半导体光催化剂BiOCl异质结的构建及应用

氯氧化铋(BiOCl)半导体因其独特的层状结构和可调控的电子结构，而在光催化解决环境问题和能源问题领域备受关注。为了提高BiOCl对太阳光的利用率、抑制光生电子-空穴对的高复合率和增强光电子的还原能力等，研究人员对此作出了巨大的努力。其中，构建异质结是最有效的削弱这些缺陷的方法之一。本文主要综述了Z-型、Ⅱ-型、p-n结以及S-型四类异质结的电荷传递机理以及重点介绍了一些具有优异光催化性能的BiOCl异质结。同时，对一些异质结的光催化降解性能进行了比较分析。其中，S型异质结不仅具有高效的电荷分离能力，还有强的氧化还原能力，因此其表现出优异的光催化性能。此外，本文还简述了BiOCl异质结在降解有机污染物、还原CO₂、还原重金属和分解H₂O等方面的应用。总结了当前BiOCl异质结遇到的一些问题。最后针对BiOCl异质结的构效关系、合成复杂等问题，提出了计算机模拟、载体负载、新技术开发的发展方向。     

Co-BiVO_4异质结光催化剂的制备及其性能

采用一步水热法合成具有高效光催化活性的Co-BiVO_4纳米复合材料。该材料通过Co氧化物包覆在钒酸铋表面构成p-n型异质结结构。通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、高倍透射电镜(HRTEM)、X射线光电子能谱(XPS)、紫外可见漫反射(UV-vis DRS)等对所制备的纳米光催化剂进行形貌、结构、组成及光电性能表征分析。发现Co是以氧化物的形式负载在BiVO_4的表面,并且复合材料的可见光吸收带发生了红移。利用亚甲基蓝(MB)作为目标污染物,以可见光作为光源考察不同材料的光催化性能。结果表明,Co-BiVO_4复合光催化剂的催化活性明显高于纯BiVO_4。当Bi和Co的复合比为2∶1时,Co-BiVO_4的光催化活性最高,与纯BiVO_4相比光催化反应速率提高了4倍。本研究完善了铋系异质结和过渡金属提高光催化活性的相关机理。     

剥离蒙脱石表面原位构建Bi_(2)O_(3)/Bi_(2)SiO_(5)异质结及其光催化活性EI北大核心CSCD

采用一步法,在剥离蒙脱石表面原位构建了Bi_(2)O_(3)/Bi_(2)SiO_(5)异质结,系统研究了其物相结构、微观形貌和光学特征。制备过程中,剥离蒙脱石除作为Bi_(2)O_(3)/Bi_(2)SiO_(5)异质结生长的骨架,还可以作为硅源得到Bi_(2)SiO_(5)。结果表明:与纯α-Bi_(2)O_(3)相比,在模拟太阳光的照射下,Bi_(2)O_(3)/Bi_(2)SiO_(5)异质结表现出对罗丹明B有优良降解性能,这主要是由于Bi_(2)O_(3)与Bi_(2)SiO_(5)之间形成的p-n结以及高的比表面积所引起的。此外,还提出了光催化反应机理。本工作提供了一种构建低成本污染物降解催化剂的新方法,拓展了蒙脱石的新应用。     

水热法合成二氧化钛/钛酸锶异质结构

文章主要开展二氧化钛/钛酸盐异质结构的合成及光催化性能研究,即以二氧化钛纳米颗粒作Ti源和模板,利用水热法在其表面原位形成钛酸盐颗粒以得到二氧化钛/钛酸盐异质结构。通过X-射线衍射、扫描电镜等手段对所制备的异质结的物性进行表征,并对其光催化性能进行测试。     

钒掺杂磷酸铋/蒙脱石复合材料的制备及可见光催化脱硫性能

采用水热法制备了钒掺杂磷酸铋/蒙脱石(BiP_(1–x)V_xO_4/MMT)复合材料,通过X射线衍射、透射电子显微镜、Fourier变换红外光谱和紫外可见吸收光谱表征复合材料的结构和组成、形态特征,并以其为催化剂进行光催化脱硫,考察了不同掺杂摩尔比x对复合材料的光催化脱硫性能的影响。结果表明:MMT的加入避免了活性组分的团聚,同时表面负载的BiP_(1–x)V_xO_4固溶相与BiVO_4析出相可形成紧密结合的异质结,提高了可见光的利用率,促进了光生电子-空穴对的分离。当x=0.6时,可见光照射3 h,BiP_(1–x)V_xO_4/MMT复合材料对模拟汽油的脱硫率可达97%。     

AgBr/TiO_2/硅藻土复合材料对罗丹明B光催化降解的研究

以硅藻土为载体,钛酸四丁酯为钛源,采用溶胶-凝胶法和沉淀-沉积法,制备了异质结结构的Ag Br/TiO_2/硅藻土复合材料,对罗丹明B(Rh B)污染物光催化降解。通过X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)对复合材料晶型结构、形貌、元素化合价态和吸光性能表征分析。考察了不同摩尔比Ag Br/TiO_2对复合材料光催化性能的影响,并探究了复合材料的稳定性。结果表明,纳米TiO_2为锐钛矿晶型,Ag Br和TiO_2之间的异质结提高了复合材料的光催化活性;Ag Br和TiO_2摩尔比为0.20时,复合材料光催化活性最好。经过8次循环使用后,对Rh B的降解率仍保持在85%以上。     

具有高效可见光活性的AgCl/AgVO_3异质结光催化剂的原位合成

以水热法合成的AgVO_3为前驱体,在其表面通过原位离子交换法合成AgCl/AgVO_3异质结光催化剂,利用XRD、SEM和UV-Vis等对其结构、形貌和光吸收性能进行表征,并以酸性橙-Ⅱ模拟环境中染料污染物,考察了AgCl/AgVO_3异质结的可见光催化性能。结果表明,AgCl/AgVO_3异质结光催化剂具有高效的可见光催化活性,在可见光照射下15 min,酸性橙-Ⅱ降解率达到80%,循环使用4次后,降解率仍能保持60%。自由基捕获实验结果表明,h~+和·O_2~-为光催化反应中的主要活性物种。光催化性能的提高主要归因于AgCl/AgVO_3异质结构的形成,这利于光生电子-空穴对转移和分离。最后探讨了增强AgCl/AgVO_3光催化性能的可能机理。     

AgBr/TiO_2/硅藻土复合材料对罗丹明B光催化降解的研究

以硅藻土为载体,钛酸四丁酯为钛源,采用溶胶-凝胶法和沉淀-沉积法,制备了异质结结构的Ag Br/TiO_2/硅藻土复合材料,对罗丹明B(Rh B)污染物光催化降解。通过X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)对复合材料晶型结构、形貌、元素化合价态和吸光性能表征分析。考察了不同摩尔比Ag Br/TiO_2对复合材料光催化性能的影响,并探究了复合材料的稳定性。结果表明,纳米TiO_2为锐钛矿晶型,Ag Br和TiO_2之间的异质结提高了复合材料的光催化活性;Ag Br和TiO_2摩尔比为0.20时,复合材料光催化活性最好。经过8次循环使用后,对Rh B的降解率仍保持在85%以上。     

自掺杂NiO/SrTiO_(3-x)异质结的合成及可见光催化性能研究

通过两步法合成了一种新颖的NiO/SrTiO_(3-x)异质结光催化剂,首先,通过高温固相法合成不同Ti~(3+)自掺杂的SrTiO_(3-x),再利用浸渍法合成NiO/SrTiO_(3-x)异质结。X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)和紫外可见漫反射(UV-vis-DRS)等仪器被系统的用来表征SrTiO_(3-x)和NiO/SrTiO_(3-x)异质结,并对它们的物理化学性质进行分析。在可见光条件下用罗丹明B来考察样品的光催化活性,研究表明NiO/SrTiO_(3-x)具有优异的光催化性能,远远优于Ti~(3+)自掺杂的SrTiO_(3-x)。而且,NiO/SrTiO_(3-x)异质结的循环实验结果表明该材料不仅具有高效的光催化剂性能,而且还拥有良好的稳定性。     

NiO/In_2O_3 p-n结型光催化剂的制备及其降解盐酸强力霉素研究

采用水热合成法制备出了具有p-n异质结结构的立方形氧化铟表面负载片状氧化镍复合光催化剂。SEM,XRD和UV-VIS,FT-IR等方法对催化剂的晶相组成、微观结构、化学键组成以及吸光性能等进行了表征。结果表明,NiO/In_2O_3复合光催化剂的形成符合牺牲模板机理。片状氧化镍的负载使复合光催化剂的吸收带边发生了明显的红移,并在可见光区产生响应。光催化降解盐酸强力霉素实验表明,与单一的In_2O_3相比,氧化镍颗粒的负载使二氧化铟的光催化效果在紫外-可见光区有了明显地提高,且在中性以及碱性条件下的光催化效果最佳,降解效率达到93%,其主要原因应归功于氧化镍晶粒与二氧化铟晶粒紧密接触形成p-n异质结,有助于催化剂表面光生电子和空穴的快速分离。     

Boron-Doped Graphene/ZnO Nanoflower Heterojunction Composite with Superior Photocatalytic Activity

The boron-doped graphene (BG) is synthesized successfully by one pot reduce-doping of graphene oxide (GO) with borane tetrahydrofuran (BH₃·THF) and the novel BG/ZnO p–n heterojunction composite between p-type BG and n-type ZnO is obtained via a simple hydrothermal method. The samples are characterized by scanning electron microscopy, the Raman spectroscopy and the UV–Vis diffuse spectroscopy. The results confirm the formation of p–n junction between BG and ZnO. The photodegradation of MB demonstrate that the BG/ZnO composite has superior photocatalytic activity under UV–Vis or visible irradiation. The photocatalytic activity k value of BG/ZnO p–n heterojunction composite is 3.1 and 4.5 times as that of r-GO/ZnO and pure ZnO under white light and is 1.8 and 3.9 times under visible light, respectively. The superior photocatalytic activity of the BG/ZnO composite is ascribed to the formation of p–n heterojunction. The p–n heterojunction can promote the separation of electron/hole pairs and inhibit the recombination of electrons in conduction band and holes in valence band by transferring holes from the valence band of n-type ZnO to the valence band of p-type BG.     

Synthesis and characterization of CeO2/Bi2O3/gC3N4 ternary Z-scheme nanocomposite

An effective and facile phytogenic method was used to prepare CeO₂/Bi₂O₃ and CeO₂/Bi₂O₃/gC₃N₄ composites using Eichhornia crassipes phytoextract. The synthesized catalysts were characterized using techniques such as XRD, FTIR, UV-DRS, PL, SEM-EDAX, XPS, zeta potential, and TGA. These catalysts showed diverse photocatalytic and optical properties due to the alteration in the bandgap. The synthesized composites exhibited good photocatalytic activity by degrading Malachite green (MG) dye. The increase in the photocatalytic activity could be attributed to the p-n heterojunction of the catalysts with efficient charge separation and strong oxidative ability. The modified photocatalysts showed excellent catalytic activity and reusability under visible light. The superior efficiency and its applications in environmental remediation make these catalysts a potential candidate for photocatalysis.     

Synthesis of a CoTiO3/BiOBr heterojunction composite with enhanced photocatalytic performance

A novel heterojunction CoTiO₃/BiOBr nanocomposite with enhanced photocatalytic performance was synthesized by a precipitation-deposition method. The samples were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV–vis spectrophotometry. Moreover, the photocatalytic activities were evaluated by decomposing the dye molecule Rhodamine B under visible light irradiation. The results showed that high photocatalytic performance can be achieved on the heterojunction photocatalysts, with the 0.15CoTiO₃/0.85BiOBr composite displaying the highest activity. The results of the study concluded that it was the introduction of CoTiO₃ into the catalyst that mainly enhanced the activity of the photocatalyst by promoting the separation of the electron-hole group on the interface between BiOBr and CoTiO₃.     

Synthesis,characterization and photocatalysis of AgAlO2/TiO2 heterojunction with sunlight irradiation

A novel photocatalyst AgAlO₂/TiO₂ with a p–n heterojunction structure was synthesized through the method that combined sol–gel and ion exchange. The as-synthesized samples were characterized by XRD, SEM and UV–vis. The photocatalytic activity of as-synthesized sample was evaluated and the possible mechanism was discussed. As-synthesized AgAlO₂/TiO₂ (in mass ratio of 90/10) exhibited remarkably high photocatalytic activity of 97.8% in decomposing formaldehyde under sunlight irradiation for 90 min. Our work provided a basic experimental process for AgAlO₂/TiO₂ heterojunction and explored the connection between p–n heterojunction and photocatalysis, which will possess a broad prospect in terms of the applications in improving indoor air quality.     

直接Z-Scheme异质结Al-PMOFs/CdZnS光催化剂的制备及其光催化苯甲胺氧化性能

摘要：采用水热法合成了具有立方柱状结构的卟啉基金属有机框架化合物(Al-PMOFs),然后通过共沉淀法将CdZnS纳米颗粒沉积在Al-PMOFs棱柱上,得到了界面接触良好的异质结Al-PMOFs/CdZnS纳米杂化材料。将催化剂应用于可见光催化苯甲胺氧化偶联反应中,结果表明,Al-PMOFs/CdZnS纳米复合材料具有较好的光催化反应活性和稳定性。室温下当溶剂为N,N-二甲基甲酰胺(DMF)时,经可见光照射7 h后,苯甲胺可以发生氧化偶联反应生成N-苄基-1-苯基甲亚胺(BPMI),苯甲胺的转化率可达97%,BPMI 的选择性超过99%,复合材料的光催化活性较相同条件下单一的CdZnS和Al-PMOFs提高了2倍。Al-PMOFs/CdZnS光催化性能的提高主要归因于Al-PMOFs与CdZnS之间形成了直接Z-scheme异质结,该异质结能够促进Al-PMOFs和CdZnS界面上的电荷传输,抑制Al-PMOFs/CdZnS杂化材料表面光生载流子的复合。通过自由基捕获实验等提出了适合该体系的直接Z-scheme光催化反应机理以及电荷转移路径。     

In-situ synthesis of 3D CdMoO4@CdS core-shell structure for efficient photocatalytic degradation

3D CdMoO₄@CdS core-shell visible-light-driven photocatalyst was successfully synthesized by in-situ method. Various analytical techniques show that CdS dots are uniformly loaded on the surface of CdMoO₄ hollow microspheres constructing a 3D core-shell CdMoO4@CdS heterojunction. The photocatalytic activity of nanocomposites was studied by degrading malachite green (MG) under visible light irradiation. It was found that the composite material can effectively degrade MG under visible light irradiation. Furthermore, the enhanced photocatalytic efficiency for the composite material is due to the effective diffusion and separation of photogenerated carriers.     

Ag3PO4/AgI光催化剂的制备及降解2-氨基-4-乙酰氨基苯甲醚机理

研究了Ag₃PO₄复合棒状AgI光催化剂的制备及降解2-氨基-4-乙酰氨基苯甲醚（AMA）的性能和机理,利用X射线衍射（XRD）、扫描电镜（SEM）、紫外可见漫反射（UV-Vis）、光电子能谱（XPS）等方法对合成样品的物相组成和形貌结构进行了表征。通过可见光催化降解AMA来评价光催化剂的催化性能。实验结果显示,Ag₃PO₄/AgI复合光催化剂比Ag₃PO₄和AgI单体具有更强的光催化氧化与还原能力,其中以I和P的比例为1∶5时效果最佳,且在五次循环使用之后仍有较好的光催化活性。自由基捕获实验证明光催化过程中光生空穴（h⁺）是主要的活性物种。投加量为30mg、光照时间60min的条件下可将AMA几乎完全去除。本文研究结果为构筑新型可见光光催化剂提供了新视角,为促进光催化降解有机污染物提供了新途径。     

BiOCl/g-C3N4异质结催化剂可见光催化还原CO2

以KCl、Bi（NO₃）₃和类石墨氮化碳（g-C₃N₄）为前体,采用水热法成功制备了BiOCl/g-C₃N₄异质结光催化剂,并进行可见光催化还原CO₂,考察了催化剂的活性及稳定性,同时研究BiOCl：g-C₃N₄（摩尔比）、催化剂用量和光照强度对光催化还原CO₂的影响。结果表明,在水蒸气的存在下,BiOCl/g-C₃N₄较纯BiOCl和g-C₃N₄具有更高的光催化还原CO₂活性,在催化剂用量为0.1 g,光照强度为2.413×10^-6 einstein·min^-1·cm^-2,BiOCl：g-C₃N₄摩尔比为1：1的异质结催化剂显示了最高的光催化还原CO₂活性,且可见光催化剂在5次套用实验后其活性基本不变。基于X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、比表面积测试（BET）和紫外-可见（UV-vis）吸收光谱表征,可以推断BiOCl和g-C₃N₄之间形成的p-n结能有效分离光生电子和空穴,是增强光催化剂活性的主要原因。     

In-situ synthesis of 0D/1D CeO2/Zn0.4Cd0.6S S-scheme heterostructures for boosting photocatalytic remove of antibiotic and chromium

The development of green and efficient photocatalytic materials for the treatment of medical and industrial wastewater has become a current research focus. In this work, the CeO₂/Zn_0.4Cd_0.6S heterojunction with a special 0D/1D morphology was synthesized by a soft chemistry method. The successful construction of the heterojunction was verified by the binding energy migration of XPS and TEM. The photocatalytic activities were determined by photoreduction of hexavalent chromium ions (Cr^VI) and photodegradation of tetracycline hydrochloride (TC). The experimental results showed that the loading of CeO₂ significantly improves the photocatalytic performance of Zn_0.4Cd_0.6S, and the loading of 10 wt% CeO₂ has the best photocatalytic activity and structural stability. The S-scheme electron transport mechanism was particularly investigated through active species trapping experiments. This work provides an effective idea for the design of highly stable metal sulfide photocatalysts.