Packing-induced selectivity switching in molecular nanoparticle photocatalysts for hydrogen and hydrogen peroxide production

Collapse authors list.
Yang, Haofan, Li, Chao, Liu, Tao, Fellowes, Thomas, Chong, Samantha Y ORCID: 0000-0002-3095-875X, Catalano, Luca, Bahri, Mounib ORCID: 0000-0002-8336-9158, Zhang, Weiwei, Xu, Yongjie, Liu, Lunjie et al (show 7 more authors) , Zhao, Wei, Gardner, Adrian M ORCID: 0000-0002-2423-8799, Clowes, Rob, Browning, Nigel D ORCID: 0000-0003-0491-251X, Li, Xiaobo, Cowan, Alexander J ORCID: 0000-0001-9032-3548 and Cooper, Andrew I ORCID: 0000-0003-0201-1021 (2023) Packing-induced selectivity switching in molecular nanoparticle photocatalysts for hydrogen and hydrogen peroxide production. Nature Nanotechnology, 18 (3). 307-+.

Text non format nature nano.docx - Author Accepted Manuscript Download (4MB)

Abstract

Molecular packing controls optoelectronic properties in organic molecular nanomaterials. Here we report a donor-acceptor organic molecule (2,6-bis(4-cyanophenyl)-4-(9-phenyl-9H-carbazol-3-yl)pyridine-3,5-dicarbonitrile) that exhibits two aggregate states in aqueous dispersions: amorphous nanospheres and ordered nanofibres with π-π molecular stacking. The nanofibres promote sacrificial photocatalytic H₂ production (31.85 mmol g^-1 h^-1) while the nanospheres produce hydrogen peroxide (H₂O₂) (3.20 mmol g^-1 h^-1 in the presence of O₂). This is the first example of an organic photocatalyst that can be directed to produce these two different solar fuels simply by changing the molecular packing. These different packings affect energy band levels, the extent of excited state delocalization, the excited state dynamics, charge transfer to O₂ and the light absorption profile. We use a combination of structural and photophysical measurements to understand how this influences photocatalytic selectivity. This illustrates the potential to achieve multiple photocatalytic functionalities with a single organic molecule by engineering nanomorphology and solid-state packing.

Item Type:	Article
Uncontrolled Keywords:	7 Affordable and Clean Energy
Divisions:	Faculty of Science and Engineering > School of Engineering Faculty of Science and Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	01 Feb 2023 09:27
Last Modified:	14 Mar 2024 18:13
DOI:	10.1038/s41565-022-01289-9
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3168022