Pd-Pt bimetallene for the energy-saving electrochemical hydrogenation of 5-hydroxymethylfurfural

doi:10.1016/S1872-2067(24)60189-0

Abstract

Abstract:

The electrochemical hydrogenation (ECH) of 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules, offering significant reductions in energy consumption while producing value-added chemicals. The conversion of HMF to DHMF is challenging due to the high reduction potential and complex intermediates of HMF ECH under neutral environment. Also, the total efficiency is hindered by sluggish anodic oxygen evolution reaction (OER) kinetics. Herein, we report a synthesis of highly alloyed Pd-Pt bimetallene (Pd₃Pt₁ BML) for HMF ECH coupled with formic acid oxidation reaction (FAOR). Through a combination of in-situ Raman spectroscopy, electron paramagnetic resonance analysis, and theoretical calculations, we elucidate that the HMF adsorption on Pd atoms, strategically separated by Pt atoms, is weakened compared to pure Pd surfaces. Additionally, Pt atoms serve as crucial providers of active hydrogen to neighboring Pd atoms, synergistically enhancing the reaction kinetics of HMF conversion with a Faradaic efficiency >93%. Meanwhile, the atomically dispersed Pt atoms endow Pd₃Pt₁ BML with high electrochemical performance for the direct pathway of FAOR at the anode. As a result, a FAOR-assisted HMF ECH system equipped with bifunctional Pd₃Pt₁ BML achieves the energy-efficient conversion of HMF to DHMF at electrolysis voltage of 0.72 V at 10 mA cm⁻². This work provides insights into the rational design of bifunctional catalysts featuring two distinct types of active sites for advanced energy electrocatalysis and ECH.

Key words: 5-Hydroxymethylfurfural, Selective hydrogenation, Formic acid oxidation, Electrocatalyst, Bifunction

Xi-Lai Liu, Wei Zhong, Yu-Fan Jin, Tian-Jiao Wang, Xue Xiao, Pei Chen, Yu Chen, Xuan Ai. Pd-Pt bimetallene for the energy-saving electrochemical hydrogenation of 5-hydroxymethylfurfural[J]. Chinese Journal of Catalysis, 2025, 69: 241-248.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60189-0

https://www.cjcatal.com/EN/Y2025/V69/I2/241

Figures/Tables 6

Fig. 1. TEM image (a), AFM image (b) and magnified TEM image (c) of Pd3Pt1 BML. (d) XRD patterns of Pd ML and Pd3Pt1 BML.

Fig. 2. (a) XPS survey spectra of Pd ML and Pd3Pt1 BML. Pd 3d (b) and Pt 4f (c) spectra of Pd3Pt1 BML. (d) Element mapping images of Pd3Pt1 BML.

Fig. 3. (a) CV curves of Pd3Pt1 BML, Pd ML and Pt cNCs in 0.5 mol L?1 H2SO4 electrolyte at 50 mV s-1. (b) CO-stripping curves of Pd3Pt1 BML, Pd ML and Pt cNCs in 0.5 mol L?1 H2SO4 electrolyte at 50 mV s-1. Without (c) and with (d) 50 mmol L?1 HMF LSV curves of Pd3Pt1 BML, Pd ML, Pd3Pt1 sNCs and Pt cNCs in 0.5 mol L?1 K2SO4 electrolyte at 50 mV s-1. (e) The electrocatalytic performance of Pd3Pt1 BML in 0.5 mol L?1 K2SO4 electrolyte with different concentrations of HMF.

Fig. 4. (a) Comparison of FE and Sel of HMF ECH after electron consumption of 50 C at Pd3Pt1 BML, Pd ML, Pd3Pt1 sNCs and Pt cNCs in 0.5 mol L-1 K2SO4 electrolyte with 50 mmol L-1 HMF. (b) Comparison of FE, Sel, Con. and yield rate of HMF ECH after electron consumption increased to 200 C at Pd3Pt1 BML in 0.5 mol L-1 K2SO4 electrolyte with 50 mmol L-1 HMF. (c) Five consecutive electrocatalytic stability tests (150 C electron consumption) for 5.5 h in 0.5 mol L-1 K2SO4 electrolyte with 0.5 mol L-1 HMF. (d) Effect of the presence of 50 mmol L-1 HMF and DHMF on the ECH performance of Pd3Pt1 BML.

Fig. 5. In-situ Raman spectra of potentiometrically varied at Pd3Pt1 BML (a) and Pd ML (b) in 50 mmol L-1 HMF electrolyte. (c) Potential-controlled Pd3Pt1 BML product Hads EPR curves. (d) Possible adsorption patterns and adsorption energy image of HMF ECH on Pd3Pt1 BML and Pd ML. (e) The density of states of Pd3Pt1 (111) and Pd (111) lattice planes. (f) Schematic diagram of HMF ECH on Pd3Pt1 BML based on dual-site catalysis mechanism.

Fig. 6. (a) FAOR curves of Pd3Pt1 BML, Pd ML, Pt cNCs and Pd3Pt1 sNCs in 0.5 mol L-1 H2SO4 and 0.5 mol L-1 FA electrolyte at 50 mV s-1. (b) Assembled Pd3Pt1 BML electrolyzer illumination. (c) Pd3Pt1 BML||Pd3Pt1 BML two-electrode electrolyzer in 0.5 mol L-1 K2SO4 + 50 mmol L-1 HMF with and without 0.5 mol L-1 FA comparison. (d) The long-term capability of Pd3Pt1 BML||Pd3Pt1 BML two-electrode electrolyzer towards HMF ECH at -0.30 V.

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