Boosting 5-hydroxymethylfurfural electrooxidation in neutral electrolytes via TEMPO-enhanced dehydrogenation and OH adsorption

doi:10.1016/S1872-2067(22)64203-7

Abstract

Abstract:

5-Hydroxymethylfurfural (HMF) electrooxidation in neutral conditions is a promising strategy to suppress the formation of humins and corrosive effects on electrochemical devices. However, scarce studies have been reported in neutral media due to the deficiency in electrophilic oxygen (eg OH^‒) required for the activation of HMF. Herein, 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO)/Co₃O₄ was utilized to co-catalyze HMF in neutral media, successfully achieving 2,5-furandicarboxylic acid (FDCA) with yield > 99%. It was found that TEMPO could promote HMF dehydrogenation to 2,5-diformylfuran (DFF) and simultaneously activated water via hydrogen-bonding interactions. As a result, the formation of OH^* in neutral electrolytes was favored, which was absorbed by electrogenerated active Co species to facilitate subsequent conversion of formyl-group-involved intermediates to FDCA. This work provides a current understanding of the catalytic mechanism for HMFOR in neutral media and guides the design of highly efficient electrocatalysts for biomass upgrading.

Key words: 5-Hydroxymethylfurfural, Electrooxidation, 2,2,6,6-tetramethyl-piperidine-1-oxyl, Neutral electrolyte, Biomass electrocatalysis

Hongfang Wang, Leitao Xu, Jingcheng Wu, Peng Zhou, Shasha Tao, Yuxuan Lu, Xianwen Wu, Shuangyin Wang, Yuqin Zou. Boosting 5-hydroxymethylfurfural electrooxidation in neutral electrolytes via TEMPO-enhanced dehydrogenation and OH adsorption[J]. Chinese Journal of Catalysis, 2023, 46: 148-156.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64203-7

https://www.cjcatal.com/EN/Y2023/V46/I3/148

Figures/Tables 5

Fig. 1. (a) XRD pattern of bare NF and Co3O4/NF. SEM (b) and TEM (c) images of Co3O4. (d) LSV curves of Co3O4 in PBS electrolytes with different substrates. (e) Conversion of HMF, yield, and Faradaic efficiency (FE) of FDCA for 10 mmol L-1 HMF oxidation on Co3O4 at 1.55 VRHE for 1.5 h in the absence and presence of 20 mmol L-1 TEMPO. (f) Yield and FE of FDCA in relationship with the electrolysis potential.

Fig. 2. (a,b) Product quantitative analysis by HPLC during HMF electrolysis on Co3O4 at 1.55 VRHE in the absence (duration 47 h) and presence of TEMPO (duration 1.5 h). (c) Two possible pathways of HMF oxidation to FDCA. (d,e) Operando ATR-SEIRAS spectra traced for Co3O4-catalyzed HMF oxidation in the absence and presence of TEMPO.

Fig. 3. HMF oxidation reaction profiles by hydration reaction mechanism (black color) and TEMPO-mediated mechanism (orange color). RC is the reaction complex of TEMPO+ and HMF. 1 is the hydrated HMF. The TS and TS-1 represent the transition state for HMF oxidation via TEMPO and hydration reaction, respectively. Int-1 and DFF-H+ are HMF intermediates formed correspondingly by two routes.

Fig. 4. Operando Bode phase plots of Co3O4 at various applied potentials in blank neutral PBS electrolytes (a) and the counterparts with 10 mmol L?1 HMF (b), 10 mmol L?1 TEMPO (c), and the coexistence of 10 mmol L?1 HMF and TEMPO (d). Preferential H-bond distance and structure change of H2O molecule under the effect of TEMPO radical (e) and TEMPO+ cation (f).

Fig. 5. (a) Co 2p3/2 XPS spectrum fitting for Co3O4 pre-treated after catalyzing HMF oxidation at corresponding potentials. (b) Current density for HMF electrolysis on different electrodes at different potentials (E = 1.05-1.65 VRHE) in 1 mol L?1 PBS neutral solutions (HMF 10 mmol L?1, TEMPO 20 mmol L?1). (c) A scheme depicts the possible reaction process for HMF electrooxidation on the Co3O4 electrode in neutral electrolytes under the effects of TEMPO.

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