Acceleration of bulk and surface charger transfer dynamics via FePi cocatalyst-coated Ti/(Sb)-Fe₂O₃:Sb/(Ti)-Fe₂O₃ type-II homojunction photoanode for photoelectrochemical performance

Hematite (α-Fe₂O₃) possesses notable benefits in the field of photoelectrochemical (PEC) water splitting. However, the overall low efficiency of the separation and transfer of photogenerated charge carriers significantly hinders its further utilization. Although the occurrence of an internal electric field has the potential to significantly augment the efficiency of charge separation and transfer, there is a crucial need to broaden the scope of its successful application. This study explores a strategy for modifying the coupling between homojunction formation with gradient doping and cocatalyst modification on hematite to boost PEC performance. The developed type II Ti-doped/(Sb-codoped) Fe₂O₃:Sb-doped/(Ti-codoped) Fe₂O₃ (Ti/(Sb)-HT:Sb/(Ti)-HT) homojunction with a staggered band alignment accelerated the bulk charge separation via an intrinsic built-in electric field, while the bulk conductivity was improved using a gradient co-doping approach. Furthermore, the deposition of a FePi cocatalyst expedited the transfer of holes from the photoanode to the electrolyte by increasing the surface states, thereby hastening the water oxidation kinetics. The resulting Ti/(Sb)-HT:Sb/(Ti)-HT@FePi photoanode exhibited a 78.7% increase in photocurrent density compared to the bare Ti-Fe₂O₃ photoanode (0.94–1.68 mA/cm² at 1.23 V_RHE), accompanied by a charge transfer efficiency of 72.5%. Comprehensive photoelectrochemical investigations revealed that the homojunction and cocatalyst play a vital role in improving the dynamics of both the bulk and surface of the hematite photoanode, thereby facilitating efficient water oxidation. These findings offer a deeper insight into the function of homojunction photoanodes adorned with cocatalysts in the solar water-splitting process.