Efficient CO2 Reduction Reaction on Cu-Decorated Biphenylene

• Published in: ACS applied materials & interfaces 2024-11, Vol.16 (44), p.60094-60102
• Main Authors: Somaiya, Radha N, Sajjad, Muhammad, Singh, Nirpendra, Alam, Aftab
• Format: Article
• Language: English
• Subjects: Energy, Environmental, and Catalysis Applications
• ISSN: 1944-8244; 1944-8252; 1944-8252
• DOI: 10.1021/acsami.4c08499

Developing efficient electrocatalysts for CO2 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 CO2 reduction to value-added hydrocarbons. It is observed that the CO2 molecules bind weakly to the pristine BPH, indicating their chemical inertness. Carbon single-vacancy defects facilitate CO2 adsorption with a strong binding energy (E b) of −3.23 eV, detrimental to the CO2 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 CO2 molecule gets adsorbed horizontally on the Cu-BPH surface with a ΔE b 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 (U L) of 0.39 eV for the production of HCOOH, while for the carboxylic pathway, the conversion of *COH to *CHOH has a U L of 0.32 eV, eventually producing CH3OH. Our findings highlight the role of Cu-BPH as an efficient SAC for CO2 catalytic activity to C1 products, as compared to the state-of-the-art Cu, and holds promise as an electrocatalyst for CRR.