Importance of broken geometric symmetry of single-atom Pt sites for efficient electrocatalysis

Abstract

Platinum single-atom catalysts hold promise as a new frontier in heterogeneous electrocatalysis. However, the exact chemical nature of active Pt sites is highly elusive, arousing many hypotheses to compensate for the significant discrepancies between experiments and theories. Here, we identify the stabilization of low-coordinated Pt-II species on carbon-based Pt single-atom catalysts, which have rarely been found as reaction intermediates of homogeneous Pt-II catalysts but have often been proposed as catalytic sites for Pt single-atom catalysts from theory. Advanced online spectroscopic studies reveal multiple identities of Pt-II moieties on the single-atom catalysts beyond ideally four-coordinated Pt-II-N-4. Notably, decreasing Pt content to 0.15 wt.% enables the differentiation of low-coordinated Pt-II species from the four-coordinated ones, demonstrating their critical role in the chlorine evolution reaction. This study may afford general guidelines for achieving a high electrocatalytic performance of carbon-based single-atom catalysts based on other d(8) metal ions. Electrochemical CO2 conversion to methane offers a promising solution for the large-scale storage of renewable electricity, yet the catalytic selectivity at high current density still needs to be refined. Here the authors report to use both dissolved CO2 and in-situ generated CO2 from bicarbonate to sustain high local CO2 concentration around Cu electrode and thus achieve selective CO2 conversion to methane.