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Research Article

Hydroxylated metal–organic-layer nanocages anchoring single atomic cobalt sites for robust photocatalytic CO2 reduction

Weiyi Pan1,2, Zhihe Wei1,2, Yanhui Su1,2, Yuebin Lian3, Zhangyi Zheng1,2, Huihong Yuan1,2, Yongze Qin1,2, Xulan Xie1,2, Qianqian Bai1,2, Zhenyang Jiao1,2, Wei Hua1,2, Jinzhou Chen1,2, Wenjun Yang1,2, Zhao Deng1,2( ), Yang Peng1,2,4( )
Soochow Institute for Energy and Materials Innovations, College of Energy, Soochow University, Suzhou 215006, China
Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Soochow University, Suzhou 215006, China
School of Photoelectric Engineering, Changzhou institute of technology, Changzhou 213032, China
Jiangsu Key Laboratory for Advanced Negative Carbon Technologies, Soochow University, Suzhou 215123, China
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Graphical Abstract

A new type of metal–organic-layer nanocages loaded with atomic cobalt catalytic sites was reported for photocatalytic CO2 reduction. The unique nanocage morphology in conjunction with the hydroxyl functional groups effectively boosts the reaction kinetics.

Abstract

Assembly of two-dimensional (2D) metal–organic layers (MOLs) based on the hard and soft acid–base theorem represents an exquisite strategy for the construction of photocatalytic platforms in virtue of the highly exposed active sites, much improved mass transport, and greatly elevated stability. Herein, nanocages composed of MOLs are produced for the first time through a cosolvent approach utilizing zirconium-based UiO-66-(OH)2 as the structural precursor. To endow the catalytic activity for CO2 conversion, single atomic Co2+ sites are appended to the Zr-oxo nodes of the MOL cages, demonstrating a remarkable CO yield of 7.74 mmol·g−1·h−1 and operational stability of 97.1% product retention after five repeated cycles. Such an outstanding photocatalytic performance is mainly attributed to the unique nanocage morphology comprising enormous 2D nanosheets for augmented Co2+ exposure and the abundant surface hydroxyl groups for local CO2 enrichment. This work underlines the tailoring of both metal–organic framework (MOF) morphology and functionality to boost the turnover rate of photocatalytic CO2 reduction reaction (CO2RR).

Keywords

photocatalytic CO2 reductionmetal–organic layernanocagesingle-atom catalystco-catalyst

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References

[1]

Singh, G.; Lee, J.; Karakoti, A.; Bahadur, R.; Yi, J. B.; Zhao, D. Y.; Albahily, K.; Vinu, A. Emerging trends in porous materials for CO2 capture and conversion. Chem. Soc. Rev. 2020, 49, 4360–4404.
Crossref Google Scholar
[2]

Gao, W. L.; Liang, S. Y.; Wang, R. J.; Jiang, Q.; Zhang, Y.; Zheng, Q. W.; Xie, B. Q.; Toe, C. Y.; Zhu, X. C.; Wang, J. Y. et al. Industrial carbon dioxide capture and utilization: State of the art and future challenges. Chem. Soc. Rev. 2020, 49, 8584–8686.
Crossref Google Scholar
[3]

Zhang, J. H.; Zhong, D. C.; Lu, T. B. Co(II)-based molecular complexes for photochemical CO2 reduction. Acta Phys. -Chim. Sin. 2021, 37, 2008068.
Crossref Google Scholar
[4]

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.
Crossref Google Scholar
[5]

Kovačič, Ž.; Likozar, B.; Huš, M. Photocatalytic CO2 reduction: A review of ab initio mechanism, kinetics, and multiscale modeling simulations. ACS Catal. 2020, 10, 14984–15007.
Crossref Google Scholar
[6]

Li, K.; Peng, B. S.; Peng, T. Y. Recent advances in heterogeneous photocatalytic CO2 conversion to solar fuels. ACS Catal. 2016, 6, 7485–7527.
Crossref Google Scholar
[7]

Gao, C.; Wang, J.; Xu, H. X.; Xiong, Y. J. Coordination chemistry in the design of heterogeneous photocatalysts. Chem. Soc. Rev. 2017, 46, 2799–2823.
Crossref Google Scholar
[8]

Materna, K. L.; Jiang, J. B.; Regan, K. P.; Schmuttenmaer, C. A.; Crabtree, R. H.; Brudvig, G. W. Optimization of photoanodes for photocatalytic water oxidation by combining a heterogenized iridium water-oxidation catalyst with a high-potential porphyrin photosensitizer. ChemSusChem 2017, 10, 4526–4534.
Crossref Google Scholar
[9]

Sabbah, A.; Shown, I.; Qorbani, M.; Fu, F. Y.; Lin, T. Y.; Wu, H. L.; Chung, P. W.; Wu, C. I.; Santiago, S. R. M.; Shen, J. L. et al. Boosting photocatalytic CO2 reduction in a ZnS/ZnIn2S4 heterostructure through strain-induced direct Z-scheme and a mechanistic study of molecular CO2 interaction thereon. Nano Energy 2022, 93, 106809.
Crossref Google Scholar
[10]

Zhang, Y. Z.; Zhi, X.; Harmer, J. R.; Xu, H. L.; Davey, K.; Ran, J. R.; Qiao, S. Z. Facet-specific active surface regulation of BixMOy (M = Mo, V, W) nanosheets for boosted photocatalytic CO2 reduction. Angew. Chem., Int. Ed. 2022, 61, e202212355.
Crossref Google Scholar
[11]

Yu, H.; Wu, X.; Mu, Q. Q.; Wei, Z. H.; Gu, Y. D.; Yuan, X. Z.; Lu, Y. T.; Deng, Z.; Peng, Y. Robust photocatalytic hydrogen production on metal-organic layers of Al-TCPP with ultrahigh turnover numbers. Chin. Chem. Lett. 2021, 32, 3833–3836.
Crossref Google Scholar
[12]

Xiong, X. Y.; Zhao, Y. F.; Shi, R.; Yin, W. J.; Zhao, Y. X.; Waterhouse, G. I. N.; Zhang, T. R. Selective photocatalytic CO2 reduction over Zn-based layered double hydroxides containing tri or tetravalent metals. Sci. Bull. 2020, 65, 987–994.
Crossref Google Scholar
[13]

Zhao, Y. F.; Waterhouse, G. I. N.; Chen, G. B.; Xiong, X. Y.; Wu, L. Z.; Tung, C. H.; Zhang, T. R. Two-dimensional-related catalytic materials for solar-driven conversion of COx into valuable chemical feedstocks. Chem. Soc. Rev. 2019, 48, 1972–2010.
Crossref Google Scholar
[14]

Liu, Q.; Cheng, H.; Chen, T. X.; Lo, T. W. B.; Xiang, Z. M.; Wang, F. X. Regulating the *OCCHO intermediate pathway towards highly selective photocatalytic CO2 reduction to CH3CHO over locally crystallized carbon nitride. Energy Environ. Sci. 2022, 15, 225–233.
Crossref Google Scholar
[15]

Su, Y. H.; Song, Z. L.; Zhu, W.; Mu, Q. Q.; Yuan, X. Z.; Lian, Y. B.; Cheng, H.; Deng, Z.; Chen, M. Z.; Yin, W. J. et al. Visible-light photocatalytic CO2 reduction using metal-organic framework derived Ni(OH)2 nanocages: A synergy from multiple light reflection, static charge transfer, and oxygen vacancies. ACS Catal. 2021, 11, 345–354.
Crossref Google Scholar
[16]

Zhang, X. W.; Wang, P.; Lv, X. Y.; Niu, X. Y.; Lin, X. Y.; Zhong, S. X.; Wang, D. M.; Lin, H. J.; Chen, J. R.; Bai, S. Stacking engineering of semiconductor heterojunctions on hollow carbon spheres for boosting photocatalytic CO2 reduction. ACS Catal. 2022, 12, 2569–2580.
Crossref Google Scholar
[17]

You, F. F.; Wan, J. W.; Qi, J.; Mao, D.; Yang, N. L.; Zhang, Q. H.; Gu, L.; Wang, D. Lattice distortion in hollow multi-shelled structures for efficient visible-light CO2 reduction with a SnS2/SnO2 junction. Angew. Chem., Int. Ed. 2020, 59, 721–724.
Crossref Google Scholar
[18]

Bie, C. B.; Zhu, B. C.; Xu, F. Y.; Zhang, L. Y.; Yu, J. G. In situ grown monolayer N-doped graphene on CdS hollow spheres with seamless contact for photocatalytic CO2 reduction. Adv. Mater. 2019, 31, 1902868.
Crossref Google Scholar
[19]

Ding, M. L.; Flaig, R. W.; Jiang, H. L.; Yaghi, O. M. Carbon capture and conversion using metal-organic frameworks and MOF-based materials. Chem. Soc. Rev. 2019, 48, 2783–2828.
Crossref Google Scholar
[20]

Mialane, P.; Mellot-Draznieks, C.; Gairola, P.; Duguet, M.; Benseghir, Y.; Oms, O.; Dolbecq, A. Heterogenisation of polyoxometalates and other metal-based complexes in metal-organic frameworks: From synthesis to characterisation and applications in catalysis. Chem. Soc. Rev. 2021, 50, 6152–6220.
Crossref Google Scholar
[21]

He, H. M.; Sun, Q.; Gao, W. Y.; Perman, J. A.; Sun, F. X.; Zhu, G. S.; Aguila, B.; Forrest, K.; Space, B.; Ma, S. Q. A stable metal-organic framework featuring a local buffer environment for carbon dioxide fixation. Angew. Chem., Int. Ed. 2018, 57, 4657–4662.
Crossref Google Scholar
[22]

Sun, K.; Qian, Y. Y.; Jiang, H. L. Metal-organic frameworks for photocatalytic water splitting and CO2 reduction. Angew. Chem., Int. Ed. 2023, 62, e202217565.
Crossref Google Scholar
[23]

He, Y. Q.; Li, C. G.; Chen, X. B.; Shi, Z.; Feng, S. H. Visible-light-responsive UiO-66(Zr) with defects efficiently promoting photocatalytic CO2 reduction. ACS Appl. Mater. Interfaces 2022, 14, 28977–28984.
Crossref Google Scholar
[24]

Li, J.; Huang, H. L.; Xue, W. J.; Sun, K.; Song, X. H.; Wu, C. R.; Nie, L.; Li, Y.; Liu, C. Y.; Pan, Y. et al. Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO2 photoreduction to CH4. Nat. Catal. 2021, 4, 719–729.
Crossref Google Scholar
[25]

Wang, J. X.; Sun, K.; Wang, D. N.; Niu, X. W.; Lin, Z. Y.; Wang, S. Y.; Yang, W. J.; Huang, J. E.; Jiang, H. L. Precise regulation of the coordination environment of single Co(II) sites in a metal-organic framework for boosting CO2 photoreduction. ACS Catal. 2023, 13, 8760–8769.
Crossref Google Scholar
[26]

Zhao, R.; Liang, Z. B.; Zou, R. Q.; Xu, Q. Metal-organic frameworks for batteries. Joule 2018, 2, 2235–2259.
Crossref Google Scholar
[27]

Cao, L. Y.; Wang, C. Metal-organic layers for electrocatalysis and photocatalysis. ACS Cent. Sci. 2020, 6, 2149–2158.
Crossref Google Scholar
[28]

Cao, L. Y.; Lin, Z. K.; Peng, F.; Wang, W. W.; Huang, R. Y.; Wang, C.; Yan, J. W.; Liang, J.; Zhang, Z. M.; Zhang, T. et al. Self-supporting metal-organic layers as single-site solid catalysts. Angew. Chem., Int. Ed. 2016, 55, 4962–4966.
Crossref Google Scholar
[29]

Li, F. L.; Wang, P. T.; Huang, X. Q.; Young, D. J.; Wang, H. F.; Braunstein, P.; Lang, J. P. Large-scale, bottom-up synthesis of binary metal-organic framework nanosheets for efficient water oxidation. Angew. Chem., Int. Ed. 2019, 58, 7051–7056.
Crossref Google Scholar
[30]

Yang, W.; Wang, H. J.; Liu, R. R.; Wang, J. W.; Zhang, C.; Li, C.; Zhong, D. C.; Lu, T. B. Tailoring crystal facets of metal-organic layers to enhance photocatalytic activity for CO2 reduction. Angew. Chem., Int. Ed. 2021, 60, 409–414.
Crossref Google Scholar
[31]

He, T.; Ni, B.; Zhang, S. M.; Gong, Y.; Wang, H. Q.; Gu, L.; Zhuang, J.; Hu, W. P.; Wang, X. Ultrathin 2D zirconium metal-organic framework nanosheets: Preparation and application in photocatalysis. Small 2018, 14, 1703929.
Crossref Google Scholar
[32]

Luo, T. K.; Fan, Y. J.; Mao, J. M.; Yuan, E.; You, E.; Xu, Z. W.; Lin, W. B. Dimensional reduction enhances photodynamic therapy of metal-organic nanophotosensitizers. J. Am. Chem. Soc. 2022, 144, 5241–5246.
Crossref Google Scholar
[33]

Rada, Z. H.; Abid, H. R.; Shang, J.; Sun, H. Q.; He, Y. D.; Webley, P.; Liu, S. M.; Wang, S. B. Functionalized UiO-66 by single and binary (OH)2 and NO2 groups for uptake of CO2 and CH4. Ind. Eng. Chem. Res. 2016, 55, 7924–7932.
Crossref Google Scholar
[34]

Saiz, P. G.; Iglesias, N.; Gonzalez Navarrete, B.; Rosales, M.; Quintero, Y. M.; Reizabal, A.; Orive, J.; Fidalgo Marijuan, A.; Larrea, E. S.; Lopes, A. C. et al. Chromium speciation in zirconium-based metal-organic frameworks for environmental remediation. Chem. -Eur. J. 2020, 26, 13861–13872.
Crossref Google Scholar
[35]

Gutterød, E. S.; Pulumati, S. H.; Kaur, G.; Lazzarini, A.; Solemsli, B. G.; Gunnaes, A. E.; Ahoba-Sam, C.; Kalyva, M. E.; Sannes, J. A.; Svelle, S. et al. Influence of defects and H2O on the hydrogenation of CO2 to methanol over Pt nanoparticles in UiO-67 metal-organic framework. J. Am. Chem. Soc. 2020, 142, 17105–17118.
Crossref Google Scholar
[36]

Planas, N.; Mondloch, J. E.; Tussupbayev, S.; Borycz, J.; Gagliardi, L.; Hupp, J. T.; Farha, O. K.; Cramer, C. J. Defining the proton topology of the Zr6-based metal-organic framework NU-1000. J. Phys. Chem. Lett. 2014, 5, 3716–3723.
Crossref Google Scholar
[37]

Ma, X.; Liu, H.; Yang, W. J.; Mao, G. Y.; Zheng, L. R.; Jiang, H. L. Modulating coordination environment of single-atom catalysts and their proximity to photosensitive units for boosting MOF photocatalysis. J. Am. Chem. Soc. 2021, 143, 12220–12229.
Crossref Google Scholar
[38]

Manna, K.; Ji, P. F.; Lin, Z. K.; Greene, F. X.; Urban, A.; Thacker, N. C.; Lin, W. B. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes. Nat. Commun. 2016, 7, 12610.
Crossref Google Scholar
[39]

Gutiérrez-Tarriño, S.; Olloqui-Sariego, J. L.; Calvente, J. J.; Espallargas, G. M.; Rey, F.; Corma, A.; Oña-Burgos, P. Cobalt metal-organic framework based on layered double nanosheets for enhanced electrocatalytic water oxidation in neutral media. J. Am. Chem. Soc. 2020, 142, 19198–19208.
Crossref Google Scholar
[40]

Li, Y.; Chen, G.; Zhu, Y. P.; Hu, Z. W.; Chan, T. S.; She, S. X.; Dai, J.; Zhou, W.; Shao, Z. P. Activating both basal plane and edge sites of layered cobalt oxides for boosted water oxidation. Adv. Funct. Mater. 2021, 31, 2103569.
Crossref Google Scholar
[41]

An, L.; Zhang, H.; Zhu, J. M.; Xi, S. B.; Huang, B. L.; Sun, M. Z.; Peng, Y.; Xi, P. X.; Yan, C. H. Balancing activity and stability in spinel cobalt oxides through geometrical sites occupation towards efficient electrocatalytic oxygen evolution. Angew. Chem., Int. Ed. 2023, 62, e202214600.
Crossref Google Scholar
[42]

Zheng, H. L.; Huang, S. L.; Luo, M. B.; Wei, Q.; Chen, E. X.; He, L.; Lin, Q. P. Photochemical in situ exfoliation of metal-organic frameworks for enhanced visible-light-driven CO2 reduction. Angew. Chem., Int. Ed. 2020, 59, 23588–23592.
Crossref Google Scholar
[43]

Ke, Y.; Liang, Q.; Zhao, S.; Zhang, Z. H.; Li, X. Z.; Li, Z. Y. In situ self-assembled ZIF-67/MIL-125-derived Co3O4/TiO2 p–n heterojunctions for enhanced photocatalytic CO2 reduction. Inorg. Chem. 2022, 61, 2652–2661.
Crossref Google Scholar
[44]

Wei, M. J.; Xu, X. Y.; Song, J. Q.; Pan, M.; Su, C. Y. A 2D layered cobalt-based metal-organic framework for photoreduction of CO2 to syngas with a controllable wide ratio range. J. Mater. Chem. A 2023, 11, 691–699.
Crossref Google Scholar
[45]

Han, C.; Zhang, X. D.; Huang, S. S.; Hu, Y.; Yang, Z.; Li, T. T.; Li, Q. P.; Qian, J. J. MOF-on-MOF-derived hollow Co3O4/In2O3 nanostructure for efficient photocatalytic CO2 reduction. Adv. Sci. 2023, 10, 2300797.
Crossref Google Scholar
[46]

Yang, H. L.; Zhang, D. D.; Luo, Y.; Yang, W. X.; Zhan, X. Q.; Yang, W. Y.; Hou, H. L. Highly efficient and selective visible-light driven photoreduction of CO2 to CO by metal-organic frameworks-derived Ni-Co-O porous microrods. Small 2022, 18, 2202939.
Crossref Google Scholar
[47]

Yang, H.; Lai, C. L.; Wu, M. L.; Wang, S. D.; Xia, Y.; Pan, F. F.; Lv, K. L.; Wen, L. L. Novel amino-functionalized Ni(II)-based MOFs for efficiently photocatalytic reduction of CO2 to CO with superior selectivity under visible-light illumination. Chem. Eng. J. 2023, 455, 140425.
Crossref Google Scholar
[48]

Zhao, Y. J.; Shao, Z. C.; Cui, Y.; Geng, K. S.; Meng, X. R.; Wu, J.; Hou, H. W. Guest-induced multilevel charge transport strategy for developing metal-organic frameworks to boost photocatalytic CO2 reduction. Small 2023, 19, 2300398.
Crossref Google Scholar
[49]

Gao, X. S.; Guo, B.; Guo, C. M.; Meng, Q. D.; Liang, J.; Liu, J. X. Zirconium-based metal-organic framework for efficient photocatalytic reduction of CO2 to CO: The influence of doped metal ions. ACS Appl. Mater. Interfaces 2020, 12, 24059–24065.
Crossref Google Scholar
[50]

Wang, Y.; Huang, N. Y.; Shen, J. Q.; Liao, P. Q.; Chen, X. M.; Zhang, J. P. Hydroxide ligands cooperate with catalytic centers in metal-organic frameworks for efficient photocatalytic CO2 reduction. J. Am. Chem. Soc. 2018, 140, 38–41.
Crossref Google Scholar
[51]

Zhong, W. F.; Sa, R. J.; Li, L. Y.; He, Y. J.; Li, L. Y.; Bi, J. H.; Zhuang, Z. Y.; Yu, Y.; Zou, Z. G. A covalent organic framework bearing single Ni sites as a synergistic photocatalyst for selective photoreduction of CO2 to CO. J. Am. Chem. Soc. 2019, 141, 7615–7621.
Crossref Google Scholar
[52]

Mu, X. X.; Jiang, J. F.; Chao, F. F.; Lou, Y. B.; Chen, J. X. Ligand modification of UiO-66 with an unusual visible light photocatalytic behavior for RhB degradation. Dalton Trans. 2018, 47, 1895–1902.
Crossref Google Scholar
[53]

Gao, C.; Chen, S. M.; Wang, Y.; Wang, J. W.; Zheng, X. S.; Zhu, J. F.; Song, L.; Zhang, W. K.; Xiong, Y. J. Heterogeneous single-atom catalyst for visible-light-driven high-turnover CO2 reduction: The role of electron transfer. Adv. Mater. 2018, 30, 1704624.
Crossref Google Scholar
[54]

Lv, G. R.; Liu, J. M.; Xiong, Z. H.; Zhang, Z. H.; Guan, Z. Y. Selectivity adsorptive mechanism of different nitrophenols on UiO-66 and UiO-66-NH2 in aqueous solution. J. Chem. Eng. Data 2016, 61, 3868–3876.
Crossref Google Scholar
Nano Research
Volume 17 Issue 4,
April 2024
Pages 2410-2419
DOI: 10.1007/s12274-023-6083-2
Cite this article:
Pan W, Wei Z, Su Y, et al. Hydroxylated metal–organic-layer nanocages anchoring single atomic cobalt sites for robust photocatalytic CO2 reduction. Nano Research, 2024, 17(4): 2410-2419. https://doi.org/10.1007/s12274-023-6083-2
Topics:
Photocatalysis

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Received: 15 June 2023
Revised: 02 August 2023
Accepted: 10 August 2023
Published: 14 September 2023
© Tsinghua University Press 2023
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