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

ZHANG Junjie; WANG Dajun; LI Shanshan; LI Jie; CHEN Yaozhuang; HAN Taiyu; YANG Zhenzhen; WANG Guangyong

doi:10.12434/j.issn.2097-2547.20230411

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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

- 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
- Vol. 49, Issue 10, Pages: 72-80(2024)
- 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：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20230411
  CLC： TQ426;O643.36
- Published：25 October 2024，
  
  Received：15 December 2023，
  
  Revised：07 March 2024，
- 稿件说明：
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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

-ZrO

-Al

（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

可以提升CZA的低温还原性能，进一步研究了不同Pr

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

吸/脱附、X射线衍射（XRD）、H

-程序升温还原（H

-TPR）和储氧量等表征结果表明，Pr

的表面改性可在一定程度上降低CeO

-ZrO

（CZ）纳米晶的烧结驱动力，抑制CZ晶粒烧结。同时，引入Pr

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

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

/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

和C

的

（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

，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

-ZrO

-Al

(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

on improving the low-temperature reducibility of CZA materials

the effects of different content of Pr

and 9%

mass fraction) on the redox performance and thermal stability of CZA materials were further studied. The characterization results of N

adsorption/desorption

X-ray diffraction (XRD)

temperature programmed reduction (H

-TPR) and oxygen storage capacity show that the surface modification of CZA by Pr

can reduce the driving force of CeO

-ZrO

(CZ) sintering and thus inhibit the growth of nanoparticles. At the same time

the introduction of Pr

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

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

/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

(required temperature at the pollutant conversion rate of 50%) of CO

and C

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

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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