Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

Zhou, Ming; Kim, Ji-Young; Han, Myung-Geun; Zu, Xiaotao; Sun, Kai; Zhang, Sa; Zhao, Fengai; Xiao, Haiyan; Xiang, Xia; Zhu, Yimei; Kotov, Nicholas A.

doi:10.1021/acs.jpcc.1c09021

Title: Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

Journal Article · Fri Mar 04 00:00:00 EST 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c09021· OSTI ID:1898589

Zhou, Ming ^[1];

^[2];

^[3]; Zu, Xiaotao ^[4];

^[2]; Zhang, Sa ^[4]; Zhao, Fengai ^[4];

^[4];

^[3];

^[2]

Univ. of Electronic Science and Technology of China, Chengdu (China); Univ. of Michigan, Ann Arbor, MI (United States)
Univ. of Michigan, Ann Arbor, MI (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science
Univ. of Electronic Science and Technology of China, Chengdu (China)

Efficient light absorption and high energy of charge carriers of zinc cadmium sulfide (ZCS) make this semiconductor attractive for many photocatalytic reactions. Despite marked successes in shape-controlled synthesis of ZCS central to their photocatalytic performance, recombination of charge carriers as they migrate through the nanoscale particles results in losses of excitation energy, markedly reducing the photocatalytic activity of ZCS and other heterogeneous photocatalysts. Here, in this study, we show that the electrostatic asymmetry of nanostructures, previously discovered for nearly spherical nanoparticles, also manifests in wurtzite ZCS with planar geometry. The electrostatic asymmetry assists charge separation and substantially increases the yield of photocatalytic reactions in monocrystalline ZCS. The synthesized ZCS nanorods and nanoplates with identical chemical composition were found to have markedly different photocatalytic activity for evolution of hydrogen in water. Despite much smaller specific surface areas, the ~500 nm wide nanoplates displayed a hydrogen evolution rate 12 times higher than the ~35 nm long nanorods, also outperforming other ZCS photocatalysts. Experimental and computational data indicate that the homo- and heterojunction-free ZCS nanoplates with continuous wurtzite lattice behave essentially as nanoscale dipoles with intrinsic dipole moment as high as 48.39 D per unit cell. Electric-field-directed migration of charge carriers stimulates their localization on opposite parts of the nanoplates. Direct imaging of the intraparticle electrical field using off-axis electron holography confirmed their electrostatic asymmetry. Polarization-enhanced charge separation provides a new pathway to efficient and stable photocatalysts for sustainable energy technologies.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); NSAF Joint Foundation of China; Chinese Scholarship Council; National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; U1830204; U1630126; 201706070097; 1463474; 1566460

OSTI ID:: 1898589

Report Number(s):: BNL-223711-2022-JAAM

Journal Information:: Journal of Physical Chemistry. C, Vol. 126, Issue 10; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

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