Journal Home > Volume 17 , Issue 3
Nano Research 2024, 17(3): 1027-1034 https://doi.org/10.1007/s12274-023-5991-5
Communication | Issue | Published: 31 July 2023

Rational design of ZnCdS/TpPa-1-COF heterostructure photocatalyst by strengthening the interface connection in solar hydrogen production reactions

Show Author's Information Di Yang1,  Zhi-Gang Li1,  Xinghao Zhang1,  Zenghuan Ren1,  Weihan Lu2,  Haining Liu2,  Xiaomeng Guo2( ),  Jijie Zhang1( ),  Xian-He Bu1,3
Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
Keywords:
quantum dots, photocatalysis, heterojunction, hydrogen generation, covalent organic frameworks
Topics:
Photocatalysts
Cite this article:
Yang D, Li Z-G, Zhang X, et al. Rational design of ZnCdS/TpPa-1-COF heterostructure photocatalyst by strengthening the interface connection in solar hydrogen production reactions. Nano Research, 2024, 17(3): 1027-1034. https://doi.org/10.1007/s12274-023-5991-5
Download citation
EndNote(RIS)
BibTeX

368

Views

47

Downloads

Citations

3

Crossref

3

WoS

3

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

ZnCdS quantum dots (QDs) are highly coveted in photocatalysis research for their exceptional visible-light responses and high light-absorption coefficients. However, their practical application is hindered by their tendency to aggregate, due to having high surface energies. To address this issue, herein, a heterostructure is synthesized by growing ZnCdS QDs with a size of approximately 5 nm onto the surface of a two-dimensional (2D) covalent organic framework (COF), TpPa-1-COF. This approach suppresses the aggregation of the QDs and improves their stability. The ZnCdS/TpPa-1-COF composite exhibited a peak hydrogen evolution rate of 6244.16 μmol·g−1·h−1, which was 2.89 and 4.18 times greater than that of ZnCdS and TpPa-1-COF, respectively. The zero-dimensional/two-dimensional (0D/2D) heterojunction formed by ZnCdS and TpPa-1-COF generates a strong interfacial force, which is attributed to the intimate contact between the interfaces. Tight connections accelerate charge separation, improve the utilisation of reduced electrons, and reduce the extent of agglomeration of the ZnCdS QDs, thereby resulting in high hydrogen production activity of the composites. Meanwhile, the photocatalytic mechanism is studied using Kelvin probe force microscopy and theoretical calculations. This study offers a novel approach for creating sulfide photocatalysts and is crucial for investigating the potential practical applications of the related photocatalysts.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Rational design of ZnCdS/TpPa-1-COF heterostructure photocatalyst by strengthening the interface connection in solar hydrogen production reactions

Show Author's information Di Yang1, Zhi-Gang Li1, Xinghao Zhang1, Zenghuan Ren1, Weihan Lu2, Haining Liu2, Xiaomeng Guo2( ), Jijie Zhang1( ), Xian-He Bu1,3
Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China

Abstract

ZnCdS quantum dots (QDs) are highly coveted in photocatalysis research for their exceptional visible-light responses and high light-absorption coefficients. However, their practical application is hindered by their tendency to aggregate, due to having high surface energies. To address this issue, herein, a heterostructure is synthesized by growing ZnCdS QDs with a size of approximately 5 nm onto the surface of a two-dimensional (2D) covalent organic framework (COF), TpPa-1-COF. This approach suppresses the aggregation of the QDs and improves their stability. The ZnCdS/TpPa-1-COF composite exhibited a peak hydrogen evolution rate of 6244.16 μmol·g−1·h−1, which was 2.89 and 4.18 times greater than that of ZnCdS and TpPa-1-COF, respectively. The zero-dimensional/two-dimensional (0D/2D) heterojunction formed by ZnCdS and TpPa-1-COF generates a strong interfacial force, which is attributed to the intimate contact between the interfaces. Tight connections accelerate charge separation, improve the utilisation of reduced electrons, and reduce the extent of agglomeration of the ZnCdS QDs, thereby resulting in high hydrogen production activity of the composites. Meanwhile, the photocatalytic mechanism is studied using Kelvin probe force microscopy and theoretical calculations. This study offers a novel approach for creating sulfide photocatalysts and is crucial for investigating the potential practical applications of the related photocatalysts.

Keywords: quantum dots, photocatalysis, heterojunction, hydrogen generation, covalent organic frameworks

References(40)

[1]

Guo, J.; Wan, Y.; Zhu, Y. F.; Zhao, M. T.; Tang, Z. Y. Advanced photocatalysts based on metal nanoparticle/metal-organic framework composites. Nano Res. 2021, 14, 2037–2052.
DOI Google Scholar
[2]

Gong, Y. N.; Guan, X. Y.; Jiang, H. L. Covalent organic frameworks for photocatalysis: Synthesis, structural features, fundamentals and performance. Coord. Chem. Rev. 2023, 475, 214889.
DOI Google Scholar
[3]

Zhang, J. J.; Bai, T. Y.; Huang, H.; Yu, M. H.; Fan, X. B.; Chang, Z.; Bu, X. H. Metal-organic-framework-based photocatalysts optimized by spatially separated cocatalysts for overall water splitting. Adv. Mater. 2020, 32, 2004747.
DOI Google Scholar
[4]

Qian, Y. Y.; Han, Y. L.; Zhang, X. Y.; Yang, G.; Zhang, G. Z.; Jiang, H. L. Computation-based regulation of excitonic effects in donor-acceptor covalent organic frameworks for enhanced photocatalysis. Nat. Commun. 2023, 14, 3083.
DOI Google Scholar
[5]

Yang, D. R.; Yu, H. D.; He, T.; Zuo, S. W.; Liu, X. Z.; Yang, H. Z.; Ni, B.; Li, H. Y.; Gu, L.; Wang, D. et al. Visible-light-switched electron transfer over single porphyrin-metal atom center for highly selective electroreduction of carbon dioxide. Nat. Commun. 2019, 10, 3844.
DOI Google Scholar
[6]

Shi, X. F.; Lian, X.; Yang, D.; Hu, X. J.; Zhang, J. J.; Bu, X. H. Facet-engineering of NH2-UiO-66 with enhanced photocatalytic hydrogen production performance. Dalton Trans. 2021, 50, 17953–17959.
DOI Google Scholar
[7]

Liu, X. Y.; Zhang, G. Z.; Chen, H.; Li, H. W.; Jiang, J.; Long, Y. T.; Ning, Z. J. Efficient defect-controlled photocatalytic hydrogen generation based on near-infrared Cu-In-Zn-S quantum dots. Nano Res. 2018, 11, 1379–1388.
DOI Google Scholar
[8]

Huang, X. B.; Li, X. J.; Luan, Q. J.; Zhang, K. Y.; Wu, Z. Y.; Li, B. Z.; Xi, Z. S.; Dong, W. J.; Wang, G. Highly dispersed Pt clusters encapsulated in MIL-125-NH2 via in situ auto-reduction method for photocatalytic H2 production under visible light. Nano Res. 2021, 14, 4250–4257.
DOI Google Scholar
[9]

Gong, Y. N.; Zhong, W. H.; Li, Y.; Qiu, Y. Z.; Zheng, L. R.; Jiang, J.; Jiang, H. L. Regulating photocatalysis by spin-state manipulation of cobalt in covalent organic frameworks. J. Am. Chem. Soc. 2020, 142, 16723–16731.
DOI Google Scholar
[10]

Di, T. M.; Deng, Q. R.; Wang, G. M.; Wang, S. G.; Wang, L. X.; Ma, Y. H. Photodeposition of CoOx and MoS2 on CdS as dual cocatalysts for photocatalytic H2 production. J. Mater. Sci. Technol. 2022, 124, 209–216.
DOI Google Scholar
[11]

Ha, E. N.; Ruan, S. H.; Li, D. Y.; Zhu, Y. M.; Chen, Y. P.; Qiu, J. Y.; Chen, Z. H.; Xu, T. T.; Su, J. Y.; Wang, L. Y. et al. Surface disorder engineering in ZnCdS for cocatalyst free visible light driven hydrogen production. Nano Res. 2022, 15, 996–1002.
DOI Google Scholar
[12]

Si, S. H.; Shou, H. W.; Mao, Y. Y.; Bao, X. L.; Zhai, G. Y.; Song, K. P.; Wang, Z. Y.; Wang, P.; Liu, Y. Y.; Zheng, Z. K. et al. Low-coordination single Au atoms on ultrathin ZnIn2S4 nanosheets for selective photocatalytic CO2 reduction towards CH4. Angew Chem., Int. Ed. 2022, 134, e202209446.
DOI Google Scholar
[13]

Palanisamy, G.; Bhuvaneswari, K.; Pazhanivel, T.; Shankar, R.; Katubi, K. M.; Alsaiari, N. S.; Ouladsmane, M. ZnS quantum dots and Bi metals embedded with two dimensional β-Bi2O4 nanosheets for efficient UV-visible light driven photocatalysis. Mater. Res. Bull. 2021, 142, 111387.
DOI Google Scholar
[14]

Bie, C. B.; Zhu, B. C.; Wang, L. X.; Yu, H. G.; Jiang, C. H.; Chen, T.; Yu, J. G. A bifunctional CdS/MoO2/MoS2 catalyst enhances photocatalytic H2 evolution and pyruvic acid synthesis. Angew. Chem., Int. Ed. 2022, 61, e202212045.
DOI Google Scholar
[15]

Duan, C. H.; Luo, W. N.; Jiu, T.; Li, J. S.; Wang, Y.; Lu, F. S. Facile preparation and characterization of ZnCdS nanocrystals for interfacial applications in photovoltaic devices. J. Colloid Interface Sci. 2018, 512, 353–360.
DOI Google Scholar
[16]

Deng, C. H; Ye, F.; Wang, T.; Ling, X. H.; Peng, L. L.; Yu, H.; Ding, K. Z.; Hu, H. M.; Dong, Q.; Le, H. R.; et al. Developing hierarchical CdS/NiO hollow heterogeneous architectures for boosting photocatalytic hydrogen generation. Nano Res. 2022, 15, 2003–2012.
DOI Google Scholar
[17]

Lei, C.; Sun, N. B.; Wu, H. Z.; Zhao, Y. G.; Yu, C.; Janani, B. J.; Fakhri, A. Bio-photoelectrochemical degradation, and photocatalysis process by the fabrication of copper oxide/zinc cadmium sulfide heterojunction nanocomposites: Mechanism, microbial community and antifungal analysis. Chemosphere 2022, 308, 136375.
DOI Google Scholar
[18]

Gang, R.; Xu, L.; Xia, Y.; Cai, J.; Zhang, L. B.; Wang, S. X.; Li, R. Fabrication of MoS2 QDs/ZnO nanosheet 0D/2D heterojunction photocatalysts for organic dyes and gaseous heavy metal removal. J. Colloid Interface Sci. 2020, 579, 853–861.
DOI Google Scholar
[19]

Wang, H. M.; Zhao, R.; Hu, H. X.; Fan, X. W.; Zhang, D. J.; Wang, D. 0D/2D heterojunctions of Ti3C2 mXene QDs/SiC as an efficient and robust photocatalyst for boosting the visible photocatalytic NO pollutant removal ability. ACS Appl. Mater. Interfaces 2020, 12, 40176–40185.
DOI Google Scholar
[20]

Kandi, D.; Behera, A.; Martha, S.; Naik, B.; Parida, K. M. Quantum confinement chemistry of CdS QDs plus hot electron of Au over TiO2 nanowire protruding to be encouraging photocatalyst towards nitrophenol conversion and ciprofloxacin degradation. J. Environ. Chem. Eng. 2019, 7, 102821.
DOI Google Scholar
[21]

Yan, X.; Jin, Z. L.; Zhang, Y. P.; Liu, H.; Ma, X. L. Controllable design of double metal oxide (NiCo2O4)-modified CdS for efficient photocatalytic hydrogen production. Phys. Chem. Chem. Phys. 2019, 21, 4501–4512.
DOI Google Scholar
[22]

Zhang, C.; Zhou, Y. M.; Bao, J. H.; Fang, J. S.; Zhao, S.; Zhang, Y. W.; Sheng, X. L.; Chen, W. X. Structure regulation of ZnS@g-C3N4/TiO2 nanospheres for efficient photocatalytic H2 production under visible-light irradiation. Chem. Eng. J. 2018, 346, 226–237.
DOI Google Scholar
[23]

Xu, H. Q.; Yang, S. Z.; Ma, X.; Huang, J. E.; Jiang, H. L. Unveiling charge-separation dynamics in CdS/metal-organic framework composites for enhanced photocatalysis. ACS Catal. 2018, 8, 11615–11621.
DOI Google Scholar
[24]

Chen, J. M.; Lv, S. M.; Shen, Z. R.; Tian, P. L.; Chen, J. Y.; Li, Y. W. Novel ZnCdS quantum dots engineering for enhanced visible-light-driven hydrogen evolution. ACS Sustainable Chem. Eng. 2019, 7, 13805–13814.
DOI Google Scholar
[25]

Yang, Q. L.; Yu, L. Q.; Zhao, X. Y.; Wang, Y. K.; Zhu, H. F.; Zhang, Y. P. Highly stable γ-NiOOH/ZnCdS photocatalyst for efficient hydrogen evolution. Int. J. Hydrogen Energy 2022, 47, 27516–27526.
DOI Google Scholar
[26]

Hao, X. Q.; Xiang, D. Z.; Jin, Z. L. Zn-vacancy engineered S-Scheme ZnCdS/ZnS photocatalyst for highly efficient photocatalytic H2 evolution. ChemCatChem 2021, 13, 4738–4750.
DOI Google Scholar
[27]

Chen, Y. J.; Zhuo, H. Y.; Pan, Y.; Liang, J. X.; Liu, C. G.; Li, J. Triazine COF-supported single-atom catalyst (Pd1/trzn-COF) for CO oxidation. Sci. China Mater. 2021, 64, 1939–1951.
DOI Google Scholar
[28]

Qian, Y. Y.; Li, D. D.; Han, Y. L.; Jiang, H. L. Photocatalytic molecular oxygen activation by regulating excitonic effects in covalent organic frameworks. J. Am. Chem. Soc. 2020, 142, 20763–20771.
DOI Google Scholar
[29]

Niu, L.; Zhao, X. L.; Tang, Z.; Wu, F. C.; Lei, Q. T.; Wang, J. Y.; Wang, X. L.; Liang, W. G.; Wang, X. Solid-solid synthesis of covalent organic framework as a support for growth of controllable ultrafine Au nanoparticles. Sci. Total. Environ. 2022, 835, 155423.
DOI Google Scholar
[30]

Li, Y.; Karimi, M.; Gong, Y. N.; Dai, N.; Safarifard, V.; Jiang, H. L. Integration of metal-organic frameworks and covalent organic frameworks: Design, synthesis, and applications. Matter 2021, 4, 2230–2265.
DOI Google Scholar
[31]

Ding, S. Y.; Gao, J.; Wang, Q.; Zhang, Y.; Song, W. G.; Su, C. Y.; Wang, W. Construction of covalent organic framework for catalysis: Pd/COF-LZU1 in Suzuki–Miyaura coupling reaction. J. Am. Chem. Soc. 2011, 133, 19816–19822.
DOI Google Scholar
[32]

Thote, J.; Aiyappa, H. B.; Deshpande, A.; Díaz, D. D.; Kurungot, S.; Banerjee, R. A covalent organic framework-cadmium sulfide hybrid as a prototype photocatalyst for visible-light-driven hydrogen production. Chem.–Eur. J. 2014, 20, 15961–15965.
DOI Google Scholar
[33]

Yao, S. C.; Liu, Z. R.; Li, L. L. Recent progress in nanoscale covalent organic frameworks for cancer diagnosis and therapy. Nano-Micro Lett. 2021, 13, 176.
DOI Google Scholar
[34]

Wang, L.; Zhang, L. L.; Lin, B. Z.; Zheng, Y. Z.; Chen, J. L.; Zheng, Y.; Gao, B. F.; Long, J. L.; Chen, Y. L. Activation of carbonyl oxygen sites in β-ketoenamine-linked covalent organic frameworks via cyano conjugation for efficient photocatalytic hydrogen evolution. Small 2021, 17, 2101017.
DOI Google Scholar
[35]

Su, T.; Xiao, L. F.; Gao, Y.; Liu, T.; Peng, X. N.; Yuan, H.; Han, Y. B.; Ji, S. H.; Wang, X. N. Multifunctional MoS2 ultrathin nanoflakes loaded by Cd0.5Zn0.5S QDs for enhanced photocatalytic H2 production. Int. J. Energy. Res. 2019, 43, 5678–5686.
DOI Google Scholar
[36]

Shang, D. D.; Li, D.; Chen, B. Y.; Luo, B. F.; Huang, Y. Y.; Shi, W. D. 2D–2D SnS2/covalent organic framework heterojunction photocatalysts for highly enhanced solar–driven hydrogen evolution without cocatalysts. ACS Sustainable Chem. Eng. 2021, 9, 14238–14248.
DOI Google Scholar
[37]

Yang, R. G.; Fu, Y. M.; Wang, H. N.; Zhang, D. P.; Zhou, Z.; Cheng, Y. Z.; Meng, X.; He, Y. O.; Su, Z. M. ZIF-8/covalent organic framework for enhanced CO2 photocatalytic reduction in gas–solid system. Chem. Eng. J. 2022, 450, 138040.
DOI Google Scholar
[38]

Yao, Y. H.; Yang, Y.; Wang, Y.; Zhang, H.; Tang, H. L.; Zhang, H. Y.; Zhang, G. L.; Wang, Y.; Zhang, F. M.; Yan, H. Photo-induced synthesis of ternary Pt/rGO/COF photocatalyst with Pt nanoparticles precisely anchored on rGO for efficient visible-light-driven H2 evolution. J. Colloid. Interface Sci. 2022, 608, 2613–2622.
DOI Google Scholar
[39]

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
[40]

Banerjee, S.; Mohapatra, S. K.; Das, P. P.; Misra, M. Synthesis of coupled semiconductor by filling 1D TiO2 nanotubes with CdS. Chem. Mater. 2008, 20, 6784–6791.
DOI Google Scholar
File
12274_2023_5991_MOESM1_ESM.pdf (2 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 17 May 2023
Revised: 25 June 2023
Accepted: 08 July 2023
Published: 31 July 2023
Issue date: March 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 21908113), the Tianjin Applied Basic Research Project (No. 21JCYBJC00140), and Science and Technology Project of Hebei Education Department (No. QN2023114).

Return