Enhanced electrocatalytic glycerol oxidation on CuCoN0.6/CP at significantly reduced potentials

doi:10.1016/S1872-2067(23)64515-2

Abstract

Abstract:

Electrocatalytic alcohol oxidation coupled with the hydrogen evolution reaction, wherein a thermodynamically favorable oxidation reaction replaces the sluggish kinetics of the oxygen evolution reaction, has recently attracted considerable attention. However, the development of nonprecious-metal electrocatalysts capable of delivering much lower oxidation potentials holds great significance. In this study, we proposed and developed CuCoN_0.6 nanowires loaded on conductive carbon paper (denoted as CuCoN_0.6/CP) as an efficient catalyst for selective glycerol oxidation to formate. Our catalyst achieved a remarkably high faradic efficiency of 90.0% towards formate production. More notably, it required an anode potential as low as 1.07 V to achieve a current density of 10 mA cm⁻², a significantly lower potential than that reported in the literature. Experimental characterizations reveal that the oxidations of Cu⁺ and Co²⁺ ions promoted the formation of reactive hydroxyl species, which are responsible for the substantially reduced oxidation potential and enhanced glycerol oxidation performance. Furthermore, we investigated the reaction pathway of glycerol oxidation and structural changes in the catalysts. The catalyst reconstruction led to the formation of CoOOH, which is considered as the active site for glycerol oxidation. Finally, we successfully separated high-purity and value-added potassium diformate product. This work not only advances the electrocatalytic conversion of biomass-derived alcohols but also provides insights into the design of electrocatalysts with broad applications.

Key words: Electrocatalysis glycerol oxidation, Reactive hydroxyl species, In-situ reconstruction, Lower potential

Kai Shi, Di Si, Xue Teng, Lisong Chen, Jianlin Shi. Enhanced electrocatalytic glycerol oxidation on CuCoN_0.6/CP at significantly reduced potentials[J]. Chinese Journal of Catalysis, 2023, 53: 143-152.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64515-2

https://www.cjcatal.com/EN/Y2023/V53/I10/143

Figures/Tables 6

Fig. 1. (a) Schematic illustration for the synthesis of CuCoN0.6/CP. (b-d) SEM images of CP, CuCo2O4/CP, and CuCoN0.6/CP. TEM (e) and HRTEM (f) images of CuCoN0.6/CP. (g) SEM-EDS mapping of CuCoN0.6/CP.

Fig. 2. (a) XRD patterns of CuCoN0.6/CP and CuCo2O4/CP. (b) Raman spectra of CuCoN0.6/CP and CuCo2O4/CP. (c) XPS survey spectrum of CuCoN0.6/CP and CuCo2O4/CP. High-resolution XPS spectra of Cu 2p (d), Co 2p (e), and N 1s (f) of CuCoN0.6/CP and CuCo2O4/CP.

Fig. 3. Electrocatalytic performances of CuCoN0.6/CP toward glycerol oxidation at the anode. (a) LSV curves of CuCoN0.6/CP anode in 1.0 mol L?1 KOH with or without 0.1 mol L?1 glycerol addition. Scan rate, 10 mV s?1. (b) Tafel plots for the anodic glycerol oxidation or OER derived from (a). (c) LSV curves of obtained electrocatalyst for glycerol anodic oxidation. (d) Tafel slopes of CuCoN0.6/CP, CuCo2O4/CP and CP. EIS plots (e) and double layer capacitance (Cdl) (f) of CuCoN0.6/CP, CuCo2O4/CP and CP. (g) Schematic illustration for concurrent electrolytic hydrogen and formate productions from glycerol solution. (h) FEs of CuCoN0.6/CP for formate production for 12 h chronoamperometry at varied potentials. (i) FEs of CuCoN0.6/CP for formate production for 5 successive electrolysis cycles.

Fig. 4. (a) In-situ electrochemical FTIR spectra of GOR catalyzed by CuCoN0.6/CP. (b) 1H NMR spectra of products before and after 3 or 12 h anodic glycerol oxidation on CuCoN0.6/CP electrode by using maleic acid as the internal standard. (c) Proposed dominant pathway of glycerol electro-catalytic oxidation to formate on CuCoN0.6/CP in an alkaline medium.

Fig. 5. (a) CV curves of CuCoN0.6/CP and CuCo2O4/CP in 1.0 mol L?1 KOH at a scan rate of 10 mV s?1. (b) LSV curves of CuCoN0.6/CP, CuCo2O4/CP, Co2N/CP and Cu/CP in 1.0 mol L?1 KOH with 0.1 mol L?1 glycerol addition. The Nyquist plots (c) and corresponding Bode phase plots (d) of CuCoN0.6/CP electrode at varied potentials in 1.0 mol L?1 KOH. The Nyquist plots (e) and corresponding Bode phase plots (f) of CuCoN0.6/CP electrode at varied potentials in 1.0 mol L?1 KOH with 0.1 mol L?1 glycerol. (g) In-situ Raman spectra of the CuCoN0.6/CP anode collected in 1.0 mol L?1 KOH with 0.1 mol L?1 glycerol. High-resolution Co 2p (h) and O 1s (i) XPS spectra of CuCoN0.6/CP before and after GOR at the anode.

Fig. 6. Membrane-free flow cell for glycerol oxidation. (a) A MEA setup for paired HER (-) // glycerol oxidation (+). (b) LSV curves of CuCoN0.6/CP in 1 mol L?1 KOH with 0.1 mol L?1 glycerol in single cell or flow cell. (c) Stability tests of CuCoN0.6/CP toward GOR. (d) XRD pattern of self-prepared C2H3KO4.

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