Photocatalytic Water Oxidation by Surface Modification of BiVO4 with Heterometallic Polyphthalocyanine

Liu, GuoquanState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China (author)

QC 20230831
Developing efficient photocatalysts for water oxidation is among the central challenges of solar energy conversion. Here, we report semiconductor-molecular photocatalysts by integration of heteronuclear bimetallic polyphthalocyanine (PPc) catalysts with particulate bismuth vanadate (BiVO4) as the photosensitizer. Their photocatalytic activity for water oxidation was modulated by tuning the Fe/Co ratio of polyphthalocyanines. At an optimal Fe/Co ratio of 3:1, the resulting Fe3CoPPc-BiVO4 hybrid exhibits an excellent oxygen evolution rate of 4557 μmol g-1 h-1 in the presence of iodate under visible light irradiation, which is nearly two orders of magnitude greater than that of pristine BiVO4 and superior to those of the corresponding homometallic counterparts. Both experimental and theoretical methods suggest that the presence of a large population of high-valent Fe/Co molecular species due to the favorable interfacial charge transfer and upshift of the d-band centers of metal sites toward Fermi level lead to a lower energy barrier for the O-O bond formation and eventually promote the oxidation of water.

Zhu, YongState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China (author)
Gao, HuaState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China (author)
Xu, SuxianState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China (author)
Wen, ZhibingState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China (author)
Sun, Licheng,1962-KTH,Organisk kemi,State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China; Center of Artificial Photosynthesis for Solar Fuels, School of Science, Westlake University, Hangzhou 310024, China; Department of Chemistry, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, Stockholm 10044, Sweden(Swepub:kth)u1umfd9h (author)
Li, FeiState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China (author)
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, ChinaOrganisk kemi (creator_code:org_t)

By the author/editor: Liu, Guoquan; Zhu, Yong; Gao, Hua; Xu, Suxian; Wen, Zhibing; Sun, Licheng, 19 ...; show more...; Li, Fei; show less...

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Materials Chemis ...

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