Step-by-Step Mechanism Insights into the TiO₂/Ce₂S₃ S-Scheme Photocatalyst for Enhanced Aniline Production with Water as a Proton Source

Abstract

Exploring new heterostructured photocatalysts for photocatalytic hydrogenation reaction with water as proton source and investigating the corresponding intrinsic step-by-step mechanism are of great interests. Here we develop a novel S-scheme heterojunction through theoretical design and implemented by solvothermal growth of Ce 2 S 3 nanoparticles onto electrospun TiO 2 nano bers. The low-dimensional (0D/1D) heterostructure unveils enhanced photocatalytic activity for aniline production by nitrobenzene hydrogenation with water as proton source. Density functional theory (DFT) calculations indicate the electrons transfer from Ce 2 S 3 to TiO 2 upon hybridization due to their Fermi level difference and creates an internal electric eld at the interface, driving the e cient separation of the photoexcited charge carriers, which is authenticated by in-situ X-ray photoelectron spectroscopy along with femtosecond transient absorption spectroscopy. The step-by-step reaction mechanism of the photocatalytic nitrobenzene hydrogenation to yield aniline is revealed by in-situ diffuse re ectance infrared Fourier transform spectroscopy, associated with DFT computational prediction.

Enhanced Selective Photooxidation of Toluene to Benzaldehyde over Co3O4‐Modified BiOBr/AgBr S‐Scheme Heterojunction

“…When Co 3 O 4 -modified BiOBr/AgBr heterojunction is exposed to the visible light, the photogenerated electrons in the CB of BiOBr can recombine with the photogenerated holes of AgBr, while the powerful electrons and holes are respectively remained in AgBr and BiOBr surface for participating in different reactions, which is a typical S-scheme charge-transfer pathway. [60][61][62] The photogenerated electrons in the CB of AgBr can react with O 2 to form •O 2 À radical, while the photogenerated holes in the VB of BiOBr will diffuse to Co 3 O 4 involving the toluene deprotonation process to produce benzyl radical (PhCH 2 •). Then, the benzyl radicals can react with •O 2 À radical to produce the peroxyl products, which can be easily decompose to benzaldehyde through a dehydration process.…”

Construction of a Novel Co2P/TiO2 Z‐Scheme Junction for Efficient Solar‐Driven Photocatalytic H2 Evolution

“…As depicted in Figure 8E, the capacitance potential difference (CPD) of Co 2 P, 3 wt% Co 2 P/TiO 2 , and TiO 2 achieved a relative stable value in the dark. The work function (W F ) and Fermi level (E F ) can be calculated as follows [ 47 ] where e is the electron charge, and W tip is the standard work function of the gold probe (≈ 4.25 eV). Hence, the W F of Co 2 P, TiO 2 , and 3 wt% Co 2 P/TiO 2 was estimated to be 3.67, 4.51, and 4.21 eV, respectively.…”

“…The build‐in electric field at the interface then could accelerate the photoexcited electrons transfer from TiO 2 to Co 2 P, resulting in the consumption of the photo‐generated holes of Co 2 P. This individual Z‐scheme charge‐transfer efficiently separates the photo‐generated electron–hole pairs, hence preventing the recombination of photoinduced electrons and holes, which is consistent with the EIS, PL, LSV, and photocurrent response results. [ 47 ] And the high photo‐generated electrons in the CB of Co 2 P with high reductibility are simultaneously retained. Then, the photo‐generated electrons would participate in the reduction reaction to generate H 2 .…”

“…As depicted in Figure 8E, the capacitance potential difference (CPD) of Co 2 P, 3 wt% Co 2 P/TiO 2 , and TiO 2 achieved a relative stable value in the dark. The work function (W F ) and Fermi level (E F ) can be calculated as follows [47] W…”

A 0D/2D Bi₄V₂O₁₁/g-C₃N₄ S-scheme Heterojunction with Rapid Interfacial Charges Migration for Photocatalytic Antibiotic Degradation

“…Among them, it is an effective strategy to construct the heterojunction photocatalysts that has attracted much attention because it can effectively restrain the photo-generated charges recombination [25][26][27] . Although traditional type-II heterojunction seems to inhibit electrons and holes recombination, it impairs the redox reaction capacity of photoinduced carriers [28][29][30] . Meanwhile, the interfacial carrier transfer mechanism of Zscheme heterojunctions needs to be further supplemented and improved [31][32][33] .…”