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光催化所定义的环境绿色化学。

Environmental green chemistry as defined by photocatalysis.

作者信息

Herrmann J-M, Duchamp C, Karkmaz M, Hoai Bui Thu, Lachheb H, Puzenat E, Guillard C

机构信息

Laboratoire d'application de la chimie à l'environnement (LACE), UMR CNRS 5634, (become IrceLyon, UMR 5256), Université Claude-Bernard Lyon-1, Bâtiment J. Raulin, Villeurbanne cedex, France.

出版信息

J Hazard Mater. 2007 Jul 31;146(3):624-9. doi: 10.1016/j.jhazmat.2007.04.095. Epub 2007 Apr 24.

Abstract

Photocatalysis is efficient in several fields. Firstly, in selective mild oxidation: oxidation of gas and liquid hydrocarbons (alkanes, alkenes, cyclo-alkanes, aromatics) into aldehydes and ketons. Primary and secondary alcohols are also oxidized into their corresponding aldehydes or ketones. The high selectivity was ascribed to a photoactive neutral, atomic oxygen species. Once platinized (only 0.5wt.% Pt) titania may catalyze reactions involving hydrogen (deuterium-alkane isotopic exchange and alcohol dehydrogenation). For fine chemicals, high initial selectivities enable titania to address most of the twelve principles of "green chemistry", such as the synthesis of 4-tert-butyl-benzaldehyde, an important intermediate in perfume industry by direct selective oxidation of 4-tert-butyl-toluene with air. A new field recently appeared: thio-photocatalysis. Oxygen was replaced by sulfur, using H(2)S as a convenient and reactive source. For instance, the conversion of propene in 1-propanthiol was successfully obtained. The reaction was performed using either CdS or TiO(2). The latter was much more active than CdS. In environmental photocatalysis, titania becomes a total oxidation catalyst once in presence of water because of the photogeneration of OH radicals by neutralization of OH(-) surface groups by positive holes. Many toxic inorganic ions are oxidized in their harmless upper oxidized state. The total degradation of organic pollutants (pesticides, herbicides, insecticides, fungicides, dyes, etc. ...) is the main field of water photocatalytic decontamination. The UVA solar spectrum can de advantageously used as demonstrated by many campaigns performed in the solar pilot plant at the "Plataforma Solar de Almeria" (Spain).

摘要

光催化在多个领域都很高效。首先,在选择性温和氧化方面:将气态和液态碳氢化合物(烷烃、烯烃、环烷烃、芳烃)氧化为醛和酮。伯醇和仲醇也能被氧化为相应的醛或酮。高选择性归因于光活性中性原子氧物种。一旦镀铂(仅0.5wt.%的铂),二氧化钛就能催化涉及氢的反应(氘 - 烷烃同位素交换和醇脱氢)。对于精细化学品,高初始选择性使二氧化钛能够符合“绿色化学”的十二条原则中的大多数,例如通过用空气直接选择性氧化4 - 叔丁基甲苯来合成4 - 叔丁基苯甲醛,这是香料工业中的一种重要中间体。最近出现了一个新领域:硫光催化。用硫化氢作为一种方便且具有反应性的源,将氧替换为硫。例如,成功实现了丙烯向1 - 丙硫醇的转化。该反应使用硫化镉或二氧化钛进行。后者比硫化镉活性高得多。在环境光催化中,由于空穴中和表面羟基基团产生羟基自由基,二氧化钛一旦有水存在就会成为一种完全氧化催化剂。许多有毒无机离子被氧化为无害的高氧化态。有机污染物(农药、除草剂、杀虫剂、杀菌剂、染料等)的完全降解是水的光催化净化的主要领域。如在西班牙“阿尔梅里亚太阳能平台”的太阳能中试装置中进行的许多试验所表明的,紫外A太阳光谱可以得到有效利用。

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