Electrochemical reduction of CO2 at the earth-abundant transition metal-oxides/copper interfaces

Metal/metal-oxide interface catalysed thermal and electrochemical CO2 conversion: a perspective from DFT-based studies

“…To overcome this limitation, metals with a moderate oxygen affinity can be used as they are Group 8-10 3d metals, including Fe, Co, and Ni, have a weaker oxophilicity than Ti and may provide a balanced C-O activation activity and oxygen affinity. Therefore, we have constructed interfacial models based on oxides of these metals and selected Cu(100) as the electrode metal 39 and anticipated that the interface would lower the limiting potential and enhance the product selectivity for electrochemical CO 2 reduction from those on copper. In fact, heterostructured Cu/oxide electrodes with appropriate oxides have been shown to offer unique interfacial boundaries for the CO 2 reduction reactions.…”

“…22 In this perspective, we focus on our recent efforts in understanding the role of metal/metal-oxide interfaces in heterogenous thermal and electrochemical CO 2 reduction and conversion. [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39]…”

“…Possible reaction pathways for electrochemical reduction from adsorbed CO 2 to CO (g) , CH 2 O (l) , HCOOH (l) , CH 3 OH (l) and CH 4(g) are presented in Scheme 1. 39 Note that the adsorbed states were also shown with ''*'' either on the left or the right of the species, depending on publications. Proton-coupled electron transfer (PCET, i.e., H + + e À ) to C and O are referred to as hydrogenation and protonation, respectively.…”

Comparative Study of Computational Hydrogen Electrodes and Constant Electrode Potential Models Applied to Electrochemical Reduction of CO2 and Oxygen Evolution Reaction on Metal Oxides/Copper Catalysts

“…Computational methods and the metal-oxide/copper model catalysts for ERCO 2 as well as the FeNi oxides for the OER have already been detailed in our previous studies using the CHE model. , A graphical representation of the model catalysts is provided in Figure S1. Briefly, we used the VASP code with PAW potentials, and PBE functional and 400 eV cutoff energy for the plane-wave basis set. − We used (FeO) 4 /Cu­(100), (CoO) 4 /Cu­(100), and (NiO) 4 /Cu­(100) as the model catalysts and treated the oxide/Cu(111) interfacial sites and top sites on the metal oxides as the active sites for ERCO 2 and the OER, respectively.…”

“…In our previous studies, we investigated ERCO 2 at metaloxide/copper interfaces and OER on FeNi oxides using the CHE model. 14,34 Herein, we studied ERCO 2 to CH 4(g) / CH 3 OH (l) and the OER on metal-oxide/copper (MO) 4 / Cu(100), M = Fe, Co, and Ni) using the CHE and CEP models. Our results show that optimized structures and free energies of some key intermediates obtained from the CEP model are different from those calculated based on the CHE model, resulting in different limiting potentials and product selectivity for ERCO 2 .…”