Ag-La loaded protonated carbon nitrides nanotubes (pCNNT) with improved charge separation in a monolithic honeycomb photoreactor for enhanced bireforming of methane (BRM) to fuels

Abstract

Well-designed Ag-La modified protonated graphitic carbon nitride nanotubes (pCNNT) are fabricated via a template-free sonicated assisted one-pot hydrothermal method. The structure and properties of the catalyst samples are obtained by XRD, SEM, TEM, EDX, N2-sorption, XPS, UV–vis DRS and PL spectroscopy characterization techniques. The effect of Ag-La-modified pCNNT is evaluated for different CH4 reforming processes such as dry reforming of methane (DRM) and bi-reforming of methane (BRM), carried out in a fixed-bed and monolithic honeycomb photoreactor systems under UV and visible light irradiations. The optimized 3%Ag-5%La/pCNNT performance displayed increased productivity under UV-light due to more production of charges with strong ability for cleaving both stable CO2 and CH4 molecules. More importantly, the performance of Ag-La loaded pCNNT is 1.45 and 2.10 folds higher for CO and H2 production, respectively compared with Ag-La loaded pCN nanosheets. CO and H2 evolutions prevailed in a monolith photoreactor compared to fixed-bed reactor. Besides, the amount of CO, H2 and CH3OH are 1.79, 2.12 and 2.13 folds higher in BRM compared to DRM. The improved performance can be ascribed to effective interfacial carrier separation due to Ag-La synergistic effect with suitable redox potentials for BRM process. The quantum yield is significantly enhanced with BRM in the monolithic honeycomb photoreactor loaded with Ag-La modified pCNNTs due to greater photon energy utilization, larger illuminated surface area, improved sorption process and surface reactions with efficient charge carrier utilization for CO2 reduction and CH4/H2O oxidation. Reaction mechanism is proposed to commensurate with the performance of Ag-La/pCNNT for BRM process based on characterization analysis and experimental results. The experimental results could provide guidance for further development of advanced and highly efficient hetero-structures for photocatalytic BRM applications.