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

Nature Nanotechnology

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

Materials Innovation Factory & Department of Chemistry, University of Liverpool, Liverpool, UK

Haofan Yang, Chao Li, Tao Liu, Thomas Fellowes, Samantha Y. Chong, Luca Catalano, Weiwei Zhang, Yongjie Xu, Lunjie Liu, Wei Zhao, Rob Clowes, Xiaobo Li & Andrew I. Cooper

Leverhulme Research Centre for Functional Materials Design, University of Liverpool, Liverpool, UK

Haofan Yang, Thomas Fellowes, Yongjie Xu, Wei Zhao & Andrew I. Cooper

Stephenson Institute for Renewable Energy, University of Liverpool, Liverpool, UK

Chao Li, Adrian M. Gardner & Alexander J. Cowan

Laboratoire de Chimie des Polymères, Université libre de Bruxelles (ULB), Brussels, Belgium

Luca Catalano

Albert Crewe Centre for Electron Microscopy, University of Liverpool, Liverpool, UK

Mounib Bahri & Nigel D. Browning

Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, China

Weiwei Zhang

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, China

Xiaobo Li

Nature Nanotechnology (2023)
https://doi.org/10.1038/s41565-022-01289-9

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