Template free synthesis of graphitic carbon nitride nanotubes mediated by lanthanum (La/g-CNT) for selective photocatalytic CO2 reduction via dry reforming of methane (DRM) to fuels

Abstract

Template-free fabrication of graphitic carbon nitride nanotubes modified with lanthanum (La/g-CNT) for dynamic photo-catalytic CO2 reduction with CH4 has been investigated. Successful fabrication of g-C3N4 nanosheets and nanotubes were obtained with enhanced photo-activity under visible-light. Using 5 wt% La/g-CNT, CO yield of 491 mu mole g-cat(-1) h(-1) was obtained which is 3.6 and 5.9 folds higher than g-CNS and g-CN samples. Similarly, production of H-2 was highest over La/g-CNT which was 2.95 folds more than g-CNT and 5.1 times higher than using g-CN. Although, pristine g-CN has more basic sites and larger BET surface area but enhanced photo-activity over La/g-CNT can be attributed to efficient transfer of electrons over 1D structure and separation of charge carriers by La. More interestingly, effect of CH4/CO2 feed ratios was obvious, whereas, highest CO was produced at CH4/CO2 ratio of 1.0 but H-2 was maximum with ratio of 2.0. Among the different reaction systems, highest CO was obtained using DRM, while CO2 reduction by H-2/H2O promoted both CO and CH4 production. This was obviously due to basic characteristics, sorption competition over the catalyst surface and favorable reverse water gas shift (RWSG) reaction. The stability test further confirmed the suitability of this material which prevailed until three cycles without obvious deactivation. This work will open new opportunities to develop structured nanocalaysts for solar energy based reutilization of CO2 and CH4 for the production of renewable fuels.