The nature of local oxygen radical boosts electrocatalytic ethanol to selectively generate CO2

doi:10.1016/S1872-2067(23)64503-6

Abstract

Abstract:

Developing a high-activity and antitoxic electrocatalyst is still a demanding task. Enhancing the enrichment of oxygen species on catalysts is beneficial for thorough oxidation of ethanol to generate CO₂, but the role of oxygen radicals in the process of ethanol oxidation is still ambiguous. Herein, an artificial oxidase that can catalyze oxygen to generate reactive oxygen species (ROS) in-situ has been applied in EOR for the first time and the roles of •OH, •O₂^-, and ¹O₂ in complete oxidation of ethanol were investigated. The mass activity of EOR is 18.2 A mg_Pt^-1 in 1 mol L^-1 KOH and the CO₂ selectivity is 98.7%. The research showed that Sn element could optimize coordination mode on catalyst surface, which enhanced oxidase activity of the catalyst. Explored the intermediates of the reaction and evaluated the performance of the catalyst using in-situ infrared testing technology. Theoretical calculations indicate that C-C bond breakage of *CH₃CO to generate *CH₃ and *CO is potential determination steps in the C1 pathway. When singlet oxygen is present on the PtSn IM/C surface, the dissociation energy of C-C bond is -0.51 eV, which is lower than the 1.07 eV of hydroxyl radicals and -0.47 eV of superoxide anions.

Key words: Ethanol, High performance, Dissociation energy, Radicals

Shuanglong Zhou, Liang Zhao, Zheng Lv, Yu Dai, Qi Zhang, Jianping Lai, Lei Wang. The nature of local oxygen radical boosts electrocatalytic ethanol to selectively generate CO₂[J]. Chinese Journal of Catalysis, 2023, 52: 154-163.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64503-6

https://www.cjcatal.com/EN/Y2023/V52/I9/154

Figures/Tables 4

Fig. 1. Structure, morphology and XPS of PtSn nanocatalyst. (a) TEM image of PtSn IM nanoclusters. The inset shows diameter-distribution of PtSn IM nanoclusters. (b) HRTEM image of PtSn IM nanoclusters. (c) Enlarged HRTEM from the green box in Fig. (b). (d) HAADF image and mapping results of PtSn IM nanoclusters. (e) XRD patterns of PtSn IM nanoclusters. (f) XPS fine spectra of Sn 3d. (g) XPS fine spectra of Pt 4f.

Fig. 2. EOR performance and in-situ infrared test. (a) CV curves in N2-saturated or O2-saturated solution containing 1.0 mol L-1 KOH and 1.0 mol L-1 ethanol with a scan rate of 50 mV s?1. (b) Activity comparison chart of in the absence or presence of artificial oxidase. (c) CO stripping curves in the absence or presence of artificial oxidase. (d) In-situ FTIR spectra without artificial oxidase. (e) In-situ FTIR spectra with artificial oxidase. (f) Faraday efficiency at different voltages in electrolytes with and without artificial oxidase. (g) Comparison of the activity of the reported electrocatalysts. (h) 40-h of i-t measurement and corresponding Faraday efficiency of CO2.

Fig. 3. Free radical test. (a) The absorption spectra of MB with or without artificial oxidase. (b) The absorption spectra of TMB with or without artificial oxidase. (c) Excitation spectra and emission spectra of TA with or without artificial oxidase. (d) The absorption spectra of DPBF with or without artificial oxidase. (e) The emission spectra of in the presence or absence of artificial oxidase. (f) The fluorescence spectra of HE in the presence or absence of artificial oxidase. ESR testing spectra of hydroxyl (g), superoxide anion (h), and singlet oxygen (i).

Fig. 4. Research on reaction mechanism. (a) The CV test results with different scavengers. (b) Faraday efficiency of artificial oxidase with different scavengers. (c) The UV absorption spectra of MB under the action of different scavengers. Transition States and Energy of C1 (d) and C2 (e) Paths. (f) The C-C bond dissociation energy of different radicals on catalyst surface. (g) The proposed reaction path.

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The nature of local oxygen radical boosts electrocatalytic ethanol to selectively generate CO₂

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