Studies of the Activation and Functionalization of Hydrocarbons at Multinuclear Metal Sites in Transition Metal-Gold Complexes

过渡金属-金配合物中多核金属位点碳氢化合物的活化和功能化研究

• 批准号: 1464596
• 负责人: Richard Adams
• 金额: $ 46万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2019-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1464596&HistoricalAwards=false
• 关键词: Studies; Activation; Functionalization; Hydrocarbons; Multinuclear

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Richard D. Adams of the Department of Chemistry and Biochemistry at the University of South Carolina is developing new methods for the synthesis of bimetallic transition metal cluster complexes containing gold to be used to create new catalysts for the transformations and reforming of hydrocarbons. Simple hydrocarbons such as methane and ethane are now available from today's abundant supplies of natural gas. There is a great need to develop catalysts to transform these resources efficiently into higher value commodity chemicals. Studies will be focused on the development of new catalysts for selective oxidation reactions that will convert simple hydrocarbons into oxygenated compounds, such as alcohols and carboxylic acids, via environmentally-friendly chemical processes. Precious metal elements, such as ruthenium, rhodium, rhenium, iridium, and platinum will be studied because of their well-known ability to activate the CH bonds of hydrocarbons. Gold will be chemically incorporated into the new catalysts because of its recently discovered ability to active oxygen and transfer it to carbon atoms. Broader impacts include the development of new processes for the conversion of natural gas and related resources into valuable chemicals for use as additives to produce higher octane fuels and for feedstocks for the synthesis of new polymers and materials. Graduate and undergraduate students are trained in the latest methods of scientific inquiry and analysis as preparation for careers in academia or the chemical industry. Hydrocarbyl containing gold-transtion metal clusters are prepared by the reaction of organogold compounds with metal carbonyl cluster complexes of the precious transition metals. These heterometallic cluster complexes are converted into bi- and multimetallic nanoparticles for use as nanocatalysts for the selective oxidation of hydrocarbons. The controlled addition of oxygen to the carbon atoms is central understanding the nature of metal-catalyzed selective oxidation reactions. Mechanistic studies are carried out and focus on understanding the nature of transformations of the CH bonds of the hydrocarbon by complexes containing two or more metal atoms. These studies include investigations of the formation of C - O bonds. The complexes and catalysts are studied by X-ray diffraction and high resolution transmission electron microscopy.

本研究由化学系化学合成计划资助，由美国加州大学伯克利分校化学系教授Richard D.南卡罗来纳州大学化学和生物化学系的亚当斯正在开发合成含金的过渡金属簇合物的新方法，用于制造碳氢化合物转化和重整的新催化剂。简单的碳氢化合物，如甲烷和乙烷，现在可以从今天丰富的天然气供应中获得。迫切需要开发催化剂，将这些资源有效地转化为更高价值的商品化学品。研究将集中于开发用于选择性氧化反应的新催化剂，通过环境友好的化学过程将简单的烃转化为含氧化合物，如醇和羧酸。贵金属元素，如钌，铑，铱，铂将被研究，因为他们众所周知的能力，激活碳氢化合物的CH键。金将被化学结合到新的催化剂中，因为它最近发现的活性氧和转移到碳原子的能力。更广泛的影响包括开发新的工艺，将天然气和相关资源转化为有价值的化学品，用作生产高辛烷值燃料的添加剂和合成新聚合物和材料的原料。研究生和本科生接受科学探究和分析的最新方法的培训，为学术界或化学工业的职业生涯做准备。通过有机金化合物与贵金属的羰基簇合物反应，制备了含烃基的金-过渡金属簇合物。这些异金属簇合物被转化为双金属和多金属纳米颗粒，用作烃的选择性氧化的纳米催化剂。碳原子上可控的氧加成是理解金属催化选择性氧化反应本质的核心。进行了机理研究，并侧重于了解含有两个或更多个金属原子的络合物的烃的CH键的转化的性质。这些研究包括C-O键形成的研究.配合物和催化剂进行了研究，通过X-射线衍射和高分辨率透射电子显微镜。