TY - JOUR
T1 - Facet-dependent spatial separation of dual cocatalysts on MOF photocatalysts for H2O2 production coupling biomass oxidation with enhanced performance
AU - Yuan, Ling
AU - Du, Peiyang
AU - Zhang, Chaoqi
AU - Xi, Yamin
AU - Zou, Yingying
AU - Li, Jiaxin
AU - Bi, Yin
AU - Bao, Tong
AU - Liu, Chao
AU - Yu, Chengzhong
N1 - Publisher Copyright:
© 2024 The Authors
PY - 2025/5/5
Y1 - 2025/5/5
N2 - Cooperative coupling of photocatalytic two-electron oxygen reduction reaction (2e-ORR) with oxidative organic synthesis holds great promise for sustainable production of valuable chemicals. To achieve high performance, the rational design of photocatalysts with effective electron-hole separation and redox capability is crucial. Herein, a MOF-based photocatalyst with crystal facet-dependent spatial separation of dual cocatalysts is constructed for photocatalytic 2e-ORR coupled with vanillyl alcohol oxidation reaction (VAOR). The facet-dependent growth of reductive Pd and oxidative CoOx cocatalysts respectively on the {100} and {001} facets of MIL-125-NH2 enables the directional migration of photogenerated carries, facilitating the charge separation for redox reactions. Additionally, the interaction between Pd and MIL-125-NH2 modulates the Pd sites into electron-sufficient state with upshifted d-band center, promoting the O2 activation and *OOH intermediate formation. The rationally designed composite photocatalyst delivers an excellent H2O2 yield of 74.8 mM g−1 h−1 and a high vanillic acid production rate of 80.9 mM h−1 g−1 with the conversion and selectivity of 96.8 % and 91.1 %, respectively.
AB - Cooperative coupling of photocatalytic two-electron oxygen reduction reaction (2e-ORR) with oxidative organic synthesis holds great promise for sustainable production of valuable chemicals. To achieve high performance, the rational design of photocatalysts with effective electron-hole separation and redox capability is crucial. Herein, a MOF-based photocatalyst with crystal facet-dependent spatial separation of dual cocatalysts is constructed for photocatalytic 2e-ORR coupled with vanillyl alcohol oxidation reaction (VAOR). The facet-dependent growth of reductive Pd and oxidative CoOx cocatalysts respectively on the {100} and {001} facets of MIL-125-NH2 enables the directional migration of photogenerated carries, facilitating the charge separation for redox reactions. Additionally, the interaction between Pd and MIL-125-NH2 modulates the Pd sites into electron-sufficient state with upshifted d-band center, promoting the O2 activation and *OOH intermediate formation. The rationally designed composite photocatalyst delivers an excellent H2O2 yield of 74.8 mM g−1 h−1 and a high vanillic acid production rate of 80.9 mM h−1 g−1 with the conversion and selectivity of 96.8 % and 91.1 %, respectively.
KW - Biomass oxidation
KW - Crystal facet engineering
KW - Metal-organic framework
KW - Photocatalytic HO production
KW - Spatial charge separation
UR - https://www.scopus.com/pages/publications/85209990302
U2 - 10.1016/j.apcatb.2024.124855
DO - 10.1016/j.apcatb.2024.124855
M3 - 文章
AN - SCOPUS:85209990302
SN - 0926-3373
VL - 364
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
M1 - 124855
ER -