2D–2D Nanoheterostructure of an Exposed {001}-Facet CuO and MoS(2) Based Bifunctional Catalyst Showing Excellent Surface Chemistry and Conductivity for Cathodic CO(2) Reduction

[Image: see text] A novel CuO-MoS(2) based heterostructure catalyst model system is proposed where a CuO nanosheet with exposed {001} facet with proper termination is the active surface for the catalysis and a MoS(2) nanosheet is the supporting layer. Density functional theory (DFT) calculations were performed to validate the model. The MoS(2) bilayer forms a stable heterostructure with {001} faceted CuO with different terminations exposing oxygen and copper atoms (active sites) on the surface. The heterostructure active sites with a low oxidation state of the copper atoms and subsurface oxygen atoms provide a suitable chemical environment for the selective production of multicarbon products from CO(2) electrocatalytic reduction. Furthermore, our heterostructure model exhibits good electrical conductivity, efficient electron transport to active surface sites, and less interfacial resistance compared to similar heterostructure systems. Additionally, we propose a photoenhanced electrocatalysis mechanism due to the photoactive nature of MoS(2). We suggest that the photogenerated carrier separation occurs because of the interface-induced dipole. Moreover, we utilized a machine learning model trained on a 2D DFT materials database to predict selected properties and compared them with the DFT results. Overall, our study provides insights into the structure–property relationship of a MoS(2) supported 2D CuO nanosheet based bifunctional catalyst and highlights the advantages of heterostructure formation with selective morphology and properly terminated surface in tuning the catalytic performance of nanocomposite materials.