TY - JOUR
T1 - Single-Atom Zinc Sites with Synergetic Multiple Coordination Shells for Electrochemical H2O2 Production
AU - Wei, Gangya
AU - Li, Yunxiang
AU - Liu, Xupo
AU - Huang, Jinrui
AU - Liu, Mengran
AU - Luan, Deyan
AU - Gao, Shuyan
AU - Lou, Xiong Wen David
PY - 2023/11/20
Y1 - 2023/11/20
N2 - Precise manipulation of the coordination environment of single-atom catalysts (SACs), particularly the simultaneous engineering of multiple coordination shells, is crucial to maximize their catalytic performance but remains challenging. Herein, we present a general two-step strategy to fabricate a series of hollow carbon-based SACs featuring asymmetric Zn−N2O2 moieties simultaneously modulated with S atoms in higher coordination shells of Zn centers (n≥2; designated as Zn−N2O2−S). Systematic analyses demonstrate that the synergetic effects between the N2O2 species in the first coordination shell and the S atoms in higher coordination shells lead to robust discrete Zn sites with the optimal electronic structure for selective O2 reduction to H2O2. Remarkably, the Zn−N2O2 moiety with S atoms in the second coordination shell possesses a nearly ideal Gibbs free energy for the key OOH* intermediate, which favors the formation and desorption of OOH* on Zn sites for H2O2 generation. Consequently, the Zn−N2O2−S SAC exhibits impressive electrochemical H2O2 production performance with high selectivity of 96 %. Even at a high current density of 80 mA cm−2 in the flow cell, it shows a high H2O2 production rate of 6.924 mol gcat−1 h−1 with an average Faradaic efficiency of 93.1 %, and excellent durability over 65 h. © 2023 Wiley-VCH GmbH.
AB - Precise manipulation of the coordination environment of single-atom catalysts (SACs), particularly the simultaneous engineering of multiple coordination shells, is crucial to maximize their catalytic performance but remains challenging. Herein, we present a general two-step strategy to fabricate a series of hollow carbon-based SACs featuring asymmetric Zn−N2O2 moieties simultaneously modulated with S atoms in higher coordination shells of Zn centers (n≥2; designated as Zn−N2O2−S). Systematic analyses demonstrate that the synergetic effects between the N2O2 species in the first coordination shell and the S atoms in higher coordination shells lead to robust discrete Zn sites with the optimal electronic structure for selective O2 reduction to H2O2. Remarkably, the Zn−N2O2 moiety with S atoms in the second coordination shell possesses a nearly ideal Gibbs free energy for the key OOH* intermediate, which favors the formation and desorption of OOH* on Zn sites for H2O2 generation. Consequently, the Zn−N2O2−S SAC exhibits impressive electrochemical H2O2 production performance with high selectivity of 96 %. Even at a high current density of 80 mA cm−2 in the flow cell, it shows a high H2O2 production rate of 6.924 mol gcat−1 h−1 with an average Faradaic efficiency of 93.1 %, and excellent durability over 65 h. © 2023 Wiley-VCH GmbH.
KW - Coordination Environment
KW - H2O2 Production
KW - Hollow Structure
KW - Single-Atom Catalysts
KW - Synergetic Effects
UR - http://www.scopus.com/inward/record.url?scp=85174230620&partnerID=8YFLogxK
UR - https://www.webofscience.com/wos/woscc/full-record/WOS:001085323300001
UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85174230620&origin=recordpage
U2 - 10.1002/anie.202313914
DO - 10.1002/anie.202313914
M3 - RGC 21 - Publication in refereed journal
SN - 1433-7851
VL - 62
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 47
M1 - e202313914
ER -