Journal Home > Volume 16 , Issue 4
Nano Research 2023, 16(4): 4736-4741 https://doi.org/10.1007/s12274-022-5181-x
Research Article | Issue | Published: 23 November 2022

Pt-surface oxygen vacancies coupling accelerated photo-charge extraction and activated hydrogen evolution

Show Author's Information Fangxu Dai1,  Mingming Zhang1,  Mingzhong Mi1,  Zhenjiang Li2,  Jun Xing1( ),  Lei Wang1,3( )
Key Laboratory of Eco-chemical Engineering, Ministry of Education, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, Qingdao 266042, China
Keywords:
hydrogen evolution reaction (HER), oxygen vacancies, photocatalytic, co-catalyst, surface hydroxyl
Topics:
Photocatalysis
Cite this article:
Dai F, Zhang M, Mi M, et al. Pt-surface oxygen vacancies coupling accelerated photo-charge extraction and activated hydrogen evolution. Nano Research, 2023, 16(4): 4736-4741. https://doi.org/10.1007/s12274-022-5181-x
Download citation
EndNote(RIS)
BibTeX

5765

Views

74

Downloads

Citations

5

Crossref

5

WoS

6

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Semiconductors-based heterogeneous photocatalytic water splitting has been extensively studied, but it still remains challenging to accelerate the separation of electron–hole pairs and facilitate the reaction kinetics. Here we report a general strategy to fabricate highly efficient Pt/TiO2 photocatalyst by coupling the Pt co-catalysts and surface oxygen vacancies (VO) of TiO2. TiO2 was pre-modified with alkali or alkaline earth metals ion solutions, which produce a large number of surface hydroxyl on TiO2. Subsequently, the photodeposited Pt sub-nanoparticles substitute surface hydroxyl and induce surface VO on TiO2. The coupling of Pt and surface VO on TiO2 can accelerate the extraction of photo-charges through the interaction of Pt–VO–Ti bonds and reduce the hydrogen evolution barrier, thereby promoting the photocatalytic activity. The synthesized Pt-VO-TiO2 sample exhibits a photocatalytic hydrogen evolution activity as high as 1.5 L·g−1·h−1, which is 2.2 times that of traditional Pt/TiO2. Our findings in-depth understand the synergistic effect of co-catalysts and defects on photocatalysis and open up new possibilities for achieving robust photocatalytic water splitting.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Pt-surface oxygen vacancies coupling accelerated photo-charge extraction and activated hydrogen evolution

Show Author's information Fangxu Dai1, Mingming Zhang1, Mingzhong Mi1, Zhenjiang Li2, Jun Xing1( ), Lei Wang1,3( )
Key Laboratory of Eco-chemical Engineering, Ministry of Education, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, Qingdao 266042, China

Abstract

Semiconductors-based heterogeneous photocatalytic water splitting has been extensively studied, but it still remains challenging to accelerate the separation of electron–hole pairs and facilitate the reaction kinetics. Here we report a general strategy to fabricate highly efficient Pt/TiO2 photocatalyst by coupling the Pt co-catalysts and surface oxygen vacancies (VO) of TiO2. TiO2 was pre-modified with alkali or alkaline earth metals ion solutions, which produce a large number of surface hydroxyl on TiO2. Subsequently, the photodeposited Pt sub-nanoparticles substitute surface hydroxyl and induce surface VO on TiO2. The coupling of Pt and surface VO on TiO2 can accelerate the extraction of photo-charges through the interaction of Pt–VO–Ti bonds and reduce the hydrogen evolution barrier, thereby promoting the photocatalytic activity. The synthesized Pt-VO-TiO2 sample exhibits a photocatalytic hydrogen evolution activity as high as 1.5 L·g−1·h−1, which is 2.2 times that of traditional Pt/TiO2. Our findings in-depth understand the synergistic effect of co-catalysts and defects on photocatalysis and open up new possibilities for achieving robust photocatalytic water splitting.

Keywords: hydrogen evolution reaction (HER), oxygen vacancies, photocatalytic, co-catalyst, surface hydroxyl

References(36)

[1]

Fujishima, A.; Honda, K. Electrochemical photolysis of water at a semiconductor electrode. Nature. 1972, 238, 37–38.
DOI Google Scholar
[2]

Thompson, T. L.; Yates, J. T. Surface science studies of the photoactivation of TiO2 new photochemical processes. Chem. Rev. 2006, 106, 4428–4453.
DOI Google Scholar
[3]

Ran, J. R.; Zhang, J.; Yu, J. G.; Jaroniec, M.; Qiao, S. Z. Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting. Chem. Soc. Rev. 2014, 43, 7787–7812.
DOI Google Scholar
[4]

Yi, S. S.; Zhang, X. B.; Wulan, B. R.; Yan, J. M.; Jiang, Q. Non-noble metals applied to solar water splitting. Energy. Environ. Sci. 2018, 11, 3128–3156.
DOI Google Scholar
[5]

Pacchioni, G.; Freund, H. Controlling the charge state of supported nanoparticles in catalysis: Lessons from model systems. Chem. Soc. Rev. 2018, 47, 8474–8502.
DOI Google Scholar
[6]

Li, X.; Yu, J. G.; Jaroniec, M.; Chen, X. B. Cocatalysts for selective photoreduction of CO2 into solar fuels. Chem. Rev. 2019, 119, 3962–4179.
DOI Google Scholar
[7]

Meng, A. Y.; Zhang, L. Y.; Cheng, B.; Yu. J. G. Dual cocatalysts in TiO2 photocatalysis. Adv. Mater. 2019, 31, 1807660.
Google Scholar
[8]

Wenderich, K.; Mul, G. Methods, mechanism, and applications of photodeposition in photocatalysis: A review. Chem. Rev. 2016, 116, 14587–14619.
DOI Google Scholar
[9]

Moss, B.; Wang, Q.; Butler, K. T.; Grau-Crespo, R.; Selim, S.; Regoutz, A.; Hisatomi, T.; Godin, R.; Payne, D. J.; Kafizas, A. et al. Linking in situ charge accumulation to electronic structure in doped SrTiO3 reveals design principles for hydrogen-evolving photocatalysts. Nat. Mater. 2021, 20, 511–517.
DOI Google Scholar
[10]

Li, L. D.; Yan, J. Q.; Wang, T.; Zhao, Z. J.; Zhang, J.; Gong, J. L.; Guan, N. J. Sub-10 nm rutile titanium dioxide nanoparticles for efficient visible-light-driven photocatalytic hydrogen production. Nat. Commun. 2015, 6, 5881.
DOI Google Scholar
[11]

Chen, H.; Yang, Z. Z.; Wang, X.; Polo-Garzon, F.; Halstenberg, P. W.; Wang, T.; Suo, X.; Yang, S. Z.; Meyer III, H. M.; Wu, Z. L. et al. Photoinduced strong metal–support interaction for enhanced catalysis. J. Am. Chem. Soc. 2021, 143, 8521–8526.
DOI Google Scholar
[12]

Liu, M. C.; Chen, Y. B.; Su, J. Z.; Shi, J. W.; Wang, X. X.; Guo, L. J. Photocatalytic hydrogen production using twinned nanocrystals and an unanchored NiSx co-catalyst. Nat. Energy 2016, 1, 16151.
DOI Google Scholar
[13]

Bi, W. T.; Li, X. G.; Zhang, L.; Jin, T.; Zhang, L. D.; Zhang, Q.; Luo, Y.; Wu, C. Z.; Xie, Y. Molecular co-catalyst accelerating hole transfer for enhanced photocatalytic H2 evolution. Nat. Commun. 2015, 6, 8647.
DOI Google Scholar
[14]

Yang, J. H.; Wang, D.; Han, H. X.; Li, C. Roles of cocatalysts in photocatalysis and photoelectrocatalysis. Acc. Chem. Res. 2013, 46, 1900–1909.
DOI Google Scholar
[15]

Li, G. K.; Jang, H.; Liu, S. G.; Li, Z. J.; Kim, M. G.; Qin, Q.; Liu, X. E.; Cho, J. The synergistic effect of Hf–O–Ru bonds and oxygen vacancies in Ru/HfO2 for enhanced hydrogen evolution. Nat. Commun. 2022, 13, 1270.
DOI Google Scholar
[16]

Ou, G.; Xu, Y. S.; Wen, B.; Lin, R.; Ge, B. H.; Tang, Y.; Liang, Y. W.; Yang, C.; Huang, K.; Zu, D. et al. Tuning defects in oxides at room temperature by lithium reduction. Nat. Commun. 2018, 9, 1302.
DOI Google Scholar
[17]

Ma, X.; Wang, L.; Zhang, Q.; Jiang, H. L. Switching on the photocatalysis of metal-organic frameworks by engineering structural defects. Angew. Chem., Int. Ed. 2019, 58, 12175–12179.
DOI Google Scholar
[18]

Pan, J. B.; Wang, B. H.; Wang, J. B.; Ding, H. Z.; Zhou, W.; Liu, X.; Zhang, J. R.; Shen, S.; Guo, J. K.; Chen, L. et al. Activity and stability boosting of oxygen-vacancy-rich BiVO4 photoanode by NiFe-MOFs thin layer for water oxidation. Angew. Chem., Int. Ed. 2021, 60, 1433–1440.
DOI Google Scholar
[19]

Zu, X. L.; Zhao, Y.; Li, X. D.; Chen, R. H.; Shao, W. W.; Wang, Z. Q.; Hu, J.; Zhu, J. F.; Pan, Y.; Sun, Y. F. et al. Ultrastable and efficient visible-light-driven CO2 reduction triggered by regenerative oxygen-vacancies in Bi2O2CO3 nanosheets. Angew. Chem., Int. Ed. 2021, 60, 13840–13846.
DOI Google Scholar
[20]

Guo, N. K.; Xue, H.; Bao, A.; Wang, Z. H.; Sun, J.; Song, T. S.; Ge, X.; Zhang, W.; Huang, K. K.; He, F. et al. Achieving superior electrocatalytic performance by surface copper vacancy defects during electrochemical etching process. Angew. Chem., Int. Ed. 2020, 59, 13778–13784.
DOI Google Scholar
[21]

Wei, Z.; Wang, W. C.; Li, W. L.; Bai, X. Q.; Zhao, J. F.; Tse, E. C. M.; Phillips, D. L.; Zhu, Y. F. Steering electron–hole migration pathways using oxygen vacancies in tungsten oxides to enhance their photocatalytic oxygen evolution performance. Angew. Chem., Int. Ed. 2021, 60, 8236–8242.
DOI Google Scholar
[22]

Zhao, Y. X.; Zhao, Y. F.; Shi, R.; Wang, B.; Waterhouse, G. I. N.; Wu, L. Z.; Tung, C. H.; Zhang, T. R. Tuning oxygen vacancies in ultrathin TiO2 nanosheets to boost photocatalytic nitrogen fixation up to 700 nm. Adv. Mater. 2019, 31, 1806482.
DOI Google Scholar
[23]

Zhao, Y. F.; Chen, G. B.; Bian, T.; Zhou, C.; Waterhouse, G. I. N.; Wu, L. Z.; Tung, C. H.; Smith, L. J.; O’Hare, D.; Zhang, T. R. Defect-rich ultrathin ZnAl-layered double hydroxide nanosheets for efficient photoreduction of CO2 to CO with water. Adv. Mater. 2015, 27, 7824–7831.
DOI Google Scholar
[24]

Liu, L. Z.; Huang, H. W.; Chen, F.; Yu, H. J.; Tian, N.; Zhang, Y. H.; Zhang, T. R. Cooperation of oxygen vacancies and 2D ultrathin structure promoting CO2 photoreduction performance of Bi4Ti3O12. Sci Bull. 2020, 65, 934–943.
DOI Google Scholar
[25]

Wang, Z. L.; Wang, L. X.; Cheng, B.; Yu, H. G.; Yu, J. G. Photocatalytic H2 evolution coupled with furfuralcohol oxidation over Pt-modified ZnCdS solid solution. Small Methods 2021, 5, 2100979.
DOI Google Scholar
[26]

Dai, F. X.; Guo, Z. Y.; Zhao, W. J.; Li, Z. J.; Xing, J.; Wang, L. Interfacial engineering boosting charge extraction for efficient photocatalytic hydrogen evolution. Chem. Eng. J. 2022, 450, 138015.
DOI Google Scholar
[27]

Tamai, K.; Hosokawa, S.; Asakura, H.; Teramura, K.; Tanaka, T. Low-temperature NOx trapping on alkali or alkaline earth metal modified TiO2 photocatalyst. Catal. Today 2019, 332, 76–82.
DOI Google Scholar
[28]

Zhang, H. B.; Zuo, S. W.; Qiu, M.; Wang, S. B.; Zhang, Y. F.; Zhang, J.; Lou, X. W. Direct probing of atomically dispersed Ru species over multi-edged TiO2 for highly efficient photocatalytic hydrogen evolution. Sci. Adv. 2020, 6, eabb9823.
DOI Google Scholar
[29]

Wang, L.; Yue, H. Q.; Hua, Z. L.; Wang, H. Y.; Li, X. B.; Li, L. C. Highly active Pt/NaxTiO2 catalyst for low temperature formaldehyde decomposition. Appl. Catal. B: Environ. 2017, 219, 301–313.
DOI Google Scholar
[30]

Liu, F.; Feng, N. D.; Wang, Q.; Xu, J.; Qi, G. D.; Wang, C.; Deng, F. Transfer channel of photoinduced holes on a TiO2 surface as revealed by solid-state nuclear magnetic resonance and electron spin resonance spectroscopy. J. Am. Chem. Soc. 2017, 139, 10020–10028.
DOI Google Scholar
[31]

Chen, Y. J.; Ji, S. F.; Sun, W. M.; Lei, Y. P.; Wang, Q. C.; Li, A.; Chen, W. X.; Zhou, G.; Zhang, Z. D.; Wang, Y. et al. Engineering the atomic interface with single platinum atoms for enhanced photocatalytic hydrogen production. Angew. Chem., Int. Ed. 2020, 59, 1295–1301.
DOI Google Scholar
[32]

Jiang, X. H.; Zhang, L. S.; Liu, H. Y.; Wu, D. S.; Wu, F. Y.; Tian, L.; Liu, L. L.; Zou, J. P.; Luo, S. L.; Chen, B. B. Silver single atom in carbon nitride catalyst for highly efficient photocatalytic hydrogen evolution. Angew. Chem., Int. Ed. 2020, 59, 23112–23116.
DOI Google Scholar
[33]

Xiao, M.; Zhang, L.; Luo, B.; Lyu, M.; Wang, Z. L.; Huang, H. M.; Wang, S. C.; Du, A. J.; Wang, L. Z. Molten-salt-mediated synthesis of an atomic nickel co-catalyst on TiO2 for improved photocatalytic H2 evolution. Angew. Chem., Int. Ed. 2020, 59, 7230–7234.
DOI Google Scholar
[34]

Zhu, K. N.; Zhu, Q.; Jiang, M. P.; Zhang, Y. W.; Shao, Z. Y.; Geng, Z. B.; Wang, X. Y.; Zeng, H.; Wu, X. F.; Zhang, W. et al. Modulating Ti t2g orbital occupancy in a Cu/TiO2 composite for selective photocatalytic CO2 reduction to CO. Angew. Chem., Int. Ed. 2022, 61, e202207600.
Google Scholar
[35]

Lv, T. P.; Xiao, B.; Xia, F. J.; Chen, M. P.; Zhao, J. H.; Ma, Y. X.; Wu, J. S.; Zhang, J.; Zhang, Y. M.; Liu, Q. J. Insights into synergistic effect of Pd single atoms and sub-nanoclusters on TiO2 for enhanced photocatalytic H2 evolution. Chem. Eng. J. 2022, 450, 137873.
DOI Google Scholar
[36]

Meng, X. Y.; Ma, C.; Jiang, L. Z.; Si, R.; Meng, X. G.; Tu, Y. C.; Yu, L.; Bao, X. H.; Deng, D. H. Distance synergy of MoS2-confined rhodium atoms for highly efficient hydrogen evolution. Angew. Chem., Int. Ed. 2020, 59, 10502–10507.
DOI Google Scholar
File
12274_2022_5181_MOESM1_ESM.pdf (4.8 MB)
12274_2022_5181_MOESM2_ESM.pdf (7.5 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 11 September 2022
Revised: 09 October 2022
Accepted: 10 October 2022
Published: 23 November 2022
Issue date: April 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 51802171, 52072197, and 21905154), Outstanding Youth Foundation of Shandong Province, China (No. ZR2019JQ14), Youth Innovation and Technology Foundation of Shandong Higher Education Institutions, China (No. 2019KJC004), Major Scientific and Technological Innovation Project (No. 2019JZZY020405), and Taishan Scholar Program, Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant (No. ZR2020ZD09).

Return