Sustainable production of hydrogen is a hopeful requirement of a strategic future economy and development.Water splitting driven by electricity is a favorable pathway for renewable hydrogen production.This critical re...Sustainable production of hydrogen is a hopeful requirement of a strategic future economy and development.Water splitting driven by electricity is a favorable pathway for renewable hydrogen production.This critical review highlighted recent efforts toward the development of the nanoscale synthesis of nonprecious metal's graphene-supported electrocatalysts and their electrocatalytic features for remarkable hydrogen evolution reaction(HER).Different essential nonprecious metal's graphene-supported electrocatalysts,including metal carbides,sulfides,phosphides,selenides,oxides,and nitrides are reviewed.In the exploration,attention is given to the strategies of activity enhancement,the synthetic approach,and the composition/structure electrocatalytic-performance relationship of these HER electrocatalysts.We are hopeful that this review confers a new momentum to the rational design of remarkable performance nonprecious metal's graphenesupported electrocatalysts and comprehensive guide for researchers to utilize the subject catalysts in regular water splitting.展开更多
In the scale-up of water electrolysis,commercial systems require catalysts that are effective,stable,and earth-abundant.Although platinum group metal(PGM)catalysts exhibit remarkable activity,the high cost and scarcit...In the scale-up of water electrolysis,commercial systems require catalysts that are effective,stable,and earth-abundant.Although platinum group metal(PGM)catalysts exhibit remarkable activity,the high cost and scarcity significantly increase the overall capital expenses for alkaline water oxidation[1].As a more sustainable alternative,non-PGM catalysts—particularly first-row(3d)transitionmetal(oxy)hydroxides—show great promise for water oxidation.However,from a theoretical standpoint(e.g.,Pourbaix diagrams)[2],these active phases are often difficult to detect compared to PGM under oxygen evolution reaction(OER)conditions,underscoring the need to stabilize them during operation.Moreover,the rapid degradation of these metal(oxy)hydroxides is potential-dependent and typically occurs at high overpotentials required to achieve practical current densities,often associated with the dissolution of catalytic metal sites or phase segregation under harsh OER conditions[3].Together,these factors present a critical challenge in the development of metal(oxy)hydroxide catalysts—namely,stabilizing both the active phases and active sites,particularly during long-term operations at high current densities[4].展开更多
Photoactive complexes of nonprecious transition metals,mainly including those in the first-row and partially the second-row of the Periodic table of elements,have received increasing attention in view of their low cos...Photoactive complexes of nonprecious transition metals,mainly including those in the first-row and partially the second-row of the Periodic table of elements,have received increasing attention in view of their low cost and long-term sustainability.They are recognized as promising alternatives to noble transition metal complex congeners that have been extensively studied in optoelectronic devices,artificial photosynthesis,photocatalysis,biodiagnostics,and therapeutics,etc.This review is devoted to a comprehensive summary on the classical and recent advances on photoactive nonprecious transition metal complexes,including photoactive Zr,V,Cr,Mo,and W complexes,Mn complexes and hybrids,Fe,Co,Ni,and Cu complexes,and Zn and Cd complexes and hybrids.A particular focus is given on the molecular design,modulation of photophysical and photochemical properties,and applications of the representative and lately-developed nonprecious metal complexes.In addition,a perspective on the future development in this field is provided at the end of this review.展开更多
A novel nonprecious metal material consisting of Coembedded porous interconnected multichannel carbon nanofibers(Co/IMCCNFs) was rationally designed for oxygen reduction reaction(ORR)electrocatalysis.In the synthesis,...A novel nonprecious metal material consisting of Coembedded porous interconnected multichannel carbon nanofibers(Co/IMCCNFs) was rationally designed for oxygen reduction reaction(ORR)electrocatalysis.In the synthesis,ZnCo2O4 was employed to form interconnected mesoporous channels and provide highly active Co3O4/Co core–shell nanoparticle-based sites for the ORR.The IMC structure with a large synergistic effect of the N and Co active sites provided fast ORR electrocatalysis kinetics.The Co/IMCCNFs exhibited a high half-wave potential of 0.82 V(vs.reversible hydrogen electrode) and excellent stability with a current retention up to 88% after 12,000 cycles in a current–time test,which is only 55% for 30 wt% Pt/C.展开更多
Catalytic oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)have garnered great attention as the key character in metal-air batteries.Herein,we developed a superior nonprecious bifunctional oxygen electr...Catalytic oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)have garnered great attention as the key character in metal-air batteries.Herein,we developed a superior nonprecious bifunctional oxygen electrocatalyst,fabricated through spatial confinement of Fe/Fe_(3)C nanocrystals in pyridinic N and Fe-Nx rich carbon nanotubes(Fe/Fe_(3)C-N-CNTs).During ORR,the resultant electrocatalyst exhibits positive onset pote ntial of 1.0 V(vs.RHE),large half-wave potentials of 0.88 V(vs.RHE),which is more positive than Pt/C(0.98 V and 0.83 V,respectively).Remarkably,Fe/Fe_(3)C-N-CNTs exhibits outstanding durability and great methanol tolerance,exceeding Pt/C and most reported nonprecious metal-based oxygen reduction electrocatalysts.Moreover,Fe/Fe_(3)C-N-CNTs show a markedly low potential at j=10 mA/cm^(2),small Tafel slopes and extremely high stability for OER.Impressively,the Fe/Fe_(3)C-N-CNTs-based Zn-air batteries demonstrate high power density of 183 mW/cm^(2)and robust charge/discharge stability.It is revealed that the spatial confinement effect can impede the aggregation and corrosion of Fe/Fe_(3)C nanocrystals.Meanwhile,Fe/Fe_(3)C and Fe-Nx play synergistic effect on boosting the ORR/OER activity,which provides an important guideline for construction of inexpensive nonprecious metal-carbon hybrid nanomaterials.展开更多
Development of efficient and promising bifunctional electrocatalysts for oxygen reduction and evolutionreactions is desirable. Herein, cobalt nanoparticles embedded in nitrogen and sulfur co-doped carbonnanotubes(Co@N...Development of efficient and promising bifunctional electrocatalysts for oxygen reduction and evolutionreactions is desirable. Herein, cobalt nanoparticles embedded in nitrogen and sulfur co-doped carbonnanotubes(Co@NSCNT) were prepared by a facile pyrolytic treatment. The cobalt nanoparticles and co-doping of nitrogen and sulfur can improve the electron donor-acceptor characteristics of the carbon nan-otubes and provide more active sites for catalytic oxygen reduction and evolution reactions. The preparedCo@NSCNT, annealed at 900℃, showed excellent electrocatalytic performance and better durability thancommercial platinum catalysts. Additionally, Co@NSCNT-900 catalysts exhibited comparable onset poten-tials and Tafel slopes to ruthenium oxide. Overall, Co@NSCNT showed high activity and improved dura-bility for both oxygen evolution and reduction reactions.展开更多
Developing non-precious metal catalyst with high activity, good stability and low cost for electrocatalytic oxygen reduction reaction（ORR） is critical for the wide application of energy conversion system. Here, we d...Developing non-precious metal catalyst with high activity, good stability and low cost for electrocatalytic oxygen reduction reaction（ORR） is critical for the wide application of energy conversion system. Here, we developed a cost–effective synthetic strategy via silica assistance to obtain a novel FeC/Fe–N–C（named as COPBP-PB-Fe-900-SiO） catalyst with effective active sites of Fe–Nand FeC from the rational design two-dimensional covalent organic polymer（COPBP-PB）. The nitrogen-rich COP effectively promotes the formation of active Fe–Nsites. Additionally, the silica not only can effectively suppress the formation of large Fe-based particles in the catalysts, but also increases the degree of carbonization of the catalyst.The as-prepared COPBP-PB-Fe-900-SiOcatalyst exhibits high electrocatalytic activity for ORR with a halfwave potential of 0.85 V vs. reversible hydrogen electrode（RHE）, showing comparable activity as compared with the commercial Pt/C catalysts in alkaline media. Moreover, this catalyst also shows a high stability with a nearly constant onset potential and half-wave potential after 10,000 cycles. The present work is highly meaningful for developing ORR electrocatalysts toward wide applications.展开更多
Effective and robust electrocatalysts are mainly based on innovative materials and unique structures.Herein,we designed a flakelike cobalt phosphide-based catalyst supporting on NiCo_(2)O_(4)nanorods array,which in-si...Effective and robust electrocatalysts are mainly based on innovative materials and unique structures.Herein,we designed a flakelike cobalt phosphide-based catalyst supporting on NiCo_(2)O_(4)nanorods array,which in-situ grew on the nickel foam(NF)current collector,referring as NCo_(2)P/NiCo_(2)O_(4)/NF electrode.By optimizing the microstructure and electronic structure through 3D hierarchy fabrication and nitrogen doping,the catalyst features with abundant electrochemical surface area,favorable surface wettability,excellent electron transport,as well as tailored d band center.Consequently,the as-prepared N-Co_(2)P/NiCo_(2)O_(4)/NF electrode exhibits an impressive HER activity with a low overpotentials of58 mV at 10 mA cm^(-2),a Tafel slop of 75 mV dec^(-1),as well as superior durability in alkaline medium.This work may provide a new pathway to effectively improve the hydrogen evolution performance of transition metal phosphides and to develop promising electrodes for practical electrocatalysis.展开更多
Transition metal and nitrogen co-doped carbons(M-N-C)have proven to be promising catalysts for CO_(2)electroreduction into co because of the high activity and selectivity.Effective enrichment of the active transition ...Transition metal and nitrogen co-doped carbons(M-N-C)have proven to be promising catalysts for CO_(2)electroreduction into co because of the high activity and selectivity.Effective enrichment of the active transition metal coordinated nitrogen sites is desirable but is challenging for a practical volumetric productivity.Herein,we report four kinds of model electrocatalysts to unveil this issue,which include the NC structures with surface N-functionalities,Ni-N-CI with one layer of surface Ni-NsC sites,NC@Ni-N-CI with surface N-functionalities and underneath Ni-N3C sites as well as Ni-N-C_II with doubled surface Ni-NsC sites.The X-ray absorption spectroscopy indicates the coordination configuration of Ni-NsC.For NC catalysts,when N-doping level increased from 3.5 at%to 8.4 at%,the CO partial current density increased from below 0.1 mA/cm^(2)to 3 mA/cm^(2).Introducing one layer of Ni-N_(3)C onto the NC structures leads to a 54 times higher CO partial current density than that of NC,in the meantime the FE_(CO) is 66 times higher.Furthermore,doubling the density of surface Ni-N_(3)C sites by a layer-by-layer method doubles the CO partial current density Gco,indicating its potential to achieve a high density of active coordinated sites and current densities.展开更多
The oxygen reduction reaction (ORR) is the cornerstone reaction of the cathode in metal±air batteries;however,slow kinetics requires high-performance catalysts to promote the reaction.Polyphthalocyanine (PPc) has...The oxygen reduction reaction (ORR) is the cornerstone reaction of the cathode in metal±air batteries;however,slow kinetics requires high-performance catalysts to promote the reaction.Polyphthalocyanine (PPc) has a typical chemical cross-linking structure and uniformly dispersed metal active sites,but its poor activity and conductivity limit its applications as an ORR catalyst.Herein,a manageable and convenient strategy is proposed to synthesize ternary ORR catalysts through the low-temperature pyrolysis of Fe PPc.The optimal catalyst,Fe_(3)O_(4)/Fe_(3)N/Fe-N-C@PC-2.5,exhibits excellent ORR activity in alkaline solution with a half-wave potential of 0.90 V,which is significantly higher than that of commercial 20%Pt/C (0.84 V).Electrochemical tests and extended X-ray absorption fine structure spectroscopy reveal that the superior ORR activity of Fe_(3)O_(4)/Fe_(3)N/Fe-N-C@PC-2.5 could be ascribed to the balance of its ternary components(i.e.,Fe_(3)O_(4),Fe_(3)N,and Fe-N;species).A Zn±air battery incorporating Fe_(3)O_(4)/Fe_(3)N/Fe-N-C@PC-2.5 as an air cathodic catalyst delivers a high open-circuit voltage and peak power density.During galvanostatic discharge,the battery demonstrates a specific capacity of 815.7 mA h g^(-1).The facile strategy of using PPc to develop high-performance composite electrocatalysts may be expanded to develop new types of catalysts in the energy field.展开更多
文摘Sustainable production of hydrogen is a hopeful requirement of a strategic future economy and development.Water splitting driven by electricity is a favorable pathway for renewable hydrogen production.This critical review highlighted recent efforts toward the development of the nanoscale synthesis of nonprecious metal's graphene-supported electrocatalysts and their electrocatalytic features for remarkable hydrogen evolution reaction(HER).Different essential nonprecious metal's graphene-supported electrocatalysts,including metal carbides,sulfides,phosphides,selenides,oxides,and nitrides are reviewed.In the exploration,attention is given to the strategies of activity enhancement,the synthetic approach,and the composition/structure electrocatalytic-performance relationship of these HER electrocatalysts.We are hopeful that this review confers a new momentum to the rational design of remarkable performance nonprecious metal's graphenesupported electrocatalysts and comprehensive guide for researchers to utilize the subject catalysts in regular water splitting.
文摘In the scale-up of water electrolysis,commercial systems require catalysts that are effective,stable,and earth-abundant.Although platinum group metal(PGM)catalysts exhibit remarkable activity,the high cost and scarcity significantly increase the overall capital expenses for alkaline water oxidation[1].As a more sustainable alternative,non-PGM catalysts—particularly first-row(3d)transitionmetal(oxy)hydroxides—show great promise for water oxidation.However,from a theoretical standpoint(e.g.,Pourbaix diagrams)[2],these active phases are often difficult to detect compared to PGM under oxygen evolution reaction(OER)conditions,underscoring the need to stabilize them during operation.Moreover,the rapid degradation of these metal(oxy)hydroxides is potential-dependent and typically occurs at high overpotentials required to achieve practical current densities,often associated with the dissolution of catalytic metal sites or phase segregation under harsh OER conditions[3].Together,these factors present a critical challenge in the development of metal(oxy)hydroxide catalysts—namely,stabilizing both the active phases and active sites,particularly during long-term operations at high current densities[4].
基金supported by the National Natural Science Foundation of China(21925112,22175181,22371063,22175191,22075027,and 22475002)。
文摘Photoactive complexes of nonprecious transition metals,mainly including those in the first-row and partially the second-row of the Periodic table of elements,have received increasing attention in view of their low cost and long-term sustainability.They are recognized as promising alternatives to noble transition metal complex congeners that have been extensively studied in optoelectronic devices,artificial photosynthesis,photocatalysis,biodiagnostics,and therapeutics,etc.This review is devoted to a comprehensive summary on the classical and recent advances on photoactive nonprecious transition metal complexes,including photoactive Zr,V,Cr,Mo,and W complexes,Mn complexes and hybrids,Fe,Co,Ni,and Cu complexes,and Zn and Cd complexes and hybrids.A particular focus is given on the molecular design,modulation of photophysical and photochemical properties,and applications of the representative and lately-developed nonprecious metal complexes.In addition,a perspective on the future development in this field is provided at the end of this review.
基金the support from the Fundamental Research Funds for the Central Universities(No.56XIA15003)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institution(PAPD)
文摘A novel nonprecious metal material consisting of Coembedded porous interconnected multichannel carbon nanofibers(Co/IMCCNFs) was rationally designed for oxygen reduction reaction(ORR)electrocatalysis.In the synthesis,ZnCo2O4 was employed to form interconnected mesoporous channels and provide highly active Co3O4/Co core–shell nanoparticle-based sites for the ORR.The IMC structure with a large synergistic effect of the N and Co active sites provided fast ORR electrocatalysis kinetics.The Co/IMCCNFs exhibited a high half-wave potential of 0.82 V(vs.reversible hydrogen electrode) and excellent stability with a current retention up to 88% after 12,000 cycles in a current–time test,which is only 55% for 30 wt% Pt/C.
基金supported financially by the National Natural Science Foundation of China(Nos.51702180,21703116,91963113,51372127)The Scientific and Technical Development Project of Qingdao,China(No.18-2-2-52-jch)The Taishan Scholar Advantage and Characteristic Discipline Team of Eco Chemical Process and Technology。
文摘Catalytic oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)have garnered great attention as the key character in metal-air batteries.Herein,we developed a superior nonprecious bifunctional oxygen electrocatalyst,fabricated through spatial confinement of Fe/Fe_(3)C nanocrystals in pyridinic N and Fe-Nx rich carbon nanotubes(Fe/Fe_(3)C-N-CNTs).During ORR,the resultant electrocatalyst exhibits positive onset pote ntial of 1.0 V(vs.RHE),large half-wave potentials of 0.88 V(vs.RHE),which is more positive than Pt/C(0.98 V and 0.83 V,respectively).Remarkably,Fe/Fe_(3)C-N-CNTs exhibits outstanding durability and great methanol tolerance,exceeding Pt/C and most reported nonprecious metal-based oxygen reduction electrocatalysts.Moreover,Fe/Fe_(3)C-N-CNTs show a markedly low potential at j=10 mA/cm^(2),small Tafel slopes and extremely high stability for OER.Impressively,the Fe/Fe_(3)C-N-CNTs-based Zn-air batteries demonstrate high power density of 183 mW/cm^(2)and robust charge/discharge stability.It is revealed that the spatial confinement effect can impede the aggregation and corrosion of Fe/Fe_(3)C nanocrystals.Meanwhile,Fe/Fe_(3)C and Fe-Nx play synergistic effect on boosting the ORR/OER activity,which provides an important guideline for construction of inexpensive nonprecious metal-carbon hybrid nanomaterials.
基金supported by the Human Resources Development(No.20184030202070) of the Korea Institute of Energy Technology Evaluation and Planning(KETEP) grant funded by the Korea government Ministry of Trade, Industry and Energy
文摘Development of efficient and promising bifunctional electrocatalysts for oxygen reduction and evolutionreactions is desirable. Herein, cobalt nanoparticles embedded in nitrogen and sulfur co-doped carbonnanotubes(Co@NSCNT) were prepared by a facile pyrolytic treatment. The cobalt nanoparticles and co-doping of nitrogen and sulfur can improve the electron donor-acceptor characteristics of the carbon nan-otubes and provide more active sites for catalytic oxygen reduction and evolution reactions. The preparedCo@NSCNT, annealed at 900℃, showed excellent electrocatalytic performance and better durability thancommercial platinum catalysts. Additionally, Co@NSCNT-900 catalysts exhibited comparable onset poten-tials and Tafel slopes to ruthenium oxide. Overall, Co@NSCNT showed high activity and improved dura-bility for both oxygen evolution and reduction reactions.
基金supported by the National Key Research and Development Program of China(2017YFA0206500)NSF of China(51502012+8 种基金2167602021620102007)Beijing Natural Science Foundation(2162032)The Start-up fund for talent introduction of Beijing University of Chemical Technology(buctrc201420buctrc201714)Talent cultivation of State Key Laboratory of OrganicInorganic CompositesThe Fundamental Research Funds for the Central Universities(ZD1502)Distinguished scientist program at BUCT(buctylkxj02)the“111”project of China(B14004)
文摘Developing non-precious metal catalyst with high activity, good stability and low cost for electrocatalytic oxygen reduction reaction（ORR） is critical for the wide application of energy conversion system. Here, we developed a cost–effective synthetic strategy via silica assistance to obtain a novel FeC/Fe–N–C（named as COPBP-PB-Fe-900-SiO） catalyst with effective active sites of Fe–Nand FeC from the rational design two-dimensional covalent organic polymer（COPBP-PB）. The nitrogen-rich COP effectively promotes the formation of active Fe–Nsites. Additionally, the silica not only can effectively suppress the formation of large Fe-based particles in the catalysts, but also increases the degree of carbonization of the catalyst.The as-prepared COPBP-PB-Fe-900-SiOcatalyst exhibits high electrocatalytic activity for ORR with a halfwave potential of 0.85 V vs. reversible hydrogen electrode（RHE）, showing comparable activity as compared with the commercial Pt/C catalysts in alkaline media. Moreover, this catalyst also shows a high stability with a nearly constant onset potential and half-wave potential after 10,000 cycles. The present work is highly meaningful for developing ORR electrocatalysts toward wide applications.
基金financially supported by the National Key R&D Program of China,China(2018YFA0703503)the National Natural Science Foundation of China,China(No.51872024,51932001,21971245)。
文摘Effective and robust electrocatalysts are mainly based on innovative materials and unique structures.Herein,we designed a flakelike cobalt phosphide-based catalyst supporting on NiCo_(2)O_(4)nanorods array,which in-situ grew on the nickel foam(NF)current collector,referring as NCo_(2)P/NiCo_(2)O_(4)/NF electrode.By optimizing the microstructure and electronic structure through 3D hierarchy fabrication and nitrogen doping,the catalyst features with abundant electrochemical surface area,favorable surface wettability,excellent electron transport,as well as tailored d band center.Consequently,the as-prepared N-Co_(2)P/NiCo_(2)O_(4)/NF electrode exhibits an impressive HER activity with a low overpotentials of58 mV at 10 mA cm^(-2),a Tafel slop of 75 mV dec^(-1),as well as superior durability in alkaline medium.This work may provide a new pathway to effectively improve the hydrogen evolution performance of transition metal phosphides and to develop promising electrodes for practical electrocatalysis.
基金financed by National Natural Science Foundation of China(Nos.22275027,21975037)the Fundamental Research Funds for the Central Universities(Nos.DUT22LAB607,DUT22QN206).
文摘Transition metal and nitrogen co-doped carbons(M-N-C)have proven to be promising catalysts for CO_(2)electroreduction into co because of the high activity and selectivity.Effective enrichment of the active transition metal coordinated nitrogen sites is desirable but is challenging for a practical volumetric productivity.Herein,we report four kinds of model electrocatalysts to unveil this issue,which include the NC structures with surface N-functionalities,Ni-N-CI with one layer of surface Ni-NsC sites,NC@Ni-N-CI with surface N-functionalities and underneath Ni-N3C sites as well as Ni-N-C_II with doubled surface Ni-NsC sites.The X-ray absorption spectroscopy indicates the coordination configuration of Ni-NsC.For NC catalysts,when N-doping level increased from 3.5 at%to 8.4 at%,the CO partial current density increased from below 0.1 mA/cm^(2)to 3 mA/cm^(2).Introducing one layer of Ni-N_(3)C onto the NC structures leads to a 54 times higher CO partial current density than that of NC,in the meantime the FE_(CO) is 66 times higher.Furthermore,doubling the density of surface Ni-N_(3)C sites by a layer-by-layer method doubles the CO partial current density Gco,indicating its potential to achieve a high density of active coordinated sites and current densities.
基金financially supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (JCYJ20200109141640095 and JCYJ20190809115413414)the National Natural Science Foundation of China (21671096 and 21905180)+2 种基金the Natural Science Foundation of Guangdong Province (2018A030310225)Guangdong Provincial Key Laboratory of Energy Materials for Electric Power (2018B030322001)support from the Center for Computational Science and Engineering and Core Research Facilities of SUSTech。
文摘The oxygen reduction reaction (ORR) is the cornerstone reaction of the cathode in metal±air batteries;however,slow kinetics requires high-performance catalysts to promote the reaction.Polyphthalocyanine (PPc) has a typical chemical cross-linking structure and uniformly dispersed metal active sites,but its poor activity and conductivity limit its applications as an ORR catalyst.Herein,a manageable and convenient strategy is proposed to synthesize ternary ORR catalysts through the low-temperature pyrolysis of Fe PPc.The optimal catalyst,Fe_(3)O_(4)/Fe_(3)N/Fe-N-C@PC-2.5,exhibits excellent ORR activity in alkaline solution with a half-wave potential of 0.90 V,which is significantly higher than that of commercial 20%Pt/C (0.84 V).Electrochemical tests and extended X-ray absorption fine structure spectroscopy reveal that the superior ORR activity of Fe_(3)O_(4)/Fe_(3)N/Fe-N-C@PC-2.5 could be ascribed to the balance of its ternary components(i.e.,Fe_(3)O_(4),Fe_(3)N,and Fe-N;species).A Zn±air battery incorporating Fe_(3)O_(4)/Fe_(3)N/Fe-N-C@PC-2.5 as an air cathodic catalyst delivers a high open-circuit voltage and peak power density.During galvanostatic discharge,the battery demonstrates a specific capacity of 815.7 mA h g^(-1).The facile strategy of using PPc to develop high-performance composite electrocatalysts may be expanded to develop new types of catalysts in the energy field.
