TY - JOUR
T1 - Atomically Dispersed Gold Nanoclusters and Single Atoms Coexisting Chiral Electrode for High-Performance Enantioselective Electrosynthesis using H2o as Hydrogen Source
AU - Chang, Wen
AU - Qi, Bo
AU - Wang, Ruoyu
AU - Liu, Huijie
AU - Chen, Guangbo
AU - Hu, Guicong
AU - Li, Zixian
AU - Sun, Jie
AU - Peng, Yung-Kang
AU - Li, Guangchao
AU - Kong, Xianggui
AU - Song, Yu-Fei
AU - Zhao, Yufei
PY - 2024/7/10
Y1 - 2024/7/10
N2 - Developing chiral electrode catalysts for enantioselective electrosynthesis is a great challenge, as it requires catalysts that possess both high activity and enantioselectivity. Precise synthesis of nanoclusters and single atoms coexisting chiral catalysts provide a promising pathway for enhancing asymmetric catalytic performance. Herein, chiral electrode catalysts are fabricated comprising gold clusters (R-AuC) and single atoms (R-AuS) on graphene oxide (R-AuC/S@GO) through an assembly-irradiation strategy. Thereinto, the R-Aus is in situ generated from R-AuC under light irradiation. The monoatomization process can be precisely regulated by changing the wavelength of the light, resulting in four Au-based chiral electrode (R-Au@GO) catalysts with different ratios of nanoclusters and single atoms. These chiral electrodes are applied in the electrocatalytic enantioselective hydrogenation of methyl benzoylformate (MB) to chiral methyl mandelate (S-MM), and the R-AuC/S-2@GO with ≈26% R-AuC and 74% R-AuS achieve the highest catalytic activity (35 µmol cm−2 h−1 productivity) and enantioselectivity [97% enantiomeric excess (ee)]. Detailed experimental analysis and density functional theory calculations reveal that the R-AuS on GO promotes the in situ generation of H* species, and R-AuC mainly drives the enantioselective conversion of MB by transferring the H* species to the carbonyl group of MB, ultimately yielding chiral S-MM. © 2024 Wiley-VCH GmbH.
AB - Developing chiral electrode catalysts for enantioselective electrosynthesis is a great challenge, as it requires catalysts that possess both high activity and enantioselectivity. Precise synthesis of nanoclusters and single atoms coexisting chiral catalysts provide a promising pathway for enhancing asymmetric catalytic performance. Herein, chiral electrode catalysts are fabricated comprising gold clusters (R-AuC) and single atoms (R-AuS) on graphene oxide (R-AuC/S@GO) through an assembly-irradiation strategy. Thereinto, the R-Aus is in situ generated from R-AuC under light irradiation. The monoatomization process can be precisely regulated by changing the wavelength of the light, resulting in four Au-based chiral electrode (R-Au@GO) catalysts with different ratios of nanoclusters and single atoms. These chiral electrodes are applied in the electrocatalytic enantioselective hydrogenation of methyl benzoylformate (MB) to chiral methyl mandelate (S-MM), and the R-AuC/S-2@GO with ≈26% R-AuC and 74% R-AuS achieve the highest catalytic activity (35 µmol cm−2 h−1 productivity) and enantioselectivity [97% enantiomeric excess (ee)]. Detailed experimental analysis and density functional theory calculations reveal that the R-AuS on GO promotes the in situ generation of H* species, and R-AuC mainly drives the enantioselective conversion of MB by transferring the H* species to the carbonyl group of MB, ultimately yielding chiral S-MM. © 2024 Wiley-VCH GmbH.
KW - chiral electrode
KW - heterogeneous catalysis
KW - heterogeneous enantioselective electrosynthesis asymmetric catalysis
KW - nanoclusters
KW - single atoms
UR - http://www.scopus.com/inward/record.url?scp=85183420112&partnerID=8YFLogxK
UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85183420112&origin=recordpage
U2 - 10.1002/adfm.202315675
DO - 10.1002/adfm.202315675
M3 - RGC 21 - Publication in refereed journal
SN - 1616-301X
VL - 34
JO - Advanced Functional Materials
JF - Advanced Functional Materials
IS - 28
M1 - 2315675
ER -