化学
氢化物
转移加氢
甲醇
阳极
动力学同位素效应
醛
过渡状态
氢
有机化学
催化作用
物理化学
氘
电极
钌
物理
量子力学
作者
Guodong Fu,Xiaomin Kang,Y. Zhang,Ying Guo,Zhiwei Li,Jianwen Liu,Lei Wang,Jiujun Zhang,Xian‐Zhu Fu,Jing‐Li Luo
标识
DOI:10.1038/s41467-023-43704-2
摘要
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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