Controllable fabrication of Fe-N-C based single-atom catalysts(SACs)for enhanced electrocatalytic performance is highly desirable but still challenging.Here,an in situ surface-confined strategy was demonstrated for th...Controllable fabrication of Fe-N-C based single-atom catalysts(SACs)for enhanced electrocatalytic performance is highly desirable but still challenging.Here,an in situ surface-confined strategy was demonstrated for the synthesis of single atomic Fe-N_(4))on N-doped carbon nanoleaves(L-FeNC).The in situ generated Zn3[Fe(CN)6]2 could not only serve as a protection layer against collapse of nanoleaves but also provide abundant Fe source for the formation of Fe-N moieties during pyrolysis,leading to high surface area and high graphitization degree of L-FeNC simultaneously.Benefiting from abundant Fe-N_(4))active sites,enhanced mass and charge transfer,the as-prepared L-FeNC manifested a half-wave potential of 0.89 V for oxygen reduction reaction(ORR)in 0.1 M KOH.A maximum power density of 140 m W cm^(-2)and stable discharge voltage even after operation for 50,000 s have been demonstrated when the L-FeNC was used as air cathode for Zn-air battery.This work not only provided a unique surfaceconfined strategy for the synthesis of two-dimensional nanocarbons,but also demonstrated the significant benefit from rational design and engineering of Fe-N-C SACs,thus offering great opportunities for fabrication of efficient energy conversion and storage devices.展开更多
Electrochemical carbon dioxide reduction(CO_(2)RR)has been generally regarded as green technologies that can convert renewable energy such as sunlight and wind into fuels and valuable chemicals.However,the large‐scal...Electrochemical carbon dioxide reduction(CO_(2)RR)has been generally regarded as green technologies that can convert renewable energy such as sunlight and wind into fuels and valuable chemicals.However,the large‐scale implementation of CO_(2)RR is severely hindered by the lack of high‐performance CO_(2)RR electrocatalysts.Heterogeneous molecular catalysts and metal‐organic framework with well‐defined structure and high tunability of the metal centers and ligands show great promise for CO_(2)RR in terms of both fundamental understanding and practical application.Here,structural and interfacial engineering of these well‐defined metal‐organic ensembles is summarized.This review starts from the fundamental electrochemistry of CO_(2)RR and its evaluation criteria,and then moves to the heterogeneous molecular catalysts and metal‐organic framework with emphasis on the engineering of metal centers and ligands,their interaction with supports,as well as in situ reconstruction of metal‐organic ensembles.Summary and outlook are present in the end,with the hope to inspire and provoke more genuine thinking on the design and fabrication of efficient CO_(2)RR electrocatalysts.展开更多
Hydrogen evolution reaction(HER) plays a key role in generating clean and renewable energy. As the most effective HER electrocatalysts, Pt group catalysts suffer from severe problems such as high price and scarcity. I...Hydrogen evolution reaction(HER) plays a key role in generating clean and renewable energy. As the most effective HER electrocatalysts, Pt group catalysts suffer from severe problems such as high price and scarcity. It is highly desirable to design and synthesize sustainable HER electrocatalysts to replace the Pt group catalysts. Due to their low cost, high abundance and high activities, cobalt-incorporated N-doped nanocarbon hybrids are promising candidate electrocatalysts for HER. In this report, we demonstrated a robust and eco-friendly host-vip approach to fabricate metallic cobalt nanoparticles embedded in N-doped carbon fibers derived from natural silk fibers. Benefiting from the onedimensional nanostructure, the well-dispersed metallic cobalt nanoparticles and the N-doped thin graphitized carbon layer coating, the best Cobased electrocatalyst manifests low overpotential(61 mV@10 mA/cm^2) HER activity that is comparable with commercial 20% Pt/C, and good stability in acid. Our findings provide a novel and unique route to explore high-performance noble-metal-free HER electrocatalysts.展开更多
High-quality Pt-based catalysts are highly desirable for ethanol oxidation reaction(EOR),which is of critical importance for the commercial applications of direct ethanol fuel cells(DEFCs).However,most of the Pt-based...High-quality Pt-based catalysts are highly desirable for ethanol oxidation reaction(EOR),which is of critical importance for the commercial applications of direct ethanol fuel cells(DEFCs).However,most of the Pt-based catalysts have suffered from high cost and low operation durability.Herein a two-step method has been developed to synthesize porous Pt nanoframes decorated with Bi(OH)3,which show excellent catalytic activity and operation durability in both alkaline and acidic media.For example,the nanoframes show a mass activity of 6.87 A·mgPt−1 in alkaline media,which is 13.5-fold higher than that of commercial Pt/C.More importantly,the catalyst can be reactivated simply,which shows negligible activity loss after running for 180,000 s.Further in situ attenuated total reflection-infrared(ATR-IR)absorption spectroscopy and CO-stripping experiments indicate that surface Bi(OH)3 species can greatly facilitate the formation of adsorbed OH species and subsequently remove carbonaceous poison,resulting in a significantly enhanced stability towards EOR.This work may favor the tailoring of desired electrocatalysts with high activity and durability for future commercial application of DEFCs.展开更多
The slow kinetics at the cathode of oxygen reduction reaction(ORR)seriously limits the efficiencies of fuel cells and metal-air batteries.Pt,the state-of-the-art ORR electrocatalyst,suffers from high cost,low earth ab...The slow kinetics at the cathode of oxygen reduction reaction(ORR)seriously limits the efficiencies of fuel cells and metal-air batteries.Pt,the state-of-the-art ORR electrocatalyst,suffers from high cost,low earth abundance,and poor stability.Here a self-templated strategy based on metal-organic frameworks(MOFs)is proposed for the fabrication of hollow nitrogen-doped carbon spheres that are embedded with cobalt nanoparticles(Co/HNC).The Co/HNC manifests better ORR activities,methanol tolerance,and stability than commercial Pt/C.The high ORR performance of Co/NHC can be attributed to the hollow structure which provides enlarged electrochemically active surface area,the formation of more Co-N species,and the introduction of defects.This work highlights the significance of rational engineering of MOFs for enhanced ORR activity and stability and offers new routes to the design and synthesis of high-performance electrocatalysts.展开更多
Electroreduction of carbon dioxide into value-added fuels or chemicals using renewable energy helps to effectively reduce carbon dioxide emission and alleviate the greenhouse effect while storing intermittent energies...Electroreduction of carbon dioxide into value-added fuels or chemicals using renewable energy helps to effectively reduce carbon dioxide emission and alleviate the greenhouse effect while storing intermittent energies.Due to the existing infrastructure of global natural gas utilization and distribution,methane produced in such a green route attracts wide interests.However,limited success has been witnessed in the practical application of catalysts imparting satisfactory methane activity and selectivity.Herein,we report the fabrication of an atomically dispersed Co-Cu alloy through the reconstruction of trace-Co doped Cu metalorganic framework.This catalyst exhibits a methane Faradaic efficiency of 60%±1%with the corresponding partial current density of 303±5 mA·cm^(−2).Operando X-ray adsorption spectroscopy and attenuated-total-reflection surface enhanced infrared spectroscopy unravel that the introduction of atomically dispersed Co in Cu favors*CO protonation via enhancing surface water activation,and suppresses C−C coupling by reducing*CO coverage,thereby leading to high methane selectivity.展开更多
Electroreduction of CO_(2) into value-added chemicals and fuels utilizing renewable electricity offers a sustainable way to meet the carbon-neutral goal and a viable solution for the storage of intermittent green ener...Electroreduction of CO_(2) into value-added chemicals and fuels utilizing renewable electricity offers a sustainable way to meet the carbon-neutral goal and a viable solution for the storage of intermittent green energy sources.At the core of this technology is the development of electrocatalysts to accelerate the redox kinetics of CO_(2) reduction reactions(CO_(2)RR)toward high targeted-product yield at minimal energy input.This perspective focuses on a unique category of CO_(2)RR electrocatalysts embodying both inorganic and organic components to synergistically promote the reaction activity,selectivity and stability.First,we summarize recent progress on the design and fabrication of organic/inorganic hybrids CO_(2)RR electrocatalysts,with special attention to the assembly protocols and structural configurations.We then carry out a comprehensive discussion on the mechanistic understanding of CO_(2)RR processes tackled jointly by the inorganic and organic phases,with respect to the regulation of mass and charge transport,modification of double-layer configuration,tailoring of intermediates adsorption,and establishment of tandem pathways.At the end,we outline future challenges in the rational design of organic/inorganic hybrids for CO_(2)RR and further extend the scope to the device level.We hope this work could incentivize more research interests to construct organic/inorganic hybrids for mobilizing electrocatalytic CO_(2)RR towards industrialization.展开更多
基金supported by the National Natural Science Foundation of China(21673150,51922073)the Natural Science Foundation of Jiangsu Province(BK20180097)+2 种基金the financial support from the 111 Projectthe Collaborative Innovation Center of Suzhou Nano Science and Technology(NANO-CIC)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Controllable fabrication of Fe-N-C based single-atom catalysts(SACs)for enhanced electrocatalytic performance is highly desirable but still challenging.Here,an in situ surface-confined strategy was demonstrated for the synthesis of single atomic Fe-N_(4))on N-doped carbon nanoleaves(L-FeNC).The in situ generated Zn3[Fe(CN)6]2 could not only serve as a protection layer against collapse of nanoleaves but also provide abundant Fe source for the formation of Fe-N moieties during pyrolysis,leading to high surface area and high graphitization degree of L-FeNC simultaneously.Benefiting from abundant Fe-N_(4))active sites,enhanced mass and charge transfer,the as-prepared L-FeNC manifested a half-wave potential of 0.89 V for oxygen reduction reaction(ORR)in 0.1 M KOH.A maximum power density of 140 m W cm^(-2)and stable discharge voltage even after operation for 50,000 s have been demonstrated when the L-FeNC was used as air cathode for Zn-air battery.This work not only provided a unique surfaceconfined strategy for the synthesis of two-dimensional nanocarbons,but also demonstrated the significant benefit from rational design and engineering of Fe-N-C SACs,thus offering great opportunities for fabrication of efficient energy conversion and storage devices.
文摘Electrochemical carbon dioxide reduction(CO_(2)RR)has been generally regarded as green technologies that can convert renewable energy such as sunlight and wind into fuels and valuable chemicals.However,the large‐scale implementation of CO_(2)RR is severely hindered by the lack of high‐performance CO_(2)RR electrocatalysts.Heterogeneous molecular catalysts and metal‐organic framework with well‐defined structure and high tunability of the metal centers and ligands show great promise for CO_(2)RR in terms of both fundamental understanding and practical application.Here,structural and interfacial engineering of these well‐defined metal‐organic ensembles is summarized.This review starts from the fundamental electrochemistry of CO_(2)RR and its evaluation criteria,and then moves to the heterogeneous molecular catalysts and metal‐organic framework with emphasis on the engineering of metal centers and ligands,their interaction with supports,as well as in situ reconstruction of metal‐organic ensembles.Summary and outlook are present in the end,with the hope to inspire and provoke more genuine thinking on the design and fabrication of efficient CO_(2)RR electrocatalysts.
基金supported by the National Natural Science Foundation of China (NSFC) (Grant No. 21203137, 51573166)the Natural Science Foundation of Zhejiang Province (Grant No. LQ16E020005)
文摘Hydrogen evolution reaction(HER) plays a key role in generating clean and renewable energy. As the most effective HER electrocatalysts, Pt group catalysts suffer from severe problems such as high price and scarcity. It is highly desirable to design and synthesize sustainable HER electrocatalysts to replace the Pt group catalysts. Due to their low cost, high abundance and high activities, cobalt-incorporated N-doped nanocarbon hybrids are promising candidate electrocatalysts for HER. In this report, we demonstrated a robust and eco-friendly host-vip approach to fabricate metallic cobalt nanoparticles embedded in N-doped carbon fibers derived from natural silk fibers. Benefiting from the onedimensional nanostructure, the well-dispersed metallic cobalt nanoparticles and the N-doped thin graphitized carbon layer coating, the best Cobased electrocatalyst manifests low overpotential(61 mV@10 mA/cm^2) HER activity that is comparable with commercial 20% Pt/C, and good stability in acid. Our findings provide a novel and unique route to explore high-performance noble-metal-free HER electrocatalysts.
基金supported by the National Key R&D Program of China(No.2016YFE0129600)the National Natural Science Foundation of China(Nos.21673150 and 21703146)+1 种基金the financial support from the 111 Project,Collaborative Innovation Center of Suzhou Nano Science and Technology(NANO-CIC)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘High-quality Pt-based catalysts are highly desirable for ethanol oxidation reaction(EOR),which is of critical importance for the commercial applications of direct ethanol fuel cells(DEFCs).However,most of the Pt-based catalysts have suffered from high cost and low operation durability.Herein a two-step method has been developed to synthesize porous Pt nanoframes decorated with Bi(OH)3,which show excellent catalytic activity and operation durability in both alkaline and acidic media.For example,the nanoframes show a mass activity of 6.87 A·mgPt−1 in alkaline media,which is 13.5-fold higher than that of commercial Pt/C.More importantly,the catalyst can be reactivated simply,which shows negligible activity loss after running for 180,000 s.Further in situ attenuated total reflection-infrared(ATR-IR)absorption spectroscopy and CO-stripping experiments indicate that surface Bi(OH)3 species can greatly facilitate the formation of adsorbed OH species and subsequently remove carbonaceous poison,resulting in a significantly enhanced stability towards EOR.This work may favor the tailoring of desired electrocatalysts with high activity and durability for future commercial application of DEFCs.
基金supported by the National Natural Science Foundation of China(Nos.21673150 and 51922073)Natural Science Foundation of Jiangsu Province(No.BK20180097)。
文摘The slow kinetics at the cathode of oxygen reduction reaction(ORR)seriously limits the efficiencies of fuel cells and metal-air batteries.Pt,the state-of-the-art ORR electrocatalyst,suffers from high cost,low earth abundance,and poor stability.Here a self-templated strategy based on metal-organic frameworks(MOFs)is proposed for the fabrication of hollow nitrogen-doped carbon spheres that are embedded with cobalt nanoparticles(Co/HNC).The Co/HNC manifests better ORR activities,methanol tolerance,and stability than commercial Pt/C.The high ORR performance of Co/NHC can be attributed to the hollow structure which provides enlarged electrochemically active surface area,the formation of more Co-N species,and the introduction of defects.This work highlights the significance of rational engineering of MOFs for enhanced ORR activity and stability and offers new routes to the design and synthesis of high-performance electrocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.22072101 and 22075193)the Natural Science Foundation of Jiangsu Province(No.BK20211306)+1 种基金Six Talent Peaks Project in Jiangsu Province(No.TD-XCL-006)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions.
文摘Electroreduction of carbon dioxide into value-added fuels or chemicals using renewable energy helps to effectively reduce carbon dioxide emission and alleviate the greenhouse effect while storing intermittent energies.Due to the existing infrastructure of global natural gas utilization and distribution,methane produced in such a green route attracts wide interests.However,limited success has been witnessed in the practical application of catalysts imparting satisfactory methane activity and selectivity.Herein,we report the fabrication of an atomically dispersed Co-Cu alloy through the reconstruction of trace-Co doped Cu metalorganic framework.This catalyst exhibits a methane Faradaic efficiency of 60%±1%with the corresponding partial current density of 303±5 mA·cm^(−2).Operando X-ray adsorption spectroscopy and attenuated-total-reflection surface enhanced infrared spectroscopy unravel that the introduction of atomically dispersed Co in Cu favors*CO protonation via enhancing surface water activation,and suppresses C−C coupling by reducing*CO coverage,thereby leading to high methane selectivity.
基金This work is supported by National Natural Science Foundation of China(No.22072101,22075193,22202020)Natural Science Foundation of Jiangsu Province(No.BK20220483,BK20211306,BK20220027)+2 种基金the Key Technology Initiative of Suzhou Municipal Science and Technology Bureau(SYG201934)Six Talent Peaks Project in Jiangsu Province(No.TD-XCL-006)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions.
文摘Electroreduction of CO_(2) into value-added chemicals and fuels utilizing renewable electricity offers a sustainable way to meet the carbon-neutral goal and a viable solution for the storage of intermittent green energy sources.At the core of this technology is the development of electrocatalysts to accelerate the redox kinetics of CO_(2) reduction reactions(CO_(2)RR)toward high targeted-product yield at minimal energy input.This perspective focuses on a unique category of CO_(2)RR electrocatalysts embodying both inorganic and organic components to synergistically promote the reaction activity,selectivity and stability.First,we summarize recent progress on the design and fabrication of organic/inorganic hybrids CO_(2)RR electrocatalysts,with special attention to the assembly protocols and structural configurations.We then carry out a comprehensive discussion on the mechanistic understanding of CO_(2)RR processes tackled jointly by the inorganic and organic phases,with respect to the regulation of mass and charge transport,modification of double-layer configuration,tailoring of intermediates adsorption,and establishment of tandem pathways.At the end,we outline future challenges in the rational design of organic/inorganic hybrids for CO_(2)RR and further extend the scope to the device level.We hope this work could incentivize more research interests to construct organic/inorganic hybrids for mobilizing electrocatalytic CO_(2)RR towards industrialization.
