journal article·2023-03Open access

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

Haofan Yang, Chao Li, Tao Liu, Thomas Fellowes, Samantha Y. Chong, Luca Catalano, Mounib Bahri, Weiwei Zhang, Yongjie Xu, Lunjie Liu, Wei Zhao, Adrian M. Gardner, Rob Clowes, Nigel D. Browning, Xiaobo Li, Alexander J. Cowan, Andrew I. Cooper

Nature Nanotechnology· Volume 18· Issue 3

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.
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Research context

OpenAlex topics: Luminescence and Fluorescent Materials · Advanced Photocatalysis Techniques · Porphyrin and Phthalocyanine Chemistry

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

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