Capturing critical gem-diol intermediates and hydride transfer for anodic hydrogen production from 5-hydroxymethylfurfural

Autor: Guodong Fu, Xiaomin Kang, Yan Zhang, Ying Guo, Zhiwei Li, Jianwen Liu, Lei Wang, Jiujun Zhang, Xian-Zhu Fu, Jing-Li Luo
Jazyk: angličtina
Rok vydání: 2023
Předmět:
Zdroj: Nature Communications, Vol 14, Iss 1, Pp 1-11 (2023)
Druh dokumentu: article
ISSN: 2041-1723
89312694
DOI: 10.1038/s41467-023-43704-2
Popis: 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.
Databáze: Directory of Open Access Journals
Externí odkaz: