Potential Link between Cu Surface and Selective CO2 Electroreduction: Perspective on Future Electrocatalyst Designs.

Electrochemical reduction of carbon dioxide (CO2 RR) product distribution has been identified to be dependent on various surface factors, including the Cu facet, morphology, chemical states, doping, etc., which can alter the binding strength of key intermediates such as *CO and *OCCO during reduction. Therefore, in-depth knowledge of the Cu catalyst surface and identification of the active species under reaction conditions aid in designing efficient Cu-based electrocatalysts. This progress report categorizes various Cu-based electrocatalysts into four main groups, namely metallic Cu, Cu alloys, Cu compounds (Cu + non-metal), and supported Cu-based catalysts (Cu supported by carbon, metal oxides, or polymers). The detailed mechanisms for the selective CO2 RR are presented, followed by recent relevant developments on the synthetic procedures for preparing Cu and Cu-based nanoparticles. Herein, the potential link between the Cu surface and CO2 RR performance is highlighted, especially in terms of the chemical states, but other significant factors such as defective sites and roughened morphology of catalysts are equally considered during the discussion of current studies of CO2 RR with Cu-based electrocatalysts to fully understand the origin of the significant enhancement toward C2 formation. This report concludes by providing suggestions for future designs of highly selective and stable Cu-based electrocatalysts for CO2 RR.

Reactive nanotemplates for synthesis of highly efficient electrocatalysts: beyond simple morphology transfer.

Efficient electrocatalysts for energy conversion in general, and fuel cell operation and water electrolysis in particular, are pivotal for carbon-free hydrogen production. While the requirements of successful electrocatalysts include a high number density of catalytically active sites, high surface-to-volume ratio, inherently high catalytic activity, and robustness of the catalyst surface structure under harsh operating conditions, it is extremely difficult to synthesize nanocatalysts that could possess all these structural characteristics. Nanotemplate-mediated synthesis, namely, the coating or filling of a template with a desired material phase followed by the removal of the template, has captured the interest of researchers because of the ease of creating hollow-structured nanocatalysts with a high surface to volume ratio. Recent studies, however, have revealed that nanotemplates could be more than just passive supports because they greatly affect catalytic performance by creating an unusual synergy between the substrate and catalyst and by providing dopants to the actual catalyst phase owing to their reactive nature. In this review, we discuss the most notable recent advances in the nanotemplate-based synthesis of electrocatalysts as well as the unusual effects of nanotemplates on the performance of nanocatalysts. We also provide an outlook for this fledgling field so that future research efforts could be focused on the development of practically useful electrocatalysts that could shape the future of energy technologies.