摘要
多金属氧酸盐(POMs)因其可调控的化学组成、丰富的电子结构和优异的物理化学性能而成为一类极具应用前景的催化材料.良好的多电子氧化还原特性使其可以有效催化一系列氧化反应.本文对POMs催化氧化反应方面的研究进行了综述,主要归纳了其在烯烃的环氧化反应、含硫化合物的氧化反应、醇的氧化反应以及烷烃的氧化反应等方面的应用.
Abstract
Polyoxometalates(POMs),as a class of multinuclear clusters,are polymerized of oxygen and early high-valent transition metals(e.g.,Mo,W,V and Nb).Based on the geometry of heteroatoms and the ratio of heteroatoms to coordination atoms,POMs can be classified into six classical configurations in-cluding Keggin-type,Dawson-type,Anderson-type,Waugh-type,Silverton-type,and Lindqvist-type.They exhibit the diverse structures and versatile properties,which enrich their applications in catalysis,medicine,electrochemistry,magnetism,and so on.The chemistry of POMs is an important branch of in-organic chemistry with a history of more than 200 years.It intersects with physical chemistry,analytical chemistry,structural chemistry,biochemistry,environmental chemistry,material chemistry and many other fields.Modern chemistry of POMs has developed from single POMs synthesis to controllable molec-ular design synthesis,from simple POMs monomer to high-dimensional,high-core and other novel struc-ture clusters constructed with POMs as building units.Especially,POMs are considered as electron stores due to their strong ability to bear and release electrons,indicating they have redox properties.Therefore,POMs have received increasing attentions as redox heterogeneous catalysts.To resolve the problem of the high solubility of POMs,the design synthesis and performance research of functional complexes with POMs as inorganic ligands or non-coordination templates have become one of hot spots.The encapsulation of POMs into the crystalline architecture results in multifunctional hybrid materials,which combine the merits of POMs and the organic frameworks to achieve specific properties.With the increase of conscious-ness for environmental protection,green oxidants such as hydrogen peroxide and oxygen are utilized as main oxidants for the oxidation.The combination of POMs-based materials with environment friendly oxi-dants can efficiently catalyze various oxidation reactions,such as epoxidation of olefin,oxidation of sulfur-containing compounds,oxidation of alcohols,oxidation of alkanes and so on.In this paper,an overview of recent advances of POMs in catalytic oxidation was presented.
基金项目
Doctoral Scientific Research Foundation of Weifang University(2023BS13)
Project of Weifang Science and Technology Development Program(2022GX 020)
Project of Weifang Science and Technology Development Program(2022GX021)
National Natural Science Foundation of China(22001032)
Doctoral Scientific Research Foundation of Weifang Vocational College()
NETL
NSTL
万方数据