Novel 0D/2D Bi2WO6/MoSSe Z-scheme heterojunction for enhanced photocatalytic degradation and photoelectrochemical activity

The catalytic activity of a single catalyst could be optimized by constructing a Z-scheme heterojunction structure with another adaptive material. 0D Bi₂WO₆ nanoparticles exhibit good oxidation ability, while 2D MoSSe nanoplates with low internal resistance show excellent reduction ability. Herein, novel 0D/2D Bi₂WO₆/MoSSe Z-scheme heterojunction catalysts (BMSS) with different Mo: Bi molar ratios were developed by combining the advantages of pure Bi₂WO₆ and MoSSe. The matched energy bands may provide the possibility to construct heterojunction, and the internal electric fields could facilitate the separation and transmission of internal carriers. Energy band structure analyses and electron spin resonance (ESR) results have further confirmed the existence of the above Z-scheme heterojunction structure and internal electric field. More importantly, as-prepared BMSS catalysts were proved to have excellent oxidation and reduction ability from photocatalytic and photoelectrochemical results. With an optimized MoSSe loading ratio of 3.66%, the BMSS3 catalyst showed 4.13 times of photocurrent density than that of pure Bi₂WO₆ and displayed an excellent degradation rate (0.0377 min^?1). It can be concluded that BMSS catalysts will have promising applications in photoelectrochemistry and photocatalysis.     

Ag3PO4/Bi2WO6 hierarchical heterostructures with enhanced visible light photocatalytic activity for the degradation of phenol

The Ag₃PO₄/Bi₂WO₆ hierarchical heterostructures were prepared by a combination of hydrothermal technique and in situ precipitation method for the first time. The Ag₃PO₄/Bi₂WO₆ hierarchical heterostructures displayed enhanced visible-light photocatalytic activity against phenol. The enhanced photocatalytic activity could be attributed to the effective separation of photogenerated carriers driven by the photoinduced potential difference generated at the Ag₃PO₄/Bi₂WO₆ heterojunction interface. Repetitive tests showed that the Ag₃PO₄/Bi₂WO₆ hierarchical heterostructures maintained high catalytic activity over several cycles, and it had a better regeneration capability under mild conditions.     

Facile one-pot synthesis of a BiOBr/Bi2WO6 heterojunction with enhanced visible-light photocatalytic activity for tetracycline degradation

Photocatalytic removal of tetracycline (TC) from the wastewater is of great value in the chemical and environmental engineering field. Here, we introduced a facile one-step method for the synthesis of BiOBr/Bi₂WO₆ heterojunctions by using cheap CTAB as the Br source. We showed the possibility of our method to fine-tune the content of BiOBr in the produced BiOBr/Bi₂WO₆ by simply changing the dosage of cetyltrimethylammonium bromide (CTAB), providing a platform for the delicate tuning of the visible-light absorbance ability of the composites. With a suitable heterojunction structure of BiOBr/Bi₂WO₆-0.2, it exhibited an ultrarapid photocatalytic activity towards TC (20 mg·L^-1), with a competitive removal efficiency of 88.1% within 60 min and an ultrahigh removal rate of 0.0349 min^-1. It could also be robustly recycled for at least 5 cycles with slight removal efficiency loss. We demonstrated that this exciting photocatalytic performance was due to the highly decreased recombination of photoinduced electrons and holes on our composites by constructing this heterojunction structure, and the resulting OH and contributed to the effective degradation of TC to CO₂.     

Fabrication of TiO2 nanofibers assembled by Bi2WO6 nanosheets with enhanced visible light photocatalytic activity

A series of Bi₂WO₆/TiO₂ nanofibers (BT NF) hierarchical photocatalysts were synthesized by a facile two-step strategy consisting of electrospinning technique and subsequent solvothermal method. The results showed that the secondary two-dimensional Bi₂WO₆ nanosheets were uniformly assembled onto the surface of the TiO₂ NF. It was also verified that the density of Bi₂WO₆ nanosheets could be tailed by controlling the precursor concentration during the solvothermal process. Photocatalytic tests demonstrated that BT NF with a low concentration of precursor (S1) possessed a much higher visible light degradation rate for Rhodamine B than TiO₂ NF, Bi₂WO₆ and their mixture. The enhanced photocatalytic activity of S1 was ascribed to the extension of the light absorption region induced by the introduction of narrow band gap Bi₂WO_6, and the formation of heterojunction accelerating the interfacial charge separation. Moreover, BT NF with a high concentration of precursor (S2) manifested a higher photocatalytic activity than S1 due to the higher loading of Bi₂WO₆ nanosheets. S2 could be reused by sedimentation, and the photocatalytic activities of S2 were retained with a slight decline after four cycles, which confirmed its stability. Therefore, BT NF composites will be ideal candidates for highly efficient and recyclable photocatalysts for the treatment of organic pollutants under visible light.     

Dual Z-scheme heterojunction g-C3N4/Ag3PO4/AgBr photocatalyst with enhanced visible-light photocatalytic activity

Recently, there has been a significant interest in developing high-performance photocatalysts for removing organic pollutants from water environment. Herein, a ternary graphitic C₃N₄ (g-C₃N₄)/Ag₃PO₄/AgBr composite photocatalyst is synthesized using an in-situ precipitation-anion-exchange process and characterized by several spectroscopic and microscopic techniques. During the photocatalytic reaction, X-ray photoelectron spectroscopy clearly illustrated the formation of metallic Ag on the g-C₃N₄/Ag₃PO₄/AgBr composite surface. The ternary composite photocatalyst demonstrated an increased photoactivity under visible light (>420 nm), achieving a complete decolorization of methyl orange (MO) in 5 min. The ternary g-C₃N₄/Ag₃PO₄/AgBr hybrid was also applied to the 2-chlorophenol degradation under visible light, further confirming its excellent photocatalytic activity. In addition, quenching experiments revealed that holes (h⁺) and O₂^?– were the major attack species in the decolorization of MO. The enhanced photoactivity of g-C₃N₄/Ag₃PO₄/AgBr results from the efficient transfer/separation of photoinduced charges with the dual Z-scheme pathway and the charge recombination sites on the formed Ag particles.     

Novel Lu-doped Bi2WO6 nanosheets: Synthesis,growth mechanisms and enhanced photocatalytic activity under UV-light irradiation

Polycrystalline systems of lutetium doped bismuth tungstates Bi₂WO₆: Lu (Lu at% 0, 2, 5 and 8) were synthesized using the coprecipitation method, followed by thermal treatment at 500 °C. The Bi₂WO₆:Lu samples were characterized by X-Ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-Ray analysis (EDS) and UV–vis diffuse reflectance spectra (DRS). The XRD and SEM analyses showed that the as-prepared samples crystallized in the same orthorhombic structure and consist of agglomerated nanosheets. To characterize the photocatalytic activities, UV–visible spectrometry was used to analyze the evolution of Rhodamine B photodegradation in presence of the Bi₂WO₆: Lu photocatalysts. The characteristic absorption band of Rhodamine B at 554 nm shifted to lower wavelengths under UV irradiation. The pure Bi₂WO₆ and the 5% Lu doped Bi₂WO₆ photocatalysts presented the lowest and highest efficiencies, respectively. An interpretation of improved photocatalytic efficiencies was proposed.     

In-situ room-temperature synthesis of amorphous/crystalline contact Bi2S3/Bi2WO6 heterostructures for improved photocatalytic ability

We developed a facile in-situ growth method to construct amorphous-based Bi₂S₃/Bi₂WO₆ heterostructures at room temperature. As demonstrated by HRTEM, XPS and EDX-mapping, amorphous state Bi₂S₃ dispersed uniformly on the surface of crystalline Bi₂WO₆ hollow spheres. The photocatalytic activities of prepared Bi₂S₃/Bi₂WO₆ heterostructures were evaluated by the photodegradation of RhB and TC under visible light irradiation, indicating that the introduction of appropriate amorphous Bi₂S₃ significantly improved the photocatalytic activity of Bi₂WO₆. The amorphous/crystalline contact in Bi₂S₃/Bi₂WO₆ heterostructures played a crucial role in the enhancement of photocatalytic efficiency. Based on DRS, photoluminescence spectra, photocurrent intensity, electrochemical impedance spectroscopy and OCVD measurements, it was proposed that the enhanced performance could be ascribed to increased visible light utilization, promoted separation efficiency and prolonged life time of photogenerated electron-hole pairs by the introduction of amorphous Bi₂S₃. This work may provide new insights into the construction of amorphous-based composited heterostructures for improving photocatalytic activity.     

BiOCl nanosheet/Bi4Ti3O12 nanofiber heterostructures with enhanced photocatalytic activity

Aurivillius oxide semiconductors are important photocatalyst because of their unique electronic structure and layered crystal. In this paper, two kinds of Aurivillius oxide semiconductors heterostructures based on Bi₄Ti₃O₁₂ nanofibers frameworks and BiOCl nanosheets are successfully synthesized by combining the electrospinning technique and solvothermal method. The high-resolution transmission electron microscopy results reveal that an intimate interface between Bi₄Ti₃O₁₂ nanofibers and BiOCl nanosheets forms in the heterojunctions. Photocatalytic tests show that the BiOCl/Bi₄Ti₃O₁₂ heterostructures exhibit enhanced photocatalytic activity than bare Bi₄Ti₃O₁₂ and BiOCl, mainly owing to the photoinduced interfacial charge transfer based on the photosynergistic effect of the BiOCl/Bi₄Ti₃O₁₂ heterojunction. At the end, the photocatalytic mechanism with O₂⁻ production was studied.     

Synthesis plasmonic Bi/BiVO4 photocatalysts with enhanced photocatalytic activity for degradation of tetracycline (TC)

In recent years, the excessive use of antibiotics has become a serious problem for human health. BiVO₄ regarded as one of the most promising visible-light-driven photocatalysts was used to degrade the antibiotics. In this paper, we fabricated Bi/BiVO₄ plasmonic photocatalysts which enhanced the photocatalytic activity of BiVO₄ for degradation of tetracycline (TC) antibiotic. The Bi/BiVO₄ photocatalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy and high-resolution transmission electron microscopy. In addition, the photocatalytic experiment results show that the 0.04-Bi/BiVO₄ sample has the best photocatalytic activity for 2 times than the pure BiVO₄ photocatalyst. The cycle experiments, after four repetitions of the experiments, showed the sample still maintained a high photocatalytic activity. Finally, the photocatalytic reaction mechanism was also studied by free radical capture experiments and electron paramagnetic resonance spectroscopy.     

Z-scheme AgSCN/Ag3PO4/C3N4 heterojunction with excellent photocatalytic degradation of ibuprofen

To develop a novel photocatalyst with high catalytic performance under sunlight, AgSCN/Ag₃PO₄/C₃N₄ heterojunction photocatalyst with Z-mechanism has been prepared, which demonstrates excellent photocatalytic performance for ibuprofen degradation. The catalytic activity of AgSCN/Ag₃PO₄/C₃N₄ is 1.5 and 3.3 times that of AgSCN/Ag₃PO₄ and Ag₃PO₄, respectively. The cyclic degradation number of AgSCN/Ag₃PO₄/C₃N₄ increases to seven because of the protection of AgSCN and C₃N₄ to Ag₃PO₄. The excellent photocatalytic performance of the AgSCN/Ag₃PO₄/C₃N₄ is attributed from the Z-mechanism with efficient separation efficiency of electron hole pair.     

Bi2WO6的静电纺丝法制备及其光催化性能

以聚乙烯吡咯烷酮(PVP)、钨酸铵[(NH4)10W12O41]和柠檬酸铋铵(C6H13BiN2O7.H2O)为原料,利用静电纺丝技术成功制备了PVP/C6H13BiN2O7.H2O-(NH4)10W12O41(简写为PVP/BiWO)前躯体,对PVP/BiWO缓慢控温处理制得Bi2WO6。采用差热-热重分析(TG-DTA)、X射线粉末衍射(XRD)、傅里叶红外光谱(FTIR)、X-射线光电子能谱(XPS)、场发射扫描电镜(FE-SEM)、紫外可见漫反射(UV-Vis-NIR/DR)等分析手段研究热处理温度对材料结构的影响,通过罗丹明B(RhB)光降解反应研究其光催化性能。结果表明,可见光照射下,热处理温度600℃时材料的光催化活性最好,并探讨了其光催化机理。     

等离子体改性TiO2/WO3/Bi2WO6纳米 复合材料及其可见光催化活性

以二水合钨酸钠和五水合硝酸铋为原料，通过优化水热法反应温度制备了WO3/Bi2WO6纳米片，将其与锐钛矿型TiO2纳米颗粒复合制备了可见光催化性能优良的TiO2/WO3/Bi2WO6复合光催化剂，并采用一种高密度管状等离子体放电装置对其进行表面改性。利用XRD、SEM、TEM、HRTEM、XPS、UV-Vis DRS、PL对样品进行了表征和分析，考察了其在可见光下降解亚甲基蓝的光催化性能。结果表明，当水热温度为120 ℃时，WO3/Bi2WO6纳米片具有较好的光催化性能；TiO2/WO3/Bi2WO6复合催化剂中掺入TiO2质量分数为10.7%时，所得三元复合材料的光催化性能远优于WO3/Bi2WO6纳米片；经等离子体改性处理后，三元复合材料的吸收边向可见光红移，放电输入功率的增加有助于提高复合材料的光催化活性，当放电电压为1.1 kV时，复合材料的降解速率常数分别是未处理样品和WO3/Bi2WO6的2.2倍和3.9倍。     

Enhanced photocatalytic activity of Bi2WO6 doped with upconversion luminescence agent

In order to utilize visible light more effectively, a novel Er³⁺:Y₃Al₅O₁₂/Bi₂WO₆ photocatalyst was designed, in which Er³⁺:Y₃Al₅O₁₂ is a kind of upconversion luminescence agent and can emit ultraviolet light under visible light excitation. The photo-degradation of a typical model pollutant, phenol, demonstrated that Er³⁺:Y₃Al₅O₁₂/Bi₂WO₆ photocatalyst exhibited much enhanced photo-activity than bare Bi₂WO₆ under simulated solar light irradiation. Moreover, the Er³⁺:Y₃Al₅O₁₂/Bi₂WO₆ photocatalyst also showed photo-activity under visible light with wavelengths beyond the absorption edge of Bi₂WO₆, further testifying the upconversion effect of Er³⁺:Y₃Al₅O₁₂.     

Construction of Z-scheme type CdS–Au–TiO2 hollow nanorod arrays with enhanced photocatalytic activity

The Z-scheme type CdS–Au–TiO₂ hollow nanorod arrays have been constructed on glass substrates by following these simple steps: firstly, highly ordered TiO₂ hollow nanorod arrays (THNAs) were synthesized by liquid phase deposition (LPD) using ZnO nanorod arrays as templates; then both Au core and CdS shell nanoparticles were achieved on the THNAs by in situ photodeposition. The prepared three-component films were characterized by field-emission scanning electron microscopy (FSEM), high-resolution transmission electron microscope (HRTEM), Raman scattering and ultraviolet–visible absorption spectrum. The results showed that Au–CdS core–shell nanoparticles were well dispersed on wall of anatase THNAs from top to bottom. The three-component nanojunction system was evaluated for their photocatalytic activity through the degradation of methylene blue (MB) in aqueous solution. It was found that the CdS–Au–TiO₂ three-component hollow nanorod arrays exhibited significantly enhanced photocatalytic activity compared with single (THNAs) and two components (Au-THNAs or CdS-THNAs) systems. Reasons for this enhanced photocatalytic activity were revealed by photoluminescence (PL) results of our samples.     

Rational design of MoS2/g-C3N4/ZnIn2S4 hierarchical heterostructures with efficient charge transfer for significantly enhanced photocatalytic H2 production

The rational design of hierarchical heterojunction photocatalysts with efficient spatial charge separation remains an intense challenge in hydrogen generation from photocatalytic water splitting. Herein, a noble-metal-free MoS₂/g-C₃N₄/ZnIn₂S₄ ternary heterostructure with a hierarchical flower-like architecture was developed by in situ growth of 3D flower-like ZnIn₂S₄ nanospheres on 2D MoS₂ and 2D g-C₃N₄ nanosheets. Benefiting from the favorable 2D-2D-3D hierarchical heterojunction structure, the resultant MoS₂/g-C₃N₄/ZnIn₂S₄ nanocomposite loaded with 3 wt% g-C₃N₄ and 1.5 wt% MoS₂ displayed the optimal hydrogen evolution activity (6291 μmol g^?1 h^?1), which was a 6.96-fold and 2.54-fold enhancement compared to bare ZnIn₂S₄ and binary g-C₃N₄/ZnIn₂S₄, respectively. Structural characterizations reveal that the significantly boosted photoactivity is closely associated with the multichannel charge transfer among ZnIn₂S₄, MoS₂, and g-C₃N₄ components with suitable band-edge alignments in the composites, where the photogenerated electrons migrate from g-C₃N₄ to ZnIn₂S₄ and MoS₂ through the intimate heterojunction interfaces, thus enabling efficient electron-hole separation and high photoactivity for hydrogen evolution. In addition, the introduction of MoS₂ nanosheets highly benefits the improved light-harvesting capacity and the reduced H₂-evolution overpotential, further promoting the photocatalytic H₂-evolution performance. Moreover, the MoS₂/g-C₃N₄/ZnIn₂S₄ ternary heterostructure possesses prominent stability during the photoreaction process owing to the migration of photoinduced holes from ZnIn₂S₄ to g-C₃N₄, which is deemed to be central to practical applications in solar hydrogen production.     

The Z-scheme heterojunction between TiO2 nanotubes and Cu2O nanoparticles mediated by Ag nanoparticles for enhanced photocatalytic stability and activity under visible light

The photocatalytic reduction method was used to introduce Ag nanoparticles (Ag NPs) into the Cu₂O-TiO₂ nanotubes (Cu₂O-TNT) prepared by electrodeposition. The Z-scheme heterojunction Cu₂O-Ag-TNT (CAT-4–60) catalysts were prepared. The mechanism of the transition from the traditional P-N heterojunction enhanced by noble metal to the Z-scheme heterojunction was studied. In addition, the Z-scheme heterojunction CAT-4–60 showed the highest light absorption and the highest photoelectrochemical activity under visible light, and the photoluminescence intensity was significantly reduced. Compared with the traditional P-N heterojunction CAT-2–60, not only the photocatalytic activity of the dual Z-scheme CAT-4–60 catalyst was improved, and the removal rate of MB was 98.58% higher than TNT (45.81%), CT-60 (69.49%), AT-2 (75.1%) and CAT-2–60 (91.2%),but also the stability of Cu₂O in CAT-4–60 was significantly enhanced. This work reveals the potential application of noble metal nanoparticles to enhance the Z-scheme heterojunction under visible light-driven photocatalysis, and provides new insights to the transition from traditional P-N heterojunctions to Z-scheme heterojunctions.     

Transformation of CeO2 into a mixed phase CeO2/Ce2O3 nanohybrid by liquid phase pulsed laser ablation for enhanced photocatalytic activity through Z-scheme pattern

Cerium-based nanohybrids have attracted considerable attention in photocatalytic research owing to their remarkable potential in the photodegradation of environmental pollutants. However, the process of nanohybrid formation suffers from complex operations with specialized equipment, extreme conditions, long durations, and low yields, making it infeasible for efficient utilization. Considering the above obstacles, we herein describe the first pulsed laser ablation (PLA) for the synthesis of oxygen vacancy affluent CeO₂/Ce₂O₃ nanohybrids, as an alternative to hydrothermal and calcination methods. The microstructures and optical properties of the nanocomposites are characterized by TEM, XRD, XPS, and DRS analysis. The photocatalytic activity of the CeO₂/Ce₂O₃ nanohybrid showed an MB dye degradation rate superior to that of bare CeO₂ nanostructures. The enhanced performance of CeO₂/Ce₂O₃ was attributed to an oxygen-vacancy-driven Z-scheme mechanism, where efficient separation of the photogenerated charge carriers significantly contributed to photocatalytic enhancement. This was further evidenced by both PL and scavenger experiment results. Moreover, the synthesized CeO₂/Ce₂O₃ nanocomposites exhibit a strong blue emission, which could have potential applications in LED manufacturing.     

Facile construction of C3N4-TE@TiO2/UiO-66 with double Z-scheme structure as high performance photocatalyst for degradation of tetracycline

In the current research, a double Z-scheme photocatalyst C₃N₄-TE@TiO₂/UiO-66 (CNTU) is fabricated via a two-steps facile solvothermal method from Z-scheme C₃N₄-TE@TiO₂ (CNT). This double Z-scheme photocatalyst reveals greater performance for the removal of tetracycline (TC) than pristine C₃N₄-TE, TiO₂, UiO-66 (U66), and their binary compounds. The optimized composite 35C₃N₄-TE@TiO₂/35UiO-66 (35CNTU), exhibitions photocatalytic performance for antibiotic removal (TC) more than 5,4 and 2 times higher than that pure TiO₂, UiO-66, and C₃N₄-TE, respectively. The physical and chemical features of synthesized samples were described via FTIR, XRD, SEM-EDX, TEM, BET, UV–Vis DRS, and PL. The key parameters on photocatalytic performances of 35CNTU such as pH, the amount of catalyst, and the primary concentration of TC were clari?ed. The advancement of the photocatalytic process for 35CNTU is due to the increase in the surface area and structure of double Z-scheme in this compound, which growths the active sites of the reaction as well as better separation of the photo-induced electron and hole pairs. Furthermore, 35CNTU can be recycled with superior stability for 5 cycles. The photocatalytic removal proficiency of TC over 35CNTU under visible light achieves 96% in 40 min. The findings of this study could inspire various novel plans for fabricating practical double Z-scheme photocatalyst for great performance and extensive useful applications.