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通过超声调整氧化钛纳米材料的物理化学特性:提升基于木质素的芳香醇的光催化选择性部分氧化。

Tuning the physicochemical features of titanium oxide nanomaterials by ultrasound: Elevating photocatalytic selective partial oxidation of lignin-inspired aromatic alcohols.

机构信息

Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.

Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland.

出版信息

Ultrason Sonochem. 2023 Mar;94:106306. doi: 10.1016/j.ultsonch.2023.106306. Epub 2023 Jan 21.

Abstract

The research for "green" and economically feasible approaches such as (photo)catalysis especially for biomass valorization such as selective oxidation of biomass derived compounds like aromatic alcohols to corresponding aldehyde by avoiding the harsh reaction conditions and the addition of reagents concentrate the focus of attention the last years. Hence, design and development of novel photocatalyst for the partial selective oxidation is highly desirable. In this research work, ultrasonication of different frequencies (22, 40, 80 kHz) and different amplitudes was utilized as synthesis tool in order to obtain novel materials by precipitation method. The synthesized samples were characterized by using different techniques such as N sorption, TEM, XPS, XRD, thermal analysis, and diffuse reflectance spectroscopy. The synthesized sample by using low ultrasound frequency (22 kHz) and amplitude showed a mixed morphological and structural nature consisting of asymmetric 1-dimensional (nanorods-like), layered nano-structures and not well-defined areas, leading to elevate for metal oxide specific surface areas up to 155 m/g. The observed 1-D nanostructures have diamentions in the range of 20-60 nm. This sample revealed the highest photo-oxidation efficiency for the selective conversion of two biomass-derived, and more specifically lignin-inspired model compounds, benzyl alcohol and cinnamyl alcohol to benzaldehyde and cinnamyl aldehyde, respectively, and hence the highest yield towards the desired aldehydes. The selective photo-oxidation activity was retained even after 5 photocatalytic cycles, while no leaching of Ti was recorded.

摘要

近年来,人们特别关注研究“绿色”且经济可行的方法,例如(光)催化,特别是针对生物质增值,如选择性氧化生物质衍生化合物,如芳香醇转化为相应的醛,避免苛刻的反应条件和试剂的添加。因此,设计和开发新型光催化剂用于部分选择性氧化受到了高度关注。在这项研究工作中,利用不同频率(22、40、80 kHz)和不同幅度的超声作为沉淀法合成的工具,以获得新型材料。通过使用不同的技术对合成的样品进行了表征,例如 N 吸附、TEM、XPS、XRD、热分析和漫反射光谱。使用低频(22 kHz)和小幅度超声合成的样品显示出混合形态和结构性质,由不对称的一维(纳米棒状)、层状纳米结构和不明确的区域组成,导致金属氧化物的比表面积提高到 155 m/g。观察到的一维纳米结构的尺寸在 20-60nm 范围内。该样品在选择性转化两种生物质衍生的、更具体地说是木质素启发的模型化合物,即苄醇和肉桂醇为相应的苯甲醛和肉桂醛方面,表现出最高的光氧化效率,因此得到的目标醛的产率最高。甚至在 5 次光催化循环后,仍然保留了选择性光氧化活性,而没有钛的浸出。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3ed1/9894921/64ea272094ec/ga1.jpg

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