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

Guodong FU; Xiaomin KANG; Yan ZHANG; Ying GUO; Zhiwei LI; Jianwen LIU; Lei WANG; Jiujun ZHANG; Xian Zhu FU; Jing Li LUO

doi:10.1038/s41467-023-43704-2

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

Guodong FU, Xiaomin KANG, Yan ZHANG, Ying GUO, Zhiwei LI, Jianwen LIU, Lei WANG, Jiujun ZHANG, Xian Zhu FU, Jing Li LUO

Research output: Journal Publications › Journal Article (refereed) › peer-review

29 Citations (Scopus)

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.

Original language	English
Article number	8395
Number of pages	11
Journal	Nature Communications
Volume	14
Issue number	1
Early online date	18 Dec 2023
DOIs	https://doi.org/10.1038/s41467-023-43704-2
Publication status	Published - Dec 2023
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2023, The Author(s).

Funding

The authors gratefully thank the financial support from the National Natural Science Foundation of China (22272108, J.W.L; 21975163, X.Z.F and 22003041, X.M.K.), Shenzhen Science and Technology Program (KQTD20190929173914967, J.L.L.; ZDSYS20220527171401003, J.L.L.) and the Senior Talent Research Start-up Fund of Shenzhen University (000263 X.Z.F. and 000265J.W.L.). We sincerely acknowledge the Instrumental Analysis Center of Shenzhen University (Xili Campus) for HRTEM measurements. G.D. Fu thanks Dr. Xiaohui Deng for useful discussions.

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This output contributes to the following UN Sustainable Development Goals (SDGs)

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

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. ",

author = "Guodong FU and Xiaomin KANG and Yan ZHANG and Ying GUO and Zhiwei LI and Jianwen LIU and Lei WANG and Jiujun ZHANG and FU, {Xian Zhu} and LUO, {Jing Li}",

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AU - LI, Zhiwei

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

Abstract

Bibliographical note

Funding

UN SDGs

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