Journal Home > Volume 17 , Issue 3
Nano Research 2024, 17(3): 1173-1181 https://doi.org/10.1007/s12274-023-5957-7
Research Article | Issue | Published: 01 August 2023

Flexo-photocatalysis in centrosymmetric semiconductors

Show Author's Information Kang Liu1,2,§,  Tong Wu2,3,§,  Luying Xu2,3,  Zhuangzhuang Zhang2,3,  Zhiyu Liu2,3,  Longfei Wang2,3( ),  Zhong Lin Wang1,2,4,5( )
Center on Nanoenergy Research, School of Physical Science & Technology, Guangxi University, Nanning 530004, China
Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences, Beijing 101400, China
College of Nanoscience and Technology, University of Chinese Academy of Sciences, Beijing 100049, China
Georgia Institute of Technology, Atlanta, GA 30332-0245, USA
Yonsei Frontier Lab, Yonsei University, Seoul 03722, Republic of Korea

§ Kang Liu and Tong Wu contributed equally to this work.

Keywords:
flexoelectricity, polarization, photocatalysis, piezo-photocatalysis, centrosymmetric semiconductor
Topics:
Photocatalysis
Cite this article:
Liu K, Wu T, Xu L, et al. Flexo-photocatalysis in centrosymmetric semiconductors. Nano Research, 2024, 17(3): 1173-1181. https://doi.org/10.1007/s12274-023-5957-7
Download citation
EndNote(RIS)
BibTeX

642

Views

82

Downloads

Citations

3

Crossref

3

WoS

3

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

The separation of photogenerated electron–hole pairs is vitally important for photocatalysis, which can be effectively promoted by polarization field. However, it only manifests in piezoelectric/pyroelectric/ferroelectric materials that have a non-centrosymmetric structure. Here, we demonstrate that the polarization enhanced photocatalysis (with wide spectra from ultraviolet (UV) light to visible light) can be achieved in centrosymmetric semiconductors, such as δ-MnO2 and TiO2 nanosheets integrated nanoflowers, by using the strain-gradient-induced flexoelectric polarization that is always overlooked in polarization-enhanced catalysis. Under ultrasonic and illumination excitation, the organic pollutants (methylene blue (MB), etc.) can be effectively degraded within 30 min with excellent stability and repeatability. Compared with photocatalysis, the flexo-photocatalytic performance of above centrosymmetric semiconductors is substantially increased by 85%. Moreover, the factors related to flexo-photocatalysis such as material morphology, mechanical stimuli source, and adsorption are explored to deeply understand the mechanism of flexo-photocatalysis. This work opens up a way for high-performance photocatalysis in centrosymmetric semiconductors.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Flexo-photocatalysis in centrosymmetric semiconductors

Show Author's information Kang Liu1,2,§, Tong Wu2,3,§, Luying Xu2,3, Zhuangzhuang Zhang2,3, Zhiyu Liu2,3, Longfei Wang2,3( ), Zhong Lin Wang1,2,4,5( )
Center on Nanoenergy Research, School of Physical Science & Technology, Guangxi University, Nanning 530004, China
Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences, Beijing 101400, China
College of Nanoscience and Technology, University of Chinese Academy of Sciences, Beijing 100049, China
Georgia Institute of Technology, Atlanta, GA 30332-0245, USA
Yonsei Frontier Lab, Yonsei University, Seoul 03722, Republic of Korea

§ Kang Liu and Tong Wu contributed equally to this work.

Abstract

The separation of photogenerated electron–hole pairs is vitally important for photocatalysis, which can be effectively promoted by polarization field. However, it only manifests in piezoelectric/pyroelectric/ferroelectric materials that have a non-centrosymmetric structure. Here, we demonstrate that the polarization enhanced photocatalysis (with wide spectra from ultraviolet (UV) light to visible light) can be achieved in centrosymmetric semiconductors, such as δ-MnO2 and TiO2 nanosheets integrated nanoflowers, by using the strain-gradient-induced flexoelectric polarization that is always overlooked in polarization-enhanced catalysis. Under ultrasonic and illumination excitation, the organic pollutants (methylene blue (MB), etc.) can be effectively degraded within 30 min with excellent stability and repeatability. Compared with photocatalysis, the flexo-photocatalytic performance of above centrosymmetric semiconductors is substantially increased by 85%. Moreover, the factors related to flexo-photocatalysis such as material morphology, mechanical stimuli source, and adsorption are explored to deeply understand the mechanism of flexo-photocatalysis. This work opens up a way for high-performance photocatalysis in centrosymmetric semiconductors.

Keywords: flexoelectricity, polarization, photocatalysis, piezo-photocatalysis, centrosymmetric semiconductor

References(44)

[1]

Yang, X. G.; Wang, D. W. Photocatalysis: From fundamental principles to materials and applications. ACS Appl. Energy Mater. 2018, 1, 6657–6693.
DOI Google Scholar
[2]

Wang, X. C.; Faungnawakij, K.; Chareonpanich, M. Editorial: Photocatalysis-from solar power to sustainable chemical production. ChemCatChem 2019, 11, 5838–5841.
DOI Google Scholar
[3]

Men, X. J.; Chen, H. B.; Chang, K. W.; Fang, X. F.; Wu, C. F.; Qin, W. P.; Yin, S. Y. Three-dimensional free-standing ZnO/graphene composite foam for photocurrent generation and photocatalytic activity. Appl. Catal. B:Environ. 2016, 187, 367–374.
DOI Google Scholar
[4]

Qu, Y. Q.; Duan, X. F. Progress, challenge and perspective of heterogeneous photocatalysts. Chem. Soc. Rev. 2013, 42, 2568–2580.
DOI Google Scholar
[5]

Ma, D. D.; Shi, J. W.; Zou, Y. J.; Fan, Z. Y.; Ji, X.; Niu, C. M.; Wang, L. Z. Rational design of CdS@ZnO core–shell structure via atomic layer deposition for drastically enhanced photocatalytic H2 evolution with excellent photostability. Nano Energy 2017, 39, 183–191.
DOI Google Scholar
[6]

Jiao, X. C.; Chen, Z. W.; Li, X. D.; Sun, Y. F.; Gao, S.; Yan, W. S.; Wang, C. M.; Zhang, Q.; Lin, Y.; Luo, Y. et al. Defect-mediated electron–hole separation in one-unit-cell ZnIn2S4 layers for boosted solar-driven CO2 reduction. J. Am. Chem. Soc. 2017, 139, 7586–7594.
DOI Google Scholar
[7]

Cui, L. F.; Song, J. L.; McGuire, A. F.; Kang, S. F.; Fang, X. Y.; Wang, J. J.; Yin, C. C.; Li, X.; Wang, Y. G.; Cui, B. X. Constructing highly uniform onion-ring-like graphitic carbon nitride for efficient visible-light-driven photocatalytic hydrogen evolution. ACS Nano 2018, 12, 5551–5558.
DOI Google Scholar
[8]

Wang, J. J.; Hu, C.; Zhang, Y. H.; Huang, H. W. Engineering piezoelectricity and strain sensitivity in CdS to promote piezocatalytic hydrogen evolution. Chin. J. Catal. 2022, 43, 1277–1285.
DOI Google Scholar
[9]

Chen, F.; Ma, Z. Y.; Ye, L. Q.; Ma, T. Y.; Zhang, T. R.; Zhang, Y. H.; Huang, H. W. Macroscopic spontaneous polarization and surface oxygen vacancies collaboratively boosting CO2 photoreduction on BiOIO3 single crystals. Adv. Mater. 2020, 32, 1908350.
DOI Google Scholar
[10]

Liu, L. Z.; Li, M. T.; Chen, F.; Huang, H. W. Recent advances on single-atom catalysts for CO2 reduction. Small Struct. 2023, 4, 2200188.
DOI Google Scholar
[11]

Chen, F.; Zhang, Y. H.; Huang, H. W. Layered photocatalytic nanomaterials for environmental applications. Chin. Chem. Lett. 2023, 34, 107523.
DOI Google Scholar
[12]

Zhang, C. X.; Lei, D.; Xie, C. F.; Hang, X. S.; He, C. X.; Jiang, H. L. Piezo-photocatalysis over metal-organic frameworks: Promoting photocatalytic activity by piezoelectric effect. Adv. Mater. 2021, 33, 2106308.
DOI Google Scholar
[13]

Zhang, S. C.; Chen, D.; Liu, Z. F.; Ruan, M. N.; Guo, Z. G. Novel strategy for efficient water splitting through pyro-electric and pyro-photo-electric catalysis of BaTiO3 by using thermal resource and solar energy. Appl. Catal. B:Environ. 2021, 284, 119686.
DOI Google Scholar
[14]

Liu, Y.; Zhang, M. J.; Wang, Z.; He, J. D.; Zhang, J.; Ye, S.; Wang, X. L.; Li, D. F.; Yin, H.; Zhu, Q. H. et al. Bipolar charge collecting structure enables overall water splitting on ferroelectric photocatalysts. Nat. Commun. 2022, 13, 4245.
DOI Google Scholar
[15]

Kogan, S. M. Piezoelectric effect during inhomogeneous deformation and acoustic scattering of carriers in crystals. Sov. Phys. Solid State 1964, 5, 2069–2070.
Google Scholar
[16]

Narvaez, J.; Vasquez-Sancho, F.; Catalan, G. Enhanced flexoelectric-like response in oxide semiconductors. Nature 2016, 538, 219–221.
DOI Google Scholar
[17]

Jiang, J.; Chen, Z. Z.; Hu, Y.; Xiang, Y.; Zhang, L. F.; Wang, Y. P.; Wang, G. C.; Shi, J. Flexo-photovoltaic effect in MoS2. Nat. Nanotechnol. 2021, 16, 894–901.
DOI Google Scholar
[18]

Shu, L. L.; Ke, S. M.; Fei, L. F.; Huang, W. B.; Wang, Z. G.; Gong, J. H.; Jiang, X. N.; Wang, L.; Li, F.; Lei, S. J. et al. Photoflexoelectric effect in halide perovskites. Nat. Mater. 2020, 19, 605–609.
DOI Google Scholar
[19]

Wang, L. F.; Liu, S. H.; Feng, X. L.; Zhang, C. L.; Zhu, L. P.; Zhai, J. Y.; Qin, Y.; Wang, Z. L. Flexoelectronics of centrosymmetric semiconductors. Nat. Nanotechnol. 2020, 15, 661–667.
DOI Google Scholar
[20]

Xue, X. Y.; Zang, W. L.; Deng, P.; Wang, Q.; Xing, L. L.; Zhang, Y.; Wang, Z. L. Piezo-potential enhanced photocatalytic degradation of organic dye using ZnO nanowires. Nano Energy 2015, 13, 414–422.
DOI Google Scholar
[21]

Li, H. D.; Sang, Y. H.; Chang, S. J.; Huang, X.; Zhang, Y.; Yang, R. S.; Jiang, H. D.; Liu, H.; Wang, Z. L. Enhanced ferroelectric-nanocrystal-based hybrid photocatalysis by ultrasonic-wave-generated piezophototronic effect. Nano Lett. 2015, 15, 2372–2379.
DOI Google Scholar
[22]

Flint, E. B.; Suslick, K. S. The temperature of cavitation. Science 1991, 253, 1397–1399.
DOI Google Scholar
[23]

Flannigan, D. J.; Suslick, K. S. Plasma formation and temperature measurement during single-bubble cavitation. Nature 2005, 434, 52–55.
DOI Google Scholar
[24]

Bhaskar, U. K.; Banerjee, N.; Abdollahi, A.; Wang, Z.; Schlom, D. G.; Rijnders, G.; Catalan, G. A flexoelectric microelectromechanical system on silicon. Nat. Nanotechnol. 2016, 11, 263–266.
DOI Google Scholar
[25]

Zubko, P.; Catalan, G.; Buckley, A.; Welche, P. R. L.; Scott, J. F. Strain-gradient-induced polarization in SrTiO3 single crystals. Phys. Rev. Lett. 2007, 99, 167601.
DOI Google Scholar
[26]

Yang, R. J.; Guo, Z. J.; Cai, L. X.; Zhu, R. S.; Fan, Y. Y.; Zhang, Y. F.; Han, P. P.; Zhang, W. J.; Zhu, X. G.; Zhao, Q. T. et al. Investigation into the phase–activity relationship of MnO2 nanomaterials toward ozone-assisted catalytic oxidation of toluene. Small 2021, 17, 2103052.
DOI Google Scholar
[27]

Zhu, S. J.; Huo, W. C.; Liu, X. Y.; Zhang, Y. X. Birnessite based nanostructures for supercapacitors: Challenges, strategies and prospects. Nanoscale Adv. 2020, 2, 37–54.
DOI Google Scholar
[28]

Li, K.; Chen, C.; Zhang, H. B.; Hu, X. J.; Sun, T. H.; Jia, J. P. Effects of phase structure of MnO2 and morphology of δ-MnO2 on toluene catalytic oxidation. Appl. Surf. Sci. 2019, 496, 143662.
DOI Google Scholar
[29]

Wang, J. L.; Wang, K.; He, Z. H.; Li, S. S.; Zhang, R. R.; Guo, P. F.; Wang, W. T.; Yang, Y.; Liu, Z. T. Solvent-induced synthesis of hierarchical TiO2 nanoflowers with tunable morphology by monolayer self-assembly for probing the photocatalytic performance. J. Nanostruct. Chem. 2022, 12, 1075–1087.
DOI Google Scholar
[30]

Kitchaev, D. A.; Peng, H. W.; Liu, Y.; Sun, J. W.; Perdew, J. P.; Ceder, G. Energetics of MnO2 polymorphs in density functional theory. Phys. Rev. B 2016, 93, 045132.
DOI Google Scholar
[31]

Wu, T.; Liu, K.; Liu, S. H.; Feng, X. L.; Wang, X. F.; Wang, L. F.; Qin, Y.; Wang, Z. L. Highly efficient flexocatalysis of two-dimensional semiconductors. Adv. Mater. 2022, 35, 2208121.
DOI Google Scholar
[32]

Wang, Z. M.; Berbille, A.; Feng, Y. W.; Li, S. T.; Zhu, L. P.; Tang, W.; Wang, Z. L. Contact-electro-catalysis for the degradation of organic pollutants using pristine dielectric powders. Nat. Commun. 2022, 13, 130.
DOI Google Scholar
[33]

Remucal, C. K.; Ginder-Vogel, M. A critical review of the reactivity of manganese oxides with organic contaminants. Environ. Sci.: Processes Impacts 2014, 16, 1247–1266.
DOI Google Scholar
[34]

Guo, R.; You, L.; Lin, W. N.; Abdelsamie, A.; Shu, X. Y.; Zhou, G. W.; Chen, S. H.; Liu, L.; Yan, X. B.; Wang, J. L. et al. Continuously controllable photoconductance in freestanding BiFeO3 by the macroscopic flexoelectric effect. Nat. Commun. 2020, 11, 2571.
DOI Google Scholar
[35]

Das, S.; Wang, B.; Paudel, T. R.; Park, S. M.; Tsymbal, E. Y.; Chen, L. Q.; Lee, D.; Noh, T. W. Enhanced flexoelectricity at reduced dimensions revealed by mechanically tunable quantum tunnelling. Nat. Commun. 2019, 10, 537.
DOI Google Scholar
[36]

Gao, P.; Yang, S. Z.; Ishikawa, R.; Li, N.; Feng, B.; Kumamoto, A.; Shibata, N.; Yu, P.; Ikuhara, Y. Atomic-scale measurement of flexoelectric polarization at SrTiO3 dislocations. Phys. Rev. Lett. 2018, 120, 267601.
DOI Google Scholar
[37]

Hu, K.; Wang, R. H.; Maimaitituersun, M.; Sun, H. J.; Liu, X. F.; Zhang, Y. Synergetic piezo-photocatalytic effect in ultrathin Bi2WO6 nanosheets for decomposing organic dye. J. Mater. Sci. :Mater. Electron. 2022, 33, 9845–9857.
DOI Google Scholar
[38]

Tang, Q.; Wu, J.; Chen, X. Z.; Sanchis-Gual, R.; Veciana, A.; Franco, C.; Kim, D.; Surin, I.; Pérez-Ramírez, J.; Mattera, M. et al. Tuning oxygen vacancies in Bi4Ti3O12 nanosheets to boost piezo-photocatalytic activity. Nano Energy 2023, 108, 108202.
DOI Google Scholar
[39]

Liu, Z.; Wang, B.; Cazorla, C. Strain engineering of two-dimensional piezophotocatalytic materials for improved hydrogen evolution reaction. ACS Sustainable Chem. Eng. 2022, 10, 16924–16934.
DOI Google Scholar
[40]

Dong, X. L.; Wang, Z. M.; Berbille, A.; Zhao, X.; Tang, W.; Wang, Z. L. Investigations on the contact-electro-catalysis under various ultrasonic conditions and using different electrification particles. Nano Energy 2022, 99, 107346.
DOI Google Scholar
[41]

Lipomi, D. J.; Vosgueritchian, M.; Tee, B. C. K.; Hellstrom, S. L.; Lee, J. A.; Fox, C. H.; Bao, Z. N. Skin-like pressure and strain sensors based on transparent elastic films of carbon nanotubes. Nat. Nanotechnol. 2011, 6, 788–792.
DOI Google Scholar
[42]

Fu, X. W.; Liao, Z. M.; Zhou, J. X.; Wu, H. C.; Zhang, R.; Jing, G. Y.; Xu, J.; Wu, X. S.; Guo, W. L.; Yu, D. P. Strain dependent resistance in chemical vapor deposition grown graphene. Appl. Phys. Lett. 2011, 99, 213107.
DOI Google Scholar
[43]

Yan, C. Y.; Wang, J. X.; Kang, W. B.; Cui, M. Q.; Wang, X.; Foo, C. Y.; Chee, K. J.; Lee, P. S. Highly stretchable piezoresistive grapheme-nanocellulose nanopaper for strain sensors. Adv. Mater. 2014, 26, 2022–2027.
DOI Google Scholar
[44]

Cohen, D. J.; Mitra, D.; Peterson, K.; Maharbiz, M. M. A highly elastic, capacitive strain gauge based on percolating nanotube networks. Nano Lett. 2012, 12, 1821–1825.
DOI Google Scholar
File
12274_2023_5957_MOESM1_ESM.pdf (2.8 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 05 May 2023
Revised: 14 June 2023
Accepted: 23 June 2023
Published: 01 August 2023
Issue date: March 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This research was supported by the National Natural Science Foundation of China (No. 52202162).

Return