The electro/photocatalytic CO2 reduction reaction (CO2RR) is a long-term avenue toward synthesizing renewable fuels and value-added chemicals, as well as addressing the global energy crisis and environmental challenges. As a result, current research studies have focused on investigating new materials and implementing numerous fabrication approaches to increase the catalytic performances of electro/photocatalysts toward the CO2RR. MXenes, also known as 2D transition metal carbides, nitrides, and carbonitrides, are intriguing materials with outstanding traits. Since their discovery in 2011, there has been a flurry of interest in MXenes in electrocatalysis and photocatalysis, owing to their several benefits, including high mechanical strength, tunable structure, surface functionality, high specific surface area, and remarkable electrical conductivity. Herein, this review serves as a milestone for the most recent development of MXene-based catalysts for the electrocatalytic and photocatalytic CO2RR. The overall structure of MXenes is described, followed by a summary of several synthesis pathways classified as top-down and bottom-up approaches, including HF-etching, in situ HF-formation, electrochemical etching, and halogen etching. Additionally, the state-of-the-art development in the field of both the electrocatalytic and photocatalytic CO2RR is systematically reviewed. Surface termination modulation and heterostructure engineering of MXene-based electro/photocatalysts, and insights into the reaction mechanism for the comprehension of the structure-performance relationship from the CO2RR via density functional theory (DFT) have been underlined toward activity enhancement. Finally, imperative issues together with future perspectives associated with MXene-based electro/photocatalysts are proposed.
The extensive examination of hexagonal molybdenum carbide (β-Mo2C) as a non-noble cocatalyst in the realm of photocatalytic H2 evolution is predominantly motivated by its exceptional capacity to adsorb H+ ions akin to Pt and its advantageous conductivity characteristics. However, the H2 evolution rate of photocatalysts modified with β-Mo2C is limited as a result of their comparatively low ability to release H through desorption. Therefore, a facile method was employed to synthesize carbon intercalated dual phase molybdenum carbide (MC@C) quantum dots (ca. 3.13 nm) containing both α-MoC and β-Mo2C decorated on g-C3N4 (gCN). The synthesis process involved a simple and efficient combination of sonication-assisted self-assembly and calcination techniques. 3-MC@C/gCN exhibited the highest efficiency in generating H2, with a rate of 4078 µmol g-1h-1 under 4 h simulated sunlight irradiation, which is 13 times higher than pristine gCN. Furthermore, from the cycle test, 3-MC@C/gCN showcased exceptional photochemical stability of 65 h, as it maintained a H2 evolution rate of 40 mmol g-1h-1. The heightened level of activity observed in the 3-MC@C/gCN system can be ascribed to the synergistic effects of MoC-Mo2C that arise due to the existence of a carbon layer. The presence of a carbon layer enhanced the transmission of photoinduced electrons, while the MoC-Mo2C@C composite served as active sites, thereby facilitating the H2 production reaction of gCN. The present study introduces a potentially paradigm-shifting concept pertaining to the exploration of novel Mo-based cocatalysts with the aim of augmenting the efficacy of photocatalytic H2 production.