文献类型：期刊文献

英文题名：Packing-induced selectivity switching in molecular nanoparticle photocatalysts for hydrogen and hydrogen peroxide production

作者：Yang, Haofan[1,2];Li, Chao[1,3];Liu, Tao[1];Fellowes, Thomas[1,2];Chong, Samantha Y. Y.[1];Catalano, Luca[1,4];Bahri, Mounib[5];Zhang, Weiwei[1,6,7];Xu, Yongjie[1,2];Liu, Lunjie[1];Zhao, Wei[1,2];Gardner, Adrian M.[3];Clowes, Rob[1];Browning, Nigel D.[5];Li, Xiaobo[1,8];Cowan, Alexander J.[3];Cooper, Andrew I.[1,2]

机构：[1]Univ Liverpool, Mat Innovat Factory, Liverpool, England;[2]Univ Liverpool, Leverhulme Res Ctr Funct Mat Design, Liverpool, England;[3]Univ Liverpool, Stephenson Inst Renewable Energy, Liverpool, England;[4]Univ Libre Bruxelles ULB, Lab Chim Polymeres, Brussels, Belgium;[5]Univ Liverpool, Albert Crewe Ctr Electron Microscopy, Liverpool, England;[6]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai, Peoples R China;[7]East China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, Shanghai, Peoples R China;[8]Zhejiang Normal Univ, Inst Phys Chem, Zhejiang Key Lab React Chem Solid Surfaces, Key Lab,Minist Educ Adv Catalysis Mat, Jinhua, Peoples R China

年份：2023

卷号：18

期号：3

起止页码：307

外文期刊名：NATURE NANOTECHNOLOGY

收录：;EI(收录号：20230513462502);WOS:【SCI-EXPANDED(收录号:WOS:000922940000001)】；

基金：We thank the Engineering and Physical Sciences Research Council (EPSRC) for financial support under grants EP/N004884/1 and EP/P034497/1. TA measurements were performed at the University of Liverpool Early Career Researcher Laser Laboratory supported by UKRI-EPSRC grant EP/S017623/1 and the University of Liverpool, maintained and operated as a shared research facility by the Faculty of Science and Engineering. We are grateful to B. Greeves (University of Liverpool) for assistance with performing the spectroelectrochemical measurements and M. Volk for discussion on 1O2. H.Y. thanks the Leverhulme Trust via the Leverhulme Research Centre for Functional Materials Design for funding. H.Y. thanks M. Little for the input on the crystal measurements and discussion. C.L. thanks the China Scholarship Council for a PhD studentship. Weiwei Zhang acknowledges support from the Fundamental Research Funds for the Central Universities and Shanghai Pujiang Program (22PJ1402400). The TEM experiments in this paper were performed in the Albert Crewe Centre for Electron Microscopy at the University of Liverpool, maintained and operated as a shared research facility by the Faculty of Science and Engineering. Computing support from the High Performance Computing facility at the University of Liverpool is gratefully acknowledged.

语种：英文

外文关键词：Charge transfer - Excited states - Hydrogen peroxide - Hydrogen production - Light absorption - Molecules - Nanofibers - Oxidation - Solar fuels

摘要：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 pi-pi molecular stacking. The nanofibres promote sacrificial photocatalytic H-2 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 O-2). 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 O-2 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. A donor-acceptor molecule assembles with different molecular packing to form photocatalysts which selectively produce either H-2 or H2O2, depending on the aggregate structure, a proof-of-concept of photoactivity polymorphism.