Nitrogen Activation and Transformation on Monometallic Niobium Boron Oxide Cluster Anions at Room Temperature: A Dual-Site Mechanism

• Published in: The journal of physical chemistry letters Vol. 12; no. 27; pp. 6313 - 6319
• Main Authors: Wang, Ming, Zhou, Hai-Yan, Messinis, Antonis M, Chu, Lan-Ye, Li, Ying, Ma, Jia-Bi
• Format: Journal Article
• Language: English
• Published: American Chemical Society 15.07.2021
• Subjects: Physical Insights into Chemistry, Catalysis, and Interfaces
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.1c01633

Dinitrogen activation and transformation at room temperature is a goal that has been long sought after. Despite that, it remains underdeveloped due to being a challenging research area and the need for a better mechanistic understanding. Herein, we report that well-defined NbB3O2 – gas-phase clusters can activate one N2 molecule and generate the products B3N2O– and B3N2O2 –, as applying mass spectrometry and theoretical calculations. This unusual N2 activation reaction results from the different functions of the Nb and B3O2 moieties in NbB3O2 –. Theoretical calculations suggest that a catalytic cycle can be completed by the recovery of NbB3O2 –, which is achieved through the reactions of Nb and NbO with B3O2 – and B3O–, respectively. This is the first example of N2 efficient transformation at a monometallic cluster, and this method for generating dual active sites by designing proper ligands may open the way toward the development of more effective N2 fixation and functionalization methodologies.