单钯三效催化剂在梯度温度老化下的失活机制

doi:10.15541/jim20250396

无机材料学报 ›› 2026, Vol. 41 ›› Issue (8): 1148-1156.DOI: 10.15541/jim20250396

• 研究快报 • 上一篇

单钯三效催化剂在梯度温度老化下的失活机制

刘栩孜¹(), 宋兆华¹, 曾路¹, 屈丽², 焦毅¹(), 蒋发军³, 李大成³, 严会成⁴, 王健礼², 陈耀强²

¹ 四川大学新能源与低碳技术研究院, 成都 610064
² 四川大学化学学院, 成都 610064
³ 中自环保科技股份有限公司, 成都 611731
⁴ 四川蜀泰化工科技有限公司, 遂宁 629300

收稿日期:2025-10-10 修回日期:2025-12-24 出版日期:2026-08-20 网络出版日期:2026-01-06
通讯作者: 焦毅, 副研究员. E-mail: jiaoyiscu@163.com
作者简介:刘栩孜(2000-), 女, 硕士研究生. E-mail: lxz@stu.scu.edu.cn

Deactivation Mechanism of Pd Only Three-way Catalysts under Aging Temperature Gradient

LIU Xuzi¹(), SONG Zhaohua¹, ZENG Lu¹, QU Li², JIAO Yi¹(), JIANG Fajun³, LI Dacheng³, YAN Huicheng⁴, WANG Jianli², CHEN Yaoqiang²

¹ Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610064, China
² College of Chemistry, Sichuan University, Chengdu 610064, China
³ SINOTECH Company Limited, Chengdu 611731, China
⁴ Sichuan Shutai Chemical Technology Co., Ltd., Suining 629300, China

Received:2025-10-10 Revised:2025-12-24 Published:2026-08-20 Online:2026-01-06
Contact: JIAO Yi, associate professor. E-mail: jiaoyiscu@163.com
About author:LIU Xuzi (2000-), female, Master candidate. E-mail: lxz@stu.scu.edu.cn
Supported by:
Advanced Materials-National Science and Technology Major Project(2024ZD0606500);National Natural Science of China(22472108);Sichuan University-Suining Municipal Government Cooperation Special Fund Project(2023CDSN-02)

摘要/Abstract

摘要：

单Pd/CZA催化剂由第三代储氧材料CeO₂-ZrO₂-Al₂O₃ (CZA)与钯(Pd)构成, 因其优异的污染物转化效率和抗烧结性能, 成为一种更具实用性的汽油车三效催化剂(TWC)。尽管已有研究证实, Pd基TWC的热失活机制与Pd颗粒烧结以及金属-载体相互作用(MSI)减弱密切相关, 但其在极端高温条件下的热老化行为仍缺乏系统研究。本研究通过制备800~1000 ℃老化的Pd/CZA催化剂, 系统分析了其热失活过程, 揭示了Pd微观化学状态随梯度老化温度的演变规律。利用一系列表征手段, 评估了Pd微观化学状态及MSI与抗老化性能的关系。研究发现TWC催化活性随老化温度的升高呈现出非线性衰减的趋势。在850~900 ℃温度区间, 催化剂活性显著下降, 一氧化碳(CO)、一氧化氮(NO)和碳氢化合物(HCs)的T₅₀与T₉₀(污染物转化率达到50%和90%时的温度)分别升高了26~40 ℃和39~67 ℃; 而在900~1000 ℃温度区间, 催化活性变化不大。这种活性急剧下降的本质是Pd的微观化学状态发生了突变, 当老化温度升高至900 ℃时, Pd-O-Ce键变弱, 导致MSI被削弱, Pd颗粒失去对Pd-O-Ce的有效锚定, 发生快速烧结和晶粒生长, 从而明显阻碍反应物和氧气的吸附与活化过程。

关键词: 温度梯度, 热老化, Pd-O-Ce键, 金属-载体相互作用, 三效催化剂

Abstract:

Pd/CZA catalyst composed of third-generation oxygen storage material CeO₂-ZrO₂-Al₂O₃ (CZA) loaded only with Pd represents a practical three-way catalyst (TWC) owing to its exceptional pollutant conversion efficiency and sintering resistance. Although the thermal degradation mechanism of Pd-based TWC has been confirmed to be closely associated with Pd sintering and the weakening of metal-support interaction (MSI), a systematic investigation into its thermal aging behavior under an extreme high-temperature gradient remains necessary. A series of Pd/CZA catalysts aged at 800-1000 ℃ were prepared in this study and their thermal degradation was systematically explored, presenting a pioneering investigation into the evolution pattern of the microchemical state of Pd with aging temperature gradient. The correlation among the microchemical state of Pd, MSI and aging resistance was evaluated through different characterization techniques. The results showed that catalytic activity exhibited a nonlinear decay with increasing aging temperature. Catalytic performance declined sharply in the range of 850-900 ℃, with increases of 26-40 ℃ and 39-67 ℃ for T₅₀ and T₉₀ (the temperatures at which the pollutant conversions are 50% and 90%, respectively) of carbon monoxide (CO), nitric oxide (NO) and hydrocarbons (HCs), while it showed little variation within the range of 900-1000 ℃. The underlying reason for this sharp decline in activity is an abrupt transformation in the microchemical state of Pd. When the aging temperature increases to 900 ℃, the Pd-O-Ce bond is weakened, which compromises the MSI. Consequently, Pd particles become unanchored, undergo rapid sintering and growth, and exhibit diminished capabilities for adsorbing and activating both reactants and oxygen.

Key words: temperature gradient, thermal aging, Pd-O-Ce bond, metal-support interaction, three-way catalyst

中图分类号:

O643

刘栩孜, 宋兆华, 曾路, 屈丽, 焦毅, 蒋发军, 李大成, 严会成, 王健礼, 陈耀强. 单钯三效催化剂在梯度温度老化下的失活机制[J]. 无机材料学报, 2026, 41(8): 1148-1156.

LIU Xuzi, SONG Zhaohua, ZENG Lu, QU Li, JIAO Yi, JIANG Fajun, LI Dacheng, YAN Huicheng, WANG Jianli, CHEN Yaoqiang. Deactivation Mechanism of Pd Only Three-way Catalysts under Aging Temperature Gradient[J]. Journal of Inorganic Materials, 2026, 41(8): 1148-1156.

图/表 10

Fig. 1 (a-d) Light-off curves of (a) CO, (b) NO, (c) propane (C3H8) and (d) propylene (C3H6); (e) Operation windows of the aged catalysts Simulated exhaust gas consisted of 4500 μL/L CO, 1200 μL/L NO, 120 μL/L C3H8, 220 μL/L C3H6, 3130 μL/L O2, 1500 μL/L H2, 110 mL/L CO2, 100 mL/L H2O, and N2 as the balance gas. Operation window was tested at 400 ℃. Colorful figures are available on website

Table 1 T50 and T90 values of CO, NO and HCs of the aged catalysts

Sample	CO		NO		C₃H₈		C₃H₆
Sample	T₅₀/℃	T₉₀/℃	T₅₀/℃	T₉₀/℃	T₅₀/℃	T₉₀/℃	T₅₀/℃	T₉₀/℃
Pd/CZA-800	233	254	252	263	269	297	241	255
Pd/CZA-850	237	256	254	266	271	295	242	256
Pd/CZA-900	263	295	292	310	311	362	275	295
Pd/CZA-950	272	302	298	313	314	353	280	300
Pd/CZA-1000	265	295	298	310	303	324	278	295

Table 2 Textural properties of catalysts

Sample	S_BET/(m²•g^-1)	Pore volume/ (mL•g^-1)	Average pore size/nm
Pd/CZA-800	61	0.44	23.2
Pd/CZA-850	67	0.42	24.5
Pd/CZA-900	67	0.41	24.7
Pd/CZA-950	69	0.43	24.6
Pd/CZA-1000	70	0.40	29.1

Fig. 2 (a) H2-TPR curves, (b) O2-TPD curves, (c-g) Pd3d XPS spectra and (h) Pd species ratio of the catalysts Colorful figures are available on website

Fig. 3 (a-c) HRTEM images of (a) Pd/CZA-900, (b) Pd/CZA-950 and (c) Pd/CZA-1000; (d) XRD patterns of the catalysts and partial enlarged view of the pink area; (e) Pd dispersion and particle size of the catalysts

Fig. 4 (a) DOSC profiles of CO-O2 alternating pulse, (b) DOSC values and (c) H2-O2 atmosphere alternating TG curves of the catalysts Colorful figures are available on website

Fig. 5 (a) C3H8 and (b) CO2 desorption signals of C3H8-TPD over the catalysts Colorful figures are available on website

Fig. 6 Schematic diagram of structure-activity relationship

Fig. S1 TEM images of (a) Pd/CZA-800, (b) Pd/CZA-850, (c) Pd/CZA-900, (d) Pd/CZA-950 and (e) Pd/CZA-1000

Fig. S2 HRTEM images of (a) Pd/CZA-800, (b) Pd/CZA-850, (c) Pd/CZA-900, (d) Pd/CZA-950 and (e) Pd/CZA-1000

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单钯三效催化剂在梯度温度老化下的失活机制

Deactivation Mechanism of Pd Only Three-way Catalysts under Aging Temperature Gradient

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