Ni₃B as p-Block Element-Modulated Cocatalyst for Efficient Photocatalytic CO₂ Reduction

Due to the multiple electron and proton transfer processes involved, the photogenerated charges are easily recombined during the photocatalytic reduction of CO₂, making the generation of the eight-electron product CH₄ kinetically more difficult. Herein, Ni₃B nanoparticles modulated by p-block element were combined with TiO₂ nanosheets to construct a novel Schottky junction photocatalyst (Ni₃B/TiO₂) for the selective photocatalytic conversion of CO₂ to CH₄. The formed Ni₃B/TiO₂ photocatalyst with Schottky junction ensures a transfer pathway of photogenerated electrons from TiO₂ to Ni₃B, which facilitates the accumulation of electrons on the surface of Ni₃B and subsequently improves the activity of photocatalytic CO₂ reduction to CH₄. The optimized Ni₃B/TiO₂ Schottky junction shows an improved CH₄ yield of 30.03 μmol g^-1 h^-1, which was much higher than those of TiO₂ (1.62 μmol g^-1 h^-1), NiO/TiO₂ (2.44 μmol g^-1 h^-1), and Ni/TiO₂ (4.3 μmol g^-1 h^-1). This work demonstrated that the introduction of p-block elements can alleviate the scaling relationship effect of pure metal cocatalysts to a certain extent, and the modified Ni₃B can be used as a promising new cocatalyst to effectively improve the selective photocatalytic of CO₂ to CH₄.