基于活性组分微化学状态调控的高性能Rh/CeO2-ZrO2-Al2O3催化剂构筑及三效催化性能

doi:10.3866/PKU.WHXB202302041

Abstract

Abstract:

With the increasing number of automobile vehicles, the exhaust emitted poses a severe menace to the environment and human health, necessitating the purification of exhaust pollutants. Meanwhile, the high price of noble metals and their limited supply require a decrease in noble metal loading to reduce the costs of three-way catalysts (TWCs). Therefore, improving the utilization efficiency of noble metals and their catalytic behavior is critical for the development of next-generation TWCs with low noble metal loading. Herein, the Rh micro-chemical state was modulated using the liquid-phase reduction method combined with atmospheric heat treatment to enhance the catalytic behavior of Rh-based catalysts with low Rh loading. The catalyst was characterized using X-ray diffraction (XRD), hydrogen temperature programmed reduction (H₂-TPR), CO chemisorption, X-ray photoelectron spectroscopy (XPS), the FTIR spectroscopy of chemisorbed CO (CO-FTIR), transmission electron microscopy (TEM), and in situ diffuse reflectance IR (in-situ DRIFTS) to illustrate the relationship between Rh micro-chemical state (including valence state ratio and dispersion) and catalytic activity. The as-prepared catalyst re-Rh/CeO₂-ZrO₂-Al₂O₃-H₂ (re-Rh/CZA-H₂) exhibited better catalytic activity and a wider air/fuel ratio (λ) operating window with T₉₀ values 30–73 ℃ and 51–86 ℃ lower than those of the catalysts synthesized by liquid-phase reduction and traditional impregnation method, respectively. In addition, aged samples prepared by the combined scheme also exhibited excellent activity and stability, where the T₅₀ and T₉₀ values were lower than the fresh catalyst. Structure-activity relationship results demonstrated that the better catalytic activity of re-Rh/CZA-H₂ could be attributed to the optimal valence state ratio and highly dispersed Rh species, which increased the number of effective active sites. The considerable stability was attributed to the stable structure of the CeO₂-ZrO₂-Al₂O₃ (CZA) support, improved dispersion, and the high contents of active Rh species, which exposed more active sites to promote reactant conversion. In addition, the synergistic effect between the metallic Rh and oxygen vacancies could facilitate the anchoring of Rh nanoparticles to inhibit Rh sintering. Therefore, adjusting the micro-chemical state of noble metals by the combinatorial scheme developed herein provides a novel route for improving the catalytic activity, high-temperature stability, and air/fuel operating window of these catalysts.

Key words: Micro-chemical state, Three-way catalyst, Liquid-phase reduction, Valence state ratio, Atmospheric heat treatment

Jialin Mou, Liuling Chen, Jun Fan, Lu Zeng, Xue Jiang, Yi Jiao, Jianli Wang, Yaoqiang Chen. Construction of a Highly Active Rh/CeO₂-ZrO₂-Al₂O₃ Catalyst Based on Rh Micro-Chemical State Regulation and Its Three-Way Catalytic Activity[J]. Acta Phys. -Chim. Sin. 2023, 39(12), 2302041. doi: 10.3866/PKU.WHXB202302041

Figures/Tables 12

References 71

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Sample	CO		NO		C₃H₈		C₃H₆
Sample	T₅₀ (℃)	T₉₀ (℃)	T₅₀ (℃)	T₉₀ (℃)	T₅₀ (℃)	T₉₀ (℃)	T₅₀ (℃)	T₉₀ (℃)
im-Rh/CZA	231	245	253	312	332	390	260	303
re-Rh/CZA	217	229	242	256	297	345	252	267
re-Rh/CZA-H₂	183	194	194	226	262	324	203	227
im-Rh/CZA-a	246	270	270	298	343	433	275	308
re-Rh/CZA-a	215	229	228	249	307	378	236	252
re-Rh/CZA-H₂-a	187	199	197	215	256	305	200	212

Sample	Binding energy (eV)			Rh ratio (%)			Ce ratio (%)	O ratio (%)
Sample	Rh⁰ 3d_5/2	Rh³⁺ 3d_5/2	Rh⁴⁺ 3d_5/2	Rh⁰	Rh³⁺	Rh⁴⁺	Ce³⁺/Ce	O_β/O
Im-Rh/CZA	306.3	308.4	310.2	44.27	11.41	44.87	32.94	35.46
Re-Rh/CZA	306.4	308.5	310.4	48.71	18.26	33.02	33.86	44.70
Re-Rh/CZA-H₂	306.6	308.2	–	68.77	31.23	–	42.29	48.12
Im-Rh/CZA-a	306.2	308.3	310.1	43.91	12.13	43.96	32.13	32.80
Re-Rh/CZA-a	306.2	308.5	310.2	48.22	15.35	36.43	32.61	36.50
Re-Rh/CZA-H₂-a	306.8	308.3	–	64.36	35.64	–	43.31	42.57

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Construction of a Highly Active Rh/CeO₂-ZrO₂-Al₂O₃ Catalyst Based on Rh Micro-Chemical State Regulation and Its Three-Way Catalytic Activity

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Construction of a Highly Active Rh/CeO₂-ZrO₂-Al₂O₃ Catalyst Based on Rh Micro-Chemical State Regulation and Its Three-Way Catalytic Activity