Abstract:

Electrochemical reduction of CO₂ to high value-added hydrocarbon fuels and chemicals has emerged as an effective strategy to achieve carbon neutrality. In conventional electrocatalytic powder-coated electrodes fabricated by spraying method, poor contact between electrocatalyst and substrate can severely impact the electrocatalytic activity and stability. Herein, a self-supporting nanotree electrode (Bi@Cu NTs) for efficient electroreduction from CO₂ to formate was structured by combing facile electrodeposition method and galvanic replacement reaction. The advantages of self-supporting nanotree structure including: 1) minimization of the interfacial resistance and improvement of the spatial structure stability; 2) rich active sites and plentiful pore structures. The charge transfer resistant could be effectively reduced while ensuring the stability of the electrode operation. Results demonstrated that the prepared Bi@Cu NTs electrode exhibited outstanding performance for CO₂ conversion in both electrochemical activity and long-term operation stability. In a wide operating potential window from -1.4 to -0.8 V (vs. RHE), the proposed Bi@Cu NTs electrode presented excellent formate selectivity, where the Faradaic efficiency of CO₂-to-formate (FE_Formate) at each operating potential was above 90%. Typically, at -1.2 V, the proposed electrode achieved a high FE_Formate of 97.9% and a current density of 170.6 mA·cm^-2, simultaneously. Meanwhile, the self-supporting Bi@Cu NTs electrode also revealed excellent stability in a long-term operation, as evidenced by maintaining an average FE_Formate of more than 90% and an average current density higher than 110 mA·cm^-2 over 50 h of continuous electrolysis at a controlled potential of -1.0 V without any degradation in performance.

Key words: electrochemical reduction CO₂, formate, self-supporting electrode, nanotree structure, Bi nanosheet