Conversion of Dinitrogen and Oxygen to Nitric Oxide Mediated by Triatomic Yttrium Cations: Reversible N–N Bond Switching

Abstract

The direct coupling of dinitrogen (N 2 ) and oxygen (O 2 ) to produce value-added chemicals such as nitric acid (HNO 3 ) at room temperature is fascinating but quite challenging because of the inertness of N 2 molecules. Herein, an interesting reaction pathway is proposed for a direct conversion of N 2 and O 2 mediated by all-metal Y 3 + cations. This reaction pattern begins with the N�N triple bond cleavage by Y 3 + to generate a dinitride cation Y 2 N 2 + , and the electrons that lead to N 2 activation in this process mainly originate from Y atoms. In the following consecutive reactions with two O 2 molecules, the electrons stored in the N atoms are gradually released to reduce O 2 through reformation and re-fracture of the N−N bonds, with concomitant release of two NO molecules. Therefore, the reversible N−N bond switching acts as an efficient electron reservoir to drive the oxidation of the reduced N atoms, leading to the formation of NO molecules. This method of producing NO by direct coupling N 2 and O 2 molecules, which is the reversible N−N bond switching, may provide a new strategy for the direct synthesis of HNO 3 , etc.

Dinitrogen Activation by Heteronuclear Metal Carbide Cluster Anions Y1‐3CoC1,2−: An Experimental and DFT Study

“…[42,43] The findings of these studies on clusters may provide some molecular-level reaction mechanisms of N 2 activation on practical NRR catalysts. Particularly, clusters containing Y [44][45][46][47] or Co [48] and some metal carbide clusters, such as Y 2 C 4 À and Y 2 C 4 H À , [46] CoTaC 2 À , [48] V 3 C + , [49] V 3 C 4 À , [50] Ta 2 C 4 À , [51] PtC 4-6 À , [52] FeV 2 C 2 À , [53] FeTaC 2 À , [54] V 3-…”

Nitrogen adsorption on Nb2C6H4+ cations: the important role of benzyne (ortho-C6H4)

“…Gas-phase studies on “isolated” reactants provide an ideal venue for investigating reaction mechanisms and kinetics at a strictly molecular level. 7,23–26 Recently, some encouraging developments in N 2 activation have been reported in the gas phase studies, 27–31 and the ligand effect significantly affects cluster reactivity. Gas-phase clusters usually contain metal atoms coupled with inorganic ligands, such as oxygen, boron, hydrogen, carbon, sulfur, and so on.…”

Coupling of N2 and O2 in the Gas Phase to Synthesize Nitric Oxide at Room Temperature: A Zeldovich-Like Strategy

“…Quite recently, we reported that Y 2 BO + and Y 3 + cations can directly form NO molecules from simple N 2 and O 2 at room temperature, which are the only two gas-phase species that can couple N 2 and O 2 . 38,39 To the best of our knowledge, no gas-phase anion has been reported to be able to react with N 2 and O 2 . According to previous literature reports, noble metal-based catalysts exhibit high reactivity for N 2 activation and conversion, 40−42 and there are few reports on quaternary clusters-mediated N 2 reduction.…”

“…Gas-phase studies provide an ideal venue for experimental and theoretical mechanistic studies of chemical processes at the strictly molecular level. − The activation and functionalization of N 2 − or O 2 − mediated by gas-phase species have been extensively studied. Quite recently, we reported that Y 2 BO + and Y 3 + cations can directly form NO molecules from simple N 2 and O 2 at room temperature, which are the only two gas-phase species that can couple N 2 and O 2 . , To the best of our knowledge, no gas-phase anion has been reported to be able to react with N 2 and O 2 . According to previous literature reports, noble metal-based catalysts exhibit high reactivity for N 2 activation and conversion, − and there are few reports on quaternary clusters-mediated N 2 reduction. , In this context, we identified the reactions for N–O coupling from N 2 and O 2 mediated by the heteronuclear metal anion AuNbBO – .…”

“…This transition from N 2 and O 2 to NO can be labeled as a Zeldovich-like mechanism. Quite recently, we reported that Y 2 BO + and Y 3 + cations can directly form NO molecules from simple N 2 and O 2 at room temperature. , Their reaction mechanisms are aromaticity-dearomative oxidation and reversible N–N bond switching, respectively. Their reactions begin with the NN triple bond cleavage by ions to generate dinitride cation ions, and the electrons that lead to N 2 activation in this process mainly originate from Y and B atoms.…”