode and HER at cathode, showing outstanding alternating operation ability for ammonia electrolysis.展开更多
Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as...Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as an attractive alternative to hydrogen,offering comparable energy density while maintaining carbon-free characteristics,along with superior storage and transport properties that give direct ammonia fuel cells(DAFCs)distinct safety advantages over hydrogen-based systems.Central to this technology is the anodic ammonia oxidation reaction(AOR),where platinum(Pt)remains the most efficient catalyst after years of intensive research.This review offers a comprehensive overview of Ptbased AOR electrocatalysts with potential for application in low-temperature DAFCs.Following an introductory section highlighting key historical developments and catalytic breakthroughs,a fundamental understanding of low-temperature DAFC operation and AOR mechanisms is systematically presented.Subsequently,it outlines the advancements in Pt-based catalysts from simple monometallic systems to sophisticated multimetallic alloys and composites,highlighting material innovations and performance enhancements.Afterward,key challenges and future research directions for advancing AOR electrocatalysts are identified,with the aim of providing valuable guidance for developing practical,highperformance,and low-temperature DAFC systems.展开更多
Electrochemical reduction of water to hydrogen(H2) offers a promising strategy for production of clean energy,but the design and optimization of electrochemical apparatus present challenges in terms of H2 recovery and...Electrochemical reduction of water to hydrogen(H2) offers a promising strategy for production of clean energy,but the design and optimization of electrochemical apparatus present challenges in terms of H2 recovery and energy consumption.Using cobalt phosphide nanoarrays(Co2 P/CoP NAs) as a charge mediator,we effectively separated the H2 and O2 evolution of alkaline water electrolysis in time,thereby achieving a membrane-free pathway for H2 purification.The hierarchical array structure and synergistic optimization of the electronic configuration of metallic Co2 P and metalloid CoP make the Co2 P/CoP NAs high-efficiency bifunctional electrocatalysts for both charge storage and hydrogen evolution.Theoretical investigations revealed that the introduction of Co2 P into CoP leads to a moderate hydrogen adsorption free energy and low water dissociation barrier,which are beneficial for boosting HER activity.Meanwhile,Co2 P/CoP NAs with high capacitance could maintain a cathodic H2 evolution time of 1500 s at 10 mA cm^(-2) driven by a low average voltage of 1.38 V.Alternatively,the energy stored in the mediator could be exhausted via coupling with the anodic oxidation of ammonia,whereby only 0.21 V was required to hold the current for 1188 s.This membrane-free architecture demonstrates the potential for developing hydrogen purification technology at low cost.展开更多
Electrocatalytic ammonia oxidation reaction(eAOR)is of significance to ammonia fuel economy and the production of valuable N-containing products,such as nitrite,nitrate and hydrazine.The study of well-defined molecula...Electrocatalytic ammonia oxidation reaction(eAOR)is of significance to ammonia fuel economy and the production of valuable N-containing products,such as nitrite,nitrate and hydrazine.The study of well-defined molecular catalysts offers rich insights in terms of the detailed mechanism of ammonia oxidation.This review analyzes the thermodynamics of ammonia oxidation reactions and summarizes the current progress in molecular electrocatalysts in this booming field.We emphasized the factors that influence the selectivity of products and further discussed the challenges in designing efficient catalysts.展开更多
The unimolccular reactions of ammonia oxide H_3NO,isomerization and dehydrogenation, are investigated by ab initio MO calculations with the 4-31G basis set.The geometries and energies of the reactant,transition states...The unimolccular reactions of ammonia oxide H_3NO,isomerization and dehydrogenation, are investigated by ab initio MO calculations with the 4-31G basis set.The geometries and energies of the reactant,transition states and products have been determined on the singlet potential energy sur- face.The reaction ergodography along the intrinsic reaction coordinate(IRC)for the two reactions have been performed.The vibrational frequency correlation diagram of the two reactions are analyzed along the IRC.展开更多
基金Research Grant Council(Nos.26206115 and 16304117)of the Hong Kong Special Administrative Region.
文摘As a promising fuel candidate,ammonia has been successtully used as anode feed in alkaline fuel cells.However,current technology in catalysts for ammonia electro-oxidation reaction(AOR)with respect to both cost and performance is inadequate to ensure large scale commercial application of direct ammonia fuel cells.Recent studies found that alloying Pt with different transition metals and controlling the morphology of catalysts can improve the AOR activity,and thus potentially can solve the cost issue.Herein,(100)-terminated Pt-M nanocubes(M=3d-transition metals Fe,Co,Ni,Zn)are synthesized via wet-chemistry method and their catalytic activities toward AOR are evaluated.The addition of Fe,Co,Ni and Zn elements can enhance the AOR activity due to decrease in oxophilicity of platinum and bifunctional mechanism.Pt-Zn exhibits the maximum mass activity and specific ativity with values of 0.41 A/mgpt and 169 mA/cm2 that are 1.6 and 1.8 times higher than Pt nanocubes,respectively.Pt-Fe,Pt-Co and PI-Ni nanocubes also ilustrate higher mass and specific activities compared to Pt nanocubes.
基金This work was supported by Westlake Education Foundation.
文摘Electrocatalytic ammonia oxidation reaction(EAOR)provides an ideal solution for on-board hydrogen supply for fuel cells,while the lack of efficient and durable EAOR catalysts has been a long-standing obstacle for its practical application.Herein,we reported that the defect engineering via in-situ electrochemically introducing oxygen vacancies(Vo)not only turns the inactive CuO into efficient EAOR catalyst but also achieves a high stability of over 400 h at a high current density of~200 mA·cm^(−2).Theoretical simulation reveals that the presence of Vo on the CuO surface induces a remarkable upshift of the d-band center of active Cu site closer to the Fermi level,which significantly stabilizes the reaction intermediates(*NHx)and efficiently oxidizes NH3 into N2.This Vo-modulated CuO shows a different catalytic mechanism from that on the conventional Pt-based catalysts,paving a new avenue to develop inexpensive,efficient,and robust catalysts,not limited to EAOR.
基金supported by the National Natural Science Foundation of China(No.22162004)the Natural Science Foundation of Guangxi Province(No.2022JJD120011)the Opening Project of Guangxi Key Laboratory of Information Materials(No.211025-K).
文摘It is still a lack of bifunctional catalysts for ammonia oxidation reaction(AOR)and hydrogen evolution reaction(HER)due to their different reaction mechanisms.In this work,P is doped into PtZn alloy by calcination with NaH_(2)PO_(2) as P source to induce the lattice tensile strain of Pt and the electronic interaction between P and Zn,which optimizes the AOR and HER activity simultaneously.The sample with the optimal P content can drive the AOR peak current density of 293.6 mA·mgPt^(-1),which is almost 2.7 times of Pt.For HER,the overpotential at^(-1)0 mA·cm^(-2) is only 23 mV with Tafel slope of 34.1 mV·dec^(-1).Furthermore,only 0.59 V is needed to obtain 50 mA·mgPt^(-1) for ammonia electrolysis under a two-electrode system.Therefore,this work shows an ingenious method to design bifunctional catalysts for ammonia electrolysis.
基金supported by the National Natural Science Foundation of China(22379031)the Guangxi Science and Technology Project of China(AB16380030)+1 种基金the National Research Foundation,SingaporeA*STAR(Agency for Science,Technology and Research)under its LCER Phase 2 Programme Hydrogen&Emerging Technologies FI,Directed Hydrogen Programme(U2305D4003)。
文摘Efficiently utilizing ammonia(carbon-free fuel)via low-temperature fuel cells is severely hindered by the sluggish kinetics of ammonia oxidation reaction(AOR).Herein,platinum-iridium-tungsten nanocubes(PtIrW-NCBs)with exposed{100}-rich facets were synthesized by a glucose-assisted solvent-thermal method,in which alloying W not only can facilitate the formation of such specific nanostructures to expose more active sites for AOR,but also modulate the electronic structure of PtIr to promote the kinetics of AOR.The PtIrW-NCBs featuring the small nanoparticle size of 5.05±0.07 nm exhibit superior AOR performance,wherein the onset potential is down to 0.319 V and the mass activity is 30.15 A g_((PGM=Pt,Ir))^(-1)at 0.50 V vs.RHE,significantly higher than those of reported majority of AOR catalysts and even commercial PtIr/C.Meanwhile,in situ Fourier transform infrared spectroscopy measurement further reveals that AOR on PtIrW-NCBs dominantly undergoes the dimerization path of NH_(x)(1≤x≤2).In addition,the theoretical calculations also identify that alloying W into PtIr can contribute additional electrons to 5d orbitals of PtIr,enabling the d-band center approaching the Femi level,which in turn induces the high-filling of bonding orbitals of N-N bond in^(*)N_(2)H_(4),promoting the dimerization of^(*)NH_(2)to^(*)N_(2)H_(4)and thus leading to high AOR activity of PtIrW.This work provides new insights for designing efficient AOR electrocatalysts.
基金National Natural Science Foundation of China,Grant/Award Numbers:22179093,22379111Department of Education of Guangdong Province for Higher Educational Institution,Grant/Award Number:2022ZDZX4104Shenzhen General Project for Institutions of Higher Education,Grant/Award Number:20231127113219001。
文摘Electrochemical nitrogen looping represents a promising carbon-free and sustainable solution for the energy transition,in which electrochemical ammonia oxidation stays at the central position.However,the various nitrogen-containing intermediates tend to poison and corrode the electrocatalysts,even the state-of-the-art noble-metal ones,which is worsened at a high applied potential.Herein,we present an ultrarapid laser quenching strategy for constructing a corrosion-resistant and nanostructured CuNi alloy metallic glass electrocatalyst.In this material,single-atom Cu species are firmly bonded with the surrounding Ni atoms,endowing exceptional resistance against ammonia corrosion relative of conventional CuNi alloys.Remarkably,a record-high durability for over 300 h is achieved.Ultrarapid quenching also allows a much higher Cu content than typical single-atom alloys,simultaneously yielding a high rate and selectivity for ammonia oxidation reaction(AOR).Consequently,an outstanding ammonia conversion rate of up to 95%is achieved with 91.8%selectivity toward nitrite after 8 h.Theoretical simulations reveal that the structural amorphization of CuNi alloy could effectively modify the electronic configuration and reaction pathway,generating stable singleatom Cu active sites with low kinetic barriers for AOR.This ultrarapid laser quenching strategy thus provides a new avenue for constructing metallic glasses with well-defined nanostructures,presenting feasible opportunities for performance enhancement for AOR and other electrocatalytic processes.
基金the National Key Research and Development Program of China(No.2022YFB4102000)the National Natural Science Foundation of China(Nos.22102018 and 52171201)+5 种基金the Huzhou Science and Technology Bureau(No.2022GZ45)the China Postdoctoral Science Foundation-Funded Project(No.2022M710601)the Huzhou Science and Technology Bureau(No.2023GZ02)the Natural Science Foundation of Sichuan Province(No.24NSFSC5779)the National Natural Science Foundation of China(Nos.22322201 and 22278067)the Natural Science Foundation of Sichuan Province(No.2023NSFSC0094)。
文摘As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.Within this context,the electrocatalytic ammonia oxidation reaction(AOR)is pivotal.Platinum(Pt),recognized as the most efficient AOR catalyst,has undergone extensive development over the years,yielding notable advancements across various domains,ranging from elucidating the reaction mechanism to exploring innovative materials.This review begins by elucidating the mechanism of ammonia oxidation,summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods.Subsequently,it outlines the research progress surrounding different Pt-based catalysts,followed by a discussion on standard protocols for electrochemical ammonia oxidation testing,which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts.Moreover,the review addresses current challenges in ammonia oxidation and outlines potential future directions,providing a comprehensive outlook on the field.
基金supported by the National Natural Science Foundation of China(22162004,22479031)the Guangxi Science and Technology Program(2023AB38061)+1 种基金the Innovation Project of Guangxi Graduate Education(YCBZ2024053)the Highperformance Computing Platform of Guangxi University。
文摘The oxophilicity of metal oxides is usually utilized to improve the ammonia oxidation reaction(AOR)activity of Pt-based catalysts.But the effect of strong interaction between Pt and metal oxides on AOR is not studied.Herein,experimental and density functional theory calculation results indicate that a strong interaction is built between Pt and reducible CeOx by high-temperature reduction,which induces the electronic interaction due to the difference of work fu nction,then optimizing the competitive adsorption behavior of*OH and*NH_(3)based on hard-soft acid-base principle.Accordingly,the optimal sample achieves an AOR peak current density of 329 mA mg_(Pt)^(-1),which is 2.4 times that of Pt.Meanwhile,it also shows satisfied hydrogen evolution reaction activity with an overpotential of only 24.3 mV at-10 mA cm^(-2)due to the optimization of*H adsorption energy on Pt by CeO_(x).Therefore,this work proposes an AOR activity enhancement mechanism of metal oxides in terms of the strong interaction,and sheds light on developing effective bifunctional catalysts for ammonia electrolysis.
基金sponsored by the National Natural Science Foundation of China (21875133 and 51873100)the Fundamental Research Funds for the Central Universities (GK201901002 and GK201902014)the 111 Project (B14041)。
文摘The ammonia electrolysis is a highly efficient and energy-saving method for ultra-pure hydrogen generation, which highly relies on electrocatalytic performance of electrocatalysts. In this work, high-quality platinum(Pt) nanocubes(Pt-NCs) with 4.5 nm size are achieved by facile hydrothermal synthesis. The physical morphology and structure of Pt-NCs are exhaustively characterized, revealing that Pt-NCs with special {100} facets have excellent uniformity, good dispersity and high crystallinity. Meanwhile, the electrocatalytic performance of Pt-NCs for ammonia electrolysis are carefully investigated in alkaline solutions, which display outstanding electroactivity and stability for both ammonia electrooxidation reaction(AEOR) and hydrogen evolution reaction(HER) in KOH solution. Furthermore, a symmetric Pt-NCs||Pt-NCs ammonia electrolyzer based on bifunctional Pt-NCs electrocatalyst is constructed, which only requires 0.68 V electrolysis voltage for hydrogen generation. Additionally, the symmetric Pt-NCs||Pt-NCs ammonia electrolyzer has excellent reversible switch capability for AEOR at anode and HER at cathode, showing outstanding alternating operation ability for ammonia electrolysis.
基金supported by the National Natural Science Foundation of China(No.52401284)the Natural Science Foundation of Jiangsu Province(No.BK20240957)+1 种基金the Key Research and Development Program of Nantong(No.GZ2024005)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX25_3677)。
文摘Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as an attractive alternative to hydrogen,offering comparable energy density while maintaining carbon-free characteristics,along with superior storage and transport properties that give direct ammonia fuel cells(DAFCs)distinct safety advantages over hydrogen-based systems.Central to this technology is the anodic ammonia oxidation reaction(AOR),where platinum(Pt)remains the most efficient catalyst after years of intensive research.This review offers a comprehensive overview of Ptbased AOR electrocatalysts with potential for application in low-temperature DAFCs.Following an introductory section highlighting key historical developments and catalytic breakthroughs,a fundamental understanding of low-temperature DAFC operation and AOR mechanisms is systematically presented.Subsequently,it outlines the advancements in Pt-based catalysts from simple monometallic systems to sophisticated multimetallic alloys and composites,highlighting material innovations and performance enhancements.Afterward,key challenges and future research directions for advancing AOR electrocatalysts are identified,with the aim of providing valuable guidance for developing practical,highperformance,and low-temperature DAFC systems.
基金financially supported by the National Natural Science Foundation of China (Nos. 51708543, 51438011 and 51722811)Water Pollution Control and Treatment National Science and Technology Major Project (Nos. 2017ZX07402001 and 2018ZX07110-007)。
文摘Electrochemical reduction of water to hydrogen(H2) offers a promising strategy for production of clean energy,but the design and optimization of electrochemical apparatus present challenges in terms of H2 recovery and energy consumption.Using cobalt phosphide nanoarrays(Co2 P/CoP NAs) as a charge mediator,we effectively separated the H2 and O2 evolution of alkaline water electrolysis in time,thereby achieving a membrane-free pathway for H2 purification.The hierarchical array structure and synergistic optimization of the electronic configuration of metallic Co2 P and metalloid CoP make the Co2 P/CoP NAs high-efficiency bifunctional electrocatalysts for both charge storage and hydrogen evolution.Theoretical investigations revealed that the introduction of Co2 P into CoP leads to a moderate hydrogen adsorption free energy and low water dissociation barrier,which are beneficial for boosting HER activity.Meanwhile,Co2 P/CoP NAs with high capacitance could maintain a cathodic H2 evolution time of 1500 s at 10 mA cm^(-2) driven by a low average voltage of 1.38 V.Alternatively,the energy stored in the mediator could be exhausted via coupling with the anodic oxidation of ammonia,whereby only 0.21 V was required to hold the current for 1188 s.This membrane-free architecture demonstrates the potential for developing hydrogen purification technology at low cost.
基金supported by the National Key R&D Program of China(2022YFC3401802)the National Natural Science Foundation of China(22279105)+4 种基金the Zhejiang Provincial Natural Science Foundation(XHD24B0201)the Starting-up Package from Westlake Universitythe Kunpeng Research Fund from Zhejiang ProvinceResearch Center for Industries of the FutureZhejiang Baima Lake Laboratory。
文摘Electrocatalytic ammonia oxidation reaction(eAOR)is of significance to ammonia fuel economy and the production of valuable N-containing products,such as nitrite,nitrate and hydrazine.The study of well-defined molecular catalysts offers rich insights in terms of the detailed mechanism of ammonia oxidation.This review analyzes the thermodynamics of ammonia oxidation reactions and summarizes the current progress in molecular electrocatalysts in this booming field.We emphasized the factors that influence the selectivity of products and further discussed the challenges in designing efficient catalysts.
基金This work was supported by the National Natural Science Foundation of China.
文摘The unimolccular reactions of ammonia oxide H_3NO,isomerization and dehydrogenation, are investigated by ab initio MO calculations with the 4-31G basis set.The geometries and energies of the reactant,transition states and products have been determined on the singlet potential energy sur- face.The reaction ergodography along the intrinsic reaction coordinate(IRC)for the two reactions have been performed.The vibrational frequency correlation diagram of the two reactions are analyzed along the IRC.
