TY - JOUR
T1 - An Unlocked Two-Dimensional Conductive Zn-MOF on Polymeric Carbon Nitride for Photocatalytic H2O2 Production
AU - Li, Yunxiang
AU - Guo, Yan
AU - Luan, Deyan
AU - Gu, Xiaojun
AU - Lou, Xiong Wen David
PY - 2023/10/26
Y1 - 2023/10/26
N2 - Developing highly efficient catalytic sites for O2 reduction to H2O2, while ensuring the fast injection of energetic electrons into these sites, is crucial for artificial H2O2 photosynthesis but remains challenging. Herein, we report a strongly coupled hybrid photocatalyst comprising polymeric carbon nitride (CN) and a two-dimensional conductive Zn-containing metal–organic framework (Zn-MOF) (denoted as CN/Zn-MOF(lc)/400; lc, low crystallinity; 400, annealing temperature in °C), in which the catalytic capability of Zn-MOF(lc) for H2O2 production is unlocked by the annealing-induced effects. As revealed by experimental and theoretical calculation results, the Zn sites coordinated to four O (Zn-O4) in Zn-MOF(lc) are thermally activated to a relatively electron-rich state due to the annealing-induced local structure shrinkage, which favors the formation of a key *OOH intermediate of 2e− O2 reduction on these sites. Moreover, the annealing treatment facilitates the photoelectron migration from the CN photocatalyst to the Zn-MOF(lc) catalytic unit. As a result, the optimized catalyst exhibits dramatically enhanced H2O2 production activity and excellent stability under visible light irradiation. © 2023 Wiley-VCH GmbH.
AB - Developing highly efficient catalytic sites for O2 reduction to H2O2, while ensuring the fast injection of energetic electrons into these sites, is crucial for artificial H2O2 photosynthesis but remains challenging. Herein, we report a strongly coupled hybrid photocatalyst comprising polymeric carbon nitride (CN) and a two-dimensional conductive Zn-containing metal–organic framework (Zn-MOF) (denoted as CN/Zn-MOF(lc)/400; lc, low crystallinity; 400, annealing temperature in °C), in which the catalytic capability of Zn-MOF(lc) for H2O2 production is unlocked by the annealing-induced effects. As revealed by experimental and theoretical calculation results, the Zn sites coordinated to four O (Zn-O4) in Zn-MOF(lc) are thermally activated to a relatively electron-rich state due to the annealing-induced local structure shrinkage, which favors the formation of a key *OOH intermediate of 2e− O2 reduction on these sites. Moreover, the annealing treatment facilitates the photoelectron migration from the CN photocatalyst to the Zn-MOF(lc) catalytic unit. As a result, the optimized catalyst exhibits dramatically enhanced H2O2 production activity and excellent stability under visible light irradiation. © 2023 Wiley-VCH GmbH.
KW - Conductive Metal–Organic Framework
KW - H2O2 Production
KW - O2 Reduction
KW - Photocatalysis
KW - Single-Atom Catalysis
UR - http://www.scopus.com/inward/record.url?scp=85171786832&partnerID=8YFLogxK
UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85171786832&origin=recordpage
U2 - 10.1002/anie.202310847
DO - 10.1002/anie.202310847
M3 - RGC 21 - Publication in refereed journal
SN - 1433-7851
VL - 62
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 44
M1 - e202310847
ER -