高熵氧化物(CrMnFeCoNi)3O4催化剂在二氧化碳加氢反应中是否需要载体来提高性能?

doi:10.1016/S1872-2067(26)65030-9

催化学报 ›› 2026, Vol. 85: 168-181.DOI: 10.1016/S1872-2067(26)65030-9

高熵氧化物(CrMnFeCoNi)₃O₄催化剂在二氧化碳加氢反应中是否需要载体来提高性能?

Ksenia A. Kokina^a, Anton S. Konopatsky^a^,^b(), Ekaterina S. Chikanova^a, Danil V. Barilyuk^a, Tatyana O. Teplakova^a, Denis V. Leybo^c, Ekaterina V. Sukhanova^d^,^e, Zakhar I. Popov^d, Alexey Y. Antonov^f, Olga A. Boeva^f, Sergey A. Efimov^f, Dmitry V. Shtansky^a

^a 国立科学技术大学莫斯科钢铁合金学院, 莫斯科, 俄罗斯
^b 诺曼底大学, 法国国立卡昂高等工程师学院, 卡昂, 法国
^c 以色列理工学院催化可持续发展中心, 海法, 以色列
^d 伊曼纽尔生物化学物理研究所, 莫斯科, 俄罗斯
^e 莫斯科物理技术学院, 莫斯科, 俄罗斯
^f 俄罗斯门捷列夫化学技术大学, 莫斯科, 俄罗斯

收稿日期:2025-10-02 接受日期:2025-12-17 出版日期:2026-06-18 发布日期:2026-05-18
通讯作者: *电子信箱: ankonopatsky@gmail.com (A. S. Konopatsky).

Does high-entropy oxide (CrMnFeCoNi)₃O₄ catalyst require support to improve performance in CO₂ hydrogenation?

^a National University of Science and Technology “MISIS”, Leninsky prospect 4, Moscow 119049, Russia
^b Normandie Univ., ENSICAEN, UNICAEN, Caen 14000, France
^c Schulich Faculty of Chemistry, and Resnick Sustainability Center for Catalysis, Technion, Israel Institute of Technology, Technion City, Haifa 32000, Israel
^d Emanuel Institute of Biochemical Physics RAS, Kosygina 4, Moscow 119334, Russia
^e Moscow Institute of Physics and Technology, Institutsky lane 9, Dolgoprudny, Moscow 141700, Russia
^f Mendeleev University of Chemical Technology of Russia, Moscow, Russia

Received:2025-10-02 Accepted:2025-12-17 Online:2026-06-18 Published:2026-05-18
Contact: *E-mail: ankonopatsky@gmail.com (A. S. Konopatsky).

摘要/Abstract

摘要：

高熵材料(HEO)含有至少五种金属元素, 具备高构型熵与丰富表面活性位点, 在热催化领域极具应用潜力. 然而, 载体材料对HEO纳米颗粒(NP)的反应动力学和稳定性具有决定性影响, 由此产生的对材料催化性能的影响仍有待深入研究. 为探究载体效应, 本文选择了传统的TiO₂和先进的非氧化物层状六方相硼化氮(h-BN). 对反应前后的催化剂进行了全面的结构表征和表面化学状态分析, 进而深入了解结构-性能关系以及富钴和富镍合金等新活性相的形成机理; 系统研究了CO₂转化率、产物选择性、稳定性和反应动力学. 此外, 采用密度泛函理论建模阐明了不同金属组分在CO₂, CO和H₂吸附中的作用. 所选的载体材料显著影响HEO NP的催化性能和反应途径(甲烷化反应vs.逆水煤气反应). 未负载的HEO NP表现出较好的固有稳定性和高CO₂转化率. TiO₂负载的HEO催化剂最初与未负载的性能一致, 但随后会迅速失活, 同时产物由CO转变为CH₄. 相比之下, h-BN-负载的催化剂体系需要一个独特的激活期来克服最初的性能不佳, 随后其活性快速增加. 本文研究结果展示了HEO在热催化CO₂减排方面的巨大潜力, 表现出优异的转化效率和稳定性, 为下一代催化系统建立了新的标准.

关键词: 高熵氧化物纳米颗粒, CO₂加氢, 多相催化剂, 催化剂底物, 催化性能

Abstract:

High-entropy materials, which contain at least five metal elements, are promising catalysts for thermocatalytic applications. They offer an unprecedented diversity of surface atomic arrangements that yield highly efficient and often unexpected active sites. However, the profound influence of the support material on the reaction kinetics and stability of high-entropy nanoparticles (NPs), and thus their catalytic performance, remains a critical and elusive factor. To evaluate these support effects fundamentally, we selected conventional TiO₂ and advanced, non-oxide layered h-BN. Comprehensive structural and surface chemical state analyses before and after the catalytic reaction provide insights into the structure-property relationships and the formation of new active phases such as Co and Ni enriched alloys. CO₂ conversion, product selectivity, stability, and reaction kinetics are systematically studied. Furthermore, density functional theory modeling is used to elucidate the role of different metal components in CO₂, CO, and H₂ adsorption. The selected support materials significantly influence the catalytic properties of HEO NPs and the reaction pathways (Sabatier process vs. RWGS reaction). Unsupported HEO NPs exhibit excellent inherent stability and high CO₂ conversion. Their TiO₂-supported counterparts initially match this performance but subsequently suffer rapid deactivation, concomitant with a product selectivity shift from CO to CH₄. In contrast, the h-BN-supported system requires a distinct activation period to overcome initially subpar performance, after which it achieves rapidly increasing conversion. Our findings highlight the remarkable potential of HEOs in thermocatalytic CO₂ reduction, demonstrating exceptional conversion efficiency and stability, setting a new benchmark for next-generation catalytic systems.

Key words: High-entropy oxides nanoparticles, CO₂ hydrogenation, Heterogeneous catalysts, Catalyst substrates, Catalytic performance

Ksenia A. Kokina, Anton S. Konopatsky, Ekaterina S. Chikanova, Danil V. Barilyuk, Tatyana O. Teplakova, Denis V. Leybo, Ekaterina V. Sukhanova, Zakhar I. Popov, Alexey Y. Antonov, Olga A. Boeva, Sergey A. Efimov, Dmitry V. Shtansky. 高熵氧化物(CrMnFeCoNi)₃O₄催化剂在二氧化碳加氢反应中是否需要载体来提高性能?[J]. 催化学报, 2026, 85: 168-181.

Ksenia A. Kokina, Anton S. Konopatsky, Ekaterina S. Chikanova, Danil V. Barilyuk, Tatyana O. Teplakova, Denis V. Leybo, Ekaterina V. Sukhanova, Zakhar I. Popov, Alexey Y. Antonov, Olga A. Boeva, Sergey A. Efimov, Dmitry V. Shtansky. Does high-entropy oxide (CrMnFeCoNi)₃O₄ catalyst require support to improve performance in CO₂ hydrogenation?[J]. Chinese Journal of Catalysis, 2026, 85: 168-181.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65030-9

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Fig. 1. High-resolution HAADF STEM image with spinel lattice superimposed on electron image (inset): yellow atoms denote metal, red atoms represent oxygen (a), and corresponding FFT pattern (b), STEM image of HEO NPs agglomerate (c) with corresponding elemental distribution maps (d).

Fig. 2. (a) XRD patterns of HEO, HEO/BN and HEO/TiO2 samples in as synthesized state. FTIR spectra (b), TGA curves (c), and specific surface area values (d) of HEO, HEO/BN and HEO/TiO2 samples and h-BN and TiO2 substrates.

Fig. 3. CO2 conversion plots and selectivity histograms of HEO (a), HEO/BN (b) and HEO/TiO2 (c) samples after activation at 400, 500, and 600 °C.

Fig. 4. Catalytic activity (a) and Arrhenius plots (b) for HEO, HEO/BN, HEO/TiO2 samples. Selectivity histograms for HEO (c), HEO/BN (d), and HEO/TiO2 (e) materials.

Fig. 5. Catalytic stability plots (a) and selectivity histograms of HEO (b), HEO/BN (c), and HEO/TiO2 (d) materials.

Fig. 6. (a) XPS spectra of HEO sample in as-synthesized state. (b) Surface compositions of HEO NPs in the as-synthesized state and after catalytic conversion and stability tests.

Fig. 7. STEM image (a) and corresponding elemental maps (b) of HEO NPs after catalytic stability tests. Chemical compositions of areas 1 and 2 are given in Table 1.

Table 1 Chemical composition of Areas 1 (Reduced HEO) and 2 (HEO).

Area	Chemical composition, at%
Area	O	Co	Cr	Fe	Mn	Ni
1	24.0	34.1	6.8	13.0	2.1	19.9
2	65.2	9.9	5.6	8.9	3.2	7.3

Fig. 8. Final TPR (a) and TPO (b) profiles for HEO NPs, HEO/TiO2 and HEO/BN materials.

Fig. 9. Slab model of CrMnFeCoNi HEA shown in various projections. The Mn, Fe, Ni, Co and Cr atoms marked by purple, orange, gray, light blue and dark blue.

Fig. 10. Adsorption energy distribution on CrMnFeCoNi HEA slab surfaces for CO (a), CO2 (b), and H2 (c) molecules.

参考文献

[1]	Q. Chen, M. Lv, Z. Tang, H. Wang, W. Wei, Y. Sun, J. CO₂ Util., 2016, 14, 1-9.
[2]	K. Saravanan, H. Ham, N. Tsubaki, J. W. Bae, Appl. Catal. B, 2017, 217, 494-522.
[3]	E. P. George, D. Raabe R. O. Ritchie, Nat. Rev. Mater., 2019, 4, 515-534.
[4]	Y. Wang, J. Mi, Z.-S. Wu, Chem Catal., 2022, 2, 1624-1656.
[5]	G. C. Mohanty, C. Chowde Gowda P,. Gakhad M,. Sanjay A,. Singh K,. Biswas C. S. Tiwary, Energy Adv., 2024, 3, 2972-2985.
[6]	J. Mi X,. Chen Y,. Ding L,. Zhang J,. Ma H,. Kang X,. Wu Y,. Liu J,. Chen Z.-S. Wu, Chin. J. Catal., 2023, 48, 235-246.
[7]	G. R. Dey, S. S. Soliman C. R., McCormick C. H., Wood R. R., Katzbaer R. E. Schaak, ACS Nanosci. Au, 2024, 4, 3-20.
[8]	Y. Pan J.-X., Liu T.-Z., Tu W,. Wang G.-J. Zhang, Chem. Eng. J., 2023, 451, 138659.
[9]	V. R. Naganaboina, M. Anandkumar A. S., Deshpande S. G. Singh, Sens. Actuat. B, 2022, 357, 131426.
[10]	A. Mao H.-Z., Xiang Z.-G., Zhang K,. Kuramoto H,. Zhang Y. Jia, J. Magn. Magn. Mater., 2020, 497, 165884.
[11]	P. Tang, Y. Cao, H. li, M. Lu, W. Qiu, Ceram. Int., 2022, 48, 2660-2669.
[12]	M. U. González-Rivas, S. S. Aamlid M. R., Rutherford J,. Freese R,. Sutarto N,. Chen E. E., Villalobos-Portillo H,. Castillo-Michel M,. Kim H,. Takagi R. J., Green A. M. Hallas, J. Am. Chem. Soc., 2024, 146, 26048-26059.
[13]	J. Dąbrowa, A. Olszewska, A. Falkenstein, C. Schwab, M. Szymczak, M. Zajusz, M. Moździerz, A. Mikuła, K. Zielińska, K. Berent, T. Czeppe, M. Martin, K. Świerczek, J. Mater. Chem. A, 2020, 8, 24455-24468.
[14]	C. Riley, A. De La Riva, J. E. Park, S. J. Percival, A. Benavidez, E. N. Coker, R. E. Aidun, E. A. Paisley, A. Datye, S. S. Chou, ACS Appl. Mater. Interfaces, 2021, 13, 8120-8128.
[15]	D. Bokov, A. Turki Jalil, S. Chupradit, W. Suksatan, M. Javed Ansari, I. H. Shewael, G. H. Valiev, E. Kianfar, Adv. Mater. Sci. Eng., 2021, 2021, 5102014.
[16]	N. Shibasaki-Kitakawa, H. Honda, H. Kuribayashi, T. Toda, T. Fukumura, T. Yonemoto, Bioresour. Technol., 2007, 98, 416-421.
[17]	B. Uysal, B. S. Oksal, Res. Chem. Intermed., 2015, 41, 3893-3911.
[18]	P. D. Kent, J. E. Mondloch R. G. Finke, J. Am. Chem. Soc., 2014, 136, 1930-1941.
[19]	J. M. Planeix, N. Coustel B,. Coq V,. Brotons P. S., Kumbhar R,. Dutartre P,. Geneste P,. Bernier P. M. Ajayan, J. Am. Chem. Soc., 1994, 116, 7935-7936.
[20]	L. E. Oi, M.-Y. Choo H. V., Lee H. C., Ong S. B. A., Hamid J. C. Juan, RSC Adv., 2016, 6, 108741-108754.
[21]	V. Subramanian, E. E. Wolf, P. V. Kamat, J. Am. Chem. Soc., 2004, 126, 4943-4950.
[22]	A. S. Konopatsky, D. V. Leybo K. L., Firestein I. V., Chepkasov Z. I., Popov E. S., Permyakova I. N., Volkov A. M., Kovalskii A. T., Matveev D. V., Shtansky D. V. Golberg, ChemCatChem, 2020, 12, 1691-1698.
[23]	A. S. Konopatsky, K. L. Firestein D. V., Leybo E. V., Sukhanova Z. I., Popov X,. Fang A. M., Manakhov A. M., Kovalskii A. T., Matveev D. V., Shtansky D. V. Golberg, Catal. Sci. Technol., 2019, 9, 6460-6470.
[24]	L. Óvári, A. P. Farkas, K. Palotás, G. Vári, I. Szenti, A. Berkó, J. Kiss, Z. Kónya, Surf. Sci. Rep., 2024, 79, 100637.
[25]	D. V. Shtansky, A. T. Matveev E. S., Permyakova D. V., Leybo A. S., Konopatsky P. B. Sorokin, Nanomaterials, 2022, 12, 2810.
[26]	A. M. Kovalskii, I. N. Volkov N. D., Evdokimenko O. P., Tkachenko D. V., Leybo I. V., Chepkasov Z. I., Popov A. T., Matveev A,. Manakhov E. S., Permyakova A. S., Konopatsky A. L., Kustov D. V., Golberg D. V. Shtansky, Appl. Catal. B, 2022, 303, 120891.
[27]	Z. Cao J,. Bu Z,. Zhong C,. Sun Q,. Zhang J,. Wang S,. Chen X. Xie, Appl. Catal. A, 2019, 578, 105-115.
[28]	A. S. Konopatsky, K. L. Firestein, N. D. Evdokimenko, A. L. Kustov, V. S. Baidyshev, I. V. Chepkasov, Z. I. Popov, A. T. Matveev, I. V. Shetinin, D. V. Leybo, I. N. Volkov, A. M. Kovalskii, D. Golberg, D. V. Shtansky, J. Catal., 2021, 402, 130-142.
[29]	T. R. Paul, I. V. Belova G. E. Murch, Mater. Chem. Phys., 2018, 210, 301-308.
[30]	R. Wang, Y. Tang, S. Li, Y. Ai, Y. Li, B. Xiao, L.-A. Zhu, X. Liu, S. Bai, J. Alloys Compd., 2020, 825, 154099.
[31]	S. Hou X,. Ma Y,. Shu J,. Bao Q,. Zhang M,. Chen P,. Zhang S. Dai, Nat. Commun., 2021, 12, 5917.
[32]	M. Zhang, Y. Gao, C. Xie, X. Duan, X. Lu, K. Luo, J. Ye, X. Wang, X. Gao, Q. Niu, P. Zhang, S. Dai, Nat. Commun., 2024, 15, 8306.
[33]	M. B. S,. Felgueiras M. F. R., Pereira O. S. G. P. Soares, Catal. Today, 2024, 441, 114900.
[34]	B. Zhao, Y. Liu, Z. Zhu, H. Guo, X. Ma, J. CO₂ Util., 2018, 24, 34-39.
[35]	W. Zhang, D. Li, C. Liu, Z. Jiang, C. Gao, L. Shen, Q. Liu, R. Qiu, H. Gu, C. Lian, J. Xu, M. Zhu, Chem Catal., 2024, 4, 101113.
[36]	R. Ye L,. Ma J,. Mao X,. Wang X,. Hong A,. Gallo Y,. Ma W,. Luo B,. Wang R,. Zhang M. S., Duyar Z,. Jiang J. Liu, Nat. Commun., 2024, 15, 2159.
[37]	W. Kohn, L. J. Sham, Phys. Rev., 1965, 140, A1133-A1138.
[38]	P. Hohenberg, W. Kohn, Phys. Rev., 1964, 136, B864-B871.
[39]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[40]	G. Kresse, J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[41]	G. Kresse, J. Hafner, Phys. Rev. B, 1994, 49, 14251-14269.
[42]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[43]	J. P. Perdew, K. Burke M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[44]	H. J. Monkhorst, J. D. Pack, Phys. Rev. B, 1976, 13, 5188-5192.
[45]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 2010, 132, 154104.
[46]	D. Lai L,. Ling M,. Su Q,. Kang F,. Gao Q. Lu, Chem. Sci., 2023, 14, 1787-1796.
[47]	H. C. Wu, Y. C. Chang J. H., Wu J. H., Lin I. K., Lin C. S. Chen, Catal. Sci. Technol., 2015, 5, 4154-4163.
[48]	A. S. Konopatsky, V. V. Kalinina A. S., Savchenko D. V., Leybo E. V., Sukhanova V. S., Baidyshev Z. I., Popov A. V., Bondarev J,. Polčák D. V. Shtansky, Nano Res., 2023, 16, 1473-1481.
[49]	C. Molinet-Chinaglia, S. Shafiq, P. Serp, ChemCatChem, 2024, 16, e202401213.
[50]	C. Scarfiello, K. Soulantica, S. Cayez, A. Durupt, G. Viau, N. Le Breton, A. K. Boudalis, F. Meunier, G. Clet, M. Barreau, D. Salusso, S. Zafeiratos, D. P. Minh, P. Serp, J. Catal., 2023, 428, 115202.
[51]	L. H. Vieira, A. H. M. da Silva C. S., Santana E. M., Assaf J. M., Assaf J. F. Gomes, ChemCatChem, 2024, 16, e202301390.
[52]	J. Liu B,. Li J,. Cao C,. Song X,. Guo J. CO₂ Util., 2022, 65, 102243.
[53]	K. Jiang, X. Zhou, Y. Gao, T. Yang, M. Zhang, Z. Xu, Z. Liu, Fuel, 2025, 397, 135413.
[54]	Y. Zhang, S. Zhan, K. Liu, M. Qiao, N. Liu, R. Qin, L. Xiao, P. You, W. Jing, N. Zheng, Angew. Chem. Int. Ed., 2023, 62, e202217191.
[55]	H. L. Huynh, J. Zhu, G. Zhang, Y. Shen, W. M. Tucho, Y. Ding, Z. Yu, J. Catal., 2020, 392, 266-277.
[56]	A. Taniguchi, T. Fujita, K. Kobiro, Dalton Trans., 2024, 53, 8124-8134.
[57]	M. Rahmati, M.-S. Safdari, T. H. Fletcher, M. D. Argyle, C. H. Bartholomew, Chem. Rev., 2020, 120, 4455-4533.

高熵氧化物(CrMnFeCoNi)₃O₄催化剂在二氧化碳加氢反应中是否需要载体来提高性能?

Does high-entropy oxide (CrMnFeCoNi)₃O₄ catalyst require support to improve performance in CO₂ hydrogenation?

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