Journal Home > Volume 15 , Issue 3
Nano Research 2022, 15(3): 1786-1795 https://doi.org/10.1007/s12274-021-3723-2
Research Article | Issue | Published: 17 August 2021

In-situ transient photovoltage study on interface electron transfer regulation of carbon dots/NiCo2O4 photocatalyst for the enhanced overall water splitting activity

Show Author's Information Haodong Nie1,  Yan Liu1,  Yi Li1,  Kaiqiang Wei1,  Zhenyu Wu1,  Hong Shi1,  Hui Huang1,  Yang Liu1( ),  Mingwang Shao1,  Zhenhui Kang1,2( )
Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, China
Macao Institute of Materials Science and Engineering, Macau University of Science and Technology, Taipa 999078, Macau SAR, China
Keywords:
normal pressure, carbon dots, photocatalytic hydrogen evolution, transient photovoltage technique, continuous wavelet analysis
Topics:
Catalysis
Cite this article:
Nie H, Liu Y, Li Y, et al. In-situ transient photovoltage study on interface electron transfer regulation of carbon dots/NiCo2O4 photocatalyst for the enhanced overall water splitting activity. Nano Research, 2022, 15(3): 1786-1795. https://doi.org/10.1007/s12274-021-3723-2
Download citation
EndNote(RIS)
BibTeX

764

Views

70

Downloads

Citations

41

Crossref

43

WoS

40

Scopus

3

CSCD

Abstract Full text About this article

Photocatalytic hydrogen production by overall water solar-splitting is a prospective strategy to solve energy crisis. However, the rapid recombination of photogenerated electron–hole pairs deeply restricts photocatalytic activity of catalysts. Here, the in-situ transient photovoltage (TPV) technique was developed to investigate the interfacial photogenerated carrier extraction, photogenerated carrier recombination and the interfacial electron delivery kinetics of the photocatalyst. The carbon dots/NiCo2O4 (CDs/NiCo2O4) composite shows weakened recombination rate of photogenerated carriers due to charge storage of CDs, which enhances the photocatalytic water decomposition activity without any scavenger. CDs can accelerate the interface electron extraction about 0.09 ms, while the maximum electron storage time by CDs is up to 0.7 ms. The optimal CDs/NiCo2O4 composite (5 wt.% CDs) displays the hydrogen production of 62 µmol·h−1·g−1 and oxygen production of 29 µmol·h−1·g−1 at normal atmosphere, which is about 4 times greater than that of pristine NiCo2O4. This work provides sufficient evidence on the charge storage of CDs and the interfacial charge kinetics of photocatalysts on the basis of in-situ TPV tests.


menu
Abstract
Full text
Outline
About this article

In-situ transient photovoltage study on interface electron transfer regulation of carbon dots/NiCo2O4 photocatalyst for the enhanced overall water splitting activity

Show Author's information Haodong Nie1, Yan Liu1, Yi Li1, Kaiqiang Wei1, Zhenyu Wu1, Hong Shi1, Hui Huang1, Yang Liu1( ), Mingwang Shao1, Zhenhui Kang1,2( )
Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, China
Macao Institute of Materials Science and Engineering, Macau University of Science and Technology, Taipa 999078, Macau SAR, China

Abstract

Photocatalytic hydrogen production by overall water solar-splitting is a prospective strategy to solve energy crisis. However, the rapid recombination of photogenerated electron–hole pairs deeply restricts photocatalytic activity of catalysts. Here, the in-situ transient photovoltage (TPV) technique was developed to investigate the interfacial photogenerated carrier extraction, photogenerated carrier recombination and the interfacial electron delivery kinetics of the photocatalyst. The carbon dots/NiCo2O4 (CDs/NiCo2O4) composite shows weakened recombination rate of photogenerated carriers due to charge storage of CDs, which enhances the photocatalytic water decomposition activity without any scavenger. CDs can accelerate the interface electron extraction about 0.09 ms, while the maximum electron storage time by CDs is up to 0.7 ms. The optimal CDs/NiCo2O4 composite (5 wt.% CDs) displays the hydrogen production of 62 µmol·h−1·g−1 and oxygen production of 29 µmol·h−1·g−1 at normal atmosphere, which is about 4 times greater than that of pristine NiCo2O4. This work provides sufficient evidence on the charge storage of CDs and the interfacial charge kinetics of photocatalysts on the basis of in-situ TPV tests.

Keywords: normal pressure, carbon dots, photocatalytic hydrogen evolution, transient photovoltage technique, continuous wavelet analysis

References(39)

1

Liu, J.; Liu, Y.; Liu, N. Y.; Han, Y. Z.; Zhang, X.; Huang, H.; Lifshitz, Y.; Lee, S. T.; Zhong, J.; Kang, Z. H. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway. Science 2015, 347, 970–974.
DOI Google Scholar
2

Martin, D. J.; Qiu, K. P.; Shevlin, S. A.; Handoko, A. D.; Chen, X. W.; Guo, Z. X.; Tang, J. W. Highly efficient photocatalytic H2 evolution from water using visible light and structure-controlled graphitic carbon nitride. Angew. Chem., Int. Ed. 2014, 53, 9240–9245.
DOI Google Scholar
3

Zhu, M. S.; Sun, Z. C.; Fujitsuka, M.; Majima, T. Z-scheme photocatalytic water splitting on a 2D heterostructure of black phosphorus/bismuth vanadate using visible light. Angew. Chem., Int. Ed. 2018, 57, 2160–2164.
DOI Google Scholar
4

Shi, W. L.; Guo, F.; Zhu, C.; Wang, H. B.; Li, H.; Huang, H.; Liu, Y.; Kang, Z. H. Carbon dots anchored on octahedral CoO as a stable visible-light-responsive composite photocatalyst for overall water splitting. J. Mater. Chem. A 2017, 5, 19800–19807.
DOI Google Scholar
5

Zhu, C.; Zhu, M. M.; Sun, Y.; Zhou, Y. J.; Gao, J.; Huang, H.; Liu, Y.; Kang, Z. H. Carbon-supported oxygen vacancy-rich Co3O4 for robust photocatalytic H2O2 production via coupled water oxidation and oxygen reduction reaction. ACS Appl. Energy Mater. 2019, 2, 8737–8746.
DOI Google Scholar
6

Zhu, C.; Liu, C. A.; Zhou, Y. J.; Fu, Y. J.; Guo, S. J.; Li, H.; Zhao, S. Q.; Huang, H.; Liu, Y.; Kang, Z. H. Carbon dots enhance the stability of CdS for visible-light-driven overall water splitting. Appl. Catal. B: Environ. 2017, 216, 114–121.
DOI Google Scholar
7

Cao, J. J.; Wang, H.; Zhao, Y. J.; Liu, Y.; Wu, Q. Y.; Huang, H.; Shao, M. W; Liu, Y.; Kang, Z. H. Phosphorus-doped porous carbon nitride for efficient sole production of hydrogen peroxide via photocatalytic water splitting with a two-channel pathway. J. Mater. Chem. A 2020, 8, 3701–3707.
DOI Google Scholar
8

Ran, J. R.; Gao, G. P.; Li, F. T.; Ma, T. Y.; Du, A. J.; Qiao, S. Z. Ti3C2 MXene Co-Catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic hydrogen production. Nat. Commun. 2017, 8, 13907.
DOI Google Scholar
9

Indra, A.; Acharjya, A.; Menezes, P. W.; Merschjann, C.; Hollmann, D.; Schwarze, M.; Aktas, M.; Friedrich, A.; Lochbrunner, S.; Thomas, A. et al. Boosting visible-light-driven photocatalytic hydrogen evolution with an integrated nickel phosphide–carbon nitride system. Angew. Chem., Int. Ed. 2017, 56, 1653–1657.
DOI Google Scholar
10

Jiao, Y. Y.; Huang, Q. Z.; Wang, J. S.; He, Z. H.; Li, Z. J. A Novel MoS2 quantum dots (QDs) decorated z-scheme g-C3N4 nanosheet/N-doped carbon dots heterostructure photocatalyst for photocatalytic hydrogen evolution. Appl. Catal. B: Environ. 2019, 247, 124–132.
DOI Google Scholar
11

Chen, Y. L.; Liu, X. Q.; Hou, L.; Guo, X. R.; Fu, R. W.; Sun, J. M. Construction of covalent bonding oxygen-doped carbon nitride/graphitic carbon nitride z-scheme heterojunction for enhanced visible-light-driven H2 evolution. Chem. Eng. J. 2020, 383, 123132.
DOI Google Scholar
12

Zhang, Z. Y.; Shao, C. L.; Li, X. H.; Wang, C. H.; Zhang, M. Y.; Liu, Y. C. Electrospun nanofibers of p-Type NiO/n-Type ZnO heterojunctions with enhanced photocatalytic activity. ACS Appl. Mater. Interfaces 2010, 2, 2915–2923.
DOI Google Scholar
13

Cui, B.; Lin, H.; Liu, Y. Z.; Li, J. B.; Sun, P.; Zhao, X. C.; Liu, C. J. Photophysical and photocatalytic properties of core-ring structured NiCo2O4 nanoplatelets. J. Phys. Chem. C 2009, 113, 14083–14087.
DOI Google Scholar
14

Liu, J.; Zhang, J. N.; Wang, D.; Li, D. Y.; Ke, J.; Wang, S. B.; Liu, S. M.; Xiao, H. N.; Wang, R. J. Highly dispersed NiCo2O4 nanodots decorated three-dimensional g-C3N4 for enhanced photocatalytic H2 generation. ACS Sustainable Chem. Eng. 2019, 7, 12428–12438.
Google Scholar
15

Jiang, J. H.; Shi, W. L.; Guo, F.; Yuan, S. L. Preparation of magnetically separable and recyclable carbon dots/NiCo2O4 composites with enhanced photocatalytic activity for the degradation of tetracycline under visible light. Inorg. Chem. Front. 2018, 5, 1438–1444.
DOI Google Scholar
16

Chang, W. X.; Xue, W. H.; Liu, E. Z.; Fan, J.; Zhao, B. R. Highly efficient H2 production over NiCo2O4 decorated G-C3N4 by photocatalytic water reduction. Chem. Eng. J. 2019, 362, 392–401.
DOI Google Scholar
17

Wei, R. B.; Huang, Z. L.; Gu, G. H.; Wang, Z.; Zeng, L. X.; Chen, Y. B.; Liu, Z. Q. Dual-cocatalysts decorated rimous CdS spheres advancing highly-efficient visible-light photocatalytic hydrogen production. Appl. Catal. B: Environ. 2018, 231, 101–107.
DOI Google Scholar
18

Meng, X. B.; Sheng, J. L.; Tang, H. L.; Sun, X. J.; Dong, H.; Zhang, F. M. Metal-organic framework as nanoreactors to co-incorporate carbon nanodots and CdS quantum dots into the pores for improved H2 evolution without noble-metal cocatalyst. Appl. Catal. B: Environ. 2019, 244, 340–346.
DOI Google Scholar
19

Yu, H. J.; Zhao, Y. F.; Zhou, C.; Shang, L.; Peng, Y.; Cao, Y. H.; Wu, L. Z.; Tung, C. H.; Zhang, T. Carbon quantum dots/TiO2 composites for efficient photocatalytic hydrogen evolution. J. Mater. Chem. A 2014, 2, 3344–3351.
DOI Google Scholar
20

Liu, Y.; Zhao, Y. J.; Sun, Y.; Cao, J. J.; Wang, H.; Wang, X.; Huang, H.; Shao, M. W.; Liu, Y.; Kang, Z. H. A 4e−–2e− cascaded pathway for highly efficient production of H2 and H2O2 from water photo-splitting at normal pressure. Appl. Catal. B: Environ. 2020, 270, 118875.
DOI Google Scholar
21

Li, Y.; Zhao, Y. J.; Nie, H. D.; Wei, K. Q.; Cao, J. J.; Huang, H.; Shao, M. W.; Liu, Y.; Kang, Z. H. Interface photo-charge kinetics regulation by carbon dots for efficient hydrogen peroxide production. J. Mater. Chem. A 2021, 9, 515–522.
DOI Google Scholar
22

Cao, J. J.; Wu, Q. Y.; Zhao, Y. J.; Wei, K. Q.; Li, Y.; Wang, X.; Liao, F.; Huang, H.; Shao, M. W.; Liu, Y. et al. In-situ photovoltage transients assisted catalytic study on H2O2 photoproduction over organic molecules modified carbon nitride photocatalyst. Appl. Catal. B: Environ. 2021, 285, 119817.
DOI Google Scholar
23
Dahlke, S.; Kunoth, A. Biorthogonal wavelets and multigrid. In Proceedings of the Ninth GAMM-Seminar, Wiesbaden, 1994, pp 99–119.
24
Wang, T.; Wang, Y. B.; Monti, A. Fault isolation in the DC distribution grid using current signature analysis. In 2019 IEEE 10th International Symposium on Power Electronics for Distributed Generation Systems (PEDG), Xi’an, 2019, pp 800–805.
25

Tang, Y. X.; Zhang, D. F.; Qiu, X. X.; Zeng, L.; Huang, B. X.; Li, H.; Pu, X. P.; Geng, Y. L. Fabrication of a NiCo2O4/Zn0.1Cd0.9S p-n heterojunction photocatalyst with improved separation of charge carriers for highly efficient visible light photocatalytic H2 evolution. J. Alloys Compd. 2019, 809, 151855.
DOI Google Scholar
26

Han, B.; Song, J. N.; Liang, S. J.; Chen, W. Y.; Deng, H.; Ou, X. W.; Xu, Y. J.; Lin, Z. Hierarchical NiCo2O4 hollow nanocages for photoreduction of diluted CO2: Adsorption and active sites engineering. Appl. Catal. B: Environ. 2020, 260, 118208.
DOI Google Scholar
27

Lin, J. H.; Yan, Y. T.; Xu, T. X.; Qu, C. Q.; Li, J.; Cao, J.; Feng, J. C.; Qi, J. L. S doped NiCo2O4 nanosheet arrays by Ar plasma: An efficient and bifunctional electrode for overall water splitting. J. Colloid Interface Sci. 2020, 560, 34–39.
DOI Google Scholar
28

Shen, Y. T.; Liang, L. J.; Zhang, S. Q.; Huang, D. S.; Zhang, J.; Xu, S. P.; Liang, C. Y.; Xu, W. Q. Organelle-targeting surface-enhanced Raman scattering (SERS) nanosensors for subcellular pH sensing. Nanoscale 2018, 10, 1622–1630.
DOI Google Scholar
29

Chakrabarty, S.; Mukherjee, A.; Basu, S. RGO-MoS2 supported NiCo2O4 catalyst toward solar water splitting and dye degradation. ACS Sustainable Chem. Eng. 2018, 6, 5238–5247.
DOI Google Scholar
30

Radziuk, D.; Möhwald, H. Ultrasonically treated liquid interfaces for progress in cleaning and separation processes. Phys. Chem. Chem. Phys. 2016, 18, 21–46.
DOI Google Scholar
31

Datsyuk, V.; Kalyva, M.; Papagelis, K.; Parthenios, J.; Tasis, D.; Siokou, A.; Kallitsis, I.; Galiotis, C. Chemical oxidation of multiwalled carbon nanotubes. Carbon 2008, 46, 833–840.
DOI Google Scholar
32

Ratso, S.; Kruusenberg, I.; Sarapuu, A.; Rauwel, P.; Saar, R.; Joost, U.; Aruväli, J.; Kanninen, P.; Kallio, T.; Tammeveski, K. Enhanced oxygen reduction reaction activity of iron-containing nitrogen-doped carbon nanotubes for alkaline direct methanol fuel cell application. J. Power Sources 2016, 332, 129–138.
DOI Google Scholar
33

Liu, Y.; Zhao, Y. J.; Wu, Q. Y.; Wang, X.; Nie, H. D.; Zhou, Y. J.; Huang, H.; Shao, M. W.; Liu, Y.; Kang, Z. H. Charge storage of carbon dot enhances photo-production of H2 and H2O2 over Ni2P/carbon dot catalyst under normal pressure. Chem. Eng. J. 2021, 409, 128184.
Google Scholar
34

Zhao, Y. J.; Liu, Y.; Wang, Z. Z.; Ma, Y. R.; Zhou, Y. J.; Shi, X. F.; Wu, Q. Y; Wang, X.; Shao, M. W.; Huang, H. et al. Carbon nitride assisted 2D conductive metal-organic frameworks composite photocatalyst for efficient visible light-driven H2O2 production. Appl. Catal. B: Environ. 2021, 289, 120035.
DOI Google Scholar
35

Li, Y.; Chen, J. X.; Cai, P. W.; Wen, Z. H. An electrochemically neutralized energy-assisted low-cost acid-alkaline electrolyzer for energy-saving electrolysis hydrogen generation. J. Mater. Chem. A 2018, 6, 4948–4954.
DOI Google Scholar
36

Zhao, Y. J.; Liu, Y.; Cao, J. J.; Wang, H.; Shao, M. W.; Huang, H.; Liu, Y.; Kang, Z. H. Efficient production of H2O2 via two-channel pathway over ZIF-8/C3N4 composite photocatalyst without any sacrificial agent. Appl. Catal. B: Environ. 2020, 278, 119289.
DOI Google Scholar
37

Liang, Q.; Liu, L. J.; Wu, Z. Y.; Nie, H. D.; Shi, H.; Li, Z. Y.; Kang, Z. H. Polytriptycene@CdS double shell hollow spheres with enhanced interfacial charge transfer for highly efficient photocatalytic hydrogen evolution. J. Mater. Chem. A 2021, 9, 9105–9112.
DOI Google Scholar
38

Jiang, W. S.; Zhao, Y. J.; Zong, X.; Nie, H. D.; Niu, L. J.; An, L.; Qu, D.; Wang, X. Y.; Kang, Z. H.; Sun, Z. C. Photocatalyst for high-performance H2 production: Ga-doped polymeric carbon nitride. Angew. Chem., Int. Ed. 2021, 60, 6124–6129.
DOI Google Scholar
39

Wang, J. W.; Qiao, L. Z.; Nie, H. D.; Huang, H. H.; Li, Y.; Yao, S.; Liu, M.; Zhang, Z. M.; Kang, Z. H.; Lu, T. B. Facile electron delivery from graphene template to ultrathin metal-organic layers for boosting CO2 photoreduction. Nat. Commun. 2021, 12, 813.
DOI Google Scholar
Publication history
Copyright
Acknowledgements

Publication history

Received: 15 May 2021
Revised: 24 June 2021
Accepted: 28 June 2021
Published: 17 August 2021
Issue date: March 2022

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This work is supported by the National Key Research and Development Program of China (Nos. 2020YFA0406104, 2020YFA0406101, and 2020YFA0406103), the National MCF Energy R&D Program (No. 2018YFE0306105), Innovative Research Group Project of the National Natural Science Foundation of China (No. 51821002), the National Natural Science Foundation of China (Nos. 51725204, 21771132, 51972216, and 52041202‬), Natural Science Foundation of Jiangsu Province (No. BK20190041), Key-Area Research and Development Program of Guangdong Province (No. 2019B010933001), Collaborative Innovation Center of Suzhou Nano Science & Technology, and the 111 Project.

Return