A New Robust Ce-Ga/H-ZSM-5 Catalyst for Enhanced Selective Catalytic Reduction of Nitric Oxide by Methane

doi:10.1007/s40242-026-5264-4

Abstract

Abstract: A new robust Ce-Ga/H-ZSM-5 zeolite catalyst was developed and applied to the selective catalytic reduction of nitric oxide by methane (CH₄-SCR). By accurately regulating the modified conditions including organic acid auxiliaries (citric acid, glutamic acid and salicylic acid) and pre-treating temperatures of H₂ and O₂ prior to the experiments, good-dispersion Ce-Ga/H-ZSM-5 catalyst was acquired, which showed a perfect NO conversion to N₂ of ca. 95% at 550 ℃ under severe conditions. Strong interaction and cooperative effect between Ce and Ga were verified by means of physical-chemical characterizations. According to the results of diffuse reflectance infrared Fourier-transform spectroscopy, the surface intermediate species, such as CO, CN/NCO, N₂O and NO⁺ were investigated and discussed to understand the mechanism in-depth. As a result, the CH₄-SCR reaction over the as-prepared Ce-Ga/H-ZSM-5 catalyst seems to be viewed as a combination of NO reduction by CO and conventional CH₄-SCR process.

Key words: CH₄-SCR, Ce-Ga/H-ZSM-5, Organic acid, Reductive oxidation, Reaction mechanism

YANG Jun, CHANG Yupeng, WU Guangjun, LI Landong. A New Robust Ce-Ga/H-ZSM-5 Catalyst for Enhanced Selective Catalytic Reduction of Nitric Oxide by Methane[J]. Chemical Research in Chinese Universities, 2026, 42(1): 94-104.

References

[1] Han J. F., Li D., Yu J. H., Chem. Soc. Rev., 2025, 54, 7933.
[2] Wang J. H., Zhao Q., Tan M. J., Qu D., Chen B. B., Shi C., Appl. Catal. B: Environ., 2025, 367, 125107.
[3] Wang R. H., Hao Z. Z., Huang X., Peng Y., Liu G. Q., Xia Y. G., Zhan S. H., Appl. Catal. B: Environ., 2023, 339, 123098.
[4] Lim J., Shin J., Ahn N., Heo I., Hong S., Appl. Catal. B: Environ., 2020, 267, 118710.
[5] Shi Y., Pu J. L., Gao L. W., Shan S. D., Chem. Eng. J., 2021, 403, 126394.
[6] Charrad R., Solt H., Domján A., Ayari F., Mhamdi M., Valyon J., Lónyi F., J. Catal., 2020, 385, 87.
[7] Yang J., Chang Y. P., Dai W. L., Wu G. J., Guan N. J., Li L. D., Chinese J. Catal., 2018, 39, 1004.
[8] Yang J., Chang Y. P., Dai W. L., Wu G. J., Guan N. J., Li L. D., Appl. Catal. B: Environ., 2018, 236, 404.
[9] Yang J., Chang Y. P., Dai W. L., Wu G. J., Guan N. J., Li L. D., Catal. Sci. Technol., 2020, 10, 6025.
[10] Zhao J. H., Zhang G. G., He J. S., Wen Z. Z., Li Z., Gu T. K., Ding R., Zhu Y. J., Zhu R. S., Chemosphere, 2020, 252, 126458.
[11] Pan H., Jian Y. F., Yu Y. K., Chen N. N., He C., He C., Appl. Surf. Sci., 2016, 390, 608.
[12] Tabata T., Kokitsu M. D., Okada O., Appl. Catal. B: Environ., 1995, 6, 225.
[13] Sun T., Fokema M. D., Ying J. Y., Catal. Today, 1997, 33, 251.
[14] Sowade T., Schmidt C., Schütze F., Berndt H., Grünert W., J. Catal., 2003, 214, 100.
[15] Armor J., Catal. Today, 1996, 31, 191.
[16] Lónyi F., E. Solt H., Pászti Z., Valyon J., Appl. Catal. B: Environ., 2014, 150/151, 218.
[17] Montanari T., Marie O., Daturi M., Busca G., Appl. Catal. B: Environ., 2007, 71, 216.
[18] Kikuchi E., Ogura M., Aratani N., Sugiura Y., Hiromoto S., Yogo K., Catal. Today, 1996, 27, 35.
[19] Li Z. J., Flytzani-Stephanopoulos M., Appl. Catal. A: Gen., 1997, 165, 15.
[20] Cant N., Liu I., Catal. Today, 2000, 63, 133.
[21] Hadjiivanov K., Tsyntsarski B., Ivanova E., Klissurski D., Marinova T., Surf. Interface Anal., 2001, 32, 205.
[22] Gil B., Janas J., Włoch E., Olejniczak Z., Datka J., Sulikowski B., Catal. Today, 2008,137, 174.
[23] Ferreira A., Capela S., Costa P., Henriques C., Ribeiro M., Ribeiro F., Catal. Today, 2007,119, 156.
[24] Mendes A., Zholobenko V., Thibault-Starzyk F., Costa P., Henriques C., Appl. Catal. B: Environ., 2016, 195, 121.
[25] Costilla I., Sanchez M., Volpe M., Gigola C., Catal. Today, 2011, 172, 84.
[26] Gutierrez L., Boix A., Decolatti H., Solt H., Lónyi F., Miró E., Micropor. Mesopor. Mater., 2012,163, 307.
[27] Fokema M., Ying J., J. Catal., 2000, 192, 54.
[28] Wu J., Qiao L. Y., Zhou Z. F., Cui G. J., Zong S. S., Xu D. J., Ye R. P., Chen R. P., Si R., Yao Y. G., ACS Catal., 2019, 9, 932.
[29] Nowak I., Quartararo J., Derouane E., Védrine J., Appl. Catal. A: Gen., 2003, 251, 107.
[30] Melo L., Díaz Y., Mediavilla M., Albornoz A., Brito J., Catal. Lett., 2004, 97, 105.
[31] Mediavilla M., Melo L., Díaz Y., Brito J., Albornoz A., Solano R., Micropor. Mesopor. Mat., 2007, 102, 86.
[32] Shpiro E., Shevchenko D., Tkachenko O., Dmitriev R., Appl. Catal. A: Gen., 1994, 107, 147.
[33] Bi J., Liu M., Song C., Wang X., Guo X., Appl. Catal B: Environ., 2011, 107, 68.
[34] Bin F., Wei X. L., Li B., K. Hui., Appl. Catal. B: Environ., 2015, 162, 282.
[35] Rane N., Kersbulck M., Santen R., Hensen E., Micropor. Mesopor. Mat., 2008, 110, 279.
[36] Xiao H., Zhang J. F., Wang X. X., Zhang Q. D., Xie H. J., Han Y. Z., Tan Y. S., Catal. Sci. Technol., 2015, 5, 4081.
[37] Carja G., Delahay G., Signorile C., Coq B., Chem. Commun., 2004, 12, 1404.
[38] Qi G., Li W., Catal. Today, 2015, 258, 205.
[39] Kikuchi E., Yogo K., Catal. Today, 1994, 22, 73.
[40] Gassan-Zade G., Mukherjee T., Alkhazov T., React. Kinet. Catal. Lett., 1979,12, 525.
[41] Penkova A., Hadjiivanov K., Mihaylov M., Daturi M., Saussey J., Lavalley J., Langmuir, 2004, 20, 5425.
[42] Henriques C., Marie O., Thibault-Starzyk F., Lavalley J., Micropor. Mesopor. Mat., 2001, 50, 167.
[43] Hadjiivanov K., Saussey J., Freysz J., Lavalley J., Catal. Lett., 1998, 52, 103.
[44] Zhang R. D., Teoh W., Amal R., Chen B., Kaliaguine S., J. Catal., 2010, 272, 210.
[45] Baidya T., Bera P., Mukri B., Parida S., Kröcher O., Elsener M., Hegde M., J. Catal., 2013, 303, 117.
[46] Makeeva A., Peskova N., Yanagihara H., Appl. Catal. B: Environ., 2012,119/120, 273.
[47] Maunula T., Ahola J., Hamada H., Appl. Catal. B: Environ., 2000, 26, 173.
[48] Maunula T., Ahola J., Hamada H., Appl. Catal. B: Environ., 2006, 64, 13.
[49] Lobree L., Aylor A., Reimer J., J. Catal., 1997, 169, 188.
[50] Shen Q., Li L. D., He C., Tian H., Hao Z. P., Xu Z. P., Appl. Catal. B: Environ., 2009, 91, 262.
[51] Beniya A., Higash S., Nat. Catal., 2019, 2, 590.
[52] Wang Y., Zhu A. M., Zhang Y. Z., Au C. T., Yang X. F., Shi C., Appl. Catal. B: Environ., 2008, 81, 141.
[53] Ilieva L., Pantaleo G., Nedyalkova R., Sobczak J., Lisowski W., Kantcheva M., Venezia A., Andreeva D., Appl. Catal. B: Environ., 2009, 90, 286.
[54] Cheng X. X., Zhang X. Y., Su D. X., Wang Z. Q., Chang J. C., Ma C. Y., Appl. Catal. B: Environ., 2018, 239, 485.
[55] Wang Y. X., Kapteijn F., Makkee M., Appl. Catal. B: Environ., 2018, 231, 200.