Electron-deficient nickel tailored by boron for coke-free methane dry reforming

doi:10.1016/S1872-2067(26)65077-2

Abstract

Abstract:

Methane dry reforming (MDR) converts two major greenhouse gases (CO₂ and CH₄) into syngas (H₂/CO) for synthesizing fuels and chemicals, which provides a process both economically viable and environmentally friendly, aligning with the goal of carbon neutrality. Ni is the most efficient and economic non-noble active metal for MDR but often suffers from deactivation caused by sintering or coking due to the fast C-H activation but sluggish carbon removal. Herein, we report a rather stable Ni catalyst (Ni_BN) derived from electrostatic-driven self-assembled 2D composites, which offered a coke-free manner for a prolonged stability (over 350 h) under typical MDR conditions. This outperformed catalyst featured with homogeneously distributed spherical Ni nanoparticles (~6 nm) stabilized within mixed-oxide matrix. Partially electron-deficient Ni species are tailored by surrounded boron species through the Ni-O-B structure, which hindered the last C-H bond cleavage of methane and accelerated CO₂ reactivity, thus balancing elementary steps to enable a coke-free operation. It marks an important step forward for C-H bond manipulation and inspires material design in other applications.

Key words: Electron-deficient, Nickel, Boron, Methane dry reforming, Coke-free

Yang Wang, Lei He, Fan Tang, Wen-Cui Li, Bowen He, Xi Liu, Liwei Chen, Dongqi Wang, Wenjie Shen, An-Hui Lu. Electron-deficient nickel tailored by boron for coke-free methane dry reforming[J]. Chinese Journal of Catalysis, 2026, 87: 353-362.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65077-2

https://www.cjcatal.com/EN/Y2026/V87/I8/353

Figures/Tables 5

Fig. 1. Structure of NiBN catalyst. (a) Schematic illustration of the synthesis process. (b) Large-scale TEM image. (c) High resolution TEM image of one typical Ni particle. (d) Particle size distribution. (e) ADF-STEM image and the corresponding EDX mapping, showing the distribution of B, N, O, Ni, Al, Mg, and overlayer of the above elements. (f) In-situ XRD measurements of NiBN catalyst in temperature programmed reduction.

Fig. 2. Electron state of Ni. ADF-STEM image (a) and corresponding STEM-EELS element mapping (b-e) of boron. (f) Integrated EELS from the selected areas and reference B EELS spectra. (g) XPS profiles of Ni 2p3/2 for NiBN and the Ni-ref catalysts.

Fig. 3. Catalytic performance of NiBN catalyst. (a) MDR stability test (GHSV = 30000 mL g?1 h?1, inserted the TEM image for the spent catalyst). (b) Anti-coking test under nearly pure CH4/CO2 mixture. (c) High pressure MDR test. (d) TG-MS results (solid lines, TG; dotted lines, mass spectra) of spent catalyst under various conditions. (e) Large area TEM image of the spent NiBN catalyst (20 h at 600 °C).

Fig. 4. Coke resistance investigation. (a) In-situ XRD results (the patterns were taken every half hour, CH4:CO2:N2 = 1:1:3, flow rate = 30 mL min?1). (b) Mass change and the corresponding mass spectra signals of the outlet gas (600 °C, flow rate = 100 mL min?1). (c) Mass change and the corresponding mass spectra signal change in alternated CH4 and CO2 atmosphere (CH4:Ar =1:4 or CO2:Ar = 1:4, 600 °C, flow rate = 100 mL min?1).

Fig. 5. (a) The free energy profile of C-H bond cleavage in methane at 873 K. (b) Carbon migration on Ni-BN and Ni(111) at 873 K. (c) MDR catalytic cycle based on experimental and DFT calculation.

References

[1]	D. Pakhare, J. Spivey, Chem. Soc. Rev., 2014, 43, 7813-7837.
[2]	L. C. Buelens, V. V. Galvita, H. Poelman, C. Detavernier, G. B. Marin, Science, 2016, 354, 449-452.
[3]	Q. Zhu, H. Zhou, L. Wang, L. Wang, C. Wang, H. Wang, W. Fang, M. He, Q. Wu, F.-S. Xiao, Nat. Catal., 2022, 5, 1030-1037.
[4]	Y. Song, E. Ozdemir, S. Ramesh, A. Adishev, S. Subramanian, A. Harale, M. Albuali, B. A. Fadhel, A. Jamal, D. Moon, S. H. Choi, C. T. Yavuz, Science, 2020, 367, 777-781.
[5]	Y. Sun, Y. Zhang, X. Yin, C. Zhang, Y. Li, J. Bai, Green Chem., 2024, 26, 5103-5126.
[6]	M. C. J. Bradford, M. A. Vannice, Catal. Rev., 1999, 41, 1-42.
[7]	F. Che, S. Ha, J.-S. McEwen, Angew. Chem. Int. Ed., 2017, 56, 3557-3561.
[8]	D. Wang, D. Astruc, Chem. Soc. Rev., 2017, 46, 816-854.
[9]	Z. Qin, J. Chen, X. Xie, X. Luo, T. Su, H. Ji, Environ. Chem. Lett., 2020, 18, 997-1017.
[10]	K. Wittich, M. Krämer, N. Bottke, S. A. Schunk, ChemCatChem, 2020, 12, 2130-2147.
[11]	S. Li, J. Gong, Chem. Soc. Rev., 2014, 43, 7245-7256.
[12]	Z. Li, Z. Wang, S. Kawi, ChemCatChem, 2019, 11, 202-224.
[13]	S. Helveg, C. López-Cartes, J. Sehested, P. L. Hansen, B. S. Clausen, J. R. Rostrup-Nielsen, F. Abild-Pedersen, J. K. Nørskov, Nature, 2004, 427, 426-429.
[14]	D. Baudouin, U. Rodemerck, F. Krumeich, A. de Mallmann, K. C. Szeto, H. Ménard, L. Veyre, J.-P. Candy, P. B. Webb, C. Thieuleux, C. Copéret, J. Catal., 2013, 297, 27-34.
[15]	M. Akri, S. Zhao, X. Li, K. Zang, A. F. Lee, M. A. Isaacs, W. Xi, Y. Gangarajula, J. Luo, Y. Ren, Y.-T. Cui, L. Li, Y. Su, X. Pan, W. Wen, Y. Pan, K. Wilson, L. Li, B. Qiao, H. Ishii, Y.-F. Liao, A. Wang, X. Wang, T. Zhang, Nat. Commun., 2019, 10, 5181.
[16]	H. Peng, X. Zhang, X. Han, X. You, S. Lin, H. Chen, W. Liu, X. Wang, N. Zhang, Z. Wang, P. Wu, H. Zhu, S. Dai, ACS Catal., 2019, 9, 9072-9080.
[17]	W. Kong, Y. Fu, L. Shi, S. Li, E. Vovk, X. Zhou, R. Si, B. Pan, C. Yuan, S. Li, F. Cai, H. Zhu, J. Zhang, Y. Yang, Y. Sun, Appl. Catal. B, 2021, 285, 119837.
[18]	J. Wang, Y. Fu, W. Kong, F. Jin, J. Bai, J. Zhang, Y. Sun, Appl. Catal. B, 2021, 282, 119546.
[19]	J. Deng, K. Bu, Y. Shen, X. Zhang, J. Zhang, K. Faungnawakij, D. Zhang, Appl. Catal. B, 2022, 302, 120859.
[20]	L. He, M. Li, W.-C. Li, W. Xu, Y. Wang, Y.-B. Wang, W. Shen, A.-H. Lu, ACS Catal., 2021, 11, 12409-12416.
[21]	L. Cai, S. Han, W. Xu, S. Chen, X. Shi, J. Lu, Angew. Chem. Int. Ed., 2024, 63, e202404398.
[23]	Z. Liu, P. Lustemberg, R. A. Gutiérrez, J. J. Carey, R. M. Palomino, M. Vorokhta, D. C. Grinter, P. J. Ramírez, V. Matolín, M. Nolan, M. V. Ganduglia-Pirovano, S. D. Senanayake, J. A. Rodriguez, Angew. Chem. Int. Ed., 2017, 56, 13041-13046.
[24]	Y.-B. Wang, L. He, B.-C. Zhou, F. Tang, J. Fan, D.-Q. Wang, A.-H. Lu, W.-C. Li, Ind. Eng. Chem. Res., 2021, 60, 15064-15073.
[25]	S. Zhang, L. Tang, J. Yu, W. Zhan, L. Wang, Y. Guo, Y. Guo, ACS Appl. Mater. Interfaces, 2021, 13, 58605-58618.
[26]	S. M. Kim, P. M. Abdala, T. Margossian, D. Hosseini, L. Foppa, A. Armutlulu, W. van Beek, A. Comas-Vives, C. Copéret, C. Müller, J. Am. Chem. Soc., 2017, 139, 1937-1949.
[27]	C. Palmer, D. C. Upham, S. Smart, M. J. Gordon, H. Metiu, E. W. McFarland, Nat. Catal., 2020, 3, 83-89.
[28]	S. Joo, K. Kim, O. Kwon, J. Oh, H. J. Kim, L. Zhang, J. Zhou, J.-Q. Wang, H. Y. Jeong, J. W. Han, G. Kim, Angew. Chem. Int. Ed., 2021, 60, 15912-15919.
[29]	D. Guo, M. Li, Y. Lu, Y. Zhao, M. Li, Y. Zhao, S. Wang, X. Ma, ACS Catal., 2022, 12, 316-330.
[30]	P. Delir Kheyrollahi Nezhad, M. F. Bekheet, N. Bonmassar, A. Gili, F. Kamutzki, A. Gurlo, A. Doran, S. Schwarz, J. Bernardi, S. Praetz, A. Niaei, A. Farzi, S. Penner, Catal. Sci. Technol., 2022, 12, 1229-1244.
[31]	J. Dong, L. Gao, Q. Fu, J. Phys. Chem. Lett., 2021, 12, 9608-9619.
[32]	J. Sheng, B. Yan, W.-D. Lu, B. Qiu, X.-Q. Gao, D. Wang, A.-H. Lu, Chem. Soc. Rev., 2021, 50, 1438-1468.
[33]	J. T. Grant, C. A. Carrero, F. Goeltl, J. Venegas, P. Mueller, S. P. Burt, S. E. Specht, W. P. McDermott, A. Chieregato, I. Hermans, Science, 2016, 354, 1570-1573.
[34]	J. Fan, W.-C. Li, Y. Zhang, W. Chen, Z. Liu, J. Jiang, Y. Zheng, L. He, L. Hua, D. Wang, A.-H. Lu, J. Am. Chem. Soc., 2025, 147, 40935-40943.
[35]	J. Dong, Q. Fu, H. Li, J. Xiao, B. Yang, B. Zhang, Y. Bai, T. Song, R. Zhang, L. Gao, J. Cai, H. Zhang, Z. Liu, X. Bao, J. Am. Chem. Soc., 2020, 142, 17167-17174.
[36]	K. Bu, J. Deng, X. Zhang, S. Kuboon, T. Yan, H. Li, L. Shi, D. Zhang, Appl. Catal. B, 2020, 267, 118692.
[37]	J. Fan, W.-C. Li, L. He, B. He, F. Tang, Z. Liu, D. Wang, X. Liu, L. Chen, A.-H. Lu, ACS Catal., 2024, 14, 17748-17759.
[38]	O. Mohan, Shambhawi, A. A. Lapkin, S. H. Mushrif, Catal. Sci. Technol., 2020, 10, 6628-6643.
[39]	J. Xu, L. Chen, K. Tan, A. Borgna, M. Saeys, J. Catal., 2009, 261, 158-165.
[40]	W. Lei, V. N. Mochalin, D. Liu, S. Qin, Y. Gogotsi, Y. Chen, Nat. Commun., 2015, 6, 8849.
[41]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[42]	V. Wang, N. Xu, J.-C. Liu, G. Tang, W.-T. Geng, Comput. Phys. Commun., 2021, 267, 108033.
[43]	L. He, Y. Huang, A. Wang, X. Wang, X. Chen, J. J. Delgado, T. Zhang, Angew. Chem. Int. Ed., 2012, 51, 6191-6194.
[44]	G. Mountjoy, A. Corrias, P. H. Gaskell, J. Non Cryst. Solids, 1995, 192-193, 616-619.
[46]	J. Wu, L. Wang, X. Yang, B. Lv, J. Chen, Ind. Eng. Chem. Res., 2018, 57, 2805-2810.
[47]	S.-Q. Cheng, X.-F. Weng, Q.-N. Wang, B.-C. Zhou, W.-C. Li, M.-R. Li, L. He, D.-Q. Wang, A.-H. Lu, Chin. J. Catal., 2022, 43, 1092-1100.
[48]	S. L. Leung, J. Wei, W. L. Holstein, M. Avalos-Borja, E. Iglesia, J. Phys. Chem. C, 2020, 124, 20143-20160.
[49]	A. C. Ferrari, J. Robertson, Phys. Rev. B, 2000, 61, 14095-14107.
[50]	J. Wei, E. Iglesia, J. Catal., 2004, 224, 370-383.
[51]	V. C. H. Kroll, H. M. Swaan, S. Lacombe, C. Mirodatos, J. Catal., 1996, 164, 387-398.
[52]	W. Tu, M. Ghoussoub, C. V. Singh, Y. C. Chin, J. Am. Chem. Soc., 2017, 139, 6928-6945.
[55]	B. Wang, S. Chen, J. Zhang, S. Li, B. Yang, J. Phys. Chem. C, 2019, 123, 30389-30397.
[56]	Z. Wang, X.-M. Cao, J. Zhu, P. Hu, J. Catal., 2014, 311, 469-480.