![]() The introduction of organic structures onto catalytically active metal surfaces has recently received attention, particularly the preparation of self-assembled monolayers (SAMs). Other nanostructured Cu materials synthesized via various preparation methods ( Tang et al., 2011 Li and Kanan, 2012 Reske et al., 2014 Ma et al., 2015 Kim et al., 2017 Zhao et al., 2017 Jeon et al., 2018 Luna et al., 2018) and alloys comprising copper and other elements are reported to show excellent performance in C2-C3 product formation ( Long et al., 2017 Ma et al., 2017 Zhang et al., 2017). Furthermore, their nano-scale morphology influences local pH, and the remaining oxygen atoms are considered to influence the electronic nature of the surface. Oxide-derived Cu nanostructures are of current interest ( Kas et al., 2014 Ren et al., 2015 Dutta et al., 2016 Handoko et al., 2016 Mistry et al., 2016 Huang et al., 2017 Mandal et al., 2018) however, their high C2-C3 selectivity has not been fully elucidated, as these materials typically include multiple Cu facets endowing various activities. Product distribution is known to be highly influenced by the applied potential ( Hori et al., 2003 Gattrell et al., 2006 Kuhl et al., 2012), Cu crystal facet ( Hori et al., 2003 Gupta et al., 2006 Schouten et al., 2012 Huang et al., 2017 Qiu et al., 2017), and proton transfer conditions ( Hori et al., 1997 Singh et al., 2016 Varela et al., 2016 Ooka et al., 2017). Since common polycrystalline copper surfaces can yield various types of hydrocarbons, product distribution is difficult to control, especially for the selective formation of valuable C2-C3 products such as ethylene and ethanol. The specific character of copper allows highly reduced hydrocarbons to be obtained at relatively large negative potentials, unlike other catalysts, which mainly afford formate and CO ( Gattrell et al., 2006 Peterson and Nørskov, 2012 Zhang et al., 2014 Feaster et al., 2017). The reduction of CO 2 on metal copper cathodes has been of interest since it was first reported by Hori in 1985 ( Hori et al., 1985, 1986). The suppression of H 2 evolution, a high methane/ethylene ratio, and the influence of stirring demonstrate that the improved CO 2 reduction activity is not only a result of the copper atom reorganization accompanied by repeating anodization for modification the organic layer also apparently plays an important role in proton transfer and CO 2 accumulation onto the copper surface. Preventing organic moieties from forming densely packed assemblies on the metal surface appears to be important to promote the CO 2 reduction process on the copper atoms. ![]() The CO 2 reduction performance of the on-surface modified copper cathode exhibited improved CO 2 reduction over H 2 evolution compared with traditional cast modification systems. ![]() The resulting structure possesses copper surface atoms that are available to participate in the CO 2 reduction reaction-comparable to close-contact organic structures-and stabilize the adsorption of organic layers through the CO 2 reduction process. ![]() Poorly soluble organic polymers were distributed onto the copper surface as a thin layer by polymerizing monomeric precursors via a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) activated by anodization of the copper substrate. In this study, organic structures were introduced onto copper cathodes to induce changes in their electrocatalytic CO 2 reduction activity. Department of Chemistry, Graduate School of Science, Hiroshima University, Higashihiroshima, Japan.Ryota Igarashi Ryuji Takeuchi Kazuyuki Kubo Tsutomu Mizuta Shoko Kume *
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