Is Cu instability during the CO2 reduction reaction governed by the applied potential or the local CO concentration?

Cu-based catalysts have shown structural instability during the electrochemical CO2 reduction reaction (CO2RR). However, studies on monometallic Cu catalysts do not allow a nuanced differentiation between the contribution of the applied potential and the local concentration of CO as the reaction intermediate since both are inevitably linked. We first use bimetallic Ag-core/porous Cu-shell nanoparticles, which utilise nanoconfinement to generate high local CO concentrations at the Ag core at potentials at which the Cu shell is still inactive for the CO2RR. Using operando liquid cell TEM in combination with ex situ TEM, we can unequivocally confirm that the local CO concentration is the main source for the Cu instability. The local CO concentration is then modulated by replacing the Ag-core with a Pd-core which further confirms the role of high local CO concentrations. Product quantification during CO2RR reveals an inherent trade-off between stability, selectivity and activity in both systems.W. S. is grateful for financial support by the Deutsche Forschungsgemeinschaft under Germany's Excellence Strategy – EXC 2033 – 390677874 – RESOLV and the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (CasCat; grant agreement No. 833408). This work was supported by the DAAD in the framework of the PPP project 57446293 as well as the Ruhr University Research School PLUS through a research stay of P. W. at UNSW. This research was financially supported by the Australian Research Council of Centre of Excellence in Convergent Bio-Nano Science and Technology (CE140100036), the ARC Laureate Fellowship (FL150100060) and the Discovery Project (DP190102659). The Mark Wainwright Analytical Centre (MWAC) at UNSW. This work used the facilities supported by Microscopy Australia at the Electron Microscope Unit at UNSW. Wei Xia is acknowledged for his contribution to the CO measurements. P. B. O'M. acknowledges the Australian Government Research Training Program Scholarship for financial support. P. W. is grateful to the Association of the Chemical Industry (VCI) for funding of the PhD fellowship