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    Home > Science: Zuo Zhiwei's research team of Shanghai University of science and technology has made a breakthrough in the field of light promoting methane conversion

    Science: Zuo Zhiwei's research team of Shanghai University of science and technology has made a breakthrough in the field of light promoting methane conversion

    • Last Update: 2018-07-27
    • Source: Internet
    • Author: User
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    Zuo Zhiwei's research team, School of material science and technology, Shanghai University of science and technology, has made a breakthrough in the field of light promoted methane conversion, an important energy chemical industry: they have successfully developed a cheap and efficient synergistic catalytic system of cerium based catalyst and alcohol catalyst This breakthrough in the field of basic research solves the scientific problem of one-step conversion of methane into liquid products by using light energy at room temperature, and provides a new, more economic and environmental protection solution for the conversion of methane into high value-added chemical products (such as rocket propellant fuel) At the same time, the further study and application of this highly efficient and sustainable photocatalytic model will provide new ideas and prospects for the efficient utilization of rare earth metal resources in China In the early morning of July 27, 2018 Beijing time, this major scientific research achievement was published online on the international top academic journal Science with the title of "selective functional of metal, ethane, and higher alkanes by ceriumphotocatalysis" The project was independently completed by the Zuo Zhiwei research group of Shanghai University of science and technology All four authors are from the school of material science and technology of Shanghai University of science and technology The average age is less than 30 years old Hu Anhua and Guo Jingjing are the co first authors, pan Hui, a 2016 graduate student with a bachelor's degree, is the second author, and Zuo Zhiwei is the corresponding author This research work was supported by the National Natural Science Foundation of China (general program) and the youth program of the thousand talents program As a kind of clean energy and chemical raw materials, natural gas has gradually become one of the most important natural resources of economic value with the increasing proved reserves and exploitation in recent years The direct chemical conversion of natural gas can not only realize the utilization of high added value, but also avoid the high cost and pollution caused by natural gas transportation Methane is the main compound in natural gas How to activate methane directly is the main challenge in science It is also the Holy Grail in the field of organic chemistry In September 2015, Dr Zuo Zhiwei, who has been engaged in the field of organic chemistry for many years, joined the University of science and technology Interestingly, Hu Anhua and Guo Jingjing, the two co first authors, were the first postdoctors to enter the research group of Zuo Zhiwei, and pan Hui, the second author, was the first postgraduates he interviewed Like the University of science and technology at the beginning of its establishment, four young people bravely started the process of scientific research "entrepreneurship" Centering on the orientation of "serving the national economic and social development strategy" of the University of science and technology, they are determined to launch a charge towards the scientific research peak of natural gas conversion and utilization from the beginning Methane is the smallest organic molecule and the most difficult to be activated in organic chemistry The low reactivity and solubility in solution brought by its inert hydrocarbon bond pose a great challenge to the activation of methane Therefore, in order to achieve high selectivity of methane conversion, rare and expensive precious metals (platinum, palladium, etc.) are generally used as high-efficiency catalysts, and high temperature is often needed to provide activation energy, which is far from the requirements of scale and economy in industry Photocatalytic oxidation-reduction catalysis transforms light energy into chemical energy through catalyst, which makes many chemical reactions go smoothly under mild room temperature They believe that using this new frontier catalytic technology to realize methane activation will open up a new direction of methane green activation With this vision, Zuo Zhiwei's team focuses on the development of cheap and sustainable catalysts, and on the efficient use of light energy to achieve the conversion and utilization of methane at room temperature The unique rare earth resources in China have aroused the strong interest of Zuo Zhiwei's research group Cerium accounts for more than 50% of China's rare earth resources Its low price and unique photophysical properties attract their attention Although cerium is rarely used as a catalyst in photoorganic reactions, through the analysis of the unique electronic structure of its high valence state, they have ventured to choose the ligand to metal electronic transition path, a previously neglected photoinduced transition process called LMCT for short, as a breakthrough point in the study of new photocatalysts After about a year of repeated experiments, they finally verified the feasibility of simple and easy to get cerium compounds in LMCT catalysis to convert light energy into chemical energy in the summer of 2016 At the end of 2017, further breakthroughs were made in the study of cerium catalyzed direct activation of primary alcohols, which enabled them to directly activate alcohols to form high-energy oxygen radicals by using light energy The completion of these two works means that the key elements of the catalytic cycle for photocatalytic conversion of methane designed by them two years ago have been possessed There is no precedent for methane activation in the field of photocatalytic oxidation-reduction catalysis The research team decided to select the main components of liquefied petroleum gas and propane as the early research object step by step Propane and methane are both inert gas molecules, and they have higher activity, which is helpful to establish the catalytic system as soon as possible The success of propane activation experiment is faster than expected Before the Spring Festival holiday in 2018, the research team has found an effective combination of cerium and alcohol catalysts As soon as they got back to the lab, they started the methane catalytic experiment Like "jigsaw puzzle", the most critical clue finally arrived unexpectedly On March 16, 2018, in the analysis spectrum of the gas chromatograph, a weak signal peak of 4.705 points relaxed their nervous mood Although it only represents 2.5% of the production rate, this signal peak marks the first appearance of methane activation products in the catalytic system After rounds of experimental parameter optimization and reactor improvement, the research team finally confirmed the optimal catalyst during the "May 1st" in 2018 through careful repeated experiments In this way, after two years of work accumulation, 148 days of sprint, 2202 attempts and optimization, zuozhiwei research group finally found a very cheap and efficient catalyst combination Under the synergism of the common trichloroethanol, the cheap rare earth metal cerium can produce methane catalytic effect comparable to the rare precious metal They successfully used the commercial LED light source as the reaction energy source, and successfully realized the conversion of highly selective methane to high value-added products at room temperature This system is characterized by breaking through the paradigm of methane activation based on the insertion of noble metal hydrocarbon bonds in homogeneous catalysis, efficiently using cerium catalyst to convert light energy into chemical energy, adopting hydrogen transfer mode to directly activate methane into highly reactive methyl radicals, combining with free radical coupling The strategy can realize a series of light promoted functional group reactions and provide a new platform for methane activation with mild conditions and diverse transformation Ding kuiling, an organic chemist, academician of the Chinese Academy of Sciences, director of the Shanghai Institute of organic chemistry of the Chinese Academy of Sciences and vice president of Shanghai University of science and technology, thinks that“ Hydrocarbon bond activation and functionalization of methane is one of the most basic chemical reactions involving energy and chemical processes Due to the high stability and weak polarity of hydrocarbon bond in methane, its transformation is very challenging, and usually requires harsh reaction conditions such as high temperature and high pressure Therefore, how to realize the functionalization of hydrocarbon bond of methane under mild conditions is considered to be one of the chemical reactions The Holy Grail of The work of Zuo Zhiwei's team represents a new major breakthrough in the research of methane conversion Through the ingenious design of catalytic reaction and the promotion of light, the conversion of methane molecules is realized at room temperature, which opens a new way for the resource and high-value utilization of methane " David Macmillan, a professor at Princeton University and an academician of the National Academy of Sciences, one of the founders of modern photo redox catalysis, commented: "the Zuo Zhiwei team has made an amazing breakthrough In the past decade, many research directions in the field of photocatalytic oxidation-reduction catalysis have had an important impact on our society This new research result creates a new direction of methane activation, and their LMCT catalytic method will have undoubted application potential in medicine, agricultural chemicals, fine chemicals and other industries This is a work completed by a young research group from China that will have a wide range of influence in the world I am looking forward to their next breakthrough " Alexander van der made, senior chief scientist of new energy technology of shell, the Netherlands, and sander van BAVEL, project manager of methane conversion agreed: "in the field of alkane activation, this work is a reflection of excellent and delicate chemical design More importantly, this discovery marks a key step in the green conversion of alkanes under mild conditions Finally, the development of this direction will provide solutions for the chemical industry to make full use of methane, a rich natural resource " It is worth mentioning that the unique cerium catalyst system developed by Zuo Zhiwei's research group has attracted the attention of the industry for its low cost and practicability At the end of 2017, Zhejiang Jiuzhou Pharmaceutical Co., Ltd., one of the leading domestic pharmaceutical enterprises, signed a cooperative transfer agreement on cerium catalytic oxidation reaction with Shanghai University of science and technology In the recent large and medium-sized pilot plant, the R & D personnel have made great progress in process amplification in a very short time At present, they have the conditions for 100kg level production Meiyi, deputy general manager of Jiuzhou pharmaceutical industry, will think: "we are very excited by the results obtained by using cerium catalytic system! Not only the catalyst cost is low, but also the reaction condition is green and environmental protection, which is very consistent with our green development strategy We have set up a backbone research team and Professor Zuo's research team to cooperate in depth The strong innovation power of USTC and the strength of promoting the integration of science, education and industry also make us confident on the road of industrialization of this internationally leading new technology " The relaxed scientific research environment and personnel training system of USTC provide scientists with a vast space Yang Peidong, founding president of the school of materials, academician of the National Academy of Sciences and professor of the University of California, Berkeley, was very pleased with the result: "since the founding of the University of science and technology, we have been committed to creating an independent and original academic environment with full academic freedom, so that our young teachers can release their energy and creativity to the maximum extent The great breakthrough of Zuo Zhiwei's team fully reflects this point In a very short period of time, the research team creatively uses China's unique rare earth resources to solve the scientific problem of methane activation, which is of great significance to China and the world " On April 15, 2016, the State Council issued the construction plan of Shanghai Science and technology innovation center, which clearly pointed out that Shanghai University of science and technology has an important task in the construction of Zhangjiang comprehensive national science center At present, the university is cooperating with the Scientific Research Institute of Shanghai Branch of Chinese Academy of Sciences and other units to be responsible for or participate in the construction of soft X-ray free electron laser user device, live cell structure and functional imaging line station project, super short laser experimental device, Shanghai light source phase II line station project, and the construction of hard X-ray free electron laser device of the lead
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