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金/二氧化钛催化苄醇在形态精确的锐钛矿纳米颗粒上的氧化反应

Au/TiO-Catalyzed Benzyl Alcohol Oxidation on Morphologically Precise Anatase Nanoparticles.

作者信息

Mahdavi-Shakib Akbar, Sempel Janine, Hoffman Maya, Oza Aisha, Bennett Ellie, Owen Jonathan S, Rahmani Chokanlu Amir, Frederick Brian G, Austin Rachel Narehood

机构信息

Department of Chemistry, Barnard College, Columbia University, New York, New York 10027, United States.

Department of Chemistry, Columbia University, New York, New York 10027, United States.

出版信息

ACS Appl Mater Interfaces. 2021 Mar 17;13(10):11793-11804. doi: 10.1021/acsami.0c20442. Epub 2021 Mar 4.

Abstract

Au nanoparticles (NP) on TiO have been shown to be effective catalysts for selective oxidation reactions by using molecular oxygen. In this work, we have studied the influence of support morphology on the catalytic activity of Au/TiO catalysts. Two TiO anatase supports, a nanoplatelet-shaped material with predominantly the {001} facet exposed and a truncated bipyramidal-shaped nanoparticle with predominantly the {101} facet exposed, were prepared by using a nonaqueous solvothermal method and characterized by using DRIFTS, XPS, and TEM. Au nanoparticles were deposited on the supports by using the deposition-precipitation method, and particle sizes were determined by using STEM. Au nanoparticles were smaller on the support with the majority of the {101} facet exposed. The resulting materials were used to catalyze the aerobic oxidation of benzyl alcohol and trifluoromethylbenzyl alcohol. Support morphology impacts the catalytic activity of Au/TiO; reaction rates for reactions catalyzed by the predominantly {101} material were higher. Much of the increased reactivity can be explained by the presence of smaller Au particles on the predominantly {101} material, providing more Au/TiO interface area, which is where catalysis occurs. The remaining modest differences between the two catalysts are likely due to geometric effects as Hammett slopes show no evidence for electronic differences between the Au particles on the different materials.

摘要

已证明负载于TiO上的金纳米颗粒(NP)是使用分子氧进行选择性氧化反应的有效催化剂。在本工作中,我们研究了载体形态对Au/TiO催化剂催化活性的影响。通过非水溶剂热法制备了两种TiO锐钛矿载体,一种是主要暴露{001}面的纳米片状材料,另一种是主要暴露{101}面的截顶双锥体状纳米颗粒,并使用漫反射红外傅里叶变换光谱(DRIFTS)、X射线光电子能谱(XPS)和透射电子显微镜(TEM)对其进行了表征。通过沉积沉淀法将金纳米颗粒沉积在载体上,并使用扫描透射电子显微镜(STEM)测定颗粒尺寸。在大部分暴露{101}面的载体上,金纳米颗粒较小。所得材料用于催化苯甲醇和三氟甲基苯甲醇的需氧氧化反应。载体形态影响Au/TiO的催化活性;主要由{101}材料催化的反应速率更高。大部分反应活性的提高可以用主要由{101}材料上存在较小的金颗粒来解释,这提供了更多的Au/TiO界面面积,而催化作用正是在该界面发生的。两种催化剂之间其余适度的差异可能是由于几何效应,因为哈米特斜率没有显示出不同材料上金颗粒之间存在电子差异的证据。

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