Separation Efficiency Of Photogenerated Carriers Research Articles

Cu/S Co-anchoring junction boosted the photogenerated carrier separation efficiency in g-C3N5 for enhanced H2 evolution

C3N5 is emerging as an important visible light catalyst because of its narrow band gap, nontoxicity and thermal stability. Herein, sulfur-doped g-C3N5 (SCN) was prepared by copolymerization of thioacetamide (TAA) and 3-amino-1,2,4-triazole (3-AT). Then copper nanoparticles (Cu NPs) were anchored onto the SCN framework, resulting in the formation of Cu/SCN. It was found that the average H2 production rate of SCN and Cu/SCN was 0.76 and 1.34 mmol g−1 h−1, which was much higher than that of C3N5, respectively. Acting as a new active spots, sulfur doping effectively reduces the band gap of g-C3N5, and the formation of S-Cu bonds further creates an efficient electron transport pathway. As a result, Cu/SCN possesses a broader visible light absorption spectrum, stronger reduction capability, and greater efficiency in photo-induced carrier separation and transfer. Therefore, this work introduces a novel strategy for design of high efficiency photocatalytic H2 evolution carbon nitride through non-noble metal and sulfur anchoring junction.

Porphyrin-prompted robust lead-free cesium bismuth bromide for efficiently photodegrading antibiotics pollutants in water

The lead-free halide perovskite represented by Cs3Bi2Br9 (CBB) has attracted intense attention as an environmentally friendly alternative for toxic lead halide perovskite (CsPbBr3). However, the limited light absorption and instability of Cs3Bi2Br9 hinder its practical application in photocatalysis. In this work, Cs3Bi2Br9 nanosheets was modified with bifunctional porphyrin (CBB-TCPP) displayed enhanced visible light absorption properties and promising water stability. The CBB-0.5TCPP shows a sharply improved photodegradation performance of 84 % in 60 min in water and demonstrating the outstanding cycling stability. Furthermore, photoelectrochemical tests suggested that the charge separation and transfer properties of the modified perovskite materials were significantly improved compared with the pristine CBB. The CBB-0.5TCPP exhibited an impressive photogenerated carrier separation efficiency of 90.74 %. This work innovatively proposes a new way to modify perovskite with double duty by boosting stability and optimizing light absorption properties.

Z-scheme heterojunction TNCoPc/BiOBr nanomicrospheres for efficient photodegradation of tetracycline and rhodamine B: Degradation performance, intrinsic mechanism and degradation pathway studies

The natural ecosystem has been significantly jeopardized due to the misuse of organic dyes and antibiotics. To treat organic wastewater safely and efficiently, this study synthesized a binary composite photocatalyst TNCoPc/BiOBr, using a solvothermal method that involved loading cobalt tetranitro phthalocyanine onto BiOBr. The results of the catalytic performance tests indicated that the composites exhibited the capacity to degrade rhodamine B and tetracycline hydrochloride by 97.75 % and 78.37 %, respectively. Moreover, the composite exhibited good cyclic stability. Subsequent analytical characterization confirmed the formation of a Z-scheme heterojunction, resulting in a synergistic effect. This Z-scheme heterojunction facilitated the capacity of photocatalyst to achieve enhanced light absorption, augmented photogenerated carrier separation efficiency, and augmented redox capacity. Additionally, theoretical calculations were employed to further elucidate the catalytic mechanism and synergistic effects. The results demonstrate that the Co-N4 sites are the active center of the TNCoPc and verify the contribution of nitro substitution to the photogenerated electron transfer mechanism on TNCoPc. Furthermore, a systematic degradation pathway was predicted and deduced based on Fukui indices and liquid chromatography-mass spectrometry data. This study presents a paradigm for the application of composite photocatalysts containing substituted phthalocyanines in the degradation of organic wastewater.

Flower-like NiFe layered double hydroxide/Bi2WO6 S-scheme heterojunction for photodegradation of ciprofloxacin under visible light

Photocatalytic degradation stands as an effective remedy to solve the global environmental pollution caused by organic pollutants. In this study, we synthesized a NiFe layered double hydroxide/Bi2WO6 (NF-LDH/BWO) Step-scheme (S-scheme) heterojunction. The attachment of NF-LDH particles on flower-like BWO increased the active sites and the interface area between two pure materials. The construction of LDH/BWO heterojunction endowed with improved light absorption capacity and boosted separation efficiency of photo-generated carriers. Consequently, compared with BWO and NF-LDH, the NF-LDH/BWO composites showed enhanced photoactivities. At NF-LDH mass ratio of 10%, the optimal degradation rate of ciprofloxacin (75.9%) within 60 min under visible illumination was achieved, 1.43- and 9.37-fold those of BWO and NF-LDH, respectively. In addition, the NF-LDH/BWO composite also demonstrated excellent cyclic stability. The S-scheme mechanism was proposed based on both experimental and density functional calculation results.

Robust photocatalytic hydrogen evolution performance of 0D/1D NiO/CdS S-scheme heterojunction

Constructing heterojunction, especially S-scheme heterojunction, is an effective strategy for achieving effective separation of photogenerated electron-hole pairs and obtaining high electrode potential. In this study, a unique 0D/1D NiO/CdS S-scheme heterojunction was constructed by solvent evaporation induced self-assembly method. The loading of NiO was found to greatly enhance the photogenerated carrier separation efficiency of CdS by photoluminescence (PL) spectroscopy, electrochemical impedance spectroscopy (EIS), Kelvin probe force microscopy (KPFM) and transient photocurrent tests. The best photogenerated carrier separation effect was observed at a NiO loading ratio of 15 wt% and the largest photocatalytic hydrogen evolution rate reached 7.89 mmol h-1g−1 under visible light, which was 24.66 times that of pristine CdS. In addition, the cycling experiments showed that the loading of NiO led to the alleviation of the photocorrosion phenomenon of CdS, and the performance remained at 94.2 % after five cycles. This is due to the fact that the formation of S-type heterojunction combines the photogenerated holes of CdS with the photogenerated electrons of NiO, which hinders the oxidation of S2- on the surface of CdS, thus alleviating the photocorrosion phenomenon of CdS and improving the stability of CdS. This work furnishes a new strategy for the development of stable and high-performance photocatalysts with inexpensive co-catalysts.

Cyanobacterial hydrothermal carbonization carbon as photocatalyst for selective aerobic oxidation of cyclohexane

The exploration of catalyst preparation techniques that incorporate environmental-friendly methodologies has consistently been the focus of scientific inquiry within the field of green synthesis of oxygen-containing organic chemicals. Herein, a metal-free hydrothermal carbonation carbon (HTCC) has been prepared utilizing cyanobacterial biomass produced during a water bloom in a freshwater lake. The HTCC produced is capable of performing photocatalytic selective oxidation of cyclohexane to cyclohexanol and cyclohexanone (KA oil) under ambient conditions. The use of cyanobacterial biomass allows for the efficient preparation of HTCC, which exhibits a conversion rate of cyclohexane that is 4.1 times of HTCC prepared with alternative carbon sources (glucose). The selectivity to KA oil over the samples are almost 100%. Characterizations and analysis reveal that cyanobacteria can lead to self-doping of nitrogen and hydrophobicity of the resulting HTCC, while sulfuric acid etching endow it with more photoactive sp2 hybridized structure units that contribute to a higher photogenerated carrier separation efficiency. The suitable band structure enables the cyanobacterial HTCC to produce superoxide radicals to oxidize cyclohexane. These findings are of great significance for the development of eco-friendly photocatalysts and the utilization of biomass resources.

WO3/g-C3N4 synergistic photocatalysts for degradation and H2 production

WO3/g-C3N4 composite samples were prepared using hydrothermal method. The photocatalytic activity was assessed by photocatalytic degradation and H2 production experiments. The experimental findings suggested that WO3/g-C3N4 (1:1) degraded 95 % of the MB in 50 min and produced H2 at a rate of 712.38 μmol⸱g−1⸱h−1, which was 10 times the H2 production rate of g-C3N4. The improved photodegradation and H2 production properties could be due to the increased specific surface area, improved photogenerated carrier separation efficiency, broadened visible light absorption range, increased photocurrent density, and reduced charge transfer resistance. Meanwhile, the synergistic effect of WO3 and g-C3N4 realizes the bifunctionality of degradation and H2 production. In addition, possible reaction mechanisms of WO3/g-C3N4 composite samples in photodegradation and H2 production were proposed.

Enhanced charge carrier separation and stable photoelectrochemical water splitting via a high-performance BiVO4/BiOBr Type-II heterojunction

The development of an ideal photoanode that exhibits broad light absorption, efficient photogenerated carrier separation, and superior transmission efficiency remains a pivotal challenge in enhancing the sluggish photoelectrochemical (PEC) water splitting reaction. Here, we present an efficacious strategy to bolster the PEC performance of oxygen evolution by fabricating a BiVO4/BiOBr heterojunction through a combined electrochemical deposition-calcination approach and the successive ionic layer adsorption and reaction (SILAR) method. The band structure of BiOBr is optimally aligned with BiVO4, enabling the heterojunction to significantly enhance the separation efficiency of photogenerated charges and accelerate the kinetics of PEC water oxidation. Under simulated sunlight irradiation, the BiVO4/BiOBr heterojunction exhibits a remarkable photocurrent density of 2.69 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE), surpassing the performance of bare BiVO4 film (0.46 mA/cm2 at 1.23 V vs. RHE) and demonstrating exceptional stability. This work offers novel insights into the rational design and fabrication of solar-driven PEC water splitting photoanodes.

Construction of sulfur-chloride co-doped triazine/heptazine homojunction carbon nitride photocatalyst for simultaneous production of H2O2 and lignin C-C bond cleavage

Photocatalytic H2O2 production and cleavage of lignin C-C bonds is a typical strategy that follows sustainable development. Unfortunately, the photocatalytic efficiency of these two reactions still faces significant challenges. Herein, a carbon nitride photocatalyst (tri/hep-CN) with sulfur-chloride co-doped triazine and heptazine structures was synthesized. It was simultaneously used for photocatalytic H2O2 production and lignin C-C bond cleavage. In the air atmosphere, the yield of H2O2 reached 1171.9 μmol•g−1•h−1 after the addition of β-1 lignin model 1,2-diphenylethanol (Dpol) to the solvent. The yield of H2O2 increased by 20 times compared with no addition of Dpol. The lignin C-C bond in Dpol is also efficiently broken, producing benzaldehyde and benzyl alcohol. tri/hep-CN has excellent photogenerated carrier separation efficiency and positive valence potential, which improves the photocatalytic H2O2 production and lignin C-C bond cleavage performance. Notably, coupling photocatalytic H2O2 production with lignin C-C bond cleavage to fully use photogenerated electrons and holes is also very important to obtain outstanding photocatalytic performance. Mechanistic studies have shown that photocatalytic H2O2 production follows an indirect reaction mechanism. Meanwhile, the cleavage of lignin C-C bond follows the Cβ radical mechanism and the single electron transfer mechanism. This work is very instructive for simultaneous photocatalytic H2O2 production and lignin C-C bond cleavage studies.

Designing a hollow MoSe2/CuS nanospheres type-II heterojunction photocatalyst with superior UV-vis-NIR absorption for photocatalytic degradation of organic pollutants.

In this work, a hollow MoSe2/CuS type-II heterojunction was fabricated using hollow MoSe2 nanospheres as the basis for structural design. UV-Vis-NIR diffuse absorption tests show that MoSe2/CuS has a broad spectral absorption to extend the optical response range from UV-Vis to NIR. The light source utilization rate and interfacial area are increased by the hollow MoSe2/CuS core-shell structure. The broad absorption ability of MoSe2/CuS can facilitate the photocatalysis process. As the electrochemical impedance of MoSe2/CuS is lower than that of the MoSe2, MoSe2/CuS has a good photogenerated carrier separation efficiency. Benefiting from the synergistic facilitation effect of the multi-level 3D hollow nanosphere and the significant space charge region in type-II heterojunction, the RhB degradation efficiency of MoSe2/CuS reached 96.0% in 120.0minunder Xe (350W) broadband spectrum light irradiation. The photocatalysis mechanism of the hollow MoSe2/CuS core-shell structure was investigated. This work provides an insight into the application of broad spectrum semiconductor heterojunctions to solve environmental problems.

A flower-like g-C3N4/CDs/Bi2WO6 hierarchical structure for enhanced photocatalytic degradation of tetracycline

Tetracycline (TC), as one of antibiotic emerging pollutants, has posed potential threats to ecological environment and human health because it is hardly biodegradable and prone to be accumulated in water. In this study, g-C3N4/CDs/Bi2WO6 S-scheme heterojunction with flower-like hierarchical structure was synthesized by hydrothermal method. The optimized composite demonstrates significantly enhanced photocatalytic activity with a TC degradation efficiency of 90.1% after 120 min of visible light irradiation and good reusability up to four consecutive cycles. This can be attributed to the improved light capture capability and efficient separation of photo-generated electron-hole pairs in the constructed S-scheme heterojunction. The introduced carbon dots (CDs) can be served as an efficient carrier transport highway, providing a superior photogenerated carrier separation efficiency and an expanded absorption spectrum. As a result, the strongest redox potentials of the CBCN and VBBWO can be retained for participating the photocatalytic reaction. Free radical capture and electron spin resonance experiments indicate that ·O2- and h+ are the principal active species in the g-C3N4/CDs/Bi2WO6 system. This work provides new strategy for the development of advanced materials in the field of photocatalytic treatment of wastewater.

Improvement in the Photocatalytic Hydrogen Production of Flower-Shaped ZnIn2S4 by Surface Modification with Amino Silane

ZnIn2S4 has attracted extensive attention in the field of photocatalytic hydrogen production because of its suitable band gap and excellent photoelectrochemical properties. However, its lower photogenerated carrier separation efficiency and high degree of photocorrosion severely restricts its photocatalytic activity. In this work, the photocatalytic hydrogen production performance of ZnIn2S4 modified with 3-aminopropylmethoxysilane was studied. Surface modification by amino silane not only regulated the band gap and enhanced the light absorption of ZnIn2S4 but it also increased the colloidal stability of the ZnIn2S4 suspension and enhanced the adsorption of H+ on the active surface sites, thereby improving the photocatalytic hydrogen production performance. Compared with that of unmodified ZnIn2S4, the photocatalytic hydrogen production rate of surface-modified ZnIn2S4 increased by 1.46 times, and after four cycles for 12 h, the hydrogen production efficiency remained at 75.14%.

Optimization of AgIO3/Bi4Ti3O12 composite photocatalyst to achieve enhanced photocatalytic performance by adjusting internal electric field via oxygen defect engineering

The construction of heterojunction is an effective and conventional method to improve the photocatalytic activity of photocatalysts. On this basis, how to further regulate the separation and migration of photogenerated carrier is worthy of further investigation. As a mature and efficient modification method, oxygen defect engineering was used to regulate the S-scheme heterojunction composed of AgIO3 and Bi4Ti3O12 to further enhance the photocatalytic activity of the constructed heterojunction in this study. In addition to improving the visible light absorption of the photocatalyst and providing active sites, the introduction of oxygen vacancies can also strengthen the internal electric field between the two semiconductors by expanding the Fermi level gap, which can be verified by Mott-Schottky experiment and DFT calculations, resulting in more efficient photogenerated carrier separation efficiency. As a result, compared with AgIO3/Bi4Ti3O12, the AgIO3/Bi4Ti3O12 heterojunction modulated by oxygen defect engineering exhibited excellent photocatalytic activity, which proves the feasibility of the regulation of the interfacial electric field. This work provides a new idea for the modulation strategy of the interface electric field.

Well-Dispersed CsPbBr3@TiO2 Heterostructure Nanocrystals from Asymmetric to Symmetric.

Metal halide perovskites (MHPs) have undergone rapid development in the fields of solar cells, light diodes, lasing, photodetectors, etc. However, the MHPs still face significant challenges, such as poor stability and heterocompositing with other functional materials at the single nanoparticle level. Herein, the successful synthesis of well-dispersed CsPbBr3@TiO2 heterostructure nanocrystals (NCs) is reported, in which each heterostructure NC has only one CsPbBr3 with a precise anatase TiO2 coating ranging from asymmetric to symmetric. Due to the protection of anatase TiO2, CsPbBr3 shows dramatically improved chemical stability and photostability. More significantly, the synthesized CsPbBr3@TiO2 heterostructure NCs form a type II heterojunction, which strongly promoted efficient photogenerated carrier separation between anatase TiO2 and CsPbBr3, hence leading to improved optoelectronic activity. This study provides a robust avenue for synthesizing stable and highly efficient MHPs@metal oxide heterostructure NCs, paving the way for the practical application of all inorganic perovskites.

Strong electron coupling between amorphous WP and MoSe2/ZnCdS S-scheme heterojunction for enhanced wide spectrum photocatalytic hydrogen production

The photogenerated carrier separation efficiency is a key factor for limiting the photocatalytic activity. In this work, an amorphous WP modified S-scheme MoSe2/ZnCdS (WP/MoSe2/ZCS) heterojunction was synthesized for wide spectrum photocatalytic hydrogen production. After initially forming an S-scheme heterojunction by compositing ZnCdS with nano flower-shaped MoSe2, the light absorption ability of the bimetallic sulfide was significantly enhanced, along with an improved photogenerated carrier separation efficiency. Additionally, the introduction of WP as a co-catalyst not only provides more active sites for photocatalytic reactions, but also enhances the photogenerated electrons transfer through the synergistic effect of strong electronic coupling and S-scheme MoSe2/ZCS heterojunction.The significant enhancement of photocatalytic hydrogen evolution activity of 7％WP/MoSe2/ZCS reached 47.7 mmol g−1 h−1, which is 4.72 times higher than that of ZnCdS (10.1 mmol g−1 h−1). The strong electron coupling effects and S-scheme electron ransfer mechanism was proved by in-situ XPS and Density functional theory (DFT) calculations. This work provides a new strategy for the construction of high-efficiency photocatalyst with strong electronic coupling.

Tuning oxygen vacancies via photoinduced defect engineering in plasma pre-treated TiO2 for efficient solar-light-driven oxidation of trace methane

Photocatalysis employing cost-effective commercial titanium dioxide offers an ideal solution for eliminating trace methane emissions from livestock and poultry farming. However, significant challenges such as the rapid recombination of photogenerated carriers, a limited light absorption spectrum, and weak adsorption capabilities considerably hinder the effectiveness of titanium dioxide in the photocatalytic treatment of trace methane. This study proposes a novel approach to activate plasma pre-treated N-doped commercial anatase TiO2 into dual-defect TiO2 (N-doped TiO2-x) featuring stable and controllable oxygen vacancies (OV) through photoinduced defect engineering. Characterizations of the photocatalyst confirm the successful creation of surface defects, further evaluated through solar-light-driven CH4 (ppm level) removal investigations. The yield of this N-doped TiO2-x in converting CH4 is 4.84 μmol h−1, 44 times greater than that of unmodified TiO2, significantly outperforming previous studies. UV–Vis diffuse reflection spectra, and photoluminescence indicate that the modified commercial anatase TiO2 possesses a narrower band gap, efficient photogenerated carrier separation, and enhanced charge transfer. Furthermore, density functional theory (DFT) calculations demonstrate that the synergistic effects of oxygen vacancies and N doping enhance the adsorption and activation of both O2 and CH4 in the rate-determining step of the reaction. This innovative strategy holds considerable promise for modifying various materials for more efficient photocatalytic applications.

Anti-Z-scheme polymer/polymer heterojunctions achieving synchronous enhancement of light absorption and directly spatial charge separation

Combining enhanced light absorption capacity with improved directly spatial charge separation efficiency remains a challenging issue for the development of efficient photocatalysts. Herein, we present a strategy for developing anti-Z-scheme poly(thiophene-co-3-ethylthiophene)/K+ implanted polymeric carbon nitride (PB-KCN) heterojunctions, which integrates the two crucial factors of light absorption and directly spatial charge separation. The ratio-optimized 20 PB-KCN exhibits remarkable visible-light-driven hydrogen production activity up to 22.86 mmol/h g−1 (∼61.8 times that of KCN) with a recorded apparent quantum yield of 31.34 % under 550 nm irradiation. Notably, it is confirmed that the efficient photogenerated-carrier separation in PB-KCN heterojunctions is mainly attributed to the firstly proved anti-Z-scheme electron transition with the electrons in the HOMO (highest occupied molecular orbital) of PB directly excited to the LUMO (lowest unoccupied molecular orbital) of KCN, resulting in the spatial separation of photogenerated carriers. The proposed anti-Z-scheme heterojunction solves the problem that traditional heterojunctions cannot achieve synchronous enhancement of light absorption and directly spatial charge separation.

An Efficient MnO2 Photocathode with an Excellent SnO2 Electron Transport Layer for Photo-Accelerated Zinc Ion Batteries.

Photo-accelerated rechargeable batteries play a crucial role in fully utilizing solar energy, but it is still a challenge to fabricate dual-functional photoelectrodes with simultaneous high solar energy harvesting and storage. This work reports an innovative photo-accelerated zinc-ion battery (PAZIB) featuring a photocathode with a SnO2@MnO2 heterojunction. The design ingeniously combines the excellent electronic conductivity of SnO2 with the high energy storage and light absorption capacities of MnO2. The capacity of the SnO2@MnO2-based PAZIB is ≈598mAh g-1 with a high photo-conversion efficiency of 1.2% under illumination at 0.1 A g-1, which is superior to that of most reported MnO2-based ZIB. The boosting performance is attributed to the synergistic effect of enhanced photogenerated carrier separation efficiency, improved conductivity, and promoted charge transfer by the SnO2@MnO2 heterojunction, which is confirmed by systematic experiments and theoretical simulations. This work provides valuable insights into the development of dual-function photocathodes for effective solar energy utilization.

Boosting the Activation of Molecular Oxygen and the Degradation of Rhodamine B in Polar-Functional-Group-Modified g-C3N4.

Molecular oxygen activation often suffers from high energy consumption and low efficiency. Developing eco-friendly and effective photocatalysts remains a key challenge for advancing green molecular oxygen activation. Herein, graphitic carbon nitride (g-C3N4) with abundant hydroxyl groups (HCN) was synthesized to investigate the relationship between these polar groups and molecular oxygen activation. The advantage of the hydroxyl group modification of g-C3N4 included narrower interlayer distances, a larger specific surface area and improved hydrophilicity. Various photoelectronic measurements revealed that the introduced hydroxyl groups reduced the charge transfer resistance of HCN, resulting in accelerated charge separation and migration kinetics. Therefore, the optimal HCN-90 showed the highest activity for Rhodamine B photodegradation with a reaction time of 30 min and an apparent rate constant of 0.125 min-1, surpassing most other g-C3N4 composites. This enhanced activity was attributed to the adjusted band structure achieved through polar functional group modification. The modification of polar functional groups could alter the energy band structure of photocatalysts, narrow band gap, enhance visible-light absorption, and improve photogenerated carrier separation efficiency. This work highlights the significant potential of polar functional groups in tuning the structure of g-C3N4 to enhance efficient molecular oxygen activation.

Investigation of the mechanism and stability of highly efficient photocatalytic degradation of Methylene blue using Ni doped CdS photocatalyst

Methylene blue (MB) is commonly utilized in chemical indicators, dyes, biological colors, and pharmaceuticals. Its aqueous solution is poisonous and carcinogenic, posing a significant threat to the ecological environment. The wurtzite-phase NixCd1−xS was synthesized using the hydrothermal technique in this study. Ni doped CdS enhanced its photocatalytic efficiency and resistance to photocorrosion, enabling its application in the photocatalytic destruction of MB. The incorporation of Ni did not change the crystal structure and microstructure of CdS, but increased the visible light absorption range and decreased the band gap width slightly, which promoted the migration of photogenerated electrons and reduced their recombination with holes, resulting in higher photogenerated carrier separation efficiency of NixCd1−xS. The photocatalytic decolorization rate of Ni0.06Cd0.94S for 100 mL of 10 mg/L MB at 240 min is 91.3 %, and the reaction rate constant is 0.01102 min−1, which is 4.42 times that of wurtzite-phase CdS. The photocatalytic mechanism of NixCd1−xS and its composite was analyzed using trap experiments in conjunction with the band structure of the sample. Additionally, the stability of NixCd1−xS was evaluated. The results indicated that the stability was superior to that of CdS. The findings demonstrate that Ni0.06Cd0.94S exhibits good catalytic activity and stability, making it a viable catalyst for the photocatalytic degradation of organic pollutants in water.