Nickel Oxide Selectively Deposited on the {101} Facet of Anatase TiO2 Nanocrystal Bipyramids for Enhanced Photocatalysis

  • Shun Kashiwaya
    Shun Kashiwaya
    Institut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351 Cours de la Libération, 33 405 Talence, France
    Fachbereich Material- und Geowissenshaften, Technische Universität Darmstadt, Petersenstr. 23, 64287 Darmstadt, Germany
  • Céline Olivier
    Céline Olivier
    Institut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351 Cours de la Libération, 33 405 Talence, France
  • Jérôme Majimel
    Jérôme Majimel
    ICMCB UMR 5026, CNRS, Univ. Bordeaux INP, F-33600 Talence, France
  • Andreas Klein
    Andreas Klein
    Fachbereich Material- und Geowissenshaften, Technische Universität Darmstadt, Petersenstr. 23, 64287 Darmstadt, Germany
  • Wolfram Jaegermann
    Wolfram Jaegermann
    Fachbereich Material- und Geowissenshaften, Technische Universität Darmstadt, Petersenstr. 23, 64287 Darmstadt, Germany
  • , and 
  • Thierry Toupance*
    Thierry Toupance
    Institut des Sciences Moléculaires, UMR 5255 CNRS, Université de Bordeaux, 351 Cours de la Libération, 33 405 Talence, France
    *E-mail: [email protected]
Cite this: ACS Appl. Nano Mater. 2019, 2, 8, 4793–4803
Publication Date (Web):July 17, 2019
Copyright © 2019 American Chemical Society
Article Views
Read OnlinePDF (5 MB)
Supporting Info (1)»


Facet-engineered anatase TiO2 with NiO nanoparticles heterocontacts were successfully prepared by selective photodeposition of NiO nanoparticles onto the {101} facet of the top-truncated bipyramidal TiO2 anatase nanocrystals coexposed with {001} and {101} facets. The morphology and electronic properties of the resulting 0.1–10 wt % NiO-decorated TiO2 were investigated by X-ray diffraction, high-resolution electron microscopy, N2 sorption analysis, and UV–vis spectroscopy. Furthermore, a careful determination of the energy band alignment diagram was conducted by a model experiment using XPS and UPS to verify charge separation at the interface of the NiO−TiO2 heterostructure. The model experiment was performed by stepwise deposition of NiO onto oriented TiO2 substrates and in-situ photoelectron spectroscopy measurements without breaking vacuum. Core levels showed shifts of 0.58 eV toward lower binding energies, meaning an upward band bending in TiO2 at the NiO–TiO2 interface. Furthermore, 0.1 wt % NiO–TiO2 exhibited 50% higher activities than the pure TiO2 for methylene blue (MB) photodecomposition under UV irradiation. This enhanced photocatalytic activity of NiO–TiO2 nanocomposites was related to the internal electric field developed at the p–n NiO−TiO2 heterojunction, leading to vectorial charge separation. Finally, mechanistic studies conducted in the presence of carrier or radical scavengers revealed that holes dominantly contributed to the photocatalytic reactions in the case of NiO–TiO2 photocatalysts while electrons played the main role in photocatalysis for the pure TiO2 materials.

Supporting Information

Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsanm.9b00729.

  • N2 adsorption–desorption isotherms along with complementary SEM/TEM images and XPS-UPS data (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 14 publications.

  1. Denny Gunawan, Cui Ying Toe, Priyank Kumar, Jason Scott, Rose Amal. Synergistic Cyanamide Functionalization and Charge-Induced Activation of Nickel/Carbon Nitride for Enhanced Selective Photoreforming of Ethanol. ACS Applied Materials & Interfaces 2021, 13 (42) , 49916-49926.
  2. Yannick Hermans, Céline Olivier, Henrik Junge, Andreas Klein, Wolfram Jaegermann, Thierry Toupance. Sunlight Selective Photodeposition of CoOx(OH)y and NiOx(OH)y on Truncated Bipyramidal BiVO4 for Highly Efficient Photocatalysis. ACS Applied Materials & Interfaces 2020, 12 (48) , 53910-53920.
  3. Wenlei Yin, Jiayan Yang, Keyang Zhao, Anyang Cui, Jiaoyan Zhou, Wei Tian, Wenwu Li, Zhigao Hu, Junhao Chu. High Responsivity and External Quantum Efficiency Photodetectors Based on Solution-Processed Ni-Doped CuO Films. ACS Applied Materials & Interfaces 2020, 12 (10) , 11797-11805.
  4. Lei Yang, Chengjie Yao, Ruyi Wang, Liang Jiang, Wenjing Zhu, Mengyao Wang, Lingli Liu, Dewei Liang, Lei Hu, Chonghai Den, Qiyi Yin, Miao Zhang, Gang He, Jianguo Lv, Zhaoqi Sun. Novel Fe2O3/{101}TiO2 nanosheet array films with stable hydrophobicity and enhanced photoelectrochemical performance. Materials Chemistry and Physics 2022, 275 , 125226.
  5. Jannat Hammouche, Kais Daoudi, Soumya Columbus, Rania Ziad, Krithikadevi Ramachandran, Mounir Gaidi. Structural and morphological optimization of Ni doped ZnO decorated silicon nanowires for photocatalytic degradation of methylene blue. Inorganic Chemistry Communications 2021, 131 , 108763.
  6. Chandran Balamurugan, Hyeonjeong Jo, Dongwan Yoo, Jaewhan Cho, Ki Min Nam, Junhyeok Seo. Electrochemical and photoelectrochemical oxygen evolution reactions by Group X hetero-metal oxides. Applied Surface Science 2021, 541 , 148523.
  7. Yuanyuan Sun, Guohui Li, Yun Gong, Zhenfan Sun, Heliang Yao, Xiaoxia Zhou. Ag and TiO2 nanoparticles co-modified defective zeolite TS-1 for improved photocatalytic CO2 reduction. Journal of Hazardous Materials 2021, 403 , 124019.
  8. Xueliang Jiang, Zitong Peng, Yanrong Gao, Feng You, Chu Yao. Preparation and visible-light photocatalytic activity of ag-loaded [email protected] hollow microspheres with double-shell structure. Powder Technology 2021, 377 , 621-631.
  9. Weichong Kong, Yunlong Zhao, Jingyue Xuan, Zhaotan Gao, Jun Wang, Shugang Tan, Fuchao Jia, Zhaolong Teng, Meiling Sun, Guangchao Yin. Synchronous etching and W-doping for 3D CdS/ZnO/TiO2 hierarchical heterostructure photoelectrodes to significantly enhance the photoelectrochemical performance. Applied Surface Science 2021, 537 , 147998.
  10. Jingjing Sun, Jing Sun, Xikui Wang. Anatase TiO 2 with Co‐exposed (001) and (101) Surface‐Based Photocatalytic Materials for Energy Conversion and Environmental Purification. Chemistry – An Asian Journal 2020, 15 (24) , 4168-4183.
  11. Abimbola E. Oluwalana, Peter A. Ajibade. Synthesis and crystal structures of Pb(II) dithiocarbamates complexes: precursors for PbS nanophotocatalyst. Journal of Sulfur Chemistry 2020, 41 (2) , 182-199.
  12. Reza Katal, Saeid Masudy-Panah, Mohammad Tanhaei, Mohammad Hossein Davood Abadi Farahani, Hu Jiangyong. A review on the synthesis of the various types of anatase TiO2 facets and their applications for photocatalysis. Chemical Engineering Journal 2020, 384 , 123384.
  13. M. Muthukumaran, P. Varun Prasath, Ravichandran Kulandaivelu, Suresh Sagadevan, Faruq Mohammad, Won Chun Oh. Fabrication of nitrogen-rich graphitic carbon nitride/Cu2O ([email protected]) composite and its enhanced photocatalytic activity for organic pollutants degradation. Journal of Materials Science: Materials in Electronics 2020, 31 (3) , 2257-2268.
  14. Yi-en Du, Xianjun Niu, Wanxi Li, Jing An, Yufang Liu, Yongqiang Chen, Pengfei Wang, Xiaojing Yang, Qi Feng. Microwave-Assisted Synthesis of High-Energy Faceted TiO2 Nanocrystals Derived from Exfoliated Porous Metatitanic Acid Nanosheets with Improved Photocatalytic and Photovoltaic Performance. Materials 2019, 12 (21) , 3614.