Direct conversion of methane to formaldehyde and CO on BO catalysts.

Direct oxidation of methane to value-added C chemicals (e.g. HCHO and CO) provides a promising way to utilize natural gas sources under relatively mild conditions. Such conversions remain, however, a key selectivity challenge, resulting from the facile formation of undesired fully-oxidized CO. Here we show that BO-based catalysts are selective in the direct conversion of methane to HCHO and CO (~94% selectivity with a HCHO/CO ratio of ~1 at 6% conversion) and highly stable (over 100 hour time-on-stream operation) conducted in a fixed-bed reactor (550 °C, 100 kPa, space velocity 4650 mL g h). Combined catalyst characterization, kinetic studies, and isotopic labeling experiments unveil that molecular O bonded to tri-coordinated BO centers on BO surfaces acts as a judicious oxidant for methane activation with mitigated CO formation, even at high O/CH ratios of the feed. These findings shed light on the great potential of designing innovative catalytic processes for the direct conversion of alkanes to fuels/chemicals.