Research group of Professor Lu Tong Department of Tianjin University of Technology: controllable synthesis of vacancy defect single atom catalyst and its application in the reduction of carbon dioxide by Electrocatalysis

In today's society, the massive consumption of fossil energy leads to the increasing concentration of carbon dioxide in the atmosphere, which brings about serious climate and environmental problems Therefore, the key to solve the problem is to reduce the concentration of carbon dioxide and realize its efficient conversion Among them, electrocatalytic reduction of carbon dioxide is considered to be a clean and potential way of carbon dioxide conversion The development of efficient electrocatalytic reduction catalysts for carbon dioxide has become a research hotspot in this field Among them, single atom catalyst (SAC) is widely used in electrocatalytic reactions because of its high atom utilization and catalytic activity Optimizing the coordination environment of metal atoms in sac is an important strategy to enhance its catalytic activity However, there is no effective method to synthesize sac with vacancy defects Recently, the research group of Professor Lu Tong of new energy materials and low carbon technology research institute of Tianjin University of science and technology has developed a method to control the preparation of sac with vacancy defects, and through the introduction of vacancy defects, sac has realized the efficient electrocatalytic reduction of CO 2 to Co The results were published in angew Chem Int ed (DOI: 10.1002 / ange 201912458) A brief introduction to the research group of Professor of Lu Tong Bu, which is mainly engaged in the research of artificial photosynthesis catalyst in recent years In the study of photocatalytic decomposition of water catalyst, the first nickel based molecular catalyst for water oxidation (angelw Chem Int ed 2014, 53, 13042) was reported A new broad spectrum photosensitizer was designed and synthesized, which significantly improved the utilization efficiency of photosensitizer for visible light (NAT Commin 2019, 10, 3155), a new type of electrocatalytic hydrogen generation molecular catalyst (angelw Chem Int ed 2019, 58, 10923) was designed and synthesized In addition, we also designed and synthesized the MOF based total water dissociation Photocatalyst (chem SCI 2016, 7, 1070), the Ni2P @ NiFe hydroxy compound heterojunction based total water dissociation bifunctional electrocatalyst (chem SCI 2018, 9, 1375), and the graphite phase carbon nitride @ graphene heterojunction based total water dissociation Photocatalyst (adv energy mater 2018, 8, 1702992), an efficient electrocatalytic hydrogen production catalyst based on single atom platinum (angelw Chem Int ed 2018, 57, 9382), etc In terms of photocatalytic carbon dioxide reduction, we designed and synthesized the heteronuclear carbon dioxide photoreduction molecular catalyst based on macrocyclic binuclear cobalt and zinc cobalt (angelw Chem Int ed 2017, 56, 738, cover paper; angelw Chem Int ed 2018, 57, 16480-16485), the concept of binuclear metal co catalysis was put forward; an efficient CO 2 reduction catalyst (angel Chem Int ed doi: 10.1002/ange.201912458) based on vacancy defect single atom nickel was proposed; a new type of Composite Photocatalyst (angel) was constructed by encapsulating perovskite quantum dots in the cavity of MOF to reduce CO 2 to methane and CO by electron generated by water oxidation Chem Int Ed 2019 , 58 , 9491）。 He was invited to write a review on coord Chem Rev (coord Chem Rev 2018, 377, 225; coord Chem Rev 2019, 378, 237), etc Prof Lu Tong, Professor, doctoral advisor In 1993, he graduated from the Department of chemistry of Lanzhou University and worked in the post doctoral mobile station of the Department of chemistry of Zhongshan University In 1995, he left the station to teach Transferred to Tianjin University of technology in 2016 Mainly engaged in the research of artificial photosynthesis catalyst He has successively presided over research subjects such as national key R & D plan (subject), National Science and technology major project, national fund for Distinguished Young Scholars project, national fund key project and general project, Guangdong Natural Science Fund team project, and "973" program subproject of Ministry of science and technology More than 250 papers have been published in core magazines at home and abroad, including J am Chem SOC., angel Chem Int ed., NAT Commun., among which more than 220 papers are included in SCI It has been granted 23 Chinese invention patents He cited more than 7000 published papers, with an H index of 47 In 2005, he was selected into the "new century excellent talents support plan" of the Ministry of education, and in 2006, he was awarded the National Outstanding Youth Fund In 2012, he received special allowance from the State Council In 2012, he won the second prize of National Natural Science (ranking No 5), and in 2013, he won the second prize of National Natural Science (ranking No 3) In 2014, he was selected as a member of the Royal Society of Chemistry (FRSC), and in 2019, he was awarded as an outstanding scientific and technological worker in Tianjin At present, he is the director of China Crystal society, vice president of Tianjin Chemical Society, member of inorganic chemistry, crystal chemistry and molecular sieve Professional Committee of China Chemical Society, vice director of Academic Committee of Tianjin University of science and technology, Chinese director of "new energy materials" innovation subject introduction base, director of International Cooperation Joint Laboratory of Ministry of education of material microstructure, crystal engcomm, current Green chemistry, current pharmaceutical design, inorganic chemistry, Chinese inorganic analytical chemistry, editorial board of Journal of surface technology, and co editor of Acta C Journal of international crystallography Cutting edge scientific research achievements: controllable synthesis of vacancy deficient monoatomic catalysts and research in electrocatalytic reduction of carbon dioxide In recent years, supported by the national key research and development plan of the Ministry of science and technology, the National Natural Science Foundation of China and the academic innovation and intelligence introduction plan (111 plan) of the Ministry of education, etc, The research group of Professor Lu Tong Bu has carried out a series of work on the conversion of CO 2 by photocatalysis and electrocatalysis and monoatomic catalyst Among them, they designed mononuclear CO (II), Cu (II) and Ni (II) complexes based on tripodal ligands, combining photosensitizers and electron sacrificial agents Driven by visible light, these complexes showed good performance of photocatalytic reduction of CO 2 to CO (inorg Chem 2017, 56, 7307; chem EUR J 2018, 24, 4503; ACS catalyst 2018, 8, 7612) and further found that optimized ligands can enhance the ability of metal center to catalyze the reduction of CO 2 to CO (chemsuschem 2018, 11, 1025; chemcatchem 2018, 10, 3435; ACS apply Energy lett 2018, 1, 2452; chem Commun 2018, 54, 11308) On this basis, considering that most of the catalytic systems in vivo are binuclear or polynuclear systems, they further designed the dinuclear cobalt complex coco based on aza hole ether and the heteronuclear cobalt zinc complex cozn, which increased the ton and TOF of the catalyst to 65000 and 1.8 S-1 respectively, and achieved 98% of the co selectivity （ Angew Chem Int Ed   2017 , 56 , 738 ; Angew Chem Int Ed   2018 , 57 , 16480-16485）。 In view of the structural characteristics similar to that of homogeneous catalysts, they further optimized the mass specific activity of the electrocatalytic decomposition of hydrogen by adjusting the coordination environment based on the graphite alkyne monoatomic platinum catalyst, and revealed the important influence of the coordination environment of metal atoms in the monoatomic catalyst on its catalytic activity (angelw Chem Int ed 2018, 57, 9382) it is an effective strategy to optimize the coordination environment of monoatomic catalyst by adjusting vacancy defects and improve the catalytic performance On the basis of the previous research work, the research group of the Ministry of Lu Tong and the researcher of Shanghai light source silui have developed a strategy of controllable synthesis of single atom catalysts with vacancy defects According to theoretical calculation, vacancy defects optimize the free energy of CO 2 conversion to COOH * intermediate and co product desorption in electrocatalytic reaction, thus showing excellent catalytic activity and selectivity (angel Chem Int ed doi: 10.1002 / ange 201912458) Fig 1 Synthesis diagram and microstructure characterization of ni-n3-v (source: angelw Chem Int ed.) by introducing oxygen-containing and nitrogen-containing ligands into the precursor at the same time, and calcining with nickel ion at high temperature, the author has controllable synthesized a single atom nickel catalyst (ni-n3-v) with vacancy defects on the carbon cloth substrate The results of electron microscopy show that nickel atoms are uniformly dispersed on nitrogen doped carbon carriers Figure 2 Fine structure characterization of ni-n3-v and ni-n4 (source: angelw Chem Int ed.) the author has proved that Ni in ni-n3-v is + 1 valence by XAFS and XPS test, and ni-n3-v and ni-n4 do not contain Ni bond, which further proves that Ni presents monatomic distribution Figure 3 Performance test of ni-n3-v, ni-n4 and NC (source: angelw Chem Int ed.) under - 0.9 V vs rhe, the CO 2 reduction current density of ni-n3-v is as high as 65 MA / cm 2, Faraday efficiency is greater than 90%, TOF is 1.35 × 105 H-1, which is far greater than the comparison samples ni-n4 and NC, showing the advantages of vacancy defect control Figure 4 Theoretical calculation (source: angelw Chem Int ed.) shows that compared with ni-n3 and ni-n4, the introduction of vacancy defects makes ni-n3-v have the optimal free energy of CO 2 conversion to COOH * and co desorption, thus promoting the reduction of CO 2 Conclusion: the single atom nickel catalyst (ni-n3-v) with vacancy defect was synthesized by introducing oxygen and nitrogen ligands into the precursor simultaneously The introduction of vacancy defects optimizes the electrocatalytic reduction of CO 2 over a single atom nickel catalyst, and achieves high activity and selectivity The research results were published in angel Chem Int ed (DOI: 10.1002 / angle 201912458) under the title of "control synthesis of safety defect single atom catalyst for boosting CO 2 electricity" Dr Rong Xin, a direct doctoral student of Tianjin University of science and technology, and Dr Wang Hongjuan are the co first authors of the paper, while Dr Lu Xiuli, researcher Si Rui and Professor Lu Tongbu are the co correspondents of the paper Tianjin University of science and technology is the first unit to complete the thesis Nowadays, people and scientific research have been paid more and more attention in the economic life China has ushered in the "node of science and technology explosion" Behind the progress of science and technology is the work of countless scientists In the field of chemistry, in the context of the pursuit of innovation driven, international cooperation has been strengthened, the influence of Returned Scholars in the field of R & D has become increasingly prominent, and many excellent research groups have emerged in China For this reason, CBG information adopts the 1 + X reporting mechanism CBG information website, chembeangoapp, chembeango official micro blog, CBG information wechat subscription number and other platforms jointly launch the column of "people and scientific research", approach the representative research groups in China, pay attention to their research, listen to their stories, record their demeanor, and explore their scientific research spirit.