JACS: Ma Jiabi, associate professor of Beijing University of science and technology, has made important progress in the field of gas cluster chemistry

Recently, Ma Jiabi, associate professor of Beijing University of science and technology, made a deep research on the reactivity and structure of N 2, Ta 3n3h − and Ta 3n3 − gas clusters by means of mass spectrometry experiment, anion photoelectron spectroscopy experiment and high-precision quantum chemistry calculation, and obtained the first transition metal nitride cluster that can fix and fully activate N 2 molecules, revealing that The important role of H ligand in the reaction Relevant achievements were published in the International Journal of the American Chemical Society (if = 14.695, DOI: 10.1021 / JACS 9b03168) under the title of "diligent fixation and reduction by TA 3n3h 0,1 − cluster anions at room temperature: Hydraulic assisted enhancement of reactivity" Zhao Yue, a master's student, is the first author of the paper Mr Ma Jiabi, an associate professor, Mr Andr é fiericke of Fritz Haber Institute in Germany, and Mr Hu Lianrui of Xihua University are the co correspondents of the paper As an inert molecule, the activation and reduction of N2 is one of the most challenging topics in chemistry As a long-term goal, to study the mechanism of N 2 activation, researchers have done a lot of experimental and theoretical research on the reactions of various reagents and nitrogen Reduction of N 2 to NH 3 in industry requires extreme conditions to weaken and destroy the strong n ≡ n bond In order to overcome this challenge, researchers usually rely on transition metal compounds to provide electron weakening or cleavage of n ≡ n bond to improve the reactivity of N 2 In addition to the activation of N2 by Fe catalyst in Haber process, the transition metal tantalum nitrogen and tantalum hydrogen compounds can also activate N2, which are closely related to the activation center In this context, it is of great scientific significance to study the reaction law of N2 and the role of transition metal nitrides and hydrides in the activation of N2 Based on the above difficulties, Ma Jiabi, associate professor of School of chemistry and chemical engineering, Beijing University of science and technology, used advanced mass spectrometry experiments to measure reactivity, anion photoelectron spectroscopy experiments to study structure, combined with high-precision quantum chemical calculation method, revealed the excellent reactivity of TA 3n3h − clusters in N 2 activation reaction, and the importance of h-ligands The results show that both TA 3N 3H − and Ta 3N 3 − clusters can completely activate 1 molecule N 2 and generate adsorption products TA 3N 5h − and Ta 3N 5 −, while the reaction rate of the former is 5 times faster than that of the latter The in-depth theoretical calculation shows that N 2 is completely dissociated in the reaction of TA 3n3h − and Ta 3n3 − clusters with N 2; in addition, two and three Ta atoms are the active sites of N 2 reduction and also the electron donors of N 2 reduction Although the hydrogen atom in ta3n3h − does not directly participate in the reaction, it changes the charge distribution and geometry of ta3n3h − and improves the reactivity of the clusters This is the first example of the complete activation of N 2 by nitrogen cluster anions at room temperature This work also highlights the importance of hydrogen assisted reactions and provides a molecular level view for the design of catalysts for the immobilization and activation of N 2 and the synthesis of NH 3 In addition, the team has made a series of progress in the activation of CO2 by transition metal nitride cationic clusters It has been found that scnh + cation can activate CO 2 efficiently and produce high value-added organic compound isocyanic acid (HNCO) This is the first example of the formation of HNCO through the activation of CO 2 mediated by gas phase ions, and the formation of C=N double bond was first realized in the activation of CO 2 This achievement was published in the Journal of physical chemistry a (2019, 123, 5762-5767), and was selected as the front cover These works provide new methods and new ideas for understanding the mechanism of CO 2 catalytic reaction.