Photocatalytic conversion of carbon dioxide (CO2) into gaseous hydrocarbon fuels is an auspicious way to produce renewable fuels in addition to greenhouse gas emission mitigation. In this work, non-metals (B, O, P, and S) doped graphitic carbon nitride (g-C3N4) was prepared via solid-state polycondensation of urea for photocatalytic CO2 reduction into highly needed methane (CH4) with water under UV light irradiation. The various physicochemical characterization results reveal the successful incorporation of B, O, P, and S elements in the g-C3N4 matrix. The maximum CH4 yield of 55.10 nmol/(mLH2O.gcat) over S-doped g-C3N4 has been obtained for CO2 reduction after 7 h of irradiation. This amount of CH4 production was 1.9, 1.4, 1.7, and 2.4-folds higher than B, O, P and bare g-C3N4 samples. The doping of S did not enlarge the surface area and photon absorption ability of the g-C3N4 sample, but this significant improvement was evidently due to effective charge separation and migration. The observed results imply that the doping of non-metal elements provides improved charge separation and is an effective way to boost photocatalyst performance. This work offers an auspicious approach to design non-metal doped g-C3N4 photocatalysts for renewable fuel production and would be promising for other energy application.
This study investigates the facile fabrication of interfacial defects assisted amorphous TiO2 nanotubes arrays (am-TNTA) for promoting gas-phase CO2 photoreduction to methane. The am-TNTA catalyst was fabricated via a one-step synthesis, without heat treatment, by anodization of Titanium in Ethylene glycol-based electrolyte in a shorter anodizing time. The samples presented a TiO2 nanostructured array with a nanotubular diameter of 100 ± 10 nm, a wall thickness of 26 ± 5 nm, and length of 3.7 ± 0.3 μm, resulting in a specific surface of 0.75 m2 g. The am-TNTA presented prolonged chemical stability, a high exposed surface area, and a large number of surface traps that can reduce the recombination of the charge carriers. The am-TNTA showed promising photoactivity when tested in the CO2 reduction reaction with water under UV irradiation with a methane production rate of 14.0 μmol gcat-1 h-1 for a pure TiO2 material without any modification procedure. This enhanced photocatalytic activity can be explained in terms of surface defects of the amorphous structure, mainly OH groups that can act as electron traps for increasing the electron lifetime. The CO2 interacts directly with those traps, forming carbonate species, which favors the catalytic conversion to methane. The am-TNTA also exhibited a high stability during six reaction cycles. The photocatalytic activity, the significantly reduced time for synthesis, and high stability for continuous CH4 production make this nanomaterial a potential candidate for a sustainable CO2 reduction process and can be employed for other energy applications.
Enhancing the catalytic performance of non-noble Ni catalysts in the selective hydrogenation of furfural to furfuryl alcohol (FA) in terms of furfural conversion, selectivity, and good recyclability is challenging. Here, spherical nickel phyllosilicate catalysts (Ni_PS) with fibrous-like structures are prepared via a modified sol-gel method with Ni loadings of 2-30 wt %. Upon exposure to air, all the reduced Ni_PS catalysts exhibit more than 80% Ni0/Niphyllosilicate species on the surface, whereas a large portion of Ni oxide species (>55%) is presented on the impregnated catalyst. The Ni2+ species in nickel phyllosilicate catalysts are active and highly stable during reduction, reaction, and regeneration, yielding stable catalytic performance for multiple recycle tests in furfural hydrogenation to FA. Furfural conversion over the Ni_PS catalysts increased monotonically with increasing Ni loading without an FA selectivity drop. The presence of both metallic Ni0 and Niphyllosilicate also produces a synergistic promotional effect for FA formation.
Synthesis of carbon nanostructures at room temperature and under atmospheric pressure is challenging but it can provide significant impact on the development of many future advanced technologies. Here, the formation and growth characteristics of nanostructured carbon films on nascent Ag clusters during room-temperature electrochemical CO2 reduction reactions (CO2RR) are demonstrated. Under a ternary electrolyte system containing [BMIm]+[BF4]-, propylene carbonate, and water, a mixture of sp2/sp3 carbon allotropes were grown on the facets of Ag nanocrystals as building blocks. We show that (i) upon sufficient energy supplied by an electric field, (ii) the presence of negatively charged nascent Ag clusters, and (iii) as a function of how far the C-C coupling reaction of CO2RR (10-390 min) has advanced, the growth of nanostructured carbon can be divided into three stages: Stage 1: sp3-rich carbon and diamond seed formation; stage 2: diamond growth and diamond-graphite transformation; and stage 3: amorphous carbon formation. The conversion of CO2 and high selectivity for the solid carbon products (>95%) were maintained during the full CO2RR reaction length of 390 min. The results enable further design of the room-temperature production of nanostructured carbon allotropes and/or the corresponding metal-composites by a viable negative CO2 emission technology.