Tailoring of Visible to Near-Infrared Active 2D MXene with Defect-Enriched Titania-Based Heterojunction Photocatalyst for Green H2 Generation

A wide solar light absorption window and its utilization, long-term stability, and improved interfacial charge transfer are the keys to scalable and superior solar photocatalytic performance. Based on this objective, a noble metal-free composite photocatalyst is developed with conducting MXene (Ti3C2) and semiconducting cauliflower-shaped CdS and porous Cu2O. XPS, HRTEM, and ESR analyses of TiOy@Ti3C2 confirm the formation of enough defect-enriched TiOy (where y is < 2) on the surface of Ti3C2 during hydrothermal treatment, thus creating a third semiconducting site with enough oxygen vacancy. The final material, TiOy@Ti3C2/CdS/Cu2O, shows a broad absorption window from 300 to 2000 nm, covering the visible to near-infrared (NIR) range of the solar spectrum. Photocatalytic H-2 generation activity is found to be 12.23 and 16.26 mmol g(-1) h(-1) in the binary (TiOy@Ti3C2/CdS) and tertiary composite (TiOy@Ti3C2/CdS/Cu2O), respectively, with good repeatability under visible-NIR light using lactic acid as the hole scavenger. A clear increase of efficiency by 1.53 mmol g(-1) h(-1) in the tertiary composite due to NIR light absorption supports the intrinsic upconversion of electrons, which will open a new prospective of solar light utilization. Decreased charge-transfer resistance from the EIS plot and a decrease in PL intensity established the improved interfacial charge separation in the tertiary composite. Compared to pure CdS, H-2 generation efficiency is 29.6 times higher on the noble metal-free tertiary composite with an apparent quantum efficiency of 12.34%. Synergistic effect of defect-enriched TiOy formation, creation of proper dual p-n junction on a Ti3C2 sheet as supported by the Mott-Schottky plot, significant NIR light absorption, increased electron mobility, and charge transfer on the conductive Ti3C2 layer facilitate the drastically increased hydrogen evolution rate even after several cycles of repetition. Expectantly, the 2D MXene-based heterostructure with defect-enriched dual p-n junctions of desired interface engineering will facilitate scalable photocatalytic water splitting over a broad range of the solar spectrum.