Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction

Yang, Hong Bin; Hung, Sung‐Fu; Liu, Song; Yuan, Kaidi; Miao, Shu; Zhang, Liping; Huang, Xiang; Wang, Hsin‐Yi; Cai, Weizheng; Chen, Rong; Gao, Jiajian; Yang, Xiaofeng; Chen, Wei; Huang, Yanqiang; Chen, Hao Ming; Li, Chang Ming; Zhang, Tao; Liu, Bin

doi:10.1038/s41560-017-0078-8

Cited by 1,847 publications

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“…[1] Electrochemical reduction is av ery promising path owing to its mild reaction conditions and high energy efficiency. [3] Therefore,i ti s desirable to develop an electrocatalyst with high selectivity for electrochemical reduction of CO 2 . [2] However,i ts till faces many challenges because of the large overpotential required for activating CO 2 to CO 2 À intermediate and the inevitably competing hydrogen evolution reaction (HER) in aqueous solution.…”

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confidence: 99%

Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi₂O₃ Nanosheets for Electrochemical Reduction of CO₂ in a Wide Negative Potential Region

et al. 2018

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Large numbers of catalysts have been developed for the electrochemical reduction of CO to value-added liquid fuels. However, it remains a challenge to maintain a high current efficiency in a wide negative potential range for achieving a high production rate of the target products. Herein, we report a 2D/0D composite catalyst composed of bismuth oxide nanosheets and nitrogen-doped graphene quantum dots (Bi O -NGQDs) for highly efficient electrochemical reduction of CO to formate. Bi O -NGQDs demonstrates a nearly 100 % formate Faraday efficiency (FE) at a moderate overpotential of 0.7 V with a good stability. Strikingly, Bi O -NGQDs exhibit a high activity (average formate FE of 95.6 %) from -0.9 V to -1.2 V vs. RHE. Additionally, DFT calculations reveal that the origin of enhanced activity in this wide negative potential range can be attributed to the increased adsorption energy of CO (ads) and OCHO* intermediate after combination with NGQDs.

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confidence: 99%

Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi₂O₃ Nanosheets for Electrochemical Reduction of CO₂ in a Wide Negative Potential Region

et al. 2018

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“…[3] Catalysts consisting of atomically dispersed transition metals (e.g. [6] Fe-N and Co-N sites show low onset potential for CO 2 RR, whereas the desorption of *CO into the gas phase lowers their reactivity due to the strong binding of CO to the single Fe-o rC o-atom site (Step 3). COOH*; 2) COOH* + H + + e À !…”

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confidence: 99%

Isolated Diatomic Ni‐Fe Metal–Nitrogen Sites for Synergistic Electroreduction of CO₂

et al. 2019

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Polynary single-atom structures can combine the advantages of homogeneous and heterogeneous catalysts while providing synergistic functions based on different molecules and their interfaces.However,the fabrication and identification of such an active-site prototype remain elusive.Here we report isolated diatomic Ni-Fesites anchored on nitrogenated carbon as an efficient electrocatalyst for CO 2 reduction. The catalyst exhibits high selectivity with CO Faradaic efficiency above 90 %overawide potential range from À0.5 to À0.9 V(98 %at À0.7 V), and robust durability,r etaining 99 %o fi ts initial selectivity after 30 hours of electrolysis.D ensity functional theory studies reveal that the neighboring Ni-Fec enters not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO,but also undergo distinct structural evolution into aC O-adsorbed moiety upon CO 2 uptake. Figure 4. a) Calculated free energy diagrams for CO 2 RR yielding CO on different catalysts.b )The catalytic mechanism on diatomic metalnitrogen site based on the optimized structures of adsorbed intermediates COOH* and CO*. c) Difference in limiting potentials for CO 2 reduction and H 2 evolution of different catalysts.

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“…[3] However,t he main problem is that most of the synthetic methods for single-atoms catalysts are based on the bottomup strategy,i nw hich the metal ions are adsorbed on the defect-containing matrix and then reduced to form single atoms in the whole support. Assisted by N-doped carbon with abundant defects,t his synthetic process not only transform the nanoparticles to single atoms,b ut also creates numerous pores to facilitate the contact of dissolved CO 2 and single Ni sites.The proposed mechanism is that the Ni nanoparticles could break surface CÀCb onds drill into the carbon matrix, leaving pores on the surface.W hen Ni nanoparticles are exposed to N-doped carbon, the strong coordination splits Ni atoms from Ni NPs.The Ni atoms are stabilized within the surface of carbon substrate.T he continuous loss of atomic Ni species from the NPs would finally result in atomization of Ni NPs.C O 2 electroreduction testing shows that the surface enriched with Ni single atoms delivers better performance than supported Ni NPs and other similar catalysts.…”

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In Situ Thermal Atomization To Convert Supported Nickel Nanoparticles into Surface‐Bound Nickel Single‐Atom Catalysts

et al. 2018

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The arrangement of the active sites on the surface of ac atalysts can reduce the problem of mass transfer and enhance the atom economy.H erein, supported Ni metal nanoparticles can be transformed to thermal stable Ni single atoms,mostly located on the surface of the support. Assisted by N-doped carbon with abundant defects,t his synthetic process not only transform the nanoparticles to single atoms,b ut also creates numerous pores to facilitate the contact of dissolved CO 2 and single Ni sites.The proposed mechanism is that the Ni nanoparticles could break surface CÀCb onds drill into the carbon matrix, leaving pores on the surface.W hen Ni nanoparticles are exposed to N-doped carbon, the strong coordination splits Ni atoms from Ni NPs.The Ni atoms are stabilized within the surface of carbon substrate.T he continuous loss of atomic Ni species from the NPs would finally result in atomization of Ni NPs.C O 2 electroreduction testing shows that the surface enriched with Ni single atoms delivers better performance than supported Ni NPs and other similar catalysts.Owing to the massive CO 2 production from consuming the carbon-based fuels,c limatic problems have been triggered, especially global warming and glaciers melting. [1] It is urgent to search for the efficient ways to decrease the CO 2 accumulation in air.R ecently,e lectroreduction of CO 2 has been regarded as ap romising approach to decrease CO 2 as well as convert it into the other useful raw materials,such as CO,C H 4 ,C 2 H 4 ,H COOH. [2] Thei deal CO 2 electroreduction heterogeneous catalyst should contain highly dispersed active species on the support and sufficient accessible surface to prevent the problem of the mass transfer.H ence,aporous support is adopted, which could not only stabilize the reactive sites but also guarantee the fast adsorption of reactants and desorption of products.R ecently,s ingle-atom catalysts have drawn much attention for the electroreduction of CO 2 owing to their electrochemical performances and atom economy. [3] However,t he main problem is that most of the synthetic methods for single-atoms catalysts are based on the bottomup strategy,i nw hich the metal ions are adsorbed on the defect-containing matrix and then reduced to form single atoms in the whole support. [4] Based on this bottom-up method, the porous supports are incapable of confining most of the atomic metal species to the surface as they cannot prevent the migration of metal within the support matrix. This will result in the homogeneous distribution of single metal sites within the entire matrix rather than on the surface,a nd results in of mass transportation issues and deactivation of the catalytic process.To tackle this challenge,w ed escribe an ovel top-down strategy,during which the Ni nanoparticles (NPs) distributed on the surface of defect-containing N-doped carbon (NC) supports can be transformed into Ni single atoms on the surface by at hermal diffusion mechanism, which is quite different to the previous reports through vaporizing the nanoparticles ...

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Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction

Cited by 1,847 publications

References 42 publications

Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi₂O₃ Nanosheets for Electrochemical Reduction of CO₂ in a Wide Negative Potential Region

Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi₂O₃ Nanosheets for Electrochemical Reduction of CO₂ in a Wide Negative Potential Region

Isolated Diatomic Ni‐Fe Metal–Nitrogen Sites for Synergistic Electroreduction of CO₂

In Situ Thermal Atomization To Convert Supported Nickel Nanoparticles into Surface‐Bound Nickel Single‐Atom Catalysts

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Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction

Cited by 1,847 publications

References 42 publications

Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi2O3 Nanosheets for Electrochemical Reduction of CO2 in a Wide Negative Potential Region

Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi2O3 Nanosheets for Electrochemical Reduction of CO2 in a Wide Negative Potential Region

Isolated Diatomic Ni‐Fe Metal–Nitrogen Sites for Synergistic Electroreduction of CO2

In Situ Thermal Atomization To Convert Supported Nickel Nanoparticles into Surface‐Bound Nickel Single‐Atom Catalysts

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Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi₂O₃ Nanosheets for Electrochemical Reduction of CO₂ in a Wide Negative Potential Region

Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi₂O₃ Nanosheets for Electrochemical Reduction of CO₂ in a Wide Negative Potential Region

Isolated Diatomic Ni‐Fe Metal–Nitrogen Sites for Synergistic Electroreduction of CO₂