Ultra-low doping 0.1(PtMnFeCoNi)/TiO2 catalysts: Modulating the electronic states of active metal sites to enhance CO oxidation through high entropy strategy

doi:10.1016/S1872-2067(25)64770-X

Abstract

Abstract:

The catalyst cost is a key factor limiting the CO purification of sintering flue gas. Here, an ultra-low-loading high-entropy catalyst was prepared by simple calcination process. By anchoring multiple active metal sites in the stable anatase TiO₂ phase, it shows efficient CO catalytic oxidation activity. The metal components (Pt, Mn, Fe, Co, Ni) were uniformly dispersed on the surface of TiO₂ in the form of high-entropy compounds and undergo strong metal and support interaction with TiO₂. The results showed that 0.1(PtMnFeCoNi)/TiO₂ achieved complete oxidation of CO at 230 °C, and its catalytic oxidation ability was significantly better than that of the corresponding monometallic and bimetallic catalysts. The high-entropy component adjusts the electronic environment between the TiO₂ support and the metal to promote the reduction of the Ti₃_d band gap, enhances the electron-induced ability of the catalytic system to gas molecules (CO and O₂), and exhibits excellent resistance to SO₂ and H₂O. The work is of great significance to understand the synergistic regulation of catalyst activity by multiple metal at the atomic level and provides a strategy for effectively reducing the content of precious metals in the catalyst.

Key words: High-entropy catalysts, Ultra-low doping, CO oxidation, Sintering flue gas, Strong metal and support interaction

Yongqi Zhao, Junjie Jiang, Yang Zou, Pu Wang, Xue Li, Xiaolong Liu, Tingyu Zhu. Ultra-low doping 0.1(PtMnFeCoNi)/TiO₂ catalysts: Modulating the electronic states of active metal sites to enhance CO oxidation through high entropy strategy[J]. Chinese Journal of Catalysis, 2025, 76: 173-184.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64770-X

https://www.cjcatal.com/EN/Y2025/V76/I9/173

Figures/Tables 8

Fig. 1. (a) Synthesis process of high-entropy 0.1(PtMnFeCoNi)/TiO2 catalyst. TEM (b) and HRTEM (c) images, SEAD (d) and elemental mapping (e-k) of 0.1(PtMnFeCoNi)/TiO2 catalyst.

Fig. 2. H2-TPR (a), O2-TPD (b), CO-TPR (c), and CO-TPD (d) profiles of the 0.1Pt/TiO2, 0.1(PtM)/TiO2, and 0.1(PtMnFeCoNi)/TiO2 catalysts.

Fig. 3. Ti 2p XPS analysis of the 0.1Pt/TiO2, 0.1(PtM)/TiO2 and 0.1(PtMnFeCoNi)/TiO2 catalyst.

Fig. 4. O 1s XPS analysis of the 0.1Pt/TiO2 (a), 0.1(PtM)/TiO2 (b-e) and 0.1(PtMnFeCoNi)/TiO2 (f) catalyst.

Fig. 5. Pt 4f XPS spectrum analysis of the 0.1Pt/TiO2 (a), 0.1(PtM)/TiO2 (b-e) and 0.1(PtMnFeCoNi)/TiO2 (f) catalyst.

Fig. 6. CO oxidation performance and stability of the catalysts, 0.1Pt/TiO2, 0.1(PtM)/TiO2 and 0.1(PtMnFeCoNi)/TiO2 (a), 0.1(Pt1M4)/TiO2 (b), the stability evaluation (c) at 60000 h-1 and 230 °C.

Fig. 7. In-situ DRIFTs spectra of 0.1Pt/TiO2 and 0.1(PtMnFeCoNi)/TiO2 catalysts. (a,d) Instantaneous changes of 1% CO adsorption for 30 min at 250 °C. (b,e) Instantaneous changes of 1% CO + 16% O2 adsorption for 30 min at 250 °C. (c,f) Changes of CO + O2 surface reaction with temperature.

Fig. 8. Optimized structure and corresponding charge density differences of CO and O2 adsorbed on 0.1Pt/TiO2 (a-d) and 0.1(PtMnFeCoNi)/TiO2 (e-h). (i,j) PDOS profiles of 0.1Pt/TiO2 and 0.1(PtMnFeCoNi)/TiO2.

References

[1]	T. Zhu, X. Liu, X. Wang, H. He, Engineering, 2023, 31, 37-49.
[2]	L. Baharudin, A. C. K. Yip, V. B. Golovko, M. I. J. Polson, K.-F. Aguey-Zinsou, M. J. Watson, Appl. Catal. B, 2020, 262, 118265.
[3]	Z. Shen, X. Xing, S. Wang, Z. Zheng, M. Lv, Catal. Today, 2023, 423, 113988.
[4]	C. Tesvara, M. R. Yousuf, M. Albrahim, D. Troya, A. Shrotri, E. Stavitski, A. M. Karim, P. Sautet, ACS Catal., 2024, 14, 7562-7575.
[5]	T. Zhang, P. Zheng, J. Gao, X. Liu, Y. Ji, J. Tian, Y. Zou, Z. Sun, Q. Hu, G. Chen, W. Chen, X. Liu, Z. Zhong, G. Xu, T. Zhu, F. Su, Nat. Commun., 2024, 15, 6827.
[6]	X. Liu, Y. Zou, X. Li, T. Xu, W. Cen, B. Li, T. Zhu, ACS Catal., 2023, 13, 14580-14597.
[7]	J. Wen, J. Chen, R. Nie, Z. Li, W. Zhang, J. Cao, P. Xie, Q. Zhang, P. Ning, J. Hao, Environ. Sci. Technol., 2025, 59, 2295-2305.
[8]	L. Zhong, T. Kropp, W. Baaziz, O. Ersen, D. Teschner, R. Schlögl, M. Mavrikakis, S. Zafeiratos, ACS Catal., 2019, 9, 8325-8336.
[9]	Y. Li, L. Guo, M. Du, C. Tian, G. Zhao, Z. Liu, Z. Liang, K. Hou, J. Chen, X. Liu, L. Jiang, B. Nan, L. Li, Nat. Commun., 2024, 15, 5598.
[10]	X. Zhou, S. Fang, T. Zhang, Z. Wu, J. Li, W. Wang, J. Zhu, J. Wu, D. Ye, R. Han, Q. Liu, S. Yao, E. Gao, D. Wu, Sep. Purif. Technol., 2025, 354, 129330.
[11]	W. Yuan, B. Zhu, K. Fang, X.-Y. Li, T. W. Hansen, Y. Ou, H. Yang, J. B. Wagner, Y. Gao, Y. Wang, Z. Zhang, Science, 2021, 371, 517-521.
[12]	X. Li, Y. Zou, Y. Zhao, X. Liu, T. Zhu, Sci. China Technol. Sci., 2025, 68, 1310501.
[13]	T. Ghosh, J. M. Arce-Ramos, W.-Q. Li, H. Yan, S. W. Chee, A. Genest, U. Mirsaidov, Nat. Commun., 2022, 13, 6176.
[14]	Y. Li, T. Qin, Y. Wei, J. Xiong, P. Zhang, K. Lai, H. Chi, X. Liu, L. Chen, X. Yu, Z. Zhao, L. Li, J. Liu, Nat. Commun., 2023, 14, 7149.
[15]	C. Chen, J.-L. Chen, L. Feng, J. Hu, X. Chai, J.-X. Liu, W.-X. Li, ACS Catal., 2024, 14, 3504-3513.
[16]	J. Saavedra, H. A. Doan, C. J. Pursell, L. C. Grabow, B. D. Chandler, Science, 2014, 345, 1599-1602.
[17]	Q. Wang, J. Gong, H. Zhang, Q.-Y. Fan, L. Xue, J. Wu, J. Li, Y. Wang, Z. Liu, R. Gao, S. Zeng, Appl. Catal. B, 2022, 306, 121117.
[18]	Z. Zhang, J. Tian, Y. Lu, S. Yang, D. Jiang, W. Huang, Y. Li, J. Hong, A. S. Hoffman, S. R. Bare, M. H. Engelhard, A. K. Datye, Y. Wang, Nat. Commun., 2023, 14, 2664.
[19]	J. Chen, Y. Su, Q. Meng, H. Qian, L. Shi, J. A. Darr, Z. Wu, X. Weng, Angew. Chem. Int. Ed., 2023, 62, e202310191.
[20]	Y. Zhou, D. E. Doronkin, M. Chen, S. Wei, J.-D. Grunwaldt, ACS Catal., 2016, 6, 7799-7809.
[21]	P. Zhao, Q. Cao, W. Yi, X. Hao, J. Li, B. Zhang, L. Huang, Y. Huang, Y. Jiang, B. Xu, Z. Shan, J. Chen, ACS Nano, 2022, 16, 14017-14028.
[22]	Y. Yao, Z. Huang, P. Xie, S. D. Lacey, R. J. Jacob, H. Xie, F. Chen, A. Nie, T. Pu, M. Rehwoldt, D. Yu, M. R. Zachariah, C. Wang, R. Shahbazian-Yassar, J. Li, L. Hu, Science, 2018, 359, 1489-1494.
[23]	X.-C. Liu, G. Wu, X. Han, Y. Wang, B. Wu, G. Wang, Y. Mu, X. Hong, Adv. Mater., 2025, 37, 2416749.
[24]	X. Lei, Q. Tang, Y. Zheng, P. Kidkhunthod, X. Zhou, B. Ji, Y. Tang, Nat. Sustain., 2023, 6, 816-826.
[25]	C. Zhan, Y. Xu, L. Bu, H. Zhu, Y. Feng, T. Yang, Y. Zhang, Z. Yang, B. Huang, Q. Shao, X. Huang, Nat. Commun., 2021, 12, 6261.
[26]	X. Xu, H. Yang, R. Tu, S. Liu, J. Hu, Y. Li, Y. Sun, Appl. Catal. B, 2024, 342, 123358.
[27]	S. Dhakar, A. Sharma, N. K. Katiyar, A. Parui, R. Das, A. K. Singh, C. S. Tiwary, S. Sharma, K. Biswas, Mater. Today Energy, 2023, 37, 101386.
[28]	Y. Wang, J. Mi, Z.-S. Wu, Chem Catal., 2022, 2, 1624-1656.
[29]	Y. Qiu, L. Xin, Y. Li, I. T. McCrum, F. Guo, T. Ma, Y. Ren, Q. Liu, L. Zhou, S. Gu, M. J. Janik, W. Li, J. Am. Chem. Soc., 2018, 140, 16580-16588.
[30]	K. Gómez-Villegas, J. C. Martínez-Fuentes, I. Martínez-López, E. Guillén-Bas, I. Martín-García, D. Lozano-Castelló, A. Bueno-López, A. Davó-Quiñonero, Int. J. Hydrogen Energy, 2025, 106, 1220-1232.
[31]	X. Tian, J. Mi, Z. Qian, L. Gan, H. Huang, J. Chen, J. Li, Appl. Catal. B, 2025, 367, 125115.
[32]	M. P. Salinas-Quezada, J. K. Pedersen, P. Sebastián-Pascual, I. Chorkendorff, K. Biswas, J. Rossmeisl, M. Escudero-Escribano, EES Catal., 2024, 2, 941-952.
[33]	J. K. Pedersen, T. A. A. Batchelor, A. Bagger, J. Rossmeisl, ACS Catal., 2020, 10, 2169-2176.
[34]	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.
[35]	D. G. Araiza, C. A. Celaya, D. A. Solís-Casados, J. Muñiz, R. Zanella, Chem. Eng. J., 2024, 494, 152921.
[36]	X. Zhang, Q. Yao, H. Wu, Y. Zhou, M. Zhu, Z.-H. Lu, Appl. Catal. B, 2023, 339, 123153.
[37]	X. Zhao, K. Gao, S. Xue, W. Ran, R. Liu, Chin. Chem. Lett., 2025, 36, 110309.
[38]	M. Mao, H. Lv, Y. Li, Y. Yang, M. Zeng, N. Li, X. Zhao, ACS Catal., 2016, 6, 418-427.
[39]	Z. Li, Z. Liu, G. Gao, W. Zhao, Y. Jiang, X. Tang, S. Dai, Z. Qu, N. Yan, L. Ma, Environ. Sci. Technol., 2024, 58, 12201-12211.
[40]	K. He, Surf. Sci., 2023, 734, 122315.
[41]	Q. Liu, P. Yang, W. Tan, H. Yu, J. Ji, C. Wu, Y. Cai, S. Xie, F. Liu, S. Hong, K. Ma, F. Gao, L. Dong, Chem. Eur. J., 2023, 29, e202203432.
[42]	W. Wan, J. Geiger, N. Berdunov, M. Lopez Luna, S. W. Chee, N. Daelman, N. López, S. Shaikhutdinov, B. Roldan Cuenya, Angew. Chem. Int. Ed., 2022, 61, e202112640.
[43]	X. Cha, J. He, Y. Fu, B. Jiang, S. Ali, S. Chen, G. Zhan, Chem. Eng. J., 2024, 501, 157643.
[44]	W. T. Figueiredo, R. Prakash, C. G. Vieira, D. S. Lima, V. E. Carvalho, E. A. Soares, S. Buchner, H. Raschke, O. W. Perez-Lopez, D. L. Baptista, R. Hergenröder, M. Segala, F. Bernardi, Appl. Surf. Sci., 2022, 574, 151647.
[45]	D. Wu, Y. Kang, F. Wang, J. Yang, Y. Xu, Y. Zhuang, J. Wu, J. Zeng, Y. Yang, J. Zhao, Adv. Energy Mater., 2023, 13, 2301145.
[46]	D. Wu, K. Kusada, Y. Nanba, M. Koyama, T. Yamamoto, T. Toriyama, S. Matsumura, O. Seo, I. Gueye, J. Kim, L. S. Rosantha Kumara, O. Sakata, S. Kawaguchi, Y. Kubota, H. Kitagawa, J. Am. Chem. Soc., 2022, 144, 3365-3369.
[47]	J. Li, T. Cai, Y. Feng, X. Liu, N. Wang, Q. Sun, Sci. China Chem., 2024, 67, 2911-2917.
[48]	L. Wang, H. Peng, S.-L. Shi, Z. Hu, B.-Z. Zhang, S.-M. Ding, S.-H. Wang, C. Chen, Appl. Surf. Sci., 2022, 573, 151611.
[49]	Y. Liu, K. Hou, Z. Guo, Y. Guo, Y. Jiang, X. Wu, Z. Fu, H. Zhang, P. Li, S. Zeng, Chem. Eng. J., 2025, 504, 158672.
[50]	P. Zhang, T. Qin, D. Li, X. Wu, Y. Ma, H. Guo, J. Xiong, X. Liu, Z. Zhao, L. Chen, J. Liu, Y. Wei, Appl. Catal. B, 2025, 361, 124674.
[51]	Y. Li, T. Qin, L. Xu, Y. Ma, H. Guo, J. Xiong, P. Zhang, Z. Zhao, X. Liu, Y. Liu, J. Zou, L. Chen, Y. Wei, Environ. Sci. Technol., 2025, 59, 2327-2338.
[52]	D. Lv, J. Liu, G. Zhang, Y. Wang, Y. Zhao, G. Li, Chem. Eng. J., 2024, 481, 148534.
[53]	C. Tang, Q. Huang, Z. Wang, Y. Sun, J. Ding, F. Wang, W. Huang, X. Wen, Z. Zhang, ACS Catal., 2025, 15, 2630-2641.
[54]	T. Zhang, J. Xu, Y. Sun, S. Fang, Z. Wu, E. Gao, J. Zhu, W. Wang, L. Dai, W. Liu, B. Zhang, J. Zhang, S. Yao, J. Li, Mol. Catal., 2023, 547, 113361.
[55]	Z. Zhang, L. Fan, W. Liao, F. Zhao, C. Tang, J. Zhang, M. Feng, J.-Q. Lu, J. Catal., 2022, 405, 333-345.
[56]	A. Beniya, S. Higashi, N. Ohba, R. Jinnouchi, H. Hirata, Y. Watanabe, Nat. Commun., 2020, 11, 1888.
[57]	A. Tripathi, Y. Kawazoe, R. Thapa, Mol. Catal., 2023, 535, 112885.
[58]	Y. Lv, P. Liu, R. Xue, Q. Guo, J. Ye, D. Gao, G. Jiang, S. Zhao, L. Xie, Y. Ren, P. Zhang, Y. Wang, Y. Qin, Adv. Sci., 2024, 11, 2309813.
[59]	T. Takeguchi, T. Yamanaka, K. Asakura, E. N. Muhamad, K. Uosaki, W. Ueda, J. Am. Chem. Soc., 2012, 134, 14508-14512.
[60]	T. Saelee, S. Boonchuay, A. Sriwattana, M. Rittiruam, P. Khajondetchairit, S. Praserthdam, A. Ektarawong, B. Alling, P. Praserthdam, Appl. Surf. Sci., 2023, 623, 157023.
[61]	S. Park, S. Woo, J. Kim, J. Lee, H. Lee, K.-M. Kim, J. Ahn, H.-T. Kim, Y. J. Kim, J. Kim, I.-D. Kim, S.-J. Kim, Chem. Eng. J., 2024, 493, 152551.
[62]	T. M. Nyathi, M. I. Fadlalla, N. Fischer, A. P. E. York, E. J. Olivier, E. K. Gibson, P. P. Wells, M. Claeys, Catal. Sci. Technol., 2023, 13, 2038-2052.

Ultra-low doping 0.1(PtMnFeCoNi)/TiO₂ catalysts: Modulating the electronic states of active metal sites to enhance CO oxidation through high entropy strategy

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