水热合成Bi2WO6/ZnO异质结型光催化剂及其光催化性能

在不同温度下(120～220℃),利用水热法制备了含1wt%、2wt%、4wt%和8wt%Bi2WO6的异质结型Bi2WO6/ZnO复合光催化剂,采用X射线粉末衍射(XRD)、扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、紫外可见漫反射(UV-Vis)吸收光谱及光致发光光谱(PL)等系列手段对所制备的光催化剂进行了表征,并以紫外光(365nm)为光源,酸性橙II为降解对象,进行光催化活性测试,考察了不同Bi2WO6复合量及不同水热温度对ZnO光催化剂反应活性的影响.研究表明,异质结型Bi2WO6/ZnO复合光催化剂的光催化活性明显优于纯ZnO和Bi2WO6.当复合4wt%Bi2WO6水热处理温度为150℃时,所制备的复合光催化剂的光催化活性最佳,为纯ZnO的2.6倍.活性提高的主要原因是形成的Bi2WO6/ZnO异质结能显著降低光生电子和空穴对的复合几率,并改善了异质结型Bi2WO6/ZnO复合光催化剂的表面性能.     

Ag-Ag_2O/Bi_2WO_6光催化剂的合成及其光催化性能

水热法合成了Bi_2WO_6催化剂后,将Ag-Ag_2O负载在Bi_2WO_6上,制备出新型Ag-Ag_2O/Bi_2WO_6异质结光催化剂,通过XRD,SEM,TEM,UV-Vis DRS等一系列测试手段对光催化剂进行了形貌、结构、吸光性能等性质的表征,并以罗丹明B(Rh B)为目标污染物研究催化剂的光催化活性。结果表明制备的Ag-Ag_2O/Bi_2WO_6异质结光催化剂主体为立体花球状结构,直径约2μm,具有较大的比表面积,且对可见光的吸收范围有明显增加(从442红移至594nm),催化活性亦高于未负载的Bi_2WO_6,反应120min后,Ag-Ag_2O/Bi_2WO_6对罗丹明B(Rh B)的降解率可达96.20%,在重复4次降解实验之后,其光催化活性虽然有一定损失,但光催化性能仍优于其余两组催化剂。     

氮掺杂SrTiO3的制备及其可见光催化产氢活性研究

采用溶胶-凝胶法制备了钛酸锶,进而用固相法制备了氮掺杂SrTiO3,并用光沉积和氢气还原法制备了Pt负载的氮掺杂SrTiO3光催化剂.用XRD、SEM、UV-Vis漫反射和荧光光谱对其进行了表征和分析,考察了光催化剂在可见光下的产氢活性.研究了不同氮源、掺杂量、烧结温度和Pt负载量对催化剂产氢活性的影响.结果表明,三种不同氮源剂其掺杂效果为六次亚甲基四胺(HMT)>EDTA>尿素,而EDTA掺氮效果稍低于HMT.当氮源剂为HMT,SrTiO3与HMT质量比为1:3,焙烧温度为450℃时,所制备的光催化剂具有最佳的光催化产氢活性.在负载金属铂后,产氢活性有较大幅度的提高,其中用氢气还原法制备所得的光催化剂较光沉积法制备的具有更高的光催化活性,在最佳负载量均为2wt%时,两种光催化剂6h内的产氢量分别为6.89mmol和2.24mmol,分别是未负载铂样品产氢量的12倍和4倍多.     

NiO(CoO)/N-SrTiO3异质结型复合光催化剂的制备及模拟太阳光催化产氢

采用固相法制备氮掺杂SrTiO₃,并用浸渍氢气还原法制备了不同NiO、CoO负载量的N－SrTiO₃异质结复合光催化剂,采用XRD、SEM、荧光光谱（FS）、紫外可见漫反射光谱（UV－Vis DRS）对其进行表征和分析,考察了在模拟太阳光下产氢活性及其变化规律,同时探讨了负载物的不同处理方法对光催化剂产氢活性的影响. 结果表明,氧化物的负载先氢还原后氧化处理较直接氧化处理有更高的光催化活性;所制备的NiO/N-SrTiO₃、CoO/N-SrTiO₃复合催化剂较单一催化剂有更高的产氢活性,当负载量分别为1.0wt%、0.5wt%时达最佳产氢活性,6h内的产氢量分别是未改性N-SrTiO₃样品的4.2、4.9倍. 导致产氢率提高的主要原因是由于负载金属氧化物在两相界面处形成的异质结成为光催化反应中光生电子和空穴的单向转移通道,促使光生电荷有效分离,提高了复合催化剂的光催化活性.     

TiO2/石墨烯纳米复合材料的合成及其光催化应用研究进展

以石墨烯材料修饰TiO2半导体光催化材料能够促进电子-空穴的有效分离,增大半导体表面的氧化物种富集程度,提高光催化活性。因而石墨烯-TiO2复合材料在光催化领域中被广泛研究。综述了TiO2负载在石墨烯膜/片上结构、TiO2-石墨烯异质结结构、TiO2-石墨烯核-壳式结构、TiO2-石墨烯及其他掺杂物纳米复合材料的制备,及其在光催化应用中的最新研究进展。     

NiO(CoO)/N-SrTiO3异质结型复合光催化剂的制备及模拟太阳光催化产氢

采用固相法制备氮掺杂SrTiO₃,并用浸渍氢气还原法制备了不同NiO、CoO负载量的N－SrTiO₃异质结复合光催化剂,采用XRD、SEM、荧光光谱（FS）、紫外可见漫反射光谱（UV－Vis DRS）对其进行表征和分析,考察了在模拟太阳光下产氢活性及其变化规律,同时探讨了负载物的不同处理方法对光催化剂产氢活性的影响. 结果表明,氧化物的负载先氢还原后氧化处理较直接氧化处理有更高的光催化活性;所制备的NiO/N-SrTiO₃、CoO/N-SrTiO₃复合催化剂较单一催化剂有更高的产氢活性,当负载量分别为1.0wt%、0.5wt%时达最佳产氢活性,6h内的产氢量分别是未改性N-SrTiO₃样品的4.2、4.9倍. 导致产氢率提高的主要原因是由于负载金属氧化物在两相界面处形成的异质结成为光催化反应中光生电子和空穴的单向转移通道,促使光生电荷有效分离,提高了复合催化剂的光催化活性.     

累托石基复合光催化材料研究进展

光催化是一种利用太阳能将有机污染物分解为水和二氧化碳的技术,该技术还可以用于催化制氢、还原CO2制备燃料以及杀菌,在应对全球环境污染和能源短缺问题方面起着至关重要的作用。光催化技术的关键在于设计高效、廉价且能循环使用的光催化剂。传统光催化剂存在太阳能利用率低、量子产率低以及光化学稳定性不足等问题,使得光催化技术的推广受到限制。近年来,研究者尝试了许多提高半导体光催化剂活性的方法,包括形貌调控、金属离子或非金属离子掺杂、半导体异质复合、表面贵金属沉积、负载以及开发新的光催化剂等。光催化反应主要是发生在催化剂表面的固-液反应,因而需要催化剂具有较好的吸附性能和较高的表面活性。而许多光催化剂比表面积较小、吸附能力有限,导致其光催化效率相对较低。另外,大多数光催化剂易团聚、难以分离回收,阻碍了其大规模的工业应用。近年来,许多学者将光催化剂负载到廉价的粘土材料累托石上,利用累托石较大的比表面积、优越的离子交换性能和稳定的结构解决吸附和分离问题,进而提高催化剂的光催化效率。同时,累托石独特的层状结构能够为光催化反应提供良好的反应场所。研究者们通过改进或优化制备工艺,成功制备出累托石负载TiO_2、Bi_2O_3、Bi_2WO_6、BiOI、Bi_2NbO_5F、ZnO、Ag_3PO_4、In_2O_3、CdS、Cu_2O和gC_3N_4等复合材料。研究发现,引入累托石载体可以有效提升光催化剂的吸附性能,抑制光生电子和空穴的复合,极大地改善光腐蚀问题,提高光催化材料对可见光的吸收能力。本文系统综述了累托石基半导体复合材料在光催化领域的研究进展,介绍了累托石基半导体复合材料的制备工艺,重点阐述了累托石对光催化剂性能提升的作用机制。此外,本文还讨论了制备和反应条件对复合材料光催化活性的影响。最后展望了未来累托石应用于光催化领域的方向,以期为累托石矿物材料在光催化领域的应用提供参考。     

ZnO/AgNbO_3光催化剂的表征及活性研究

采用浸渍法合成ZnO/AgNbO3异质结光催化环境净化材料.利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、紫外漫反射(DRS)等分析方法对催化剂进行了表征.XRD分析结果表明,Zn的掺杂并未改变本体AgNbO3的晶型结构;随着Zn掺杂量和热处理温度的提高,异质结光催化剂体系中ZnO晶相结构逐渐出现;同时,XPS结果也说明Zn以ZnO的形式存在.DRS分析说明ZnO的引入有助于提高可见光区的吸收强度.无论在可见光还是紫外光照射下,光催化降解亚甲基蓝染料(MB)实验证明ZnO掺杂有利于提高AgNbO3的活性.当Zn掺杂量为3wt%,热处理温度为300℃时,紫外光照射3h下MB降解率达到93.5%.并对ZnO引入后光催化活性提高的机理进行了分析.     

ZnIn2S4双空位调控极化电场用以提升光催化产氢及协同氧化苄胺(英文)

光生载流子无定向的迁移及高的反应能垒,严重地抑制了光催化产氢及协同苄胺氧化的效率.本文利用简单的水热与碱刻蚀法制备了富含锌、硫双空位的硫铟化锌.在无共催化剂的条件下,该催化剂展现出优异的光催化产氢性能与苄胺转化速率.实验数据及理论计算表明,双空位重置了硫铟化锌的电子结构,并增强了其极化电场.这些调控将有助于激子的分离及载流子的定向迁移.另外,Zn与S空位充当了氢离子与苄胺吸附的活性位点,极大地提高了其催化活性.因此,本文不仅提供了一种调控极化电场的方法,也为苄胺氧化与协同产氢提供了更深入的见解.     

泡沫镍负载TiO2和TiO2/Al2O3薄膜的光催化性能研究

以泡沫镍为载体，Al2O3作为过渡中间层，用溶胶-凝胶法在泡沫镍上负载锐钛矿相的TiO2薄膜，制成泡沫金属基的TiO2和TiO2／Al2O3光催化剂，利用XRD和FE-SEM等测试手段对其性质进行表征，用乙醛气体的光催化降解测试其活性．研究表明：泡沫镍负载的TiO2和TiO2／Al2O3薄膜具有良好的光催化活性，特别是TiO2／Al2O3薄膜具有更高的催化活性．这是由于负载的Al2O3过渡中间层增大了载体的比表面积，具有吸附浓缩作用，同时也增加了负载光催化剂的活性位数量．实验表明：TiO2／Al2O3薄膜的光催化活性和稳定性较单一的TiO2薄膜有非常显著的提高．     

Reversible Stacking of 2D ZnIn2S4 Atomic Layers for Enhanced Photocatalytic Hydrogen Evolution

It is technically challenging to reversibly tune the layer number of 2D materials in the solution. Herein, a facile concentration modulation strategy is demonstrated to reversibly tailor the aggregation state of 2D ZnIn₂S₄ (ZIS) atomic layers, and they are implemented for effective photocatalytic hydrogen (H₂) evolution. By adjusting the colloidal concentration of ZIS (ZIS-X, X = 0.09, 0.25, or 3.0 mg mL⁻¹), ZIS atomic layers exhibit the significant aggregation of (006) facet stacking in the solution, leading to the bandgap shift from 3.21 to 2.66 eV. The colloidal stacked layers are further assembled into hollow microsphere after freeze-drying the solution into solid powders, which can be redispersed into colloidal solution with reversibility. The photocatalytic hydrogen evolution of ZIS-X colloids is evaluated, and the slightly aggregated ZIS-0.25 displays the enhanced photocatalytic H₂ evolution rates (1.11 µmol m⁻² h⁻¹). The charge-transfer/recombination dynamics are characterized by time-resolved photoluminescence (TRPL) spectroscopy, and ZIS-0.25 displays the longest lifetime (5.55 µs), consistent with the best photocatalytic performance. This work provides a facile, consecutive, and reversible strategy for regulating the photo-electrochemical properties of 2D ZIS, which is beneficial for efficient solar energy conversion.     

Promoted Photocharge Separation in 2D Lateral Epitaxial Heterostructure for Visible-Light-Driven CO2 Photoreduction

Photocarrier recombination remains a big barrier for the improvement of solar energy conversion efficiency. For 2D materials, construction of heterostructures represents an efficient strategy to promote photoexcited carrier separation via an internal electric field at the heterointerface. However, due to the difficulty in seeking two components with suitable crystal lattice mismatch, most of the current 2D heterostructures are vertical heterostructures and the exploration of 2D lateral heterostructures is scarce and limited. Here, lateral epitaxial heterostructures of BiOCl @ Bi₂O₃ at the atomic level are fabricated via sonicating-assisted etching of Cl in BiOCl. This unique lateral heterostructure expedites photoexcited charge separation and transportation through the internal electric field induced by chemical bonding at the lateral interface. As a result, the lateral BiOCl @ Bi₂O₃ heterostructure demonstrates superior CO₂ photoreduction properties with a CO yield rate of about 30 µmol g⁻¹ h⁻¹ under visible light illumination. The strategy to fabricate lateral epitaxial heterostructures in this work is expected to provide inspiration for preparing other 2D lateral heterostructures used in optoelectronic devices, energy conversion, and storage fields.     

基于对氯苄胺的2D/3D钙钛矿太阳能电池

三维(3D)有机–无机金属卤化物钙钛矿薄膜的表面和晶界处存在大量缺陷,容易导致载流子的非辐射复合并加快3D钙钛矿分解,进而影响钙钛矿太阳能电池(PSCs)能量转换效率(PCE)及稳定性.本研究通过引入对氯苄胺阳离子,与3D钙钛矿薄膜及其表面过剩的碘化铅反应后原位形成了二维(2D)钙钛矿,实现了对3D钙钛矿薄膜表面和晶界...     

Magnetic Field-Assisted Interface Embedding Strategy to Construct 2D/3D Composite Structure for Stable Perovskite Solar Cells with Efficiency Over 24%

Perovskite solar cells (PSCs) based on 2D/3D composite structure have shown enormous potential to combine high efficiency of 3D perovskite with high stability of 2D perovskite. However, there are still substantial non-radiative losses produced from trap states at grain boundaries or on the surface of conventional 2D/3D composite structure perovskite film, which limits device performance and stability. In this work, a multifunctional magnetic field-assisted interfacial embedding strategy is developed to construct 2D/3D composite structure. The composite structure not only improves crystallinity and passivates defects of perovskite layer, but also can efficiently promote vertical hole transport and provide lateral barrier effect. Meanwhile, the composite structure also forms a good surface and internal encapsulation of 3D perovskite to inhibit water diffusion. As a result, the multifunctional effect effectively improves open-circuit voltage and fill factor, reaching maximum values of 1.246 V and 81.36%, respectively, and finally achieves power conversion efficiency (PCE) of 24.21%. The unencapsulated devices also demonstrate highly improved long-term stability and humidity stability. Furthermore, an augmented performance of 21.23% is achieved, which is the highest PCE of flexible device based on 2D/3D composite perovskite films coupled with the best mechanical stability due to the 2D/3D alternating structure.     

超级电容器用CeO_2-MnO/3D石墨烯复合材料的制备

以西瓜瓜瓤为碳源,采用两步碳化法制备三维石墨烯(3D-Fiberbased Graphene,3D G)材料,并使用水热法制备了CeO_2-MnO/3DG复合材料,以期获得比电容高,循环寿命好的石墨烯超级电容器电极材料。结果表明:3DG材料具有较高比表面积,最高可达到332m~2·g~(-1)。CeO_2-MnO/3DG复合材料具有三维导电网络结构,金属氧化物颗粒在石墨烯片层间生长均匀,粒径在10nm左右。电化学测试结果显示:在0.5 mol·L~(-1)的Na_2SO_4溶液中,电流密度1A·g~(-1),当摩尔比MnO∶CeO_2=4∶1,复合负载量在80%时得到的CeO_2-MnO/3D G复合材料拥有最高比电容,达308.5F·g~(-1),经过1 000次循环充放电测试比电容保持率为95.5%。CeO_2-MnO/3DG复合材料电化学性能的提高主要是因为两种金属氧化物复合负载与石墨烯的协同作用。     

Continuously Flow Photothermal Catalysis Efficiently CO2 Reduction Over S-Scheme 2D/0D Bi5O7I-OVs/Cd0.5Zn0.5S Heterojunction with Strong Interfacial Electric Field

Using CO₂, water, and sunlight to produce solar fuel is a very attractive process, which can synchronously reduce carbon and convert solar energy into hydrocarbons. However, photocatalytic CO₂ reduction is often limited by the low selectivity of reduction products and poor photocatalytic activity. In this study, S-scheme Bi₅O₇I-OVs/Cd_0.5Zn_0.5S (Bi₅O₇I-OVs/CZS-0.5) heterojunction with strong interfacial electric field (IEF) is prepared by in situ growth method. The performance of reduction CO₂ to CO is studied by continuous flow photothermal catalytic (PTC) CO₂ reduction platform. 12.5% Bi₅O₇I-OVs/CZS-0.5 shows excellent CO yield of 58.6 µmol g⁻¹ h⁻¹ and selectivity of 98.4%, which are 35.1 times than that of CZS-0.5 under visible light. The charge transfer path of the S-scheme through theoretical calculation (DFT), in situ irradiation Kelvin probe force microscope (ISI-KPFM) and in situ irradiation X-ray photoelectron spectroscopy (ISI-XPS) analysis, is verified. The study can provide useful guidance and reference for improving activity by oxygen vacancy induced strong IEF and the development of a continuous flow PTC CO₂ reduction system.     

多巴胺@氮化硼-碳纳米管/聚酰亚胺复合气凝胶太阳能蒸发器的制备与性能

利用太阳能蒸发器进行水蒸发是生产清洁用水的重要途径之一。为了提高聚酰亚胺(PI)气凝胶的太阳能蒸发性能,本文通过添加多巴胺改性氮化硼(PDA@BN)和羟基化碳纳米管(CNT),采用四定向冷冻干燥和亚胺化工艺制备了PDA@BN-CNT/PI复合气凝胶。研究了PDA@BN和CNT的加入对气凝胶的形貌结构、润湿性能、太阳能蒸发性能的影响。结果表明：PDA@BN-CNT/PI复合气凝胶不仅具有良好的亲水性和太阳能光热转换能力,而且其独特的低弯曲度管状结构促进了水在气凝胶内部的运输,提高了太阳能蒸发性能。该气凝胶在2 kW/m²光照下的蒸发速率为1.95 kg/(m²·h),并展现出优异的循环使用性能、化学稳定性和高效的污水净化能力。     

Photocatalytic H2 evolution over sulfur vacancy-rich ZnIn2S4 hierarchical microspheres under visible light

In this work, the sulfur vacancies were successfully introduced into the ZnIn₂S₄ (ZIS) lattice through two facile approaches, plasma etching and annealing, for enhancing the photocatalytic performance. The optimized plasma-etched ZIS exhibited an enhanced H₂ generation rate of 706 μmol g^?1 h^?1, which was 5 and 1.2 times higher than that of pure ZIS and annealed ZIS, respectively. Theoretical calculation demonstrated that surface S vacancy could arouse the catalytic activity of the adjacent S atoms in inert (001) basal plane, serving as the active site for hydrogen evolution reaction (HER). Although annealing could produce much more S vacancies than the plasma etching, a majority of bulk S vacancies usually acted as charge recombination center to lower the photocatalytic activity. Hence, even plasma-etched ZIS presented poor light absorption capacity, plasma etching showed a better effect on the HER improvement of ZIS than annealing. This work presents a simple and promising pathway for optimization of 3D ZIS photocatalysts to improve photocatalytic hydrogen evolution.

     

Graded 2D/3D Perovskite Heterostructure for Efficient and Operationally Stable MA-Free Perovskite Solar Cells

Almost all highly efficient perovskite solar cells (PVSCs) with power conversion efficiencies (PCEs) of greater than 22% currently contain the thermally unstable methylammonium (MA) molecule. MA-free perovskites are an intrinsically more stable optoelectronic material for use in solar cells but compromise the performance of PVSCs with relatively large energy loss. Here, the open-circuit voltage (V_oc) deficit is circumvented by the incorporation of β-guanidinopropionic acid (β-GUA) molecules into an MA-free bulk perovskite, which facilitates the formation of quasi-2D structure with face-on orientation. The 2D/3D hybrid perovskites embed at the grain boundaries of the 3D bulk perovskites and are distributed through half the thickness of the film, which effectively passivates defects and minimizes energy loss of the PVSCs through reduced charge recombination rates and enhanced charge extraction efficiencies. A PCE of 22.2% (certified efficiency of 21.5%) is achieved and the operational stability of the MA-free PVSCs is improved.     

Highly Efficient and Stable Solar Cells Based on Crystalline Oriented 2D/3D Hybrid Perovskite

Highly efficient and stable 2D/3D hybrid perovskite solar cells using 2‐thiophenemethylammonium (ThMA) as the spacer cation are successfully demonstrated. It is found that the incorporation of ThMA spacer cation into 3D perovskite, which forms a 2D/3D hybrid structure, can effectively induce the crystalline growth and orientation, passivate the trap states, and hinder the ion motion, resulting in improved carrier lifetime and reduced recombination losses. The optimized device exhibits a power conversion efficiency (PCE) of 21.49%, combined with a high V_OC of 1.16 V and a notable fill factor (FF) of 81%. More importantly, an encapsulated 2D/3D hybrid perovskite device sustains ≈99% of its initial PCE after 1680 h in the ambient atmosphere, whereas the control 3D perovskite device drops to ≈80% of the original performance. Importantly, the device stability under continuous light soaking (100 mW cm^?2) is enhanced significantly for 2D/3D perovskite device in comparison with that of the control device. These results reveal excellent photovoltaic properties and intrinsic stabilities of the 2D/3D hybrid perovskites using ThMA as the spacer cation.