pH-Induced selective electrocatalytic hydrogenation of furfural on Cu electrodes

doi:10.1016/S1872-2067(22)64119-6

Abstract

Abstract:

The efficient and selective electrocatalytic hydrogenation (ECH) of furfural is considered a green strategy for achieving biomass-derived high-value chemicals. Regulating an aqueous electrolytic environment, a green hydrogen energy source of water, is significant for improving the selectivity of products and reducing energy consumption. In this study, we systematically investigated the mechanism of pH dependence of product selectivity in the ECH of furfural on Cu electrodes. Under acidic conditions, the oxygen atom dissociated directly from hydrogenated furfural-derived alkoxyl intermediates, followed by stepwise hydrogenation until H₂O formation via a thermodynamically favorable proton-coupled electron transfer process, thereby inducing a high proportion of the hydrogenolysis product (2-methylfuran). However, under partial alkaline conditions, furfural could be directly hydrogenated to furfuryl alcohol (selectivity ~98%) due to the high-energy barrier of the deoxidation process via a surface hydride (H_ad) transfer. Our results highlight the vital role of the electrolytic environment in furfural selective conversion and broaden our fundamental understanding of hydrodeoxygenation reactions in ECH.

Key words: Electrocatalytic hydrogenation, Biomass, pH Dependence, Mechanism

Ling Zhou, Yingying Li, Yuxuan Lu, Shuangyin Wang, Yuqin Zou. pH-Induced selective electrocatalytic hydrogenation of furfural on Cu electrodes[J]. Chinese Journal of Catalysis, 2022, 43(12): 3142-3153.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64119-6

https://www.cjcatal.com/EN/Y2022/V43/I12/3142

Figures/Tables 6

Fig. 1. (a) Proposed reaction pathway for the ECH of FF in the aqueous electrolyte on the Cu electrode. (b) Observed FE% of corresponding product and the selectivity after electrolysis on electrodeposited Cu foam electrodes at -20 mA cm-2 for 30 min in phosphate buffers with 25 mmol L-1 FF of various pH electrolytes. (c) LSVs on electrodeposited Cu foam electrodes in pH 2 electrolytes with the addition of 25 mmol L-1 FF or 25 mmol L-1 FA. (d) Electrolyte composition after electrolysis on electrodeposited Cu foam electrodes at -20 mA cm-2 for 30 min in phosphate buffers with 25 mmol L-1 FA in pH = 2 and 8.

Table 1 Reaction pathways of HER and ECH of FF on the Cu electrode in acid and alkaline electrolytes.

Reaction	Mechanism	Possible rate-determining step	Tafel slope (mV dec^-1)	Reaction (acidic solution)	Reaction (alkaline solution)
HER reaction	Volmer-Heyrovsky mechanism	Volmer reaction: electrochemical adsorption	≈ 120	M + H⁺ + e^- ⇌ M-H* (1)	M + H₂O + e^- ⇌ M-H* + OH^- (3)
HER reaction	Volmer-Heyrovsky mechanism	Heyrovsky reaction: Electrochemical desorption	≈ 40	M-H* + H⁺ + e^- ⇌ M + H₂(2)	M-H* + H₂O + e^- ⇌ M + OH^- + H (4)
ECH reaction	PCET mechanism	PCET reaction: electrochemical desorption	≈ 120	M-B* + H⁺ + e^- ⇌ M + BH (5)	M-B* + H₂O + e^- ⇌ M + BH (7)
	LH mechanism	Volmer reaction: electrochemical adsorption	≈ 120	M + H⁺ + e^- ⇌ M-H* (1)	M + H₂O + e^- ⇌ M-H* + OH^- (3)
	LH mechanism	LH reaction: chemical desorption	≈ 60	M-A* + M-H* ⇌ M+AH (6)	M-A* + M-H* ⇌ M + AH (6)

Fig. 2. The FE% of the corresponding product and selectivity during the ECH of FF on electrodeposited Cu foam at varying cathode potentials in pH = 2 (a) and pH = 8 (b) with 30 C charge transferred. (c) Scheme illustrating the LH and PCET mechanisms in the ECH process (A and B represent the organic intermediates to be hydrogenated through the LH or PCET path, respectively). (d) HER LSVs and corrected ECH LSVs recorded with the RRDE at pH = 1.5 and 13. (e) Collected current density from HER LSVs and corrected ECH LSVs recorded with the RRDE for pH = 1.5-4 at -0.6 V and pH = 11.5-13 at -0.4 V. (f) Corresponding Tafel plots of HER and ECH at pH = 1.5-4 and 11.5-13.

Fig. 3. (a) Illustration of the SHINERS detection of the ECH process. In situ SHINERS spectra of the ECH of FF on electrodeposited Cu in phosphate buffers with 25 mmol L?1 FF in pH = 2 electrolytes (b,e), and pH = 13 electrolytes (c,f). (d) Top-view and side-view illustrations of Oad and OHad on the Cu(111) top site, assuming a threefold bridge coordination with the Cu atom. O, red; H, white; Cu, orange spheres.

Fig. 4. (a) Potential energy surfaces of the ECH of FF on the Cu(111) surface for FF conversion to MF and FA. (b) Top and side views of the adsorption pattern of FF on Cu(111). (c) Energetics of the Oad reduction reaction on Cu(111) to form *H2O via the PCET and LH paths.

Fig. 5. Proposed pathways of the ECH of FF on the Cu electrode in acidic electrolytes.

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