Efficient CO Reduction Reaction on Cu-Decorated Biphenylene.

Developing efficient electrocatalysts for CO reduction into value-added products is crucial for a green economy. Inspired by the recent experimental synthesis of biphenylene (BPH) and the excellent catalytic activity of copper dispersed on two-dimensional (2D) materials, we chose to systematically investigate the pristine, defective, and Cu-decorated BPH for the electrocatalytic CO reduction to value-added hydrocarbons. It is observed that the CO molecules bind weakly to the pristine BPH, indicating their chemical inertness. Carbon single-vacancy defects facilitate CO adsorption with a strong binding energy () of -3.23 eV, detrimental to the CO reduction reaction (CRR) mechanism. We have further investigated the binding energy and kinetic stability of Cu-decorated BPH as a single-atom-catalyst (SAC). The molecular dynamics simulations confirm the kinetic stability, revealing that the Cu-atom avoids agglomeration under low metal dispersal conditions. The CO molecule gets adsorbed horizontally on the Cu-BPH surface with a Δ of -0.52 eV. The CRR mechanism is investigated using two pathways beginning with two different initial states, formate (*OCOH) and carboxylic (*COOH). The formate pathway confirms the conversion of *OCOH to *HCOOH with the rate-limiting potential () of 0.39 eV for the production of HCOOH, while for the carboxylic pathway, the conversion of *COH to *CHOH has a of 0.32 eV, eventually producing CHOH. Our findings highlight the role of Cu-BPH as an efficient SAC for CO catalytic activity to C1 products, as compared to the state-of-the-art Cu, and holds promise as an electrocatalyst for CRR.