Shandong Provincial Key Laboratory of Molecular Engineering, School of Chemistry and Chemical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353 China

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Guangshan Zhu,

Corresponding Author

Guangshan Zhu

[email protected]

College of Chemistry, Northeast Normal University, Changchun, 130021 China

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Mengying Li,

Mengying Li

College of Chemistry, Northeast Normal University, Changchun, 130021 China

These authors contributed equally to this work.

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Xin Liu,

Xin Liu

College of Chemistry, Northeast Normal University, Changchun, 130021 China

These authors contributed equally to this work.

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Yan Che,

Yan Che

College of Chemistry, Northeast Normal University, Changchun, 130021 China

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Hongzhu Xing,

Corresponding Author

Hongzhu Xing

[email protected]

orcid.org/0000-0001-7179-0394

College of Chemistry, Northeast Normal University, Changchun, 130021 China

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Fanfei Sun,

Fanfei Sun

Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201800 China

Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204 China

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Wei Zhou,

Corresponding Author

Wei Zhou

[email protected]

Shandong Provincial Key Laboratory of Molecular Engineering, School of Chemistry and Chemical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353 China

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Guangshan Zhu,

Corresponding Author

Guangshan Zhu

[email protected]

College of Chemistry, Northeast Normal University, Changchun, 130021 China

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First published: 19 July 2023

https://doi.org/10.1002/anie.202308651

Citations: 15

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Graphical Abstract

A straightforward method of controlled partial linker thermolysis allows the microporous metal–organic framework (MOF) photocatalyst UiO-66-NH₂ to expand its porosity with a tailored pore environment. The resulting material accommodates single-site Cu species, shows significant mesoporosity and enhanced charge photogeneration. It has excellent performance in photocatalytic reactions for the functionalization of terminal alkynes.

Abstract

Metal–organic frameworks (MOFs) with expanding porosity and tailored pore environments are intriguing for catalytic applications. We report herein a straightforward method of controlled partial linker thermolysis to introduce desirable mesopores into mono-ligand MOFs, which is different from the classical thermolyzing method that starts from mixed-linker MOFs. UiO-66-NH₂, after partial ligand thermolysis, exhibits significant mesoporosity, retained crystal structure, improved charge photogeneration and abundant anchoring sites, which is ideal to explore single-site photocatalysis. Atomically dispersed Cu is then accommodated in the tailored pore. The resulting single-site Cu catalyst exhibits excellent performance for photocatalytic alkylation and oxidation coupling for the functionalization of terminal alkynes. The study highlights the advantage of controlled partial linker thermolysis to synthesize hierarchical MOFs to achieve the advanced single-site photocatalysis.

Conflict of interest

The authors declare no conflict of interest.

Open Research

Data Availability Statement

The data that support the findings of this study are available in the supplementary material of this article.

Supporting Information

References

1Q. Wang, D. Astruc, Chem. Rev. 2020, 120, 1438–1511.
10.1021/acs.chemrev.9b00223
CAS PubMed Web of Science® Google Scholar
2M. Z. Hussain, Z. Yang, Z. Huang, Q. Jia, Y. Zhu, Y. Xia, Adv. Sci. 2021, 8, 2100625.
10.1002/advs.202100625
CAS Web of Science® Google Scholar
3Z. Guo, X. Liu, Y. Che, D. Chen, H. Xing, Inorg. Chem. 2022, 61, 2695–2705.
10.1021/acs.inorgchem.1c03961
CAS PubMed Web of Science® Google Scholar
4L. Feng, K. Y. Wang, G. S. Day, H. C. Zhou, Chem. Soc. Rev. 2019, 48, 4823–4853.
10.1039/C9CS00250B
CAS PubMed Web of Science® Google Scholar
5G. Cai, P. Yan, L. Zhang, H. C. Zhou, H. L. Jiang, Chem. Rev. 2021, 121, 12278–12326.
10.1021/acs.chemrev.1c00243
CAS PubMed Web of Science® Google Scholar
6X. Han, T. Zhang, X. Wang, Z. Zhang, Y. Li, Y. Qin, B. Wang, A. Han, J. Liu, Nat. Commun. 2022, 13, 2900.
10.1038/s41467-022-30520-3
CAS PubMed Web of Science® Google Scholar
7M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O′Keeffe, O. M. Yaghi, Science 2002, 295, 469–472.
10.1126/science.1067208
CAS PubMed Web of Science® Google Scholar
8L. B. Sun, J. R. Li, J. Park, H. C. Zhou, J. Am. Chem. Soc. 2012, 134, 126–129.
10.1021/ja209698f
CAS PubMed Web of Science® Google Scholar
9X. Liu, Z. Guo, Y. Che, R. Bai, Y. Chi, C. Guo, H. Xing, ACS Appl. Mater. Interfaces 2021, 13, 34114–34123.
10.1021/acsami.1c06391
CAS PubMed Web of Science® Google Scholar
10G. Cai, H. L. Jiang, Angew. Chem. Int. Ed. 2017, 56, 563–567.
10.1002/anie.201610914
CAS PubMed Web of Science® Google Scholar
11T. Li, M. T. Kozlowski, E. A. Doud, M. N. Blakely, N. L. Rosi, J. Am. Chem. Soc. 2013, 135, 11688–11691.
10.1021/ja403810k
CAS PubMed Web of Science® Google Scholar
12G. Cai, X. Ma, M. Kassymova, K. Sun, M. Ding, H. L. Jiang, ACS Cent. Sci. 2021, 7, 1434–1440.
10.1021/acscentsci.1c00743
CAS PubMed Web of Science® Google Scholar
13J. J. Low, A. I. Benin, P. Jakubczak, J. F. Abrahamian, S. A. Faheem, R. R. Willis, J. Am. Chem. Soc. 2009, 131, 15834–15842.
10.1021/ja9061344
CAS PubMed Web of Science® Google Scholar
14M. K. Albolkany, C. Liu, Y. Wang, C. H. Chen, C. Zhu, X. Chen, B. Liu, Angew. Chem. Int. Ed. 2021, 60, 14601–14608.
10.1002/anie.202103104
CAS PubMed Web of Science® Google Scholar
15S. Naghdi, A. Cherevan, A. Giesriegl, R. Guillet-Nicolas, S. Biswas, T. Gupta, J. Wang, T. Haunold, B. C. Bayer, G. Rupprechter, M. C. Toroker, F. Kleitz, D. Eder, Nat. Commun. 2022, 13, 282.
10.1038/s41467-021-27775-7
CAS PubMed Web of Science® Google Scholar
16L. Feng, S. Yuan, L. L. Zhang, K. Tan, J. L. Li, A. Kirchon, L. M. Liu, P. Zhang, Y. Han, Y. J. Chabal, H. C. Zhou, J. Am. Chem. Soc. 2018, 140, 2363–2372.
10.1021/jacs.7b12916
CAS PubMed Web of Science® Google Scholar
17Q. Zuo, T. Liu, C. Chen, Y. Ji, X. Gong, Y. Mai, Y. Zhou, Angew. Chem. Int. Ed. 2019, 58, 10198–10203.
10.1002/anie.201904058
CAS PubMed Web of Science® Google Scholar
18Q. Mo, L. Zhang, S. Li, H. Song, Y. Fan, C. Y. Su, J. Am. Chem. Soc. 2022, 144, 22747–22758.
10.1021/jacs.2c10801
CAS PubMed Web of Science® Google Scholar
19K. Y. Wang, Z. Yang, J. Zhang, S. Banerjee, E. A. Joseph, Y. C. Hsu, S. Yuan, L. Feng, H. C. Zhou, Nat. Protoc. 2023, 18, 604–625.
10.1038/s41596-022-00759-7
CAS PubMed Web of Science® Google Scholar
20M. J. Cliffe, W. Wan, X. Zou, P. A. Chater, A. K. Kleppe, M. G. Tucker, H. Wilhelm, N. P. Funnell, F. X. Coudert, A. L. Goodwin, Nat. Commun. 2014, 5, 4176.
10.1038/ncomms5176
CAS PubMed Web of Science® Google Scholar
21H. Wu, Y. S. Chua, V. Krungleviciute, M. Tyagi, P. Chen, T. Yildirim, W. Zhou, J. Am. Chem. Soc. 2013, 135, 10525–10532.
10.1021/ja404514r
CAS PubMed Web of Science® Google Scholar
22G. C. Shearer, S. Chavan, S. Bordiga, S. Svelle, U. Olsbye, K. P. Lillerud, Chem. Mater. 2016, 28, 3749–3761.
10.1021/acs.chemmater.6b00602
CAS Web of Science® Google Scholar
23K. Chakarova, I. Strauss, M. Mihaylov, N. Drenchev, K. Hadjiivanov, Microporous Mesoporous Mater. 2019, 281, 110–122.
10.1016/j.micromeso.2019.03.006
CAS Web of Science® Google Scholar
24P. C. Lemaire, D. T. Lee, J. J. Zhao, G. N. Parsons, ACS Appl. Mater. Interfaces 2017, 9, 22042–22054.
10.1021/acsami.7b05214
CAS PubMed Web of Science® Google Scholar
25M. Kandiah, S. Usseglio, S. Svelle, U. Olsbye, K. P. Lillerud, M. Tilset, J. Mater. Chem. 2010, 20, 9848–9851.
10.1039/c0jm02416c
CAS Web of Science® Google Scholar
26M. Kandiah, M. H. Nilsen, S. Usseglio, S. Jakobsen, U. Olsbye, M. Tilset, C. Larabi, E. A. Quadrelli, F. Bonino, K. P. Lillerud, Chem. Mater. 2010, 22, 6632–6640.
10.1021/cm102601v
CAS Web of Science® Google Scholar
27H. Q. Xu, J. Hu, D. Wang, Z. Li, Q. Zhang, Y. Luo, S. H. Yu, H. L. Jiang, J. Am. Chem. Soc. 2015, 137, 13440–13443.
10.1021/jacs.5b08773
CAS PubMed Web of Science® Google Scholar
28T. Song, L. Zhang, P. Zhang, J. Zeng, T. Wang, A. Ali, H. Zeng, J. Mater. Chem. A 2017, 5, 6013–6018.
10.1039/C7TA00095B
CAS Web of Science® Google Scholar
29X. Fang, Q. Shang, Y. Wang, L. Jiao, T. Yao, Y. Li, Q. Zhang, Y. Luo, H. L. Jiang, Adv. Mater. 2018, 30, 1705112.
10.1002/adma.201705112
Web of Science® Google Scholar
30G. Wang, C. T. He, R. Huang, J. Mao, D. Wang, Y. Li, J. Am. Chem. Soc. 2020, 142, 19339–19345.
10.1021/jacs.0c09599
CAS PubMed Web of Science® Google Scholar
31J. Büker, X. Huang, J. Bitzer, W. Kleist, M. Muhler, B. Peng, ACS Catal. 2021, 11, 7863–7875.
10.1021/acscatal.1c01468
CAS Web of Science® Google Scholar
32Q. Xiao, S. Sarina, E. R. Waclawik, J. Jia, J. Chang, J. D. Riches, H. Wu, Z. Zheng, H. Zhu, ACS Catal. 2016, 6, 1744–1753.
10.1021/acscatal.5b02643
CAS Web of Science® Google Scholar
33H. Cheng, X. Wu, X. Li, X. Nie, S. Fan, M. Feng, Z. Fan, M. Tan, Y. Chen, G. He, Chem. Eng. J. 2021, 407, 126842.
10.1016/j.cej.2020.126842
CAS Web of Science® Google Scholar
34Z. Yang, B. Chen, W. Chen, Y. Qu, F. Zhou, C. Zhao, Q. Xu, Q. Zhang, X. Duan, Y. Wu, Nat. Commun. 2019, 10, 3734.
10.1038/s41467-019-11796-4
PubMed Web of Science® Google Scholar
35F. Yu, X. Jing, Y. Wang, M. Sun, C. Duan, Angew. Chem. Int. Ed. 2021, 60, 24849–24853.
10.1002/anie.202108892
CAS PubMed Web of Science® Google Scholar
36Q. Zhang, Y. Jin, L. Ma, Y. Zhang, C. Meng, C. Duan, Angew. Chem. Int. Ed. 2022, 61, e202204918.
10.1002/anie.202204918
CAS PubMed Web of Science® Google Scholar
37Z. Q. Song, Z. Liu, Q. C. Gan, T. Lei, C. H. Tung, L. Z. Wu, Org. Lett. 2020, 22, 832–836.
10.1021/acs.orglett.9b04277
CAS PubMed Web of Science® Google Scholar
38A. Sagadevan, V. P. Charpe, A. Ragupathi, K. C. Hwang, J. Am. Chem. Soc. 2017, 139, 2896–2899.
10.1021/jacs.6b13113
CAS PubMed Web of Science® Google Scholar
39A. Sagadevan, A. Ragupathi, K. C. Hwang, Angew. Chem. Int. Ed. 2015, 54, 13896–13901.
10.1002/anie.201506579
CAS PubMed Web of Science® Google Scholar
40A. Sagadevan, V. K. K. Pampana, K. C. Hwang, Angew. Chem. Int. Ed. 2019, 58, 3838–3842.
10.1002/anie.201813315
CAS PubMed Web of Science® Google Scholar
41A. T. Lindhardt, R. Simonssen, R. H. Taaning, T. M. Gøgsig, G. N. Nilsson, G. Stenhagen, C. S. Elmore, T. Skrydstrup, J. Labelled Compd. Radiopharm. 2012, 55, 411–418.
10.1002/jlcr.2962
CAS Web of Science® Google Scholar
42S. Bal-Tembe, J. Blumbach, A. Dohadwana, N. S. Punekar, R. Rajgopalan, R. H. Rupp, M. Bickel, U. S. Patent 5821252, 1998.
Google Scholar
43G. Guazzi, U. S. Patent US2004073058(A1), 2004.
Google Scholar
44J. Li, J. Zhang, H. Tan, D. Z. Wang, Org. Lett. 2015, 17, 2522–2525.
10.1021/acs.orglett.5b01053
CAS PubMed Web of Science® Google Scholar
45H. Huang, X. Jing, J. Deng, C. Meng, C. Duan, J. Am. Chem. Soc. 2023, 145, 2170–2182.
10.1021/jacs.2c09348
CAS PubMed Web of Science® Google Scholar
46H. Huang, X. Jing, B. Zhong, C. Meng, C. Duan, ACS Appl. Mater. Interfaces 2021, 13, 58498–58507.
10.1021/acsami.1c16280
CAS PubMed Web of Science® Google Scholar
47A. M. Abdel-Mageed, B. Rungtaweevoranit, M. Parlinska-Wojtan, X. Pei, O. M. Yaghi, R. J. Behm, J. Am. Chem. Soc. 2019, 141, 5201–5210.
10.1021/jacs.8b11386
CAS PubMed Web of Science® Google Scholar

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Volume62, Issue36

September 4, 2023

e202308651

Controlled Partial Linker Thermolysis in Metal-Organic Framework UiO-66-NH₂ to Give a Single-Site Copper Photocatalyst for the Functionalization of Terminal Alkynes

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Controlled Partial Linker Thermolysis in Metal-Organic Framework UiO-66-NH2 to Give a Single-Site Copper Photocatalyst for the Functionalization of Terminal Alkynes

Graphical Abstract

Abstract

Conflict of interest

Open Research

Data Availability Statement

Supporting Information

References

Citing Literature

References

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Controlled Partial Linker Thermolysis in Metal-Organic Framework UiO-66-NH₂ to Give a Single-Site Copper Photocatalyst for the Functionalization of Terminal Alkynes