Boosting Photocatalytic Oxygen Evolution: Purposely Constructing Direct Z-Scheme Photoanode by Modulating the Interface Electric Field

Ti-Fe₂O₃ photoanode has received widespread attention in photoelectrochemical(PEC) water spilling because of its optimized oxidative and reductive capability of composites catalyst. However, its low efficiency could limit its development. Herein, in order to improve the efficiency of PEC water spilling, the all-solid-state direct Z-scheme Ti-ZnFe₂O₄/Ti-Fe₂O₃(TZFO/Ti-Fe₂O₃) nanorod arrays composited with the ideal energy band structure are synthesized by modulating the Fermi level of TZFO for PEC water splitting. The photophysical methods in this work, including the Kelvin probe measurement and transient photovoltage spectroscopy(TPV) measurement, are applied to explore the migration behavior of electric charges at the enhanced interface electric field. Finally, the Z-scheme charge transfer mechanism of TZFO/Ti-Fe₂O₃ photoanode is proved successfully. Benefiting from the desirable charge transfer at interface electric field, the TZFO/Ti-Fe₂O₃ exhibits the outstanding photocatalytic oxygen evolution reaction(OER) performance, and the photocurrent of 60TZFO/Ti-Fe₂O₃ photoanode reaches 2.16 mA/cm² at 1.23 V vs. reversible hydrogen electrode(RHE), which is three times higher than that of pure Ti-Fe₂O₃ photoanode. This work provides a facile approach of modulating interface electric field to optimize the Z-scheme charge-transfer process.     

Z-机制g-C3N4/Bi/BiOBr异质结光催化剂制备及其可见光降解甲醛气体研究

通过将BiOBr纳米片与g-C₃N₄复合,然后原位还原,合成了具有纳米花状结构的三元异质结光催化剂g-C₃N₄/Bi/BiOBr.对g-C₃N₄/Bi/BiOBr的结构、形貌、元素价态和光学性能等进行了表征和研究.评估了g-C₃N₄/Bi/BiOBr对气体甲醛的光催化降解活性. g-C₃N₄/Bi/BiOBr在可见光照射下降解甲醛的活性与g-C₃N₄、 BiOBr单体和g-C₃N₄/BiOBr二元复合物相比显著提高. 20%-g-C₃N₄/Bi/BiOBr复合物可以在60 min内(λ> 400 nm)降解80%的气态甲醛(初始浓度0.16 mg·L^-1).     

Z型光催化剂Sb2WO6/g-C3N4的制备及光催化性能

通过水热反应合成了Sb₂WO₆改性的g-C₃N₄复合材料(Sb₂WO₆ /g-C₃N₄). 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 紫外-可见漫散射反射光谱(UV-Vis DRS)和光致发光光谱(PL)等表征了样品的性质. 结果表明, Sb₂WO₆在g-C₃N₄的表面上生长, 并且复合材料光吸收能力有一定的增强, 光生电子-空穴的重组率降低. 通过罗丹明B(RhB)的光降解评价了Sb₂WO₆/g-C₃N₄复合材料的光催化性能. 结果表明, 模拟日光下Sb₂WO₆质量分数为10%的Sb₂WO₆/g-C₃N₄复合材料在60 min内对RhB的降解率为99.3%, 高于纯g-C₃N₄和Sb₂WO₆. Sb₂WO₆/g-C₃N₄复合材料的这种高度增强的光催化活性主要归因于强的界面相互作用促进了光生电子-空穴分离和迁移. 添加自由基清除剂的实验结果表明, ·O^2-和h⁺是光催化反应中的主要活性物质. Sb₂WO₆/g-C₃N₄复合材料在几个反应周期内表现出优异的稳定性. 根据实验结果提出了一种可能的Z型光催化机理.     

全固态Z-Scheme光催化材料应用于二氧化碳还原和光催化分解水研究进展

由两种不同的半导体催化剂和电子传输介质建立的Z-Scheme光催化体系,通过在可见光照射下分别在两种半导体催化剂上进行氧化反应和还原反应,实现两步法光催化分解水和二氧化碳还原.相较于离子型Z-Scheme光催化体系,全固态Z-Scheme光催化体系具有适用范围广、无副反应、光源利用率高等特性,具有更加广阔的应用前景.在此,我们简述了Z-Scheme光催化体系的反应机理,综述了全固态Z-Scheme光催化体系在光催化分解水和光催化还原CO₂领域的应用,并对未来全固态Z-Scheme光催化体系的发展进行了展望.     

利用Ni(OH)x助催化剂修饰提高g-C3N4纳米片/WO3纳米棒Z型纳米体系的可见光产氢活性的研究

光催化技术是目前解决能源和环境问题最具前景的手段之一,因此寻找高效光催化剂已成为光催化技术的研究热点.而在众多半导体催化剂中,廉价、环保且性能稳定的g-C3N4光催化剂在太阳光开发利用方面尤其引人关注.然而,由于g-C3N4的比表面小,活性位点少,以及光生电子/空穴对易复合等不足,严重导致其较低的光催化量子效率.因此,构造Z型体系和负载助催化剂等策略被广泛应用于提高g-C3N4光催化效率.在过去几年中,TiO2,Bi2WO6,WO3,Bi2MoO6,Ag3PO4和ZnO已经被成功证实可以与g-C3N4耦合而构造Z型光催化剂体系.其中,WO3/g-C3N4光催化剂体系,具有可见光活性的WO3导带中的光生电子和g-C3N4价带中的光生空穴容易实现Z型复合,从而保留了WO3的强氧化能力和g-C3N4的高还原能力,最终大幅度提高了整个体系的光催化活性.在g-C3N4的各种产氢助催化剂中,由于常用的Pt,Ag和Au等贵金属的高成本和低储量等问题严重限制了它们的实际应用,所以近年来各种非贵金属助催化剂(包括纳米碳,Ni,NiS,Ni(OH)2,WS2和MoS2等)得到了广泛的关注.我们采取廉价且丰富的Ni(OH)x助催化剂修饰g-C3N4/WO3耦合形成的Z型体系,开发出廉价高效的WO3/g-C3N4/Ni(OH)x三元产氢光催化体系.在该三元体系中,Ni(OH)x和WO3分别用于促进g-C3N4导带上光生电子和价带的光生空穴的分离及利用,从而使得高能的g-C3N4的光生电子在Ni(OH)x富集并应用于光催化产氢,而高能的WO3的光生空穴被应用于氧化牺牲剂三乙醇胺,最终实现了整个体系的高效光催化产氢活性及稳定性.我们通过直接焙烧钨酸铵和硫脲制备出WO3纳米棒/g-C3N4,并采用原位光沉积方法将Ni(OH)x纳米颗粒负载到WO3/g-C3N4上.随后,我们采取X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)、X射线光电子能谱分析(XPS)和比表面和孔径分布等表征手段来研究光催化剂的结构与形貌;采取紫外-可见漫反射表征方法来研究其光学性能;采取荧光光谱,阻抗和瞬态光电流曲线等表征手段来测试光催化剂的电荷分离性能;采取极化曲线和电子自旋共振谱等表征手段来证明光催化机理;采取光催化分解水产氢的性能测试来研究光催化剂的光催化活性与稳定性.XRD,HRTEM和XPS表征结果,表明WO3为有缺陷的正交晶系的晶体,直径为20–40纳米棒且均匀嵌入在g-C3N4纳米片上;Ni(OH)x为Ni(OH)2与Ni的混合物,其Ni(OH)2与Ni的摩尔比为97.4 : 2.6,Ni(OH)x粒径为20–50 nm且均匀分散在g-C3N4纳米片上,WO3/g-C3N4/Ni(OH)x催化剂界面之间结合牢固,其中WO3和Ni(OH)x均匀分布在g-C3N4上.紫外-可见漫反射表征结果表明,随着缺陷WO3的负载量增加,复合体系的吸收边与g-C3N4相比产生明显的红移,而加入Ni(OH)x助催化剂使得催化剂体系的颜色由黄变黑,明显地增加了可见光的吸收.荧光光谱,阻抗和瞬态光电流曲线结果表明,WO3和Ni(OH)x的加入能有效地促进光生电子/空穴的分离.极化曲线结果表明,掺入WO3和Ni(OH)x能降低g-C3N4的析氢过电位,从而提高光催化剂表面的产氢动力学.?O2?和?OH 电子自旋共振谱表明成功形成了WO3/g-C3N4 耦合Z 型体系.光催化分解水产氢的性能测试表明,20%WO3/g-C3N4/4.8%Ni(OH)x产氢效率最高(576 μmol/(g?h)),分别是g-C3N4/4.8%Ni(OH)x,20%WO3/g-C3N4和纯g-C3N4的5.7,10.8和230倍.上述结果充分证明,Ni(OH)x助催化剂修饰和g-C3N4/WO3 Z型异质结产生了极好的协同效应,最终实现了三元体系的极高的光催化产氢活性.     

Fabrication of Z-Scheme WO3/KNbO3 Photocatalyst with Enhanced Separation of Charge Carriers

Z-Scheme photocatalysts as a research focus perform strong redox capability and high photocatalytic performance. WO₃/KNbO₃ photocatalysts were fabricated by ball milling method, and performed higher photocatalytic activity in liquid degradation(rhodamine B, methylene blue and bisphenol A), compared with WO₃ or KNbO₃ monomer. This is due to that Z-scheme heterojunction is formed between WO₃ and KNbO₃, and the holes photo-excited in valence band of KNbO₃ are quickly combined with the electrons in conduction band of WO₃. The electrons accumulated in conduction band of KNbO₃ show high reducibility, thereby reducing O₂ to ^·O₂^-, and the holes in valence band of WO₃ show high oxidative to oxidize H₂O to ^·OH, respectively. Furthermore, it is proved by means of electron spin resonance(ESR) spectra, terephthalic acid photoluminescence probing technique(TA-PL), and UV-Vis absorption spectra of nitroblue tetrazolium. This work indicates that the fabrication of Z-scheme structure can improve the photocatalytic activity by efficiently separating the photogenerated electrons and holes in the photocatalytic reaction system, which is helpful to deeply understand the migration mechanism of photoexcited carrier(band-band transfer and Z-scheme transfer) in heterojunction photocatalysts.     

A Metal-Organic-Framework-Derived g-C3N4/α-Fe2O3 Hybrid for Enhanced Visible-Light-Driven Photocatalytic Hydrogen Evolution

As one of the most efficient systems for photocatalytic hydrogen evolution, the Z-Scheme system, consisting of different semiconductors with a reversible donor–acceptor pair, has attracted great attention. Considering the non-toxicity and low cost of photocatalysts, a series of g-C₃N₄/α-Fe₂O₃ hybrids were rationally constructed based on the Z-Scheme mechanism for the first time, using a metal-organic framework template approach that can fine tune the compositions and properties of the hybrids. An optimized hybrid, g-C₃N₄/α-Fe₂O₃-2, exhibited prominent photocatalytic water splitting performance with a visible light response. Under irradiation of visible light (λ>420 nm), the hybrid shows a high durability and superior hydrogen production rate of 2066.2 μmol g⁻¹ h⁻¹ from water splitting, which is approximately three times greater than that of bulk g-C₃N₄ because of the effective separation of photo-excited charge carriers by two narrow band gap semiconductors, tightly coupled with the Z-Scheme structural feature.     

A Label-free Photoelectrochemical Sensor Based on Bi2S3@Nitrogen Doped Graphene Quantum Dots for Ascorbic Acid Determination

We report a photoelectrochemical(PEC) sensor for selective detection of ascorbic(AA) by introducing Z-scheme Bi₂S₃@nitrogen doped graphene quantum dots(Bi₂S₃@NGQDs) heterojunctions as efficient photoactive species. The Bi₂S₃@NGQDs were successfully prepared by a simple hydrothermal process, and the microstructures and components were investigated by various characterized techniques. The photocurrent of the Bi₂S₃@NGQDs-based sensor increased significantly in the presence of AA and showed excellent selectivity and stability for AA detection in the presence of some other antioxidants and small molecules. A wide linear range of 0.1-5 μmol/L and 5-1380 μmol/L was achieved for the AA detection with a detection limit of 36 nmol/L(S/N=3). Moreover, the proposed PEC sensor achieved the determination of AA in real red peppers and commercially available vitamin C tablets samples.     

Fabrication of ternary dual Z-Scheme AgI/ZnIn2S4/BiVO4 heterojunction photocatalyst with enhanced photocatalytic degradation of tetracycline under visible light

In this study, a novel ternary AgI/ZnIn₂S₄/BiVO₄(AZB) composite photocatalyst was successfully prepared by hydrothermal method and in-situ precipitation method. The as-synthesized samples were characterized by XRD, SEM, TEM, XPS and so on, and the photocatalytic activity was evaluated through photocatalytic degradation of tetracycline (TC) under visible light irradiation. When the molar ratio of Bi to Ag was 1:1, the degradation rate of TC can reach 91.44 % within 150 min. The AZB heterojunction demonstrated outstanding efficiency with the apparent reaction rate constants of 0.02118 min^?1 for TC removal, was 4.68, 3.27 and 3.27 times higher than that of pure BiVO₄, AgI and ZnIn₂S₄. Based on active species trapping experiments and ESR analysis, a dual Z-Scheme pathways among BiVO₄, AgI and ZnIn₂S₄ for effective separation of photogenerated charges was recommended. This work provided a promising insight for the design of ternary dual Z-scheme heterojunction with multilevel electron transfer to present greater photo-absorption, charge separation, and photodegradation for environmental decontamination.     

Studies on the fabrication and characteristics of photoelectrochemical cells using IrO2-coated TiO2 photoanode for Z-scheme water splitting and perovskite solar cell bias

ABSTRACT

In the present work, to build a water splitting system using only a neutral electrolyte solution and light source, we investigated the photoelectrochemical properties and interface resistances of an IrO₂-coated TiO₂ photoanode in Z-scheme configuration. The photoelectrochemical cell was connected to the perovskite solar cell with to realize the system with no need for an external electrical bias. Photoanodes with IrO₂ were found to support hole transport and to reduce the overpotential, therefore increasing the current density of the system consisting of photoelectrochemical cells. A maximum solar-to-hydrogen efficiency of 8.2% was achieved in a neutral electrolyte.