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Porphyrin Conjugated Polymer Grafted onto BiVO4 Nanosheets for Efficient Z‐Scheme Overall Water Splitting via Cascade Charge Transfer and Single‐Atom Catalytic Sites

Porphyrin Conjugated Polymer Grafted onto BiVO4 Nanosheets for Efficient Z‐Scheme Overall Water... This work shows a novel artificial Z‐scheme photosystem based on a heterometallic Zn‐/Pt‐porphyrin conjugated polymer (ZnPtP‐CP) grafted onto ultrathin BiVO4 nanosheets via Zn–O–V bridging bonds for high‐efficiency overall water photosplitting. An impressive apparent quantum yield of 9.85% at λ = 400 nm is achieved over the resulting ZnPtP–CP/BiVO4 composite, in which BiVO4 nanosheets are in close contact with ZnPtP‐CP nanosheets via Zn–O–V bridging bonds to promote a Z‐scheme charge transfer mechanism with ZnPtP‐CP serving as electron‐rich unit and BiVO4 as hole‐rich one. The photoexcited electrons of BiVO4 transfer to the interface and recombine with the photogenerated holes of ZnPtP‐CP through the Zn–O–V bonds, and thus the strong reducibility of the photoinduced electrons in ZnPtP‐CP and the strong oxidation ability of the photogenerated holes in BiVO4 are maintained. Moreover, the highly dispersed Pt centers (PtN4) in Pt‐porphyrin bridging units act as single‐atom catalytic sites to facilitate a cascade charge transfer by fast migration of the photogenerated electrons from Zn‐porphyrin to Pt‐porphyrin units for the water reduction reaction. This Z‐scheme mechanism with two‐step excitation and cascade charge transfer pathway makes the composite acting as Z‐scheme dual‐function photocatalyst responsible for the efficient solar‐driven overall water photosplitting without the aid of a sacrificial reagent or external bias. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Advanced Energy Materials Wiley

Porphyrin Conjugated Polymer Grafted onto BiVO4 Nanosheets for Efficient Z‐Scheme Overall Water Splitting via Cascade Charge Transfer and Single‐Atom Catalytic Sites

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Publisher
Wiley
Copyright
© 2021 Wiley‐VCH GmbH
ISSN
1614-6832
eISSN
1614-6840
DOI
10.1002/aenm.202003575
Publisher site
See Article on Publisher Site

Abstract

This work shows a novel artificial Z‐scheme photosystem based on a heterometallic Zn‐/Pt‐porphyrin conjugated polymer (ZnPtP‐CP) grafted onto ultrathin BiVO4 nanosheets via Zn–O–V bridging bonds for high‐efficiency overall water photosplitting. An impressive apparent quantum yield of 9.85% at λ = 400 nm is achieved over the resulting ZnPtP–CP/BiVO4 composite, in which BiVO4 nanosheets are in close contact with ZnPtP‐CP nanosheets via Zn–O–V bridging bonds to promote a Z‐scheme charge transfer mechanism with ZnPtP‐CP serving as electron‐rich unit and BiVO4 as hole‐rich one. The photoexcited electrons of BiVO4 transfer to the interface and recombine with the photogenerated holes of ZnPtP‐CP through the Zn–O–V bonds, and thus the strong reducibility of the photoinduced electrons in ZnPtP‐CP and the strong oxidation ability of the photogenerated holes in BiVO4 are maintained. Moreover, the highly dispersed Pt centers (PtN4) in Pt‐porphyrin bridging units act as single‐atom catalytic sites to facilitate a cascade charge transfer by fast migration of the photogenerated electrons from Zn‐porphyrin to Pt‐porphyrin units for the water reduction reaction. This Z‐scheme mechanism with two‐step excitation and cascade charge transfer pathway makes the composite acting as Z‐scheme dual‐function photocatalyst responsible for the efficient solar‐driven overall water photosplitting without the aid of a sacrificial reagent or external bias.

Journal

Advanced Energy MaterialsWiley

Published: Feb 1, 2021

Keywords: ; ; ; ;

References