Inspired by natural photosynthesis, constructing inorganic/organic heterojunctions is regarded as an effective strategy to design high-efficiency photocatalysts. Herein, a step (S)-scheme heterojunction photocatalyst is prepared by in situ growth of an inorganic semiconductor firmly on an organic semiconductor. A new pyrene-based conjugated polymer, pyrene-alt-triphenylamine (PT), is synthesized via the typical Suzuki-Miyaura reactions, and then employed as a substrate to anchor CdS nanocrystals. The optimized CdS/PT composite, coupling 2 wt% PT with CdS, exhibits a robust H2 evolution rate of 9.28 mmol h-1 g-1 with continuous release of H2 bubbles, as well as a high apparent quantum efficiency of 24.3%, which is ≈8 times that of pure CdS. The S-scheme charge transfer mechanism between PT and CdS, is systematically demonstrated by photoirradiated Kelvin probe measurement and in situ irradiated X-ray photoelectron spectroscopy analyses. This work provides a protocol for preparing specific S-scheme heterojunction photocatalysts on the basis of inorganic/organic coupling.

An Inorganic/Organic S-Scheme Heterojunction H 2 -Production Photocatalyst and its Charge Transfer Mechanism

Reasonable design of efficient hierarchical photocatalysts has gained significant attention. Herein, a step-scheme (S-scheme) core-shell TiO2 @ZnIn2 S4 heterojunction is designed for photocatalytic CO2 reduction. The optimized sample exhibits much higher CO2 photoreduction conversion rates (the sum yield of CO, CH3 OH, and CH4 ) than the blank control, i.e., ZnIn2 S4 and TiO2 . The improved photocatalytic performance can be attributed to the inhibited recombination of photogenerated charge carriers induced by S-scheme heterojunction. The improvement is also attributed to the large specific surface areas and abundant active sites. Meanwhile, S-scheme photogenerated charge transfer mechanism is testified by in situ irradiated X-ray photoelectron spectroscopy, work function calculation, and electron paramagnetic resonance measurements. This work provides an effective strategy for designing highly efficient heterojunction photocatalysts for conversion of solar fuels.

In situ Irradiated XPS Investigation on S-Scheme TiO2@ZnIn2S4 Photocatalyst for Efficient Photocatalytic CO2 Reduction

S-scheme heterojunction based on p-type ZnMn2O4 and n-type ZnO with improved photocatalytic CO2 reduction activity

Novel S-scheme 2D/2D BiOBr/g-C3N4 heterojunctions with enhanced photocatalytic activity

Solar radiation is a sustainable, unlimited source of energy for electricity and chemical reactions, yet the conversion efficiency of actual processes is limited and controlled by photocarriers migration and separation. Enhancing the conversion efficiency would require to suppress the recombination of photogenerated electron–hole pairs and improve the low redox potentials. This can be done during the growth of step-scheme (S-scheme) heterojunctions. Here we review the charge transfer of S-scheme heterojunctions involving a reduction and oxidation photocatalyst in staggered band arrangement with Fermi level differences. We present factors determining the validation of the S-scheme mechanism with respective characterization techniques, including in situ and ex situ experiments, and theoretical studies. We show mechanistic drawbacks of traditional photocatalytic systems to highlight the advantages of S-scheme photocatalysts. We describe co-catalyst loading, bandgap tuning, and interfacial optimization that ultimately achieve highly efficient photocatalysis. Last, application for water splitting, CO2 conversion, pollutant degradation, bacterial inactivation and others is discussed.

Juan Wang

Papers

Sulfur-doped g-C3N4/TiO2 S-scheme heterojunction photocatalyst for Congo Red photodegradation