CuAu合金吸附行为调控及单电子脱氢电催化5-羟甲基糠醛氧化协同双极制氢

doi:10.1016/S1872-2067(26)65019-X

催化学报 ›› 2026, Vol. 85: 226-236.DOI: 10.1016/S1872-2067(26)65019-X

CuAu合金吸附行为调控及单电子脱氢电催化5-羟甲基糠醛氧化协同双极制氢

杜濮宇^a^,¹, 沈奕^b^,¹, 彭涛^b, 余子晟^b, 杜婷婷^b, 马猛^a, 何泓雨^b, 贾志林^b, 刘阳^a, 沈少华^b()

^a 国家电投集团科学技术研究院有限公司, 北京 100029
^b 西安交通大学能源与动力工程学院, 多相流工程国家重点实验室, 陕西西安 710049

收稿日期:2025-09-27 接受日期:2025-11-24 出版日期:2026-06-18 发布日期:2026-05-18
通讯作者: *电子信箱: shshen_xjtu@mail.xjtu.edu.cn (沈少华).
作者简介:
¹共同第一作者.
基金资助:
国家自然科学基金(52225606);国家自然科学基金(52488201)

Steering adsorption behavior of 5-hydroxymethylfurfural at CuAu alloys for one-electron dehydrogenation electrocatalysis pairing anodic 5-hydroxymethyl-2-furancarboxylic acid and bipolar hydrogen production

Puyu Du^a^,¹, Yi Shen^b^,¹, Tao Peng^b, Zisheng Yu^b, Tingting Du^b, Meng Ma^a, Hongyu He^b, Zhilin Jia^b, Yang Liu^a, Shaohua Shen^b()

^a State Power Investment Corporation Central Research Institute, Beijing 100029, China
^b State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China

Received:2025-09-27 Accepted:2025-11-24 Online:2026-06-18 Published:2026-05-18
Contact: *E-mail: shshen_xjtu@mail.xjtu.edu.cn (S. Shen).
About author:
¹Contributed equally to this work.
Author contributions
‡P. Du and ‡Y. Shen carried out the sample preparation, characterizations and theoretical calculations. T. Peng and Z. Yu detected the HMFOR liquid products and H₂ product. M. Ma conducted the electrochemical measurements. T. Du, H. He, and Z. Jia helped with the in-situ Raman spectra measurements. Y. Liu helped the assembly of membrane electrode assembly (MEA) electrolyzer. P. Du and Y. Shen conceived the idea and supervised the project. Y. Shen and S. Shen wrote the paper. All authors have given approval to the final version of the manuscript. ‡These authors contributed equally.
Supported by:
National Natural Science Foundation of China(52225606);National Natural Science Foundation of China(52488201)

摘要/Abstract

摘要：

电催化有机分子氧化能在电解水过程中替代动力学缓慢的阳极析氧反应, 与阴极析氢反应耦合, 从而降低整体能耗并获得高附加值产品. 其中, 基于生物质平台分子5-羟甲基糠醛(HMF)的电催化氧化反应(HMFOR)因条件温和、过程绿色而备受关注. 然而, 实现低电位下HMF选择性部分氧化醛基, 定向生成高值化学品5-羟甲基-2-呋喃甲酸(HMFCA)并同步实现阳极产氢, 目前仍面临显著挑战. 研究表明, HMF在催化剂表面的吸附行为是调控其低电位选择性脱氢氧化的关键因素.

本研究通过一步电沉积法制备了一系列不同Cu/Au摩尔比的铜金合金催化剂, 利用合金化效应调控其电子结构及表面吸附行为, 实现了高效的HMF选择性氧化制备HMFCA与氢气. 其中, 制备的Cu_0.25Au_0.75催化剂在0.4 V vs. RHE电位下实现84.8 mA cm⁻²的电流密度, 分别为纯Cu和纯Au的1.6倍. 在相同电位下, 该催化剂获得了94.5%的HMFCA产率、98.6%的HMFCA法拉第效率及94.6%的H₂法拉第效率, 其性能优于目前已报道的用于HMFCA制备的电催化剂. 进一步构建了以Cu_0.25Au_0.75为阳极、Pt/C为阴极的膜电极组装电解槽, 该器件可在0.45 V的超低槽压下稳定运行, 同步进行HMFOR与双极产氢, 在60 mA cm⁻²电流密度下保持94.5%的HMFCA法拉第效率和约200%的H₂法拉第效率, 展现出优异的能量转换效率与工艺可行性. 实验表征与密度泛函理论计算结果表明, 合金化诱导了Cu与Au之间发生显著的电荷重分布, 电子由Au向Cu转移. 该电子效应有效调控了Cu与Au的d带中心位置, 进而优化了催化剂表面对HMF反应物、中间体及产物HMFCA的吸附行为. 纯Cu催化剂对HMF的吸附能力较弱, 导致HMFOR反应动力学迟缓; 而纯Au催化剂虽表现出较强的HMF吸附能力, 却因HMFCA难以脱附而容易阻塞活性位点, 同样限制反应速率. 相比之下, 合金化后的Cu_0.25Au_0.75在保持优异的HMF吸附能力以快速引发反应的同时, 又避免了HMFCA的过强吸附, 实现了吸附与脱附过程的理想平衡, 从而显著提升催化性能. 此外, 电化学原位红外与原位质谱分析揭示了低电位下HMF经单电子路径氧化的反应机理: HMF首先吸附于催化剂表面, 与OH⁻反应生成^*HMFOH⁻中间体; 该中间体经脱氢释放氢离子, 通过单电子转移生成^*HMFCA与吸附态^*H; 随后^*HMFCA脱附形成产物HMFCA. 另一HMF分子经历同样氧化脱氢过程, 生成一个HMFCA与^*H; 最终, 两个相邻的^*H结合形成H₂.

综上, 本工作通过合理的合金化设计, 实现了对表面吸附行为的精准调控, 为理解和设计用于生物质衍生分子高效、高选择性电催化转化的先进催化剂提供了新视角, 并有望加速实现绿色、高效电催化制备高附加值化学品与氢能的产业化进程.

关键词: 5-羟甲基糠醛氧化, 氢气生产, 双金属合金, 吸附行为, 膜电极组装电解槽

Abstract:

Selective electrocatalytic 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) is believed to be highly dependent on the surface adsorption behaviors. Herein, a series of CuAu alloys with various metallic compositions and steered surface adsorption behaviors were prepared by a one-step electrodeposition method. By optimizing the Cu molar ratios, a superior electrocatalytic performance for HMFOR via one-electron dehydrogenation could be observed over Cu_0.25Au_0.75, reaching a current density of 84.8 mA cm^-2 at 0.4 V vs. RHE, with 94.5% 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) yield, 98.6% HMFCA faradaic efficiency (FE) and 94.6% H₂ FE. Remarkably, with Cu_0.25Au_0.75 as the anode and Pt/C as the cathode, the integrated membrane electrode assembly electrolyzer could operate at a low cell voltage of 0.45 V for simultaneous HMFOR and bipolar H₂ production, with 94.5% HMFCA FE and ~200% H₂ FE. Experimental investigations and theoretical calculations demonstrate that the alloying induced charge redistribution between Cu and Au could modulate the d-band centers, and then steer the surface adsorption behaviors to balance HMF adsorption and HMFCA desorption at surface, ensuring the active site availability for one-electron dehydrogenation HMFOR. This work presents a facile strategy for designing efficient electrocatalysts for ultralow-potential HMFOR, with fundamental surface adsorption behaviors deepened for biomass electrooxidation.

Key words: HMF oxidation, Hydrogen production, Bimetallic alloys, Adsorption behavior, Membrane electrode assembly electrolyzer

杜濮宇, 沈奕, 彭涛, 余子晟, 杜婷婷, 马猛, 何泓雨, 贾志林, 刘阳, 沈少华. CuAu合金吸附行为调控及单电子脱氢电催化5-羟甲基糠醛氧化协同双极制氢[J]. 催化学报, 2026, 85: 226-236.

Puyu Du, Yi Shen, Tao Peng, Zisheng Yu, Tingting Du, Meng Ma, Hongyu He, Zhilin Jia, Yang Liu, Shaohua Shen. Steering adsorption behavior of 5-hydroxymethylfurfural at CuAu alloys for one-electron dehydrogenation electrocatalysis pairing anodic 5-hydroxymethyl-2-furancarboxylic acid and bipolar hydrogen production[J]. Chinese Journal of Catalysis, 2026, 85: 226-236.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65019-X

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Fig. 1. (a) Schemed process for the synthesis of CuxAu1-x (x = 0, 0.25, 0.5, 0.75, 1). SEM image (b), EDX images (c), and HRTEM image (d) of Cu0.25Au0.75. (e) XRD patterns of Au, Cu0.25Au0.75, Cu0.5Au0.5, Cu0.75Au0.25 and Cu. (f) Cu 2p XPS spectra of Cu and Cu0.25Au0.75. (g) Au 4f XPS spectra of Au and Cu0.25Au0.75.

Fig. 2. (a) LSV curves of Au, Cu0.25Au0.75 and Cu in 1 mol L-1 KOH solution with 50 mmol L-1 HMF. (b) LSV curves of Cu0.25Au0.75 in 1 mol L-1 KOH solution with and without 50 mmol L-1 HMF. (c) HMF conversion, HMFCA yield and FE for HMFOR over Au, Cu0.25Au0.75 and Cu at 0.4 V vs. RHE. Concentrations of HMF, oxidation products (d) and volume of H2 produced (e) during HMFOR over Cu0.25Au0.75 at 0.4 V vs. RHE. (f) HMFOR performance of Cu0.25Au0.75 for ten cycles at 0.4 V vs. RHE. Nyquist plots (g), Tafel slopes (h), and TOF values (i) in 1 mol L-1 KOH solution with 50 mmol L-1 HMF.

Fig. 3. (a) Time dependent open-circuit potentials of Au, Cu0.25Au0.75 and Cu in 1 mol L-1 KOH solution before and after HMF injection. In-situ Raman spectra collected at 200-650 cm-1 of Au (b), Cu0.25Au0.75 (c), and Cu (d) in 1 mol L-1 KOH solution containing 50 mmol L-1 HMF. (e) I-t curves for HMFOR over Cu0.25Au0.75 and Au at 0.4 V vs. RHE, with surface adsorbed HMF cleaned by DI water. (f) In-situ Raman spectra collected at 800-2150 cm-1 for Cu0.25Au0.75 in 1 mol L-1 KOH solution containing 50 mmol L-1 HMF. (g) In-situ DEMS signals of m/z?=?2, 3 and 4 detected over Cu0.25Au0.75 during HMFOR.

Fig. 4. (a) PDOS of Cu for Cu0.25Au0.75 and Cu. (b) PDOS of Au for Cu0.25Au0.75 and Au. (c) Calculated adsorption energy of HMF at Au, Cu0.25Au0.75 and Cu. (d) Gibbs free energy diagrams of HMFOR over Au, Cu0.25Au0.75, and Cu. (e) Desorption energy (ΔGdes) of HMFCA on Au, Cu0.25Au0.75 and Cu. (f) Schemed HMF adsorption and HMFCA desorption behaviors at Au, Cu0.25Au0.75 and Cu.

Fig. 5. (a) Schematic illustration of HMFOR and HER in MEA electrolyzer. (b) LSV curves of Cu0.25Au0.75 in 1 mol L-1 KOH electrolyte with and without 50 mmol L-1 HMF in MEA electrolyzer. (c) Anode products and FE over Cu0.25Au0.75 in MEA electrolyzer. (d) Experimentally collected and theoretically calculated amounts of H2 at different accumulated charges. (e) HMFOR performance of Cu0.25Au0.75 for five cycles at 0.45 V.

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CuAu合金吸附行为调控及单电子脱氢电催化5-羟甲基糠醛氧化协同双极制氢

Steering adsorption behavior of 5-hydroxymethylfurfural at CuAu alloys for one-electron dehydrogenation electrocatalysis pairing anodic 5-hydroxymethyl-2-furancarboxylic acid and bipolar hydrogen production

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