Direct observation of carrier migration in heterojunctions to discuss the p-n and direct Z-scheme heterojunctions

Type II p-n heterojunction and direct Z-scheme heterojunction are identical staggered band alignments, but were reported ambiguously in many composite photocatalysts because their carriers migrate in opposite directions. In this research, metal oxides CuO, NiO and Co₃O₄-based heterojunctions with Na_0.9Mg_0.45Ti_3.55O₈(NMTO) were synthesized via a simple hydrothermal method. The CuO/NMTO heterojunction was demonstrated as a direct Z-scheme heterojunction, whereas the NiO/NMTO and Co₃O₄/NMTO heterojunctions showed type II p-n band alignment, distinguished by the direct observation of carrier migration under light illumination, and confirmed by the x-ray photoelectron spectroscopy, Mott-Schottky measurements, ultraviolet photoelectron spectra and capture experiments. These all heterojunctions enjoyed better photocatalytic performance to degrade methylene blue and antibiotics (Enrofloxacin, Metronidazole and tetracycline) than the pure NMTO, attributed to their effective separation of the photoinduced electron-hole pairs owing to the staggered band alignment. Prominently, the NiO/NMTO and Co₃O₄/NMTO p-n heterojunctions exhibited superior degradation ability to the CuO/NMTO Z-scheme heterojunction. The initial relative Fermi position of two semiconductors is the prerequisite to determine whether the p-n heterojunction or direct Z-scheme heterojunction is built because the electrons diffuse from one semiconductor with a higher Fermi level to another with a lower Fermi level while the holes diffuse reversely until a united Fermi level when they combine. The built-in electric field at the heterojunction interface is determined by the difference in the initial Fermi levels or work functions of two semiconductors, regulating the separation ability of photogenerated electrons and holes to affect the photocatalytic performance. Thus, the high difference in the initial Fermi levels of semiconductors is crucial in the development of heterojunctions with staggered band alignment to obtain high performance in photocatalytic reactions.