Tong Tao, Douthwaite Mark, Chen Lu, Engel Rebecca, Conway Matthew B, Guo Wanjun, Wu Xin-Ping, Gong Xue-Qing, Wang Yanqin, Morgan David J, Davies Thomas, Kiely Christopher J, Chen Liwei, Liu Xi, Hutchings Graham J
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, CardiffCF10 3AT, U.K.
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai200237, China.
ACS Catal. 2023 Jan 5;13(2):1207-1220. doi: 10.1021/acscatal.2c04347. eCollection 2023 Jan 20.
The hydrogen-borrowing amination of alcohols is a promising route to produce amines. In this study, experimental parameters involved in the preparation of Pt/CeO catalysts were varied to assess how physicochemical properties influence their performance in such reactions. An amination reaction between cyclopentanol and cyclopentylamine was used as the model reaction for this study. The Pt precursor used in the catalyst synthesis and the properties of the CeO support were both found to strongly influence catalytic performance. Aberration corrected scanning transmission electron microscopy revealed that the most active catalyst comprised linearly structured Pt species. The formation of these features, a function result of epitaxial Pt deposition along the CeO [100] plane, appeared to be dependent on the properties of the CeO support and the Pt precursor used. Density functional theory calculations subsequently confirmed that these sites were more effective for cyclopentanol dehydrogenation-considered to be the rate-determining step of the process-than Pt clusters and nanoparticles. This study provides insights into the desirable catalytic properties required for hydrogen-borrowing amination but has relevance to other related fields. We consider that this study will provide a foundation for further study in this atom-efficient area of chemistry.
醇的借氢胺化反应是生产胺类的一条有前景的途径。在本研究中，改变了制备Pt/CeO催化剂所涉及的实验参数，以评估物理化学性质如何影响它们在这类反应中的性能。环戊醇与环戊胺之间的胺化反应被用作本研究的模型反应。结果发现，催化剂合成中使用的Pt前驱体和CeO载体的性质均对催化性能有强烈影响。像差校正扫描透射电子显微镜显示，活性最高的催化剂包含线性结构的Pt物种。这些特征的形成是沿CeO [100]平面外延沉积Pt的函数结果，其似乎取决于CeO载体的性质和所使用的Pt前驱体。密度泛函理论计算随后证实，与Pt团簇和纳米颗粒相比，这些位点对环戊醇脱氢（被认为是该过程的速率决定步骤）更有效。本研究为借氢胺化反应所需的理想催化性质提供了见解，且与其他相关领域相关。我们认为，本研究将为在这个原子经济高效的化学领域进行进一步研究奠定基础。
