Defective UiO-66(Ce) supported Ni nanoparticles with optimized microenvironment and electronic state for efficient olefin hydrogenation reaction

doi:10.1016/S1872-2067(24)60284-6

Abstract

Abstract:

Defect engineering improves the catalytic performance of metal-organic frameworks (MOFs) loaded metal nanoparticles (MNPs@MOFs), but there is still a challenge in defining the structure-activity relationships. Herein, the content of linker-missing defects in UiO-66(Ce) was systematically regulated via formic acid as the modulators, and defective UiO-66(Ce) loaded Ni nanoparticles (NPs) were constructed for dicyclopentadiene (DCPD) hydrogenation. The fine regulation of defect engineering and reduction conditions affected the structure properties of UiO-66(Ce) and the electronic metal-support interaction between MOFs and Ni NPs, thereby optimizing the microenvironment and electronic state of Ni NPs. The optimized U(Ce)-40eq with suitable defects, small size and structure stability effectively promoted the production of highly dispersed abundant electron-deficient Ni⁰ active sites, enhancing the adsorption and activation of H₂ and C=C bonds, especially accelerating the rate-determining step. Therefore, U(Ce)-40eq loaded 5 wt% Ni NPs achieved DCPD saturated hydrogenation to tetrahydrodicyclopentadiene (70 °C, 2 MPa, 90 min), superior to most high-loading Ni-based catalysts. This work reveals the synergistic mechanism of MOFs defect engineering and electronic structure of Ni NPs, providing effective guidance for the precise preparation of highly efficient and stable MNPs@MOFs heterogeneous catalysts.

Key words: Metal-organic frameworks, Linker-missing defects, Ni⁰ species, Structure stability, Hydrogenation

Rushuo Li, Tao Ban, Danfeng Zhao, Fajie Hu, Jing Lin, Xiubing Huang, Zhiping Tao, Ge Wang. Defective UiO-66(Ce) supported Ni nanoparticles with optimized microenvironment and electronic state for efficient olefin hydrogenation reaction[J]. Chinese Journal of Catalysis, 2025, 72: 344-358.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60284-6

https://www.cjcatal.com/EN/Y2025/V72/I5/344

Figures/Tables 9

Fig. 1. (a) The schematic illustration for the synthesis process of U(Ce)-xeq (x = 0, 10, 20, 30, 40, 50) loaded Ni NPs. SEM and size distribution statistical images of U(Ce)-0eq (b), U(Ce)-10eq (c), U(Ce)-20eq (d), U(Ce)-30eq (e), U(Ce)-40eq (f), and U(Ce)-50eq (g).

Fig. 2. (a) The BDC linker-missing defect number and size distribution tendency chart of U(Ce)-xeq with the increase of FA modulators addition. (b) Schematic illustration for the introduction of BDC linker-missing defects in the U(Ce)-xeq due to introduce different FA modulators. (c) NH3-TPD curves for U(Ce)-40eq and Ni5@U(Ce)-40eq-5. Low-magnification TEM image and size distribution for Ni NPs (d), high-magnification TEM and corresponding interplanar spacing images (e), HAADF-STEM and EDX elemental mapping images (f) of Ni5@U(Ce)-40eq-5.

Fig. 3. (a) DCPD conversion (Con.DCPD) and THDCPD selectivity (Sel.THDCPD) for Ni5@U(Ce)-xeq-5 (x = 0, 10, 20, 30, 40, 50) (90 min, 2 MPa H2, 70 °C). XPS survey (b), Ni 2p XPS spectra (c), and Ce 3d XPS spectra (d) for Ni5@U(Ce)-40eq-5 and Air-Ni5@U(Ce)-40eq-5. Ni 2p XPS spectra (e), and Ce 3d XPS spectra (f) for Ni5@U(Ce)-40eq-5 in different Ar+ etching depths.

Fig. 4. XPS survey (a), Ni 2p XPS spectra (b), and Ce 3d XPS spectra (c) for Ni5@U(Ce)-xeq-5 (x = 0, 10, 20, 30, 40, 50). (d) The ratio of Ce4+/CeTotal, Ni0/NiTotal and Ce3+/CeTotal for Ni5@U(Ce)-xeq-5. (e) Radar image of DCPD hydrogenation performance, defect content, Ni0/NiTotal and Ce4+/CeTotal for Ni5@U(Ce)-xeq-5. (f) XRD patterns of Ni5@U(Ce)-xeq-5.

Fig. 5. Normalized XANES Ce L-edge (a) and Ni K-edge (b) spectra of Ni5@U(Ce)-0eq-5 and Ni5@U(Ce)-40eq-5. (c) Schematic illustration of electron-deficient Ni0 d-orbital and C=C bond orbital electronic configuration. (d) The possible electronic interaction between electron-deficient Ni0 and C=C bond orbital. (e) Schematic diagram of DCPD adsorbed on Ni NPs of Ni5@U(Ce)-40eq-5.

Fig. 6. DCPD conversion (Con.DCPD) and THDCPD selectivity (Sel.THDCPD) (90 min, 2 MPa H2, 70 °C) (a), XRD patterns (b), and FT-IR spectra (c) for Ni5@U(Ce)-40eq-5-H2O, Ni5@U(Ce)-40eq-5-H2O+Hex, Ni5@U(Ce)-40eq-5-EtOH, and Ni5@U(Ce)-40eq-5. (d) SEM image for Ni5@U(Ce)-40eq-5-EtOH. XRD (e) and TEM images (f) for Ni5@U(Ce)-40eq-5-TB. SEM (g) and HAADF-STEM with elemental mapping images (h) for Ni5@CeO2-5.

Fig. 7. DCPD conversion (Con.DCPD) and THDCPD selectivity (Sel.THDCPD) for Niy@U(Ce)-40eq-5 (a) and Ni5@U(Ce)-40eq-z (b) (90 min, 2 MPa H2, 70 °C). XRD pattern (c), XPS survey spectra (d), Ni 2p spectra (e), Ce 3d spectra (f), and the ratio of Ce4+/CeTotal, Ni0/NiTotal and Ce3+/CeTotal (g) for Ni5@U(Ce)-40eq-z. (h) Radar image of DCPD hydrogenation performance, Ni0/NiTotal and Ce4+/CeTotal for Ni5@U(Ce)-40eq-z.

Fig. 8. DCPD hydrogenation performance cycle test (a), XRD pattern (b), Ni 2p XPS spectra (c), and elemental mapping images (d) of AF-Ni5@U(Ce)-40eq-5.

Fig. 9. H2-TPD profiles (a), FT-IR spectra (b,c) of DCPD substrate molecule adsorption on the surface of different samples, respectively. The DCPD hydrogenation performance of Ni5@U(Ce)-40eq-5 under different reaction conditions: different reaction times (30-90 min, 2 MPa H2, 70 °C) (d), different H2 pressures (90 min, 0.5-2 MPa H2, 70 °C) (e), different reaction temperatures (90 min, 2 MPa H2, 40-70 °C) (f). (g) The potential mechanism of DCPD hydrogenation on the surface of Ni5@U(Ce)-40eq-5.

References

[1]	M. Monai, K. Jenkinson, A. E. M. Melcherts, J. N. Louwen, E. A. Irmak, S. Van Aert, T. Altantzis, C. Vogt, W. van der Stam, T. Duchoň, B. Šmíd, E. Groeneveld, P. Berben, S. Bals, B. M. Weckhuysen, Science, 2023, 380, 644-651.
[2]	C. Gao, F. Lyu, Y. Yin, Chem. Rev., 2020, 121, 834-881.
[3]	H. Meng, Y. Yang, T. Shen, W. Liu, L. Wang, P. Yin, Z. Ren, Y. Niu, B. Zhang, L. Zheng, H. Yan, J. Zhang, F.-S. Xiao, M. Wei, X. Duan, Nat. Commun., 2023, 14, 3189.
[4]	J. C. Matsubu, S. Zhang, L. DeRita, N. S. Marinkovic, J. G. Chen, G. W. Graham, X. Pan, P. Christopher, Nat. Chem., 2016, 9, 120-127.
[5]	T. Song, R. Li, J. Wang, C. Dong, X. Feng, S. Li, R. Mu, Q. Fu, Appl. Catal. B, 2023, 321, 122021.
[6]	Q. Hu, Z. Han, X. Wang, G. Li, Z. Wang, X. Huang, H. Yang, X. Ren, Q. Zhang, J. Liu, C. He, Angew. Chem. Int. Ed., 2020, 59, 19054-19059.
[7]	X. Gao, R. Ma, Z. Liu, S. Wang, Y. Wu, G. Song, Appl. Catal. B, 2024, 352, 124059.
[8]	G. Lu, F. Chu, X. Huang, Y. Li, K. Liang, G. Wang, Coord. Chem. Rev., 2022, 450, 214240.
[9]	K. Sun, Y. Huang, Q. Wang, W. Zhao, X. Zheng, J. Jiang, H.-L. Jiang, J. Am. Chem. Soc., 2024, 146, 3241-3249.
[10]	H. Jiang, S. M. Moosavi, J. Czaban-Jóźwiak, B. Torre, A. Shkurenko, Z. O. Ameur, J. Jia, N. Alsadun, O. Shekhah, E. Di Fabrizio, B. Smit, M. Eddaoudi, Matter, 2023, 6, 285-295.
[11]	D. Zhao, X. Li, K. Zhang, J. Guo, X. Huang, G. Wang, Coord. Chem. Rev., 2023, 487, 215159.
[12]	L. Chen, Q. Xu, Matter, 2019, 1, 57-89.
[13]	M. Zhao, K. Yuan, Y. Wang, G. Li, J. Guo, L. Gu, W. Hu, H. Zhao, Z. Tang, Nature, 2016, 539, 76-80.
[14]	Q. Yang, Q. Xu, H.-L. Jiang, Chem. Soc. Rev., 2017, 46, 4774-4808.
[15]	P. Y. Zhou, J. J. Lv, X. B. Huang, Y. F. Lu, G. Wang, Coord. Chem. Rev., 2023, 478, 214969.
[16]	M. Garai, C. T. Yavuz, Matter, 2021, 4, 10-12.
[17]	K. Li, J. Yang, R. Huang, S. Lin, J. Gu, Angew. Chem. Int. Ed., 2020, 59, 14124-14128.
[18]	S. Dai, C. Simms, G. Patriarche, M. Daturi, A. Tissot, T. N. Parac-Vogt, C. Serre, Nat. Commun., 2024, 15, 3434.
[19]	X. Zhou, H. Jin, B. Y. Xia, K. Davey, Y. Zheng, S. Z. Qiao, Adv. Mater., 2021, 33, 2104341.
[20]	W. Wang, T. Sheng, S. Chen, Z. Xiang, F. Zhou, W. Zhu, H. Wang, Chem. Eng. J., 2023, 453, 139711.
[21]	Y. Liu, X. Li, S. Zhang, Z. Wang, Q. Wang, Y. He, W.-H. Huang, Q. Sun, X. Zhong, J. Hu, X. Guo, Q. Lin, Z. Li, Y. Zhu, C.-C. Chueh, C.-L. Chen, Z. Xu, Z. Zhu, Adv. Mater., 2023, 35, 2300945.
[22]	X. Li, K. Zhang, X. Huang, Z. Wu, D. Zhao, G. Wang, Nanoscale, 2021, 13, 19671-19681.
[23]	R. Li, L. Wang, P. Zhou, J. Lin, Z. Liu, J. Chen, D. Zhao, X. Huang, Z. Tao, G. Wang, Chin. J. Catal., 2024, 56, 150-165.
[24]	J. Park, Q. Jiang, D. Feng, L. Mao, H.-C. Zhou, J. Am. Chem. Soc., 2016, 138, 3518-3525.
[25]	L. Chen, J. Lu, X. Li, N. Luan, Y. Song, S. Yang, M. Yuan, H. Qin, H. Zhu, X. Dong, K. Li, D. Zhang, L. Chen, X. Dai, Y. Wang, Y. Wang, C. Xu, Z. Chai, S. Wang, J. Am. Chem. Soc., 2024, 146, 6697-6705.
[26]	G. C. Shearer, S. Chavan, S. Bordiga, S. Svelle, U. Olsbye, K. P. Lillerud, Chem. Mater., 2016, 28, 3749-3761.
[27]	P. Ji, T. Drake, A. Murakami, P. Oliveres, J. H. Skone, W. Lin, J. Am. Chem. Soc., 2018, 140, 10553-10561.
[28]	D. Zhao, J. Lin, R. Li, L. Chu, Z. Wang, X. Huang, G. Wang, Chin. Chem. Lett., 2024, DOI: 10.1016/j.cclet.2024.110172.
[29]	R. Li, T. Ban, D. Zhao, J. Lin, Z. Liu, L. Wang, X. Huang, Z. Tao, G. Wang, Nano Res., 2024, 17, 9550-9563.
[30]	C. Huang, J. Dong, W. Sun, Z. Xue, J. Ma, L. Zheng, C. Liu, X. Li, K. Zhou, X. Qiao, Q. Song, W. Ma, L. Zhang, Z. Lin, T. Wang, Nat. Commun., 2019, 10, 2779.
[31]	Z. Liu, L. Wang, C. Wang, R. Li, P. Zhou, H. Gao, G. Wang, Chem. Eng. J., 2024, 479, 147601.
[32]	W. Liu, H. Feng, Y. Yang, Y. Niu, L. Wang, P. Yin, S. Hong, B. Zhang, X. Zhang, M. Wei, Nat. Commun., 2022, 13, 3188.
[33]	J. Sun, L. Tao, C. Ye, Y. Wang, G. Meng, H. Lei, S. Zheng, C. Xing, X. Tao, P. Wu, J. Chen, S. Du, D. Wang, Y. Li, J. Am. Chem. Soc., 2023, 145, 7113-7122.
[34]	M. Irshad, H.-J. Chun, M. K. Khan, H. Jo, S. K. Kim, J. Kim, Appl. Catal. B, 2024, 340, 123201.
[35]	C. Wu, X. Chen, J. Liang, J. Fu, Z. Zhang, X. Wei, L. Wang, Chem. Eng. J., 2023, 462, 142141.
[36]	D. Jia, J. Zhao, Z. Tao, H. Gao, Z. Fu, R. Yan, Z. Zhu, X. Shu, G. Wang, Carbon, 2021, 184, 855-863.
[37]	F. Wang, X. Han, D. Wu, Z. Wang, X. Xiong, J. Li, X. Gao, G. Wang, L. Huo, Y. Hua, C. Wang, H. Wen, Q. Chen, X. Tian, P. Deng, Adv. Funct. Mater., 2024, 34, 2314453.
[38]	H. Qu, W. Hu, X. Li, R. Xu, X. Han, J. Li, Y. Lu, Y. Ye, C. Wang, Z. Wang, W. Yang, Chin. J. Catal., 2024, 60, 253-261.
[39]	P. Y. Zhou, G. T. Hai, G. C. Zhao, R. S. Li, X. B. Huang, Y. F. Lu, G. Wang, Appl. Catal. B, 2023, 325, 122364.
[40]	G. Zhao, G. Hai, P. Zhou, Z. Liu, Y. Zhang, B. Peng, W. Xia, X. Huang, G. Wang, Adv. Funct. Mater., 2023, 33, 2213170.
[41]	X. Shi, M. Xie, K. Yang, Y. Niu, H. Ma, Y. Zhu, J. Li, T. Pan, X. Zhou, Y. Cui, Z. Li, Y. Yu, X. Yu, J. Ma, H. Cheng, Angew. Chem. Int. Ed., 2024, 63, e202406750.
[42]	H.-G. Jin, M. Wang, J.-X. Wen, S.-H. Han, X.-J. Hong, Y.-P. Cai, G. Li, J. Fan, Z.-S. Chao, ACS Appl. Mater. Interfaces, 2021, 13, 3899-3910.
[43]	X.-P. Wu, L. Gagliardi, D. G. Truhlar, J. Am. Chem. Soc., 2018, 140, 7904-7912.
[44]	L. Yin, S. Zhang, M. Sun, S. Wang, B. Huang, Y. Du, Adv. Mater., 2023, 35, 2302485.
[45]	Y. Chu, E. Luo, Y. Wei, S. Zhu, X. Wang, L. Yang, N. Gao, Y. Wang, Z. Jiang, C. Liu, J. Ge, W. Xing, Chem Catal., 2023, 3, 100532.
[46]	Y. Li, Y. Wu, T. Li, M. Lu, Y. Chen, Y. Cui, J. Gao, G. Qian, Carbon Energy, 2022, 5, e265.
[47]	K. Li, Y. Kuwahara, H. Yamashita, Chin. J. Catal., 2024, 64, 66-76.
[48]	J. Wang, Y.-C. Huang, Y. Wang, H. Deng, Y. Shi, D. Wei, M. Li, C.-L. Dong, H. Jin, S. S. Mao, S. Shen, ACS Catal., 2023, 13, 2374-2385.
[49]	M. Guo, F. Wang, M. Zhang, L. Wang, X. Zhang, G. Li, J. Catal., 2023, 424, 221-235.
[50]	Y. Guo, R. Zhang, S. Zhang, H. Hong, P. Li, Y. Zhao, Z. Huang, C. Zhi, Angew. Chem. Int. Ed., 2024, 63, e202401501.
[51]	Z. Wang, Y. Kang, Y. Shi, C. Liu, Y. Liu, J. Lin, J. Bi, L. Wu, Appl. Catal. B, 2024, 340, 123162.
[52]	P. Wang, X. Li, P. Zhang, X. Zhang, Y. Shen, B. Zheng, J. Wu, S. Li, Y. Fu, W. Zhang, F. Huo, ACS Appl. Mater. Interfaces, 2020, 12, 23968-23975.
[53]	Q. Fu, L. Yan, D. Liu, S. Zhang, H. Jiang, W. Xie, L. Yang, Y. Wang, H. Wang, X. Zhao, Appl. Catal. B, 2024, 343, 123501.
[54]	L. Zhao, X. Qin, X. Zhang, X. Cai, F. Huang, Z. Jia, J. Diao, D. Xiao, Z. Jiang, R. Lu, N. Wang, H. Liu, D. Ma, Adv. Mater., 2022, 34, 2110455.
[55]	Z. Liu, C. Wang, P. Yang, W. Wang, H. Gao, G. An, S. Liu, J. Chen, T. Guo, X. Xu, G. Wang, Chin. J. Catal., 2024, 64, 112-122.