Journal
APPLIED CATALYSIS B-ENVIRONMENTAL
Volume 317, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.apcatb.2022.121706
Keywords
Two -electron oxygen reduction; Metal-ligand coupling; Conductive MOFs; H2O2 selectivity; In situ characterizations
Funding
- National Natural Science Foundation of China [U1932212, U1932109, 11875257, 12135012]
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The covalent coupling between metal and ligand is crucial for manipulating the activity and selectivity of metal-organic framework (MOF) nanomaterials. By utilizing conjugated coordination chemistry, conductive MOFs have been developed as efficient oxygen reduction reaction (ORR) electrocatalysts with adjustable H2O2 selectivity.
The metal-ligand (M-L) covalent coupling is of very significance for tailoring the activity and selectivity of metal -organic-framework (MOF) functional nanomaterials, yet it still remains elusive. Herein, based on the ??-conju-gated coordination chemistry, we have developed several conductive MOFs as active oxygen reduction (ORR) electrocatalysts with tunable H2O2 selectivity. Through tailoring the central metal and the first coordination sphere, weakly-electrophilic Cu sites coupled with strongly-oxidized aromatic 2, 3, 6, 7, 10, 11-hexahydroxytri-phenylene (HHTP) linkers are of high favor in a two-electron ORR pathway, resulting in an impressive H2O2 selectivity of 95 % and a superior H2O2 yield rate of 792.7 mmol.g(cat)(-1)1.h(-1) during ORR for conductive Cu-HHTP MOF catalysts. By correlative in situ synchrotron radiation XAFS and FTIR spectroscopies, the potential -dependent dynamic-coupling hydroxyl over Cu sites is found to effectively trigger the self-polarization of ??-conjugated metal-ligand Cu-O-C centers of Cu-HHTP MOF via shrinking the first Cu-O coordination sphere, realizing fast 2e(-) ORR kinetics.
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