Rational Design of a Perovskite-Type Catalyst for Toluene Oxidation Via Simultaneous Phosphorus Doping and Post-Synthesis Acidic Etching

Abstract

Perovskite oxides are highly promising catalysts for the combustion removal of volatile organic compounds (VOCs) due to their excellent stability, structural flexibility, and compositional versatility. This study presents a novel perovskite oxide that exhibits enhanced catalytic activity and superior durability for toluene combustion at reduced temperatures. This improvement is achieved by phosphorus doping at the B-site of LaCoO_3-δ (LC) perovskite oxide, followed by post-synthesis acid etching for a proper time. The resulting catalyst demonstrates increased specific surface area, higher total pore volume, and enhanced oxygen vacancy concentration both in the bulk and on the surface. Additionally, the activity of surface lattice oxygen species is significantly improved, leading to enhanced catalytic performance in toluene combustion. Notably, the optimized catalyst shows an exceptionally low activation energy (E_a) of 49.3 kJ mol⁻¹, with a T₉₀ reduction of over 214 °C compared to the phosphorus doped LC and 190 °C compared to pristine LC. Phosphorus doping plays a main role in significantly improving the long-term durability, particularly in the presence of CO₂ and H₂O, while acid etching boosts the catalytic activity. This work introduces a rational and innovative strategy for optimizing VOC oxidation by improving the structure and surface chemical states of perovskite catalysts.

Keywords

acidic etching / oxygen species / perovskite oxides / phosphorus doping / toluene oxidation

References

[1] H. Zhang, Z. Wang, L. Wei, Y. Liu, H. Dai, J. Deng, Chin. J. Catal. 2024, 61, 71.

[2] C. Jiang, H. Wang, Y. Wang, C. Xue, Z. Yang, C. Yu, H. Ji, J. Hazard. Mater. 2020, 390, 122182.

[3] Y. Guo, M. Wen, G. Li, T. An, Appl. Catal. B Environ. 2021, 281, 119447.

[4] P. Wu, X. Jin, Y. Qiu, D. Ye, Environ. Sci. Technol. 2021, 55, 4268.

[5] Y. Zheng, Y. Su, C. Pang, L. Yang, C. Song, N. Ji, D. Ma, X. Lu, R. Han, Q. Liu, Environ. Sci. Technol. 1905, 2022, 56.

[6] Y. Yang, W. Si, Y. Peng, Y. Wang, H. Liu, Z. Su, J. Li, Environ. Sci. Technol. 2022, 56, 16249.

[7] J. Yuan, G. Li, X. Liu, Y. Yang, F. Yu, J. Cao, Z. Fei, J. Ma, M. K. Nazeeruddin, P. J. Dyson, Adv. Funct. Mater. 2024, 34, 2401281.

[8] L. Yang, Y. Li, Y. Sun, W. Wang, Z. Shao, Energy Environ. Mater. 2022, 5, 751.

[9] Y. Zheng, K. Fu, Z. Yu, Y. Su, R. Han, Q. Liu, J Mater Chem A 2022, 10, 14171.

[10] Y. Li, S. Liu, K. Yin, D. Jia, Y. Sun, X. Zhang, J. Yan, L. Yang, J. Environ. Chem. Eng. 2023, 11, 109050.

[11] M. Ma, Q. Liu, D. Guo, L. Xia, J. Wang, R. Albilali, C. He, Chem. Eng. J. 2024, 498, 155426.

[12] G. Li, K. He, F. Zhang, G. Jiang, Z. Zhao, Z. Zhang, J. Cheng, Z. Hao, Appl. Catal. B Environ. 2022, 309, 121231.

[13] W. Si, Y. Wang, Y. Peng, J. Li, Angew. Chem. 2015, 127, 8065.

[14] S. Wu, Z. Shi, F. Dong, X. Song, W. Han, W. Han, H. Zhang, X. Dong, Z. Tang, J Mater Chem A 2025, 13, 7539.

[15] J. Yi, J. Liu, B. Gao, L. Bo, L. Cao, M. Sillanpää, J. Environ. Chem. Eng. 2025, 13, 115691.

[16] R. B. Wexler, G. S. Gautam, E. B. Stechel, E. A. Carter, J. Am. Chem. Soc. 2021, 143, 13212.

[17] Z. Zhang, Y. Chen, Z. Dai, S. Tan, D. Chen, Electrochim. Acta 2019, 312, 128.

[18] H. Chen, C. Lim, M. Zhou, Z. He, X. Sun, X. Li, Y. Ye, T. Tan, H. Zhang, C. Yang, J. W. Han, Y. Chen, Adv. Sci. 2021, 8, 2102713.

[19] F. Moradkhani, A. S. Kootenaei, S. Maghsoodi, M. Mirzaei, A. Azimi, Pet. Chem. 2023, 63, 1322.

[20] M. Ma, Y. Chen, Q. Liu, L. Xia, Z. Xie, Y. Yu, J. Xu, C. Chen, C. He, Appl. Catal. B Environ. 2025, 364, 124846.

[21] H. Huang, X. Xie, F. Xiao, B. Liu, T. Zhang, F. Feng, B. Lan, C. Zhang, Environ. Sci. Technol. 2024, 58, 18456.

[22] S. Wang, P. Xiao, J. Yang, S. A. C. Carabineiro, M. Wiśniewski, J. Zhu, X. Liu, Front. Chem. Sci. Eng. 2023, 17, 1649.

[23] Y. Wang, L. Ding, Q. Shi, S. Liu, L. Qian, Z. Yu, H. Wang, J. Lei, Z. Gao, H. Long, C. Charles Xu, Chem. Eng. J. 2022, 448, 137601.

[24] Z. Liu, D. Cheng, Y. Zhu, M. Liang, M. Yang, G. Yang, R. Ran, W. Wang, W. Zhou, Z. Shao, Chem. Eng. J. 2022, 450, 137787.

[25] Z. Liu, Z. Hu, H. Di, M. Yang, G. Yang, W. Wang, R. Ran, W. Zhou, Ceram. Int. 2024, 50, 40409.

[26] J. He, X. Xu, H. Sun, T. Miao, M. Li, S. Zhou, W. Zhou, ACS Appl. Mater. Interfaces 2023, 28, 1122.

[27] Y. Shen, Y. Zhu, J. Sunarso, D. Guan, B. Liu, H. Liu, W. Zhou, Z. Shao, Chem. Eur. J. 2018, 24, 6950.

[28] Z. Li, L. Lv, J. Wang, X. Ao, Y. Ruan, D. Zha, G. Hong, Q. Wu, Y. Lan, C. Wang, J. Jiang, M. Liu, Nano Energy 2018, 47, 199.

[29] Z. Wang, C. Jin, J. Sui, C. Li, R. Yang, Int. J. Hydrog. Energy 2018, 43, 20727.

[30] Y. Luo, Y. Zheng, X. Feng, D. Lin, Q. Qian, X. Wang, Y. Zhang, Q. Chen, X. Zhang, ACS Appl. Mater. Interfaces 2020, 12, 23789.

[31] M. Xu, H. Sun, W. Wang, Y. Shen, W. Zhou, J. Wang, Z.-G. Chen, Z. Shao, J. Mater. Sci. Technol. 2020, 39, 22.

[32] W. Qin, Z. Yuan, Y. Shen, R. Zhang, F. Meng, Chem. Eng. J. 2022, 431, 134280.

[33] B. Wang, Y. Xuan, G. Zhu, Y. Liang, Y. Peng, Q. Chang, T. Luan, D. Wang, J. Li, ACS Appl. Mater. Interfaces 2025, 17, 21168.

[34] Y. Liu, H. Huang, L. Xue, J. Sun, X. Wang, P. Xiong, J. Zhu, Nanoscale 2021, 13, 19840.

[35] Y. Zhu, W. Zhou, J. Yu, Y. Chen, M. Liu, Z. Shao, Chem. Mater. 2016, 28, 1691.

[36] Y. Zhu, W. Zhou, J. Sunarso, Y. Zhong, Z. Shao, Adv. Funct. Mater. 2016, 26, 5862.

[37] C. Shan, Y. Zhang, Q. Zhao, K. Fu, Y. Zheng, R. Han, C. Liu, N. Ji, W. Wang, Q. Liu, Environ. Sci. Technol. 2022, 56, 10381.

[38] K. Chu, W. Zong, G. Xue, H. Guo, J. Qin, H. Zhu, N. Zhang, Z. Tian, H. Dong, Y.-E. Miao, M. B. J. Roeffaers, J. Hofkens, F. Lai, T. Liu, J. Am. Chem. Soc. 2023, 145, 21387.

[39] K. Chu, F. Liu, J. Zhu, H. Fu, H. Zhu, Y. Zhu, Y. Zhang, F. Lai, T. Liu, Adv. Energy Mater. 2021, 11, 2003799.

[40] Z. Su, W. Yang, C. Wang, S. Xiong, X. Cao, Y. Peng, W. Si, Y. Weng, M. Xue, J. Li, Environ. Sci. Technol. 2020, 54, 12684.

[41] Y. Ma, L. Wang, J. Ma, H. Wang, C. Zhang, H. Deng, H. He, ACS Catal. 2021, 11, 6614.

[42] H. Zhang, L. Wu, R. Feng, S. Wang, C.-S. Hsu, Y. Ni, A. Ahmad, C. Zhang, H. Wu, H.-M. Chen, W. Zhang, Y. Li, P. Liu, F. Song, ACS Catal. 2023, 13, 6000.

[43] Q. Huang, P. Zhao, L. Lv, W. Zhang, B. Pan, Environ. Sci. Technol. 2023, 57, 9096.

[44] Y. Yang, W. Si, Y. Peng, J. Chen, Y. Wang, D. Chen, Z. Tian, J. Wang, J. Li, Appl. Catal. B Environ. 2024, 340, 123142.

[45] K. Zha, W. Sun, Z. Huang, H. Xu, W. Shen, ACS Catal. 2020, 10, 12127.

[46] G. Li, N. Li, Y. Sun, Y. Qu, Z. Jiang, Z. Zhao, Z. Zhang, J. Cheng, Z. Hao, Appl. Catal. B Environ. 2021, 282, 119512.

[47] G. Chai, W. Zhang, L. F. Liotta, M. Li, Y. Guo, A. Giroir-Fendler, Appl. Catal. B Environ. 2021, 298, 120606.

[48] M. Wu, S. Chen, W. Xiang, Chem. Eng. J. 2020, 387, 124101.

[49] S. Mo, Q. Zhang, Y. Sun, M. Zhang, J. Li, Q. Ren, M. Fu, J. Wu, L. Chen, D. Ye, J Mater Chem A 2019, 7, 16197.

[50] A. Lu, H. Sun, N. Zhang, L. Che, S. Shan, J. Luo, J. Zheng, L. Yang, D.-L. Peng, C.-J. Zhong, B. Chen, ACS Catal. 2019, 9, 7431.

[51] F. Zasada, J. Janas, W. Piskorz, M. Gorczyńska, Z. Sojka, ACS Catal. 2017, 7, 2853.

[52] X. Mu, H. Ding, W. Pan, Q. Zhou, W. Du, K. Qiu, J. Ma, K. Zhang, J. Environ. Chem. Eng. 2021, 9, 105650.

[53] Y. Liu, L. Yan, W. Gao, S.-R. Zhu, J. Zhan, R. Cao, H. Zhou, Appl. Surf. Sci. 2020, 500, 144043.

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2025 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.