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Research Article

Engineering the axial coordination of cobalt single atom catalysts for efficient photocatalytic hydrogen evolution

Ning Kang1, Lingwen Liao2, Xue Zhang1, Zhen He3,4, Binlu Yu1, Jiahong Wang1, Yongquan Qu5, Paul K. Chu6, Seeram Ramakrishna7, Xue-Feng Yu1, Xin Wang1( ), Licheng Bai1( )
Materials Interfaces Center, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences (CAS), Shenzhen 518055, China
Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China
Department of Chemistry, City University of Hong Kong, Kowloon, Hong Kong 999077, China
Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), City University of Hong Kong, Kowloon, Hong Kong 999077, China
Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710072, China
Department of Physics and Department of Materials Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong 999077, China
National University of Singapore (NUS) Centre for Nanofibers and Nanotechnology, Department of Mechanical Engineering, National University of Singapore, Singapore 117542, Singapore
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Graphical Abstract

An axial Co–S bond was designed to tailor the charge density of active Co single atom anchored onto graphite carbon nitride (C3N4) nanosheets to generate Co-(N, S)/C3N4 photocatalyst in ambient condition for highly efficient photocatalytic H2 evolution. Owing to the delicate optimization of charge density to an intermediate level by axial Co–S bond, extremely high H2 production was obtained, which is even superior to C3N4/Pt and transition metal/C3N4 single atom photocatalysts in reported works.

Abstract

Improving the catalytic activity of non-noble metal single atom catalysts (SACs) has attracted considerable attention in materials science. Although optimizing the local electronic structure of single atom can greatly improve their catalytic activity, it often involves in-plane modulation and requires high temperatures. Herein, we report a novel strategy to manipulate the local electronic structure of SACs via the modulation of axial Co–S bond anchored onto graphitic carbon nitride (C3N4) at room temperature (RT). Each Co atom is bonded to four N atoms and one S atom (Co-(N, S)/C3N4). Owing to the greater electronegativity of S in the Co–S bond, the local electronic structure of the Co atoms is available to be controlled at a relatively moderate level. Consequently, when employed for the photocatalytic hydrogen evolution reaction, the adsorption energy of intermediate hydrogen (H*) on the Co atoms is remarkably low. In the presence of the Co-(N, S)/C3N4 SACs, the hydrogen evolution rates reach up to 10 mmol/(g·h), which is nearly 10 and 2.5 times greater than the rates in the presence of previously reported transition metal/C3N4 and noble platinum nanoparticles (PtNPs)/C3N4 catalysts, respectively. Attributed to the tailorable axial Co–S bond in the SAC, the local electronic structure of the Co atoms can be further optimized for other photocatalytic reactions. This axial coordination engineering strategy is universal in catalyst designing and can be used for a variety of photocatalytic applications.

Keywords

transition metal single-atomlocal electronic structurephotocatalytic hydrogen evolutiongraphitic carbon nitrideaxial coordination environment

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References

[1]

Jiang, K.; Siahrostami, S.; Akey, A. J.; Li, Y. B.; Lu, Z. Y.; Lattimer, J.; Hu, Y. F.; Stokes, C.; Gangishetty, M.; Chen, G. X. et al. Transition-metal single atoms in a graphene shell as active centers for highly efficient artificial photosynthesis. Chem 2017, 3, 950–960.
Crossref Google Scholar
[2]

Lu, T. T.; Wang, H. Graphdiyne-supported metal electrocatalysts: From nanoparticles and cluster to single atoms. Nano Res. 2022, 15, 9764–9778.
Crossref Google Scholar
[3]

Zhu, P.; Xiong, X.; Wang, D. S. Regulations of active moiety in single atom catalysts for electrochemical hydrogen evolution reaction. Nano Res. 2022, 15, 5792–5815.
Crossref Google Scholar
[4]

Yuan, S.; Zhang, J. W.; Hu, L. Y.; Li, J. N.; Li, S. W.; Gao, Y. N.; Zhang, Q. H.; Gu, L.; Yang, W. X.; Feng, X. et al. Decarboxylation-induced defects in MOF-derived single cobalt atom@carbon electrocatalysts for efficient oxygen reduction. Angew. Chem., Int. Ed. 2021, 60, 21685–21690.
Crossref Google Scholar
[5]

Li, L. H.; Liu, X. J.; Wang, J. M.; Liu, R.; Liu, Y. R.; Wang, C. L.; Yang, W. X.; Feng, X.; Wang. B. Atomically dispersed co in a cross-channel hierarchical carbon-based electrocatalyst for high-performance oxygen reduction in Zn-air batteries. J. Mater. Chem. A 2022, 10, 18723–18729.
Crossref Google Scholar
[6]

Liu, Y. R.; Liu, X. J.; Lv, Z. H.; Liu, R.; Li, L. H.; Wang, J. M.; Yang, W. X.; Jiang, X.; Feng, X.; Wang, B. Tuning the spin state of the iron center by bridge-bonded Fe-O-Ti ligands for enhanced oxygen reduction. Angew. Chem., Int. Ed. 2022, 61, e202117617.
Crossref Google Scholar
[7]

Johnson, J. A.; Zhang, X.; Reeson, T. C.; Chen, Y. S.; Zhang, J. Facile control of the charge density and photocatalytic activity of an anionic indium porphyrin framework via in situ metalation. J. Am. Chem. Soc. 2014, 136, 15881–15884.
Crossref Google Scholar
[8]

Cao, S. W.; Li, H.; Tong, T.; Chen, H. C.; Yu, A. C.; Yu, J. G.; Chen, H. M. Single-atom engineering of directional charge transfer channels and active sites for photocatalytic hydrogen evolution. Adv. Funct. Mater. 2018, 28, 1802169.
Crossref Google Scholar
[9]

Zhang, W. W.; Zhang, J. Y.; Lan, X.; Chen, Z. Y.; Wang, T. M. Photocatalytic performance of ZnGa2O4 for degradation of methylene blue and its improvement by doping with Cd. Catal. Commun. 2010, 11, 1104–1108.
Crossref Google Scholar
[10]

Li, Q. H.; Chen, W. X.; Xiao, H.; Gong, Y.; Li, Z.; Zheng, L. R.; Zheng, X. S.; Yan, W. S.; Cheong, W. C.; Shen, R. A. et al. Fe isolated single atoms on S, N codoped carbon by copolymer pyrolysis strategy for highly efficient oxygen reduction reaction. Adv. Mater. 2018, 30, 1800588.
Crossref Google Scholar
[11]

Duan, L. L.; Bozoglian, F.; Mandal, S.; Stewart, B.; Privalov, T.; Llobet, A.; Sun, L. C. A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II. Nat. Chem. 2012, 4, 418–423.
Crossref Google Scholar
[12]

Wang, L.; Duan, L. L.; Stewart, B.; Pu, M. P.; Liu, J. H.; Privalov, T.; Sun, L. C. Toward controlling water oxidation catalysis: Tunable activity of ruthenium complexes with axial imidazole/DMSO ligands. J. Am. Chem. Soc. 2012, 134, 18868–18880.
Crossref Google Scholar
[13]

Xiao, M. L.; Gao, L. Q.; Wang, Y.; Wang, X.; Zhu, J. B.; Jin, Z.; Liu, C. P.; Chen, H. Q.; Li, G. R.; Ge, J. J. et al. Engineering energy level of metal center: Ru single-atom site for efficient and durable oxygen reduction catalysis. J. Am. Chem. Soc. 2019, 141, 19800–19806.
Crossref Google Scholar
[14]

Huang, L.; Chen, J. X.; Gan, L. F.; Wang, J.; Dong, S. J. Single-atom nanozymes. Sci. Adv. 2019, 5, eaav5490.
Crossref Google Scholar
[15]

Lai, Q. X.; Zheng, L. R.; Liang, Y. Y.; He, J. P.; Zhao, J. X.; Chen, J. H. Metal-organic-framework-derived Fe-N/C electrocatalyst with five-coordinated Fe-N x sites for advanced oxygen reduction in acid media. ACS Catal. 2017, 7, 1655–1663.
Crossref Google Scholar
[16]

Liu, X. J.; Liu, Y. R.; Yang, W. X.; Feng, X.; Wang, B. Controlled modification of axial coordination for transition-metal single-atom electrocatalyst. Chem.—Eur. J. 2022, 28, e202201471.
Crossref Google Scholar
[17]

Zhao, L.; Zhang, Y.; Huang, L. B.; Liu, X. Z.; Zhang, Q. H.; He, C.; Wu, Z. Y.; Zhang, L. J.; Wu, J. P.; Yang, W. L. et al. Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts. Nat. Commun. 2019, 10, 1278.
Crossref Google Scholar
[18]

Zhang, Z. Q.; Chen, Y. G.; Zhou, L. Q.; Chen, C.; Han, Z.; Zhang, B. S.; Wu, Q.; Yang, L. J.; Du, L. Y.; Bu, Y. F. et al. The simplest construction of single-site catalysts by the synergism of micropore trapping and nitrogen anchoring. Nat. Commun. 2019, 10, 1657.
Crossref Google Scholar
[19]

He, X. H.; He, Q.; Deng, Y. C.; Peng, M.; Chen, H. Y.; Zhang, Y.; Yao, S. Y.; Zhang, M. T.; Xiao, D. Q.; Ma, D. et al. A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation. Nat. Commun. 2019, 10, 3663.
Crossref Google Scholar
[20]

Qiao, Y. Y.; Yuan, P. F.; Hu, Y. F.; Zhang, J. N.; Mu, S. C.; Zhou, J. H.; Li, H.; Xia, H. C.; He, J.; Xu, Q. Sulfuration of an Fe-N-C catalyst containing Fe x C/Fe species to enhance the catalysis of oxygen reduction in acidic media and for use in flexible Zn-air batteries. Adv. Mater. 2018, 30, 1804504.
Crossref Google Scholar
[21]

Shen, H. J.; Gracia-Espino, E.; Ma, J. Y.; Zang, K. T.; Luo, J.; Wang, L.; Gao, S. S.; Mamat, X.; Hu, G. Z.; Wagberg, T. et al. Synergistic effects between atomically dispersed Fe-N-C and C-S-C for the oxygen reduction reaction in acidic media. Angew. Chem., Int. Ed. 2017, 56, 13800–13804.
Crossref Google Scholar
[22]

Kunitski, M.; Eicke, N.; Huber, P.; Köhler, J.; Zeller, S.; Voigtsberger, J.; Schlott, N.; Henrichs, K.; Sann, H.; Trinter, F. et al. Double-slit photoelectron interference in strong-field ionization of the neon dimer. Nat. Commun. 2019, 10, 1.
Crossref Google Scholar
[23]

Pu, Z. H.; Zhao, J. H.; Amiinu, I. S.; Li, W. Q.; Wang, M.; He, D. P.; Mu, S. C. A universal synthesis strategy for P-rich noble metal diphosphide-based electrocatalysts for the hydrogen evolution reaction. Energy Environ. Sci. 2019, 12, 952–957.
Crossref Google Scholar
[24]

Zhang, P.; Wang, T.; Gong, J. L. Current mechanistic understanding of surface reactions over water-splitting photocatalysts. Chem 2018, 4, 223–245.
Crossref Google Scholar
[25]

Chernyshev, V. M.; Astakhov, A. V.; Chikunov, I. E.; Tyurin, R. V.; Eremin, D. B.; Ranny, G. S.; Khrustalev, V. N.; Ananikov, V. P. Pd and Pt catalyst poisoning in the study of reaction mechanisms: What does the mercury test mean for catalysis? ACS Catal. 2019, 9, 2984–2995.
Crossref Google Scholar
[26]

Zhao, S. L.; Wang, D. W.; Amal, R.; Dai, L. M. Carbon-based metal-free catalysts for key reactions involved in energy conversion and storage. Adv. Mater. 2019, 31, 1801526.
Crossref Google Scholar
[27]

Liu, W. G.; Zhang, L. L.; Yan, W. S.; Liu, X. Y.; Yang, X. F.; Miao, S.; Wang, W. T.; Wang, A. Q.; Zhang, T. Single-atom dispersed Co-N-C catalyst: Structure identification and performance for hydrogenative coupling of nitroarenes. Chem. Sci. 2016, 7, 5758–5764.
Crossref Google Scholar
[28]

Chen, S. S.; Takata, T.; Domen, K. Particulate photocatalysts for overall water splitting. Nat. Rev. Mater. 2017, 2, 17050.
Crossref Google Scholar
[29]

Ong, W. J.; Tan, L. L.; Ng, Y. H.; Yong, S. T.; Chai, S. P. Graphitic carbon nitride (g-C3N4)-based photocatalysts for artificial photosynthesis and environmental remediation: Are we a step closer to achieving sustainability? Chem. Rev. 2016, 116, 7159–7329.
Crossref Google Scholar
[30]

Cao, S. W.; Low, J.; Yu, J. G.; Jaroniec, M. Polymeric photocatalysts based on graphitic carbon nitride. Adv. Mater. 2015, 27, 2150–2176.
Crossref Google Scholar
[31]

Chen, K.; Chai, Z. G.; Li, C.; Shi, L. R.; Liu, M. X.; Xie, Q.; Zhang, Y. F.; Xu, D. S.; Manivannan, A.; Liu, Z. F. Catalyst-free growth of three-dimensional graphene flakes and graphene/g-C3N4 composite for hydrocarbon oxidation. ACS Nano 2016, 10, 3665–3673.
Crossref Google Scholar
[32]

Lin, L. H.; Yu, Z. Y.; Wang, X. C. Crystalline carbon nitride semiconductors for photocatalytic water splitting. Angew. Chem., Int. Ed. 2019, 58, 6164–6175.
Crossref Google Scholar
[33]

Jiang, J. X.; Ding, W.; Li, W.; Wei, Z. D. Freestanding single-atom-layer Pd-based catalysts: Oriented splitting of energy bands for unique stability and activity. Chem 2020, 6, 431–447.
Crossref Google Scholar
[34]

Wang, A. Q.; Li, J.; Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2018, 2, 65–81.
Crossref Google Scholar
[35]

Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. T.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt1/FeO x . Nat. Chem. 2011, 3, 634–641.
Crossref Google Scholar
[36]

Liu, P. X.; Zhao, Y.; Qin, R. X.; Mo, S. G.; Chen, G. X.; Gu, L.; Chevrier, D. M.; Zhang, P.; Guo, Q.; Zang, D. D. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 2016, 352, 797–800.
Crossref Google Scholar
[37]

Chen, Y. J.; Ji, S. F.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D. Single-atom catalysts: Synthetic strategies and electrochemical applications. Joule 2018, 2, 1242–1264.
Crossref Google Scholar
[38]

Jones, J.; Xiong, H. F.; Delarive, A. T.; Peterson, E. J.; Pham, H.; Challa, S. R.; Qi, G.; Oh, S.; Wiebenga, M. H.; Hernández, X. I. P. et al. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping. Science 2016, 353, 150–154.
Crossref Google Scholar
[39]

Wang, Y.; Phua, S. Z. F.; Dong, G.; Liu, X. Q.; He, B.; Zhai, Q. L.; Li, Y. C.; Zheng, C. C.; Quan, H. P.; Li, Z. et al. Structure tuning of polymeric carbon nitride for solar energy conversion: From nano to molecular scale. Chem 2019, 5, 2775–2813.
Crossref Google Scholar
[40]

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.
Crossref Google Scholar
[41]

Wang, X. C.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, J. M.; Domen, K.; Antonietti, M. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat. Mater. 2009, 8, 76–80.
Crossref Google Scholar
[42]

Zhou, G.; Shan, Y.; Hu, Y. Y.; Xu, X. Y.; Long, L. Y.; Zhang, J. L.; Dai, J.; Guo, J. H.; Shen, J. C.; Li, S. et al. Half-metallic carbon nitride nanosheets with micro grid mode resonance structure for efficient photocatalytic hydrogen evolution. Nat. Commun. 2018, 9, 3366.
Crossref Google Scholar
[43]

Cao, Y. J.; Chen, S.; Luo, Q. Q.; Yan, H.; Lin, Y.; Liu, W.; Cao, L. L.; Lu, J. L.; Yang, J. L.; Yao, T. et al. Atomic-level insight into optimizing the hydrogen evolution pathway over a Co1-N4 single-site photocatalyst. Angew. Chem., Int. Ed. 2017, 56, 12191–12196.
Crossref Google Scholar
[44]

Liu, W.; Cao, L. L.; Cheng, W. R.; Cao, Y. J.; Liu, X. K.; Zhang, W.; Mou, X. L.; Jin, L. L.; Zheng, X. S.; Che, W. et al. Single-site active cobalt-based photocatalyst with a long carrier lifetime for spontaneous overall water splitting. Angew. Chem., Int. Ed. 2017, 56, 9312–9317.
Crossref Google Scholar
[45]

Arcon, I.; Tuel, A.; Kodre, A.; Martin, G.; Barbier, A. EXAFS determination of the size of Co clusters on silica. J. Synchrotron Rad. 2001, 8, 575–577.
Crossref Google Scholar
[46]

Yang, H.; Duan, X. H.; Zhao, J. F.; Guo, L. N. Transition-metal-free tandem radical thiocyanooxygenation of olefinic amides: A new route to SCN-containing heterocycles. Org. Lett. 2015, 17, 1998–2001.
Crossref Google Scholar
[47]

Zhao, G. X.; Sun, Y. B.; Zhou, W.; Wang, X. K.; Chang, K.; Liu, G. G.; Liu, H. M.; Kako, T.; Ye, J. H. Superior photocatalytic H2 production with cocatalytic Co/Ni species anchored on sulfide semiconductor. Adv. Mater. 2017, 29, 1703258.
Crossref Google Scholar
[48]

Fang, X. Z.; Shang, Q. C.; Wang, Y.; Jiao, L.; Yao, T.; Li, Y. F.; Zhang, Q.; Luo, Y.; Jiang, H. L. Single Pt atoms confined into a metal-organic framework for efficient photocatalysis. Adv. Mater. 2018, 30, 1705112.
Crossref Google Scholar
[49]

Qiao, M.; Liu, J.; Wang, Y.; Li, Y. F.; Chen, Z. F. PdSeO3 monolayer: Promising inorganic 2D photocatalyst for direct overall water splitting without using sacrificial reagents and cocatalysts. J. Am. Chem. Soc. 2018, 140, 12256–12262.
Crossref Google Scholar
[50]

Lopato, E. M.; Eikey, E. A.; Simon, Z. C.; Back, S.; Tran, K.; Lewis, J.; Kowalewski, J. F.; Yazdi, S.; Kitchin, J. R.; Ulissi, Z. W. et al. Parallelized screening of characterized and DFT-modeled bimetallic colloidal cocatalysts for photocatalytic hydrogen evolution. ACS Catal. 2020, 10, 4244–4252.
Crossref Google Scholar
Nano Research
Volume 17 Issue 6,
June 2024
Pages 5114-5121
DOI: 10.1007/s12274-024-6411-1
Cite this article:
Kang N, Liao L, Zhang X, et al. Engineering the axial coordination of cobalt single atom catalysts for efficient photocatalytic hydrogen evolution. Nano Research, 2024, 17(6): 5114-5121. https://doi.org/10.1007/s12274-024-6411-1
Topics:
Hydrogen economy

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Received: 22 August 2023
Revised: 21 November 2023
Accepted: 12 December 2023
Published: 13 January 2024
© Tsinghua University Press 2024
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