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助剂Pr6O11掺杂对CeO2-ZrO2-Al2O3材料及其负载单Pd三效催化剂性能的影响研究
Study on effects of surface modification by Pr6O11 as promoter on performances of CeO2-ZrO2-Al2O3 material and its supported Pd-only three-way catalyst
- 低碳化学与化工 2024, 49(10): 72-80.
- 作者机构：
1.西南化工研究设计院有限公司 工业排放气综合利用国家重点实验室，国家碳一化学工程技术研究中心，四川 成都 610225
2.四川大学 化学学院，四川 成都 610064
- 作者简介：
张俊杰（1989—），博士，高级工程师，研究方向为C1化工与多相催化，E-mail：zhangjj@swchem.com。
李珊珊（1992—），博士，实验师，研究方向为多相催化，E-mail：shanshanli@scu.edu.cn。
- 基金信息：四川省自然科学基金-青年科学基金(2022NSFSC1206)
DOI：10.12434/j.issn.2097-2547.20230411
中图分类号： TQ426;O643.36纸质出版日期：2024-10-25，
收稿日期：2023-12-15，
修回日期：2024-03-07，
- 稿件说明：
移动端阅览
张俊杰,王大军,李珊珊等.助剂Pr6O11掺杂对CeO2-ZrO2-Al2O3材料及其负载单Pd三效催化剂性能的影响研究[J].低碳化学与化工,2024,49(10):72-80.
ZHANG Junjie,WANG Dajun,LI Shanshan,et al.Study on effects of surface modification by Pr6O11 as promoter on performances of CeO2-ZrO2-Al2O3 material and its supported Pd-only three-way catalyst[J].Low-carbon Chemistry and Chemical Engineering,2024,49(10):72-80.
张俊杰,王大军,李珊珊等.助剂Pr6O11掺杂对CeO2-ZrO2-Al2O3材料及其负载单Pd三效催化剂性能的影响研究[J].低碳化学与化工,2024,49(10):72-80. DOI： 10.12434/j.issn.2097-2547.20230411.
ZHANG Junjie,WANG Dajun,LI Shanshan,et al.Study on effects of surface modification by Pr6O11 as promoter on performances of CeO2-ZrO2-Al2O3 material and its supported Pd-only three-way catalyst[J].Low-carbon Chemistry and Chemical Engineering,2024,49(10):72-80. DOI： 10.12434/j.issn.2097-2547.20230411.
摘要
助剂表面改性是提高铈基材料热稳定性、还原性能及其负载单Pd三效催化剂低温活性的经典方法之一。揭示助剂表面改性的作用机制，对于研发高性能CeO
2
-ZrO
2
-Al
2
O
3
（CZA）材料，满足日趋严格的汽油车尾气污染物排放标准，解决尾气污染具有现实意义。基于引入助剂Pr
6
O
11
可以提升CZA的低温还原性能，进一步研究了不同Pr
6
O
11
含量（0、3%、5%、7%和9%，质量分数）对其氧化还原性能和热稳定性的影响。N
2
吸/脱附、X射线衍射（XRD）、H
2
-程序升温还原（H
2
-TPR）和储氧量等表征结果表明，Pr
6
O
11
的表面改性可在一定程度上降低CeO
2
-ZrO
2
（CZ）纳米晶的烧结驱动力，抑制CZ晶粒烧结。同时，引入Pr
6
O
11
促进材料产生了更多氧空位，从而提高了其还原性能和储氧性能。其中，Pr
6
O
11
含量为5%时，改性CZA表现出最佳的热稳定性、还原性能和储氧性能，1000 ℃下老化4 h后比表面积和孔容最大（85 m
2
/g和0.33 mL/g），CZ晶粒尺寸最小（6.9 nm），还原峰温低至532 ℃，400 ℃储氧量增至109 μmol/g。因此，该改性CZA负载的单Pd三效催化剂表现出最优的催化活性，其CO、NO、C
3
H
8
和C
3
H
6
的
t
50
（污染物转化率为50%时所需温度）较未改性催化剂分别降低了6 ℃、15 ℃、18 ℃和6 ℃。综上，在CZA材料中添加适量的Pr
6
O
11
，可有效提高其负载单Pd三效催化剂的低温活性。该方法简单经济，具有较好的应用前景。
Abstract
Surface modification by promoters is one of the classic methods to improve the thermal stability
reducibility
and low-temperature activity of cerium-based materials and their supported Pd-only three-way catalysts. Revealing the mechanism of surface modification by promoters
is of practical significance for the development of high-performance CeO
2
-ZrO
2
-Al
2
O
3
(CZA) materials to meet the increasingly strict regulations on gasoline vehicle exhaust emission and to solve the exhaust pollution. On the basis of the promoting effects of Pr
6
O
11
on improving the low-temperature reducibility of CZA materials
the effects of different content of Pr
6
O
11
(0
3%
5%
7%
and 9%
mass fraction) on the redox performance and thermal stability of CZA materials were further studied. The characterization results of N
2
adsorption/desorption
X-ray diffraction (XRD)
H
2
temperature programmed reduction (H
2
-TPR) and oxygen storage capacity show that the surface modification of CZA by Pr
6
O
11
can reduce the driving force of CeO
2
-ZrO
2
(CZ) sintering and thus inhibit the growth of nanoparticles. At the same time
the introduction of Pr
6
O
11
also promotes to produce more oxygen vacancies in the material
thus improving its reducibility and oxygen storage performance. Among them
when the content of Pr
6
O
11
is 5%
the modified CZA exhibits the best thermal stability
redox performance and oxygen storage performance. After aging at 1000 ℃ for 4 h
it exhibits the highest specific surface area (85 m
2
/g) and pore volume (0.33 mL/g)
the smallest crystal size of CZ (6.9 nm)
the lowest reduction temperature (532 ℃) and the highest oxygen storage capacity of 109 μmol/g
at 400 ℃. Therefore
the modified CZA supported Pd-only three-way catalyst exhibits the optimal catalytic activity
with the
t
50
(required temperature at the pollutant conversion rate of 50%) of CO
NO
C
3
H
8
and C
3
H
6
reduced by 6 ℃
15 ℃
18 ℃ and 6 ℃
respectively
compared to the unmodified catalysts. In summary
the low-temperature activity of Pd-only the
e-way catalysts can be improved by adding an appropriate amount of Pr
6
O
11
to the CZA support
which is simple
economical
and has great application prospects.
关键词
尾气净化表面改性CeO2-ZrO2-Al2O3Pr6O11
Keywords
exhaust purificationsurface modificationCeO2-ZrO2-Al2O3Pr6O11
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