TY - JOUR
T1 - Capturing critical gem-diol intermediates and hydride transfer for anodic hydrogen production from 5-hydroxymethylfurfural
AU - FU, Guodong
AU - KANG, Xiaomin
AU - ZHANG, Yan
AU - GUO, Ying
AU - LI, Zhiwei
AU - LIU, Jianwen
AU - WANG, Lei
AU - ZHANG, Jiujun
AU - FU, Xian Zhu
AU - LUO, Jing Li
N1 - 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.
PY - 2023/12
Y1 - 2023/12
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85180248635&partnerID=8YFLogxK
U2 - 10.1038/s41467-023-43704-2
DO - 10.1038/s41467-023-43704-2
M3 - Journal Article (refereed)
C2 - 38110431
AN - SCOPUS:85180248635
SN - 2041-1723
VL - 14
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 8395
ER -
