KSCN-induced Interfacial Dipole in Black TiO₂ for Enhanced Photocatalytic CO₂ Reduction

Tuning the electronic band structure of black titania to improve photocatalytic performance through conventional band engineering methods has been challenging because of the defect-induced charge carrier and trapping sites. In this study, KSCN-modified hydrogenated nickel nanocluster-modified black TiO₂ (SCN-H-Ni-TiO₂) exhibits enhanced photocatalytic CO₂ reduction due to the interfacial dipole effect. Upon combining the experimental and theoretical simulation approach, the presence of an electrostatic interfacial dipole associated with chemisorption of SCN has dramatic effects on the photocatalyst band structure in SCN-H-Ni-TiO₂. An interfacial dipole possesses a more negative zeta potential shift of the isoelectric point from 5.20 to 3.20, which will accelerate the charge carrier separation and electron transfer process. Thiocyanate ion passivation on black TiO₂ demonstrated an increased work function around 0.60 eV, which was induced by the interracial dipole effect. Overall, the SCN-H-Ni-TiO₂ photocatalyst showed an enhanced CO₂ reduction to solar fuel yield by 2.80 times higher than H-Ni-TiO₂ and retained around 88% product formation yield after 40 h.