Molecular Scaffolding Strategy with Synergistic Active Centers To Facilitate Electrocatalytic CO Reduction to Hydrocarbon/Alcohol.

A major impediment to the electrocatalytic CO reduction reaction (CRR) is the lack of electrocatalysts with both high efficiency and good selectivity toward liquid fuels or other valuable chemicals. Effective strategies for the design of electrocatalysts are yet to be discovered to substitute the co...

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Publicado en:Journal of the American Chemical Society Vol. 139; no. 49; pp. 18093 - 18101
Autores principales: Yan Jiao, Yao Zheng, Ping Chen, Jaroniec, Mietek, Shi-Zhang Qiao
Formato: Artículo
Publicado: American Chemical Society 12/13/2017
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Acceso en línea:Ver este registro en EBSCOhost
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      jtl: Journal of the American Chemical Society
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      dt: 12/13/2017
      vid: 139
      iid: 49
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      pub: American Chemical Society
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        126761890
        10.1021/jacs.7b10817
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        atl: Molecular Scaffolding Strategy with Synergistic Active Centers To Facilitate Electrocatalytic CO Reduction to Hydrocarbon/Alcohol.
      aug:
        au:
          Yan Jiao
          Yao Zheng
          Ping Chen
          Jaroniec, Mietek
          Shi-Zhang Qiao
        affil:
          School of Chemical Engineering, The University of Adelaide, Adelaide, South Australia 5005, Australia
          School of Chemistry and Chemical Engineering, Anhui University, Hefei 230000, P. R. China
          Department of Chemistry and Biochemistry, Kent State University, Kent, Ohio 44242, United States
          School of Materials Science and Engineering, Tianjin University, Tianjin 300072, P. R. China
      su:
        Carbon dioxide reduction
        Electrocatalysis
        Scaffold proteins
        Hydrocarbons
        Alcohols (Chemical class)
        Density functional theory
      sug:
        subj:
          Carbon dioxide reduction
          Electrocatalysis
          Scaffold proteins
          Hydrocarbons
          Alcohols (Chemical class)
          Density functional theory
      ab: A major impediment to the electrocatalytic CO reduction reaction (CRR) is the lack of electrocatalysts with both high efficiency and good selectivity toward liquid fuels or other valuable chemicals. Effective strategies for the design of electrocatalysts are yet to be discovered to substitute the conventional trial-and-error approach. This work shows that a combination of density functional theory (DFT) computation and experimental validation of molecular scaffolding to coordinate the metal active centers presents a new molecular-level strategy for the development of electrocatalysts with high CRR selectivity toward hydrocarbon/ alcohol. Taking the most widely investigated Cu as a probe, our study reveals that the use of graphitic carbon nitride (g-CN) as a molecular scaffold allows for an appropriate modification of the electronic structure of Cu in the resultant Cu-CN complex. As a result, the adsorption behavior of some key reaction intermediates can be optimized on the Cu-CN surface, which greatly benefits the activation of CO and leads to a more facile CO reduction to desired products as compared with those on the Cu(111) surface and other kinds of Cu complexes formed on nitrogen-doped carbons. Remarkably, different from the most studied elementary metal surfaces, an intramolecular synergistic catalysis with dual active centers was for the first time observed on the Cu-CN complex model, which possesses a unique capability to generate C products. A good agreement between electrochemical measurements and the DFT analysis of the CRR has been achieved on the basis of the newly designed and synthesized Cu-CN electrocatalyst.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2017
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