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SBA-15负载的镍、钯和铂单金属及双金属催化剂上苯甲醚的加氢脱氧反应:金属性质对催化活性和选择性的影响

Hydrodeoxygenation of anisole over SBA-15-supported Ni, Pd, and Pt mono- and bimetallic catalysts: effect of the metal's nature on catalytic activity and selectivity.

作者信息

Pérez-Estrada Daniel E, Vargas-Villagrán Haydee, Mendoza-Cruz Rubén, Klimova Tatiana E

机构信息

Laboratorio de Nanocatálisis, Facultad de Química, Universidad Nacional Autónoma de México (UNAM), Cd. Universitaria, Coyoacán, C.P. 04510, Ciudad de México, Mexico.

Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México (UNAM), Cd. Universitaria, Coyoacán, C.P. 04510, Ciudad de México, Mexico.

出版信息

Nanoscale. 2024 Jun 20;16(24):11575-11591. doi: 10.1039/d4nr01222d.

DOI:10.1039/d4nr01222d
PMID:38856673
Abstract

Monometallic Ni, Pd and Pt and bimetallic catalysts formed by combinations of the above metals supported on SBA-15 silica were synthesized, characterized and tested in the hydrodeoxygenation reaction of anisole. The objective of the work was to detect the effect of the nature of metals on the activity of the catalysts at different steps of anisole hydrodeoxygenation: hydrogenation of the aromatic ring of anisole and C-O bond cleavage in the intermediate cyclohexyl methyl ether. The support and the catalysts were characterized by N physisorption, X-ray diffraction, UV-vis diffuse reflectance spectroscopy, temperature-programmed reduction, scanning electron microscopy-energy dispersive X-ray spectroscopy, transmission electron microscopy and HAADF-STEM. The catalytic activity tests were carried out in a batch reactor at 280 °C and 7.3 MPa pressure. The activity results show that the NiPd/SBA-15 catalyst had the greatest ability for hydrogenation of the aromatic ring of anisole, while its NiPt/SBA-15 analog resulted in better activity for C-O bond hydrogenolysis. The bimetallic NiPt/SBA-15 catalyst showed the best catalytic performance in the HDO of anisole ascribed to the formation of a Ni-Pt alloy. On the other hand, the combination of Pd and Pt metals in the PdPt/SBA-15 catalyst resulted in the formation of bimetallic particles with Pd-rich and Pt-rich domains, showing high selectivity for the formation of the cyclohexyl methyl ether, which can be useful for the hydrogenation of aromatic rings in O-containing reactants with the formation of saturated O-containing products. According to the characterization results (HAADF-STEM), the different catalytic behavior of NiPd/SBA-15, NiPt/SBA-15, and PdPt/SBA-15 catalysts could be attributed to different characteristics of the bimetallic active phases in them.

摘要

合成了负载在SBA - 15二氧化硅上的单金属镍、钯和铂以及由上述金属组合形成的双金属催化剂,并对其进行了表征,同时在苯甲醚的加氢脱氧反应中进行了测试。该工作的目的是检测金属性质对苯甲醚加氢脱氧不同步骤中催化剂活性的影响:苯甲醚芳环的氢化以及中间产物环己基甲基醚中C - O键的断裂。通过N物理吸附、X射线衍射、紫外可见漫反射光谱、程序升温还原、扫描电子显微镜 - 能量色散X射线光谱、透射电子显微镜和高角度环形暗场扫描透射电子显微镜对载体和催化剂进行了表征。催化活性测试在间歇式反应器中于280℃和7.3MPa压力下进行。活性结果表明,NiPd/SBA - 15催化剂对苯甲醚芳环的氢化能力最强,而其类似物NiPt/SBA - 15在C - O键氢解方面表现出更好的活性。双金属NiPt/SBA - 15催化剂在苯甲醚的加氢脱氧反应中表现出最佳的催化性能,这归因于形成了Ni - Pt合金。另一方面,PdPt/SBA - 15催化剂中钯和铂金属的组合导致形成了具有富钯和富铂区域的双金属颗粒,对环己基甲基醚的形成表现出高选择性,这对于含氧化合物反应物中芳环的氢化以形成饱和含氧化合物产物可能是有用的。根据表征结果(高角度环形暗场扫描透射电子显微镜),NiPd/SBA - 15、NiPt/SBA - 15和PdPt/SBA - 15催化剂不同的催化行为可归因于它们中双金属活性相的不同特性。

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