NO2-catalyzed deep oxidation of methanol: Experimental and theoretical studies

Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH3OH+OH reaction

“…Their calculated energy barriers are in agreement with those obtained for HNO 2 + CH 2 OH/CH 3 O by Xiao et al, but their overall rate coefficient is much lower than predicted by Xiao et al due to the absence of the HONO formation channels. The experimental values from Anastasi and Hancock 136 for 639–713 K are in line with the faster reaction rate proposed by Xiao et al 135, whereas the results from Koda and Tanaka 31 support the lower rate constant from Teng et al 137. In the present mechanism, the more extensive theoretical treatment by Xiao et al is preferred yielding rate expressions for both HONO (R83) and HNO 2 formation (R84), but further experimental work is needed for verification.…”

“…The H‐abstraction reaction of NO 2 + CH 3 OH (R83, R84) is the primary initiation reaction in the CH 3 OH/O 2 /NO x system. Recent ab initio calculations by Xiao et al 135 indicate that CH 2 OH + cis ‐HONO are the major products, formed via two possible transition state configurations depending on the attacking orientation of NO 2 . Xiao et al calculated energy barriers of 21.2 and 20.5 kcal/mol for these channels in good agreement with experimental results from Anastasi and Hancock 136, and Koda and Tanaka 31, who obtained activation energies of 21.4 and 22.6 kcal/mol respectively for the overall reaction.…”

Recent Advances in the Catalytic Oxidation of Volatile Organic Compounds: A Review Based on Pollutant Sorts and Sources

“…This higher oxidation capacity of NO2 than O2 in the reoxidation of the vanadia reduced sites induced a speeding up of the oxidation cycle in the first step, which corresponds to the increase in CB conversion. 1078 Zhang and co-workers 1079 proposed that the existence of NOx could dramatically promote the oxidation of methanol as demonsrated by the reduced reaction temperature and significantly enhanced CO2 selectivity.…”

“…This higher oxidation capacity of NO 2 than O 2 in the reoxidation of the vanadia reduced sites led to an acceleration of the oxidation cycle in the first step, which corresponds to an increase in CB conversion. 1078 and co-workers 1079 proposed that the existence of NO x could dramatically promote the oxidation of methanol, as demonstrated by the reduced reaction temperature and significantly enhanced CO 2 selectivity. Mrad et al 1029 found that NO can compete with propene for the active metal sites, causing a reduction in propene conversion over CuMgAlFeO x hydrotalcite-like catalysts.…”

Methanol-Promoted Oxidation of Nitrogen Oxide (NOx) by Encapsulated Ionic Liquids

“…This interesting difference in the trends might be explained by increased HNO 3 formation when more water is present in the system (see figure S4 of the Supporting Information). An interesting work by Xiao et al 66 3and (4) may be occurring in our system due to the observed nitrous acid (HONO) and the absence of NO 2 in the UV-Vis spectrum (see Figure S5 in Supporting Information), not only while adding the first droplets but also at the steady state (especially when high conversions were found). This was immediately found when methanol was added to the system.…”