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Sulfur-resistant Mo-based catalysts have become promising for the one-step synthesis of methanethiol (CH3SH) from CO/H2/H2S, but the low reactant conversion and poor product selectivity have constrained its development. Herein, we synthesized K-MoS2/Al2O3 and K-Mo2C/Al2O3 catalysts via the sulfurization and carbonization of K-Mo-based catalysts in the oxidized state, respectively. During the synthesis of CH3SH, both K-Mo2C/Al2O3 and K-MoS2/Al2O3 showed excellent catalytic performance, and the activity of the former is superior to that of the latter. The effect of different treatments on the catalytic performance of Mo-based catalysts was investigated by XRD, BET, Raman spectroscopy, H2-TPR, and reactants-TPD characterization. The results showed that the sulfide-treated sample showed stronger metal-support interactions and contributed to the formation of K2S, which exposed more active sites and stabilized the formation of C-S bonds. Carbonized samples enhanced the activation of H2, which promoted the hydrogenation of the intermediate species of carbonyl sulfide (COS) and thus improved the selectivity of CH3SH.

Nitrous acid (HONO) and nitrogen oxides (NOx = NO + NO2) are important atmospheric pollutants and key intermediates in the global nitrogen cycle, but their sources and formation mechanisms are still poorly understood. Here, we investigated the effect of soluble iron (Fe3+) on the photochemical behaviour of a widely used neonicotinoid (NN) insecticide, nitenpyram (NPM), in the aqueous phase. The yields of HONO and NOx increased significantly when NPM solution was irradiated in the presence of iron ions (Fe3+). We propose that the enhanced HONO and NO2 emissions from the photodegradation of NPM in the presence of iron ions result from the redox cycle between Fe3+ and Fe2+ and the generated reactive oxygen species (ROS) by the electron transfer between the excited triplet state of NPM and the molecular oxygen O2). Using the laboratory-derived parametrization based on kinetic data and gridded downward solar radiation, we estimate that the photochemistry of NPM induced by Fe3+ releases 0.50 and 0.77 Tg N year-1 of NOx and HONO to the atmosphere, respectively. This study suggests a novel source of HONO and NOx during daytime and potentially helps to narrow the gap between the field observations and model outcomes of HONO in the atmosphere. The suggested photochemistry of NPM can be an important contribution to the global nitrogen cycle affecting the atmospheric oxidizing capacity as well as the climate change. [ABSTRACT FROM AUTHOR]