MXene-based 2D/2D Ti3C2/TiO2 heterojunction with spatially separated redox sites for efficient photocatalytic N2 reduction towards NH3

doi:10.1016/j.jmst.2024.06.038

Abstract

Abstract: Herein, a new type of two-dimensional (2D)/2D Ti₃C₂/TiO₂ heterojunction was developed for efficient photocatalytic nitrogen reduction reaction (NRR), in which TiO₂ nanosheets (TiO₂ Ns) were designed as the main catalyst, while Ti₃C₂ MXene served as the co-catalyst. Experimental and theoretical results revealed that Ti₃C₂ MXene introduced electron-rich unsaturated Ti sites, serving as highly active sites for both the adsorption and activation of N₂ on the Ti₃C₂/TiO₂ heterojunction. Furthermore, the 2D/2D Ti₃C₂/TiO₂ heterostructure greatly promoted the directional separation and transfer of charge carriers, facilitated by the internal electric field. This structural feature enabled the spatial separation of the N₂ reduction and H₂O oxidation half-reactions on the distinct surfaces of Ti₃C₂ (001) and TiO₂ (001), consequently reducing the reaction energy barrier for each respective process. The synergistic effects arising from the interface and surface interactions within the heterojunction conspicuously improved the photocatalytic NRR activity. As a result, the optimized Ti₃C₂/TiO₂ heterojunction exhibited a high NH₃ production rate of 24.4 µmol g^-1 h^-1 in the absence of sacrificial agents, representing a remarkable 12.8-fold increase compared to individual TiO₂ Ns. This work provides new insights into rational design of high-performance heterogeneous photocatalysts and offers a deeper understanding of the mechanism underlying surface active sites in the photocatalytic NRR process.

Key words: 2D/2D heterojunction, Ti₃C₂ MXene, Photocatalytic N₂ reduction reaction, N₂ adsorption and activation, Spatially separated redox sites

Chi Cao, Jinshuo Li, Linfeng Zhang, Yang Hu, Lin Zhang, Wensheng Yang. MXene-based 2D/2D Ti₃C₂/TiO₂ heterojunction with spatially separated redox sites for efficient photocatalytic N₂ reduction towards NH₃[J]. J. Mater. Sci. Technol., 2025, 214: 180-193.

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MXene-based 2D/2D Ti₃C₂/TiO₂ heterojunction with spatially separated redox sites for efficient photocatalytic N₂ reduction towards NH₃

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