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在无有机溶剂的环境中,介孔分级 Pt/Bi2WO6 光催化剂高效、高选择性地氧化芳香醇。

Highly efficient and selective oxidation of aromatic alcohols photocatalyzed by nanoporous hierarchical Pt/Bi2WO6 in organic solvent-free environment.

机构信息

Center of Excellence in Nanotechnology (CENT), ‡Department of Chemistry, King Fahd University of Petroleum and Minerals , Dhahran 31261, Kingdom of Saudi Arabia.

出版信息

ACS Appl Mater Interfaces. 2015 Jan 21;7(2):1257-69. doi: 10.1021/am507428r. Epub 2015 Jan 9.

Abstract

Selective conversion of aromatic alcohols into corresponding aldehydes is important from energy and environmental stance. Here, we describe highly selective (>99%) and efficient conversion (>99%) of aromatic alcohols (e.g., 4-methoxybenzyl alcohol and 4-nitrobenzyl alcohol) into their corresponding aldehydes in the presence of Pt-modified nanoporous hierarchical Bi2WO6 spheres in water under simulated sunlight at ambient conditions. Overoxidation of p-anisaldehyde, formed during photooxidation process, was not observed until comprehensive alcohol oxidation was attained. Furthermore, the catalyst showed substantial oxidation under dark and course of conversion was different than that of under light. Dependency of alcohol oxidation on substrate concentration, photocatalyst amount, and Pt loading was studied. The effect of various radical scavengers was investigated, and the rate-determining step was elucidated. It has been envisaged that the reduction site of semiconductor photocatalysts plays more decisive role in determining the selectivity as alcohol preferably get oxidized over that of water. Furthermore, the chemical stability and recyclability of the photocatalyst were investigated.

摘要

从能源和环境的角度来看,选择性地将芳香醇转化为相应的醛类非常重要。在这里,我们描述了在模拟阳光下,在水相中,Pt 修饰的介孔分级 Bi2WO6 球作为催化剂,能够高度选择性(>99%)和高效(>99%)地将芳香醇(例如 4-甲氧基苄醇和 4-硝基苄醇)转化为相应的醛。在全面氧化醇之前,不会观察到对苯甲醛的过度氧化,苯甲醛是在光氧化过程中形成的。此外,催化剂在黑暗中也能进行大量氧化,而且其转化过程与光照下的转化过程不同。研究了醇氧化对底物浓度、光催化剂用量和 Pt 负载量的依赖性。考察了各种自由基清除剂的影响,并阐明了速率决定步骤。可以预见,半导体光催化剂的还原位点在确定选择性方面起着更决定性的作用,因为醇比水更容易被氧化。此外,还研究了光催化剂的化学稳定性和可回收性。

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