BiOBr/g-C3N4 S型异质结无H2O2光-自芬顿高效催化降解RhB

通过焙烧-超声混合法成功地制备了BiOBr/g-C₃N₄ S型异质结复合光催化剂。采用多种表征手段对样品物理属性进行了表征,包括X射线多晶粉末衍射仪(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-VisDRS)。研究了所制备样品有/无Fe³⁺的光-自芬顿催化/光催化降解罗丹明B (RhB)性能。通过捕获实验确定了光催化反应中的主要活性物种,提出了光-自芬顿反应的降解机理。研究结果表明,BiOBr/g-C₃N₄ S型异质结能原位生成H₂O₂,添加Fe³⁺后,H₂O₂被原位活化成活性物种且光生电流和载流子分离效率获得显著提高。该光-自芬顿过程能高效降解RhB,其反应速率常数为0.208 min^-1,约为无Fe³⁺光催化反应速率常数的5.3倍,在光-自芬顿循环使用过程中表现出良好的稳定性。Fe³⁺的加入促进了光生电荷的分离和H₂O₂的活化,超氧阴离子自由基(·O₂^-)、空穴和羟基是光-自芬顿催化过程中的主要活性物种,且·O₂^-作用更大。     

直接Z型MIL-100(Fe)/BiOBr异质结的构建及光芬顿降解磺胺甲恶唑的性能

通过原位共沉淀法可控制备了系列直接Z型MIL-100(Fe)/Bi OBr异质结。使用粉末X射线衍射(PXRD)、傅里叶红外变换(FTIR)光谱、紫外可见漫反射光谱(UV-Vis DRS)、扫描电镜(SEM)、高倍透射电镜(HRTEM)以及X射线光电子能谱(XPS)对MIL-100(Fe)/Bi OBr异质结晶体结构、微观形貌、光学性能、化学组成进行表征。以低功率发光二级管可见光为光源,探究了MIL-100(Fe)/Bi OBr异质结光芬顿降解磺胺甲恶唑(SMX)性能。最佳反应体系MB-7/Vis/H₂O₂(MB-7是MIL-100(Fe)质量为Bi OBr质量的70%时制备的样品)在光源照射70 min后可降解99.8%SMX(5 mg·L^-1)。同时,还考察了H₂O₂浓度、催化剂投加量、p H值以及无机阴离子对MB-7/Vis/H₂O₂降解SMX影响。MB-7/Vis/H₂O₂能够在经过...     

表面缺陷α-Fe2O3(001)纳米片双活性位点类芬顿催化剂用于降解污染物

纯Fe₂O₃表面活性位点较少具有较低的催化活性限制了其在多相芬顿催化体系中的应用。通常采用元素掺杂、贵金属负载以及与其它化合物质复合等改性措施来提升催化活性,然而这些措施存在催化剂制备复杂,制备成本高以及催化剂的精细结构难以精准控制等问题。因此,本文提出在α-Fe₂O₃表面引入氧空位缺陷构筑双活性位点（Fe²⁺和氧空位）用于促进H₂O₂分解提高降解污染物降解效率。实验结果发现α-Fe₂O_3-x-330/H₂O₂体系具有较宽的pH使用范围（pH=2~10）。当pH=4时,罗丹明B的降解速率常数为0.834 h^-1,而且催化剂具有磁性,易回收重复使用。催化机理研究表明氧空位缺陷α-Fe₂O_3-x催化剂的氧空位和Fe²⁺两种活性位点均可促进H₂O₂分解,而且氧空位的引入有利于污染物在催化剂表面的吸附进一步提高催化性能。     

表面相变及Pt负载的BiOBr纳米片的协同光催化效应

通过热处理手段考察了BiOBr纳米片的表面相变过程。通过XRD,Raman,SEM,TEM,UV-Vis-DRS等手段对不同热处理温度下样品的结构进行表征。结果表明,高温热处理下（≥400℃）,BiOBr相向Bi₂₄O₃₁Br₁₀相转变,可形成BiOBr/Bi₂₄O₃₁Br₁₀异质结。通过气相乙醛的降解,并与商用P₂₅TiO₂做比较来评估催化剂的光催化性能,测得活性顺序为：P₂₅TiO₂>BiOBr>BiOBr/Bi₂₄O₃₁Br₁₀。能带结构分析可知BiOBr与Bi₂₄O₃₁Br₁₀间形成I型异质结不利于电荷分离,因而活性降低。然而,当同样条件下于上述催化剂表面负载Pt后,测得光催化活性顺序为：（BiOBr/Bi₂₄O₃₁Br₁₀）-Pt> BiOBr-Pt >P25 TiO₂-Pt。（BiOBr/Bi₂₄O₃₁Br₁₀）-Pt的最高活性归因于BiOBr/Bi₂₄O₃₁Br₁₀异质结与Pt负载的协同分离光生载流子过程,即与BiOBr/Bi₂₄O₃₁Br₁₀界面的光生空穴转移,BiOBr/Pt及Bi₂₄O₃₁Br₁₀/Pt界面的光生电子转移、累积及开启双电子还原O₂的一系列过程有关。     

N2O活化的Fe/ZSM-5表面活性氧的表征(英)

Temperature-programmed reduction (H₂-TPR) was employed to quantitatively characterize the active oxygen species generated from a high Fe-loading Fe/ZSM-5 catalyst exposed to N₂O at 250 ℃. [Fe-O-Fe]²⁺ dimer was determined as the active iron complex for N₂O decomposition to produce the active oxygen. Reduction of Fe³⁺ to Fe²⁺ by H₂ in the dimer and removal of OH^- groups from Fe²⁺ dimer by heating Fe/ZSM-5 to 700 ℃ were the prerequisites for the formation of this active Fe complex. A linear correlation with a slope of 1.0 between the amount of [Fe-O-Fe]²⁺ and that of active oxygen species was observed. Maximum amount of active oxygen species can be generated by reducing Fe/ZSM-5 catalyst with H₂ at the temperatures over 500 ℃ and then heating the resulting product in Ar to 700 ℃, followed by N₂O exposure at 250 ℃. The ratio of the total number of oxygen atoms (Ode) deposited by interaction of [Fe-O-Fe]²⁺ with N₂O to the amount of [Fe-O-Fe]²⁺ was 2. However, not all the deposited oxygen atoms were active oxygen (O_a); the ratio of O_a and O_de was 0.5. The iron dimer complex composing active oxygen is a five-atom ion [Fe₂O₃]²⁺; the most probable structure is as follows:     

新型磁性荧光Fe3O4-CdSe纳米复合材料的制备

以1-十八烯作为高沸点溶剂, 在磁性粒子表面沉积量子点获得新型的磁性荧光Fe₃O₄-CdSe 纳米异质结构. 首先以乙酰丙酮铁(Fe(acac)₃)为前驱体, 二苯醚为溶剂, 油酸为表面活性剂和油胺(OAm)为表面活性剂兼还原剂, 通过溶剂热法制备单分散性的Fe₃O₄ 纳米粒子. 然后以1-十八烯为高沸点溶剂, CdO 为镉源,TOP-Se为硒源, 十六胺为表面活性剂以及硬脂酸为生长促进剂和成核剂制备得到新型的Fe₃O₄-CdSe纳米异质结构. 通过透射电镜(TEM), 傅里叶变换红外(FTIR)光谱, X射线衍射(XRD)谱, X射线光电子能谱(XPS)分析仪, 振动样品磁强计(VSM), 紫外-可见(UV-Vis)光谱和光致发光(PL)等手段对Fe₃O₄-CdSe 纳米复合材料的结构和性能进行表征. 结果表明, CdSe纳米粒子成功地吸附在Fe₃O₄纳米粒子表面, 并沿着c轴生长, 形成了宽3.6 nm, 长分别为14.5 和32.5 nm的新型枣核状和钉子状的异质结构体. 这种新型的Fe₃O₄-CdSe纳米复合材料是由磁铁矿Fe₃O₄和六方形的CdSe棒状结构组成, 具有较好的荧光性能和超顺磁性. 随着CdSe棒长度的增加, 荧光吸收峰向长波方向移动. Fe₃O₄纳米粒子, 枣核状和钉子状的Fe₃O₄-CdSe纳米复合材料的饱和磁化强度分别是57.80, 40.76和31.10 emu·g^-1.     

Ti3+自掺杂的TiO2(A)/TiO2(R)/In2O3纳米异质结的制备与可见光催化性能

以TiCl₃和InCl₃为Ti源和In源,在不使用还原剂的条件下,首先通过液相沉淀反应制备前驱体沉淀,然后采用后续水热处理制备Ti³⁺自掺杂的TiO₂(A)/TiO₂(R)/In₂O₃纳米异质结,考察了水热处理温度对材料结构和性能的影响。利用X射线衍射、透射电子显微镜、X射线光电子能谱和紫外-可见漫反射光谱对样品进行表征。分别以罗丹明B和苯酚溶液为模拟废水评价了样品的可见光催化降解性能。结果表明,与纯的TiO₂、In₂O₃以及Ti³⁺自掺杂的TiO₂相比,Ti³⁺自掺杂的TiO₂(A)/TiO₂(R)/In₂O₃纳米异质结在可见光区有明显的吸收,并具有良好的可见光催化降解性能,200℃下水热处理24 h所得样品光催化降解罗丹明B的反应速率常数(0.0444 min^-1)分别是纯TiO₂和In₂O₃的17.76倍和8.71倍。瞬态光电流时间响应结果表明样品的光催化性能主要来源于TiO₂(A)/TiO₂(R)/In₂O₃纳米异质结导致的提高的光生电子和空穴分离效率。     

一锅法制备S型异质结光催化剂Fe2O3/Fe2TiO5及其高效降解有机污染物性能

首次采用简单的一锅法制备了Fe₂O₃/Fe₂TiO₅异质结纳米材料。构建S型异质结后,与纯的Fe₂O₃和Fe₂TiO₅相比,Fe₂O₃/Fe₂TiO₅复合材料表现出更高的光催化降解速率和效率。经过2.5 h的光照后,Fe₂O₃/Fe₂TiO₅可以降解接近100%的亚甲基蓝（MB）。在Fe₂O₃/Fe₂TiO₅复合材料中,Fe₂O₃和Fe₂TiO₅之间形成了内建电场,可以促进光生电子-空穴对的分离。因此,具有更高能量的Fe₂TiO₅导带中的电子和具有更高能量的Fe₂O₃价带中的空穴可以得到有效的保留,从而使它们更加有效地扩散到催化剂表面,并参加降解反应。此外,Fe₂O₃/Fe₂TiO₅复合材料具有很好的光催化稳定性。     

碳纳米管负载纳米Fe2O3的研究

本文研究了用液相化学沉积法制备的碳纳米管负载Fe₂O₃。首先用浓HCl、浓HNO₃和浓HNO₃ / H₂SO₄(混酸)三种酸对碳纳米管进行改性处理，对样品进行了TEM形貌观察和FTIR光谱分析，FTIR分析表明浓HCl处理后不能在碳纳米管表面引入官能团，而浓HNO₃能在碳纳米管表面引入-OH和-C=O，浓HNOO₃ / H₂SO₄能在碳纳米管表面引入大量的-OH、-C=O、COOH。制备了以上三种碳纳米管分别负载Fe₂O₃。TEM分析表明，负载效果：混酸>浓HNO₃>浓HCl。经混酸处理后的碳纳米管所负载的Fe₂O₃的XRD分析，表明所负载的是α-Fe₂O₃。机理分析表明碳纳米管上的含氧基团能增强其在水溶液中的分散性，同时能增强其对Fe³⁺吸附和离子交换能力，使吸附在碳纳米管表面的Fe³⁺成为结晶成核中心，调节溶液pH值后，使Fe₂O₃沉积在碳纳米管表面。     

油水自组装制备Ag@AgBr/BiOBr高效可见光催化剂

采用油水自组装法制备Ag@AgBr表面修饰三维花状结构BiOBr复合光催化剂(Ag@AgBr/BiOBr),利用XRD、SEM、TEM、EDX、DRS、XPS、PL及EIS等手段对光催化剂的结构和性能进行了表征,并研究了可见光下降解亚甲基蓝(MB)的催化性能.研究表明:Ag@AgBr粒径约为20nm,均匀分散在花状微球BiOBr表面上;贵金属Ag的表面等离子体效应可显著增强可见光利用率,并有效促进光生电子空穴对的分离,Ag@AgBr(15wt%)/BiOBr光催化剂展现出最优的催化活性,可见光照射30min对MB的降解率将近90%,淬灭实验表明·O₂^-,h⁺和Br⁰均为活性物种.结合理论分析与实验结果提出复合光催化剂的降解机理.     

BiOBr/g-C3N4 S型异质结无H2O2光-自芬顿高效催化降解RhB

通过焙烧-超声混合法成功地制备了BiOBr/g-C₃N₄S型异质结复合光催化剂。采用多种表征手段对样品物理属性进行了表征,包括X射线多晶粉末衍射仪(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-Vis DRS)。研究了所制备样品有/无Fe³⁺的光-自芬顿催化/光催化降解罗丹明B(RhB)性能。通过捕获实验确定了光催化反应中的主要活性物种,提出了光-自芬顿反应的降解机理。研究结果表明,BiOBr/g-C₃N₄S型异质结能原位生成H₂O₂,添加Fe³⁺后,H₂O₂被原位活化成活性物种且光生电流和载流子分离效率获得显著提高。该光-自芬顿过程能高效降解RhB,其反应速率常数为0.208 min^-1,约为无Fe³⁺光催化反应速率常数的5.3倍,在光-自芬顿循环使用过程中表现出良好的稳定性。Fe...     

Effective norfloxacin elimination via photo-Fenton process over the MIL-101(Fe)-NH2 immobilized on α-Al2O3 sheet

MIL-101(Fe)-NH₂@Al₂O₃ (MA) catalysts were successfully synthesized by reactive seeding (RS) method on α-Al₂O₃ substrate, which demonstrated excellent photo-Fenton degradation performance toward fluoroquinolone antibiotics (i.e., norfloxacin, ciprofloxacin, and enrofloxacin). The structure and morphology of the obtained MA were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), atomic force microscope (AFM). The as-prepared MA could accomplish > 90% of norfloxacin degradation efficiency for 10 cycles’ photo-Fenton processes, owing to its excellent chemical and water stability. In addition, the effects of operational factors including H₂O₂ concentration, foreign ions, and pH on the photo-Fenton degradation of norfloxacin over MA were clarified. The ESR spectra further document that ^?O₂^?, ¹O₂ and ^?OH radicals are prominent in the decomposition process of antibiotic molecules. Finally, the plausible photo-Fenton norfloxacin degradation mechanisms were proposed and verified.     

Photocatalytic Cr(VI) sequestration and photo-Fenton bisphenol A decomposition over white light responsive PANI/MIL-88A(Fe)

Polyaniline (PANI)/MIL-88A(Fe) (Px@M88) composites were constructed through a simple one-pot hydrothermal method. The photocatalytic and photo-Fenton activities of Px@M88 composites toward reduction of Cr(VI) and degradation organic pollutants were explored by white light irradiation. PANI, as a conductive polymer, can improve MIL-88A(Fe)’s conductivity and the efficiency of photogenerated e⁻–h⁺ pair separation. In the presence of H₂O₂, a photo-Fenton reaction occured to boost the degradation efficiency of organic pollutants like bisphenol A. In addition, P9@M88 showed excellent recycling and stability in cycling experiments. Finally, a possible reaction mechanism for photocatalytic degradation was proposed and verified by X-ray photoelectron spectroscopy and electron spin resonance determination and electrochemical characterizations.     

Photo-Fenton and photo-Fenton-like processes for the degradation of methyl orange in aqueous medium: Influence of oxidation states of iron

Degradation of methyl orange (MO) was carried out by the photo-Fenton process (Fe²⁺/H₂O₂/UV) and photo-Fenton-like processes (Fe³⁺/H₂O₂/UV, Fe²⁺/S₂O₈²⁻/UV, and Fe³⁺/S₂O₈²⁻/UV) at the acidic pH of 3 using hydrogen peroxide and ammonium persulfate (APS) as oxidants. Oxidation state of iron had a significant influence on the efficiency of photo-Fenton/photo-Fenton-like processes. It was found that a process with a source of Fe³⁺ ions as the catalyst showed higher efficiency compared to a process with the Fe²⁺ ion as the catalyst. H₂O₂ served as a better oxidant for both oxidation states of iron compared to APS. The lower efficiency of APS is attributed to the generation of excess protons which scavenges the hydroxyl radicals necessary for degradation. Further, the sulfate ions produced from S₂O₈²⁻ form a complex with Fe²⁺/Fe³⁺ ions thereby reducing the concentration of free iron ions in the solution. This process can also reduce the concentration of hydroxyl radicals in the solution. Efficiency of the various MO degradation processes follows the order: Fe³⁺/H₂O₂/UV, Fe³⁺/APS/UV, Fe²⁺/H₂O₂/UV, Fe²⁺/APS/UV.     

ZnO修饰提升花状BiOBr的可见光催化降解罗丹明B性能

以Bi(NO3)3·5H2O、Zn(CH3COO)2·2H2O和NaBr为前驱体,采用简单溶剂热法制备BiOBr/ZnO三维花状微纳米复合材料.采用X射线衍射、扫描电子显微镜、X射线光子能谱、N2吸附-脱附、光致发光和电子顺磁共振等分析技术对其理化性质进行了表征.通过可见光催化降解罗丹明B(RhB)的实验测试了复合材料...     

Study on catalytic mechanisms of Fe3O4-rGOx in three typical advanced oxidation processes for tetracycline hydrochloride degradation

This study explored the catalytic mechanism and performance impacted by the materials ratio of Fe₃O₄-GO_x composites in three typical advanced oxidation processes (AOPs) of O₃, peroxodisulfate (PDS) and photo-Fenton processes for tetracycline hydrochloride (TCH) degradation. The ratio of GO in the Fe₃O₄-GO_x composites exhibited different trends of degradation capacity in each AOPs based on different mechanisms. Fe₃O₄-rGO_20wt% exhibited the optimum catalytic performance which enhanced the ozone decomposition efficiency from 33.48% (ozone alone) to 51.83% with the major reactive oxygen species (ROS) of O₂^??. In PDS and photo-Fenton processes, Fe₃O₄-rGO_5wt% had the highest catalytic performance in PDS and H₂O₂ decomposition for SO₄^??, and ^?OH generation, respectively. Compared with using PDS alone, PDS decomposition rate and TCH degradation rate could be increased by 5.97 and 1.73 times under Fe₃O₄-rGO_5wt% catalysis. In the photo-Fenton system, Fe₃O₄-rGO_5wt% with the best catalyst performance in H₂O₂ decomposition, and TCH degradation rate increased by 2.02 times compared with blank group. Meantime, the catalytic mechanisms in those systems of that the ROS produced by conversion between Fe²⁺/Fe³⁺ were also analyzed.     

Photo-Fenton degradation of resorcinol mediated by catalysts based on iron species supported on polymers

Novel Fe supported catalysts were prepared by immobilizing iron species on commercial polyethylene via three different methods: (1) acidic pre-treatment of the polyethylene followed by impregnation in aqueous Fe(NO₃)₃, (2) TiO₂ photo-catalytic pre-treatment of the polyethylene followed by forced hydrolysis of Fe(NO₃)₃, and (3) direct photo-Fenton attack with concomitant iron deposition on the polyethylene surface. The last method required soft conditions and led to the most photo-active Fe–polyethylene film. With this material, at a non-adjusted initial pH of 5.6 in the presence of H₂O₂, total degradation and 50% of resorcinol mineralization were observed in 40 and 60 min, respectively. Photo-Fenton functionalization/Fe-deposition process was also applied to polypropylene, high-impact polystyrene, and polymethylmethacrylate films. The efficiencies of all the prepared heterogeneous photo-catalysts were similar to that of an homogeneous photo-Fenton system containing the same amount of Fe^3+/2+ that leached during “heterogeneous” processes. That demonstrated than in our systems mainly homogeneous photo-Fenton reactions were responsible for the resorcinol degradation. The photo-catalytic activity observed for the Fe/polymer was a function of the specific polymer capacity to release the initially deposited iron into the solution.     

Novel organic/inorganic PDI-Urea/BiOBr S-scheme heterojunction for improved photocatalytic antibiotic degradation and H2O2 production

The matched energy band structure and efficient carrier separation efficiency are the keys to heterogeneous photocatalytic reactions. A novel organic/inorganic step scheme (S-scheme) heterojunction PDI-Urea/BiOBr composite photocatalyst was constructed by simple solvothermal reaction combined with in-situ growth strategy. The composite photocatalyst not only has high chemical stability, but also can generate and accumulate a large number of active species (h⁺, ^?O₂^?, ^?OH, H₂O₂). PDI-Urea/BiOBr showed higher photocatalytic activity for the degradation of antibiotic such as ofloxacin (OFLO), tetracycline (TC) and the production of H₂O₂ in the spectral range of 400–800 nm. The apparent rate constant of 15% PDI-Urea/BiOBr for photocatalytic degradation of TC (or OFLO) was 2.7 (or 2.5) times that of pure BiOBr and 1.7 (or 1.8) times that of pure PDI-Urea. The H₂O₂ evolution rate of 15% PDI-Urea/BiOBr was 2.5 times that of PDI-Urea and 1.5 times that of BiOBr, respectively. This work has formed a mature S-scheme heterojunction design thought and method, which offers new visions for the development of heterogeneous photocatalysts.