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Regulating the Ammonia Oxidation Selectivity via the Quantified Provision of Molecular Oxygen

Jielin Wang, Xin Li, Shujie Shen, Ruimin Chen, Qin Ren, Jieyuan Li, Fan Dong

2023ACS Catalysis14 citationsDOI

Abstract

Molecular oxygen (O 2 ) activation has been utilized as a feasible approach to promoting the oxidative capacity of general environmental and energy catalytic reactions. However, the selectivity of oxidation reactions regulated by quantification of molecular O 2 activation has not yet been clarified. By adjusting the concentration of dissolved oxygen ( C DO ), the quantified provision of molecular O 2 can be facilely accomplished, which could directly regulate the production of reactive oxygen species (ROS) for targeted oxidative products. Herein, by taking ammonia oxidation as a typical multielectron-involved reaction, the selectivity is precisely tailored by quantified activation of molecular O 2, in which P25 is utilized as the photocatalyst. Under the sufficient provision of molecular O 2 activation ( C DO = 20.0 mg L –1 ), the deep oxidation of NH 3 into NO x – (NO 2 – and NO 3 – ) is achieved via the ROS-driven mechanism. In contrast, selective production of N 2 from partial NH 3 oxidation is noted along with the h + -driven direct oxidation mechanism ( C DO = 0.1 mg L –1 ). Then comprehensive in situ characterization under different C DO and theoretical calculations are combined, revealing that the regulation of product selectivity by quantified provision of the O 2 can be attributed to the selective generation of ROS. It is proposed that the strategy of quantified activation of molecular O 2 can be developed as an effective method, which offers opportunities for regulating the oxidation selectivity for important environmental and energy reactions.

Topics & Concepts

SelectivityChemistryCatalysisReactive oxygen speciesOxygenRedoxAmmoniaMolecular oxygenPhotochemistryOxidative phosphorylationReaction mechanismCombinatorial chemistryInorganic chemistryOrganic chemistryBiochemistryAdvanced Photocatalysis TechniquesCatalytic Processes in Materials ScienceAmmonia Synthesis and Nitrogen Reduction
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