Efficient Electrochemical CO2 Reduction Reaction over Cu-decorated Biphenylene

Abstract: Developing efficient electrocatalysts for CO$_2$ reduction into value-added products is crucial for the green economy. Inspired by the recent synthesis of Biphenylene (BPH), we have systematically investigated pristine, defective, and Cu-decorated BPH as an electrocatalyst for the CO$_2$ reduction reactions (CRR). Our first-principles calculations show the CO$_2$ molecules weakly interact with the pristine BPH surface while defective BPH facilitates the CO$_2$ adsorption with a binding energy ($E_b$) of -3.22 eV, indicating the detrimental process for the CRR on the surface of both systems. Furthermore, we have 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$_2$ molecule gets adsorbed horizontally on the Cu-BPH surface with $E_b$ of -0.52 eV. The CRR mechanism is investigated using two pathways beginning with two different initial intermediate states, formate ($\mathrm{^*OCOH}$) and the carboxylic ($\mathrm{^*COOH}$) pathways. The formate pathway confirms the conversion of $\mathrm{^*OCOH}$ to $\mathrm{^*HCOOH}$ with the rate-limiting potential ($U_L$) of 0.57 eV for the production of HCOOH, while for the carboxylic pathway, the conversion of $\mathrm{^*COH}$ to $\mathrm{^*CHOH}$ has $U_L$ of 0.49 eV for the production of CH$_3$OH. We have also investigated the effect of protons using charged hydrogen pseudopotential, which hints towards the possible formation of CH$_3$OH as fuel. Our findings propose Cu-BPH as an efficient single-atom catalyst for CO$_2$ conversion compared to the well-known Cu metal.