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Updated: Jul 8, 2025
Hydrogen Production and Utilization in a Membrane Reactor
Published on: March 10, 2023
Capturing critical gem-diol intermediates and hydride transfer for anodic hydrogen production from
Guodong Fu1, Xiaomin Kang2, Yan Zhang3
1Shenzhen Key Laboratory of Energy Electrocatalytic Materials, Guangdong Research Center for Interfacial Engineering of Functional Materials, College of Materials Science and Engineering, Shenzhen University, 518060, Shenzhen, China.
Abstract:
The non-classical anodic H2 production from 5-hydroxymethylfurfural (HMF) is very appealing for energy-saving H2 production with value-added chemical conversion due to the low working potential (~0.1 V vs RHE). However, the reaction mechanism is still not clear due to the lack of direct evidence for the critical intermediates. Herein, the detailed mechanisms are explored in-depth using in situ Raman and Infrared spectroscopy, isotope tracking, and density functional theory calculations. The HMF is observed to form two unique inter-convertible gem-diol intermediates in an alkaline medium: 5-(Dihydroxymethyl)furan-2-methanol anion (DHMFM-) and dianion (DHMFM2-). The DHMFM2- is easily oxidized to produce H2 via H- transfer, whereas the DHMFM- is readily oxidized to produce H2O via H+ transfer. The increases in potential considerably facilitate the DHMFM- oxidation rate, shifting the DHMFM- ↔ DHMFM2- equilibrium towards DHMFM- and therefore diminishing anodic H2 production until it terminates. This work captures the critical intermediate DHMFM2- leading to hydrogen production from aldehyde, unraveling a key point for designing higher performing systems.
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