Nitrogenous Intermediates in NOx-involved Electrocatalytic Reactions.

Chemical manufacturing utilizing renewable sources and energy emerges as a promising path towards sustainability and carbon neutrality. The electrocatalytic reactions involving nitrogen oxides (NOx) offered a potential strategy for synthesizing various nitrogenous chemicals. However, it is currently hindered by low selectivity/efficiency and limited reaction pathways, mainly due to the difficulties in controllable generation and utilization of nitrogenous intermediates. In this minireview, focusing on nitrogenous intermediates in NOx-involved electrocatalytic reactions, we discuss newly developed methodologies for studying and controlling the generation, conversion, and utilizing of nitrogenous intermediates, which enable recent developments in NOx-involved electrocatalytic reactions that yield various products, including ammonia (NH3), organonitrogen molecules, and nitrogenous compounds exhibiting unconventional oxidation states. Furthermore, we also make an outlook to highlight future directions in the emerging field of NOx-involved electrocatalytic reactions.

In situ Generation of Cyclohexanone Drives Electrocatalytic Upgrading of Phenol to Nylon-6 Precursor.

Coupling in situ generated intermediates with other substrates/intermediates is a viable approach for diversifying product outcomes of catalytic reactions involving two or multiple reactants. Cyclohexanone oxime is a key precursor for caprolactam synthesis (the monomer of Nylon-6), yet its current production uses unsustainable carbon sources, noble metal catalysts, and harsh conditions. Herein, we report the first work to synthesize cyclohexanone oxime through electroreduction of phenol and hydroxylamine. The Faradaic efficiency reached 69.1% over Cu catalyst, accompanied by a corresponding cyclohexanone oxime formation rate of 82.0 g h-1 gcat-1. In addition, the conversion of phenol was up to 97.5%. In situ characterizations, control experiments, and theoretical calculations suggested the importance of balanced activation of water, phenol, and hydroxylamine substrates on the optimal metallic Cu catalyst for achieving high-performance cyclohexanone oxime synthesis. Besides, a tandem catalytic route for the upgrading of lignin to caprolactam has been successfully developed through the integration of thermal catalysis, electrocatalysis, and Beckmann rearrangement, which achieved the synthesis of 0.40 g of caprolactam from 4.0 g of lignin raw material.

Dehydroaromatization of Indolines and Cyclohexanones with Thiol Access to Aryl Sulfides under Basic Conditions.

Aryl sulfides are common and ubiquitous motifs in natural products and pharmaceuticals. Presented herein is the first example of the synthesis of diaryl sulfide derivatives via dehydroaromatization under simple basic conditions. Dehydroaromatization reactions between indolines or cyclohexanones with aryl thiols are performed in an environmentally benign manner by the use of air (molecular oxygen) as the oxidant, with producing water as the only byproduct. The methodology provides a simple and practical route to diaryl sulfides with wide functional groups in good to excellent yields. Preliminary mechanistic studies suggest that a radical process is involved in the transformation.