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关于在CeO上构建具有令人满意稳定性的坚固Pt团簇用于CO催化氧化的见解。

Insights into the Construction of Robust Pt Clusters with Satisfactory Stability on CeO for the Catalytic Oxidation of CO.

作者信息

Yang Peng, Luo Chaoyi, Tan Wei, Liu Qinglong, Zhang Shaoxiong, Hong Song, Gao Fei, Dong Lin

机构信息

State Key Laboratory of Pollution Control and Resource Reuse, School of Environment, Jiangsu Key Laboratory of Vehicle Emissions Control, Center of Modern Analysis, Nanjing University, Nanjing 210023, China.

College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China.

出版信息

ACS Appl Mater Interfaces. 2024 May 1;16(17):21782-21789. doi: 10.1021/acsami.4c00342. Epub 2024 Apr 18.

Abstract

Improving the efficiency of platinum group metals (Pt, Pd, Rh, etc.) in catalytic oxidation reactions remains an urgent topic. The conflict between the low-temperature activity and high-temperature stability of noble metals can hardly reach a consensus. For instance, Pt cluster catalysts supported on CeO with high low-temperature activity will suffer from deactivation due to the redispersion under high-temperature lean-burn reaction conditions. Herein, two Pt/CeO prepared by the incipient wetness impregnation method using different Pt precursors possessed varied Pt-O and Pt-O-Ce coordination numbers (CNs). They showed various priorities in CO oxidation versus NH selective catalytic oxidation, materials with higher CN selectively catalyzing NH oxidation to N more superior, conversely materials with lower CN performing better in CO oxidation. After activation by H reduction, both formed massive Pt clusters on the CeO surface but showed drastically distinct stability in lean-burn CO oxidation reactions. By summarizing the experimental results of high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, Raman spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, ., it is beyond doubt that the difference in the initial states of Pt due to distinct precursors indeed determine the redispersion behavior of the reduced Pt clusters on CeO. Materials with lower CN and higher CN are more likely to form robust Pt clusters, as they are not conducive to Pt anchoring, thus restricting the reversible structural evolution occurring under lean-burn CO oxidation and reductive conditions. This approach serves as a guide for the convenient and efficient construction and exploration of robust Pt cluster catalysts.

摘要

提高铂族金属(Pt、Pd、Rh等)在催化氧化反应中的效率仍然是一个紧迫的课题。贵金属的低温活性和高温稳定性之间的矛盾很难达成共识。例如,负载在CeO上具有高低温活性的Pt簇催化剂在高温贫燃反应条件下会因再分散而失活。在此,通过初湿浸渍法使用不同的Pt前驱体制备的两种Pt/CeO具有不同的Pt-O和Pt-O-Ce配位数(CNs)。它们在CO氧化与NH选择性催化氧化方面表现出不同的优先顺序,具有较高CN的材料选择性催化NH氧化为N更具优势,相反,具有较低CN的材料在CO氧化中表现更好。经过H还原活化后,两者在CeO表面都形成了大量的Pt簇,但在贫燃CO氧化反应中表现出截然不同的稳定性。通过总结高角度环形暗场扫描透射电子显微镜、X射线吸收光谱、拉曼光谱、漫反射红外傅里叶变换光谱等的实验结果,毫无疑问,由于前驱体不同导致的Pt初始状态差异确实决定了还原后的Pt簇在CeO上的再分散行为。具有较低CN和较高CN的材料更有可能形成稳定的Pt簇,因为它们不利于Pt的锚定,从而限制了在贫燃CO氧化和还原条件下发生的可逆结构演变。这种方法为便捷高效地构建和探索稳定的Pt簇催化剂提供了指导。

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