Bi2WO6/UiO-66复合材料的制备与光催化性能研究

以冰乙酸作为模板剂,采用溶剂热法制备了一种Bi₂WO₆/UiO-66复合光催化剂,探究了不同UiO-66掺杂量对其光催化性能的影响,通过XRD、FTIR、SEM、N₂吸附-脱附、UV-Vis DRS、PL等手段对复合材料进行表征,以有机染料罗丹明B（RhB）作为目标降解物评价复合材料的光催化性能. 结果表明,该复合材料在可见光下光催化降解RhB时具有很强的活性. 经过4次循环实验,光催化剂的催化活性没有明显降低. 通过自由基捕获实验证明起主要作用的活性物质为空穴（h⁺）,并提出了可能的光催化降解机理为：UiO-66均匀分布在Bi₂WO₆的表面,增大了复合材料的比表面积,Bi₂WO₆光生电子转移到UiO-66的表面,降低了电子空穴复合率,h⁺则位于Bi₂WO₆表面,直接氧化有机物达到净化效果.     

Ti0.7W0.3O2@BiVO4 p-n复合异质结构界面光催化剂的制备及其可见光催化降解苯酚机理的研究

设计并制备了新型Ti_0.7W_0.3O₂/BiVO₄ p-n复合异质结构界面光催化剂应用于可见光条件下降解模拟含苯酚污染物的废水.采用粉末X射线衍射（PXRD）、扫描电镜（SEM）、固体粉末紫外漫反射（DRS）及X射线光电子能谱（XPS）等技术表征了Ti_0.7W_0.3O₂/BiVO₄ p-n复合异质结构界面的性状.结果显示BiVO₄纳米粒子均匀地分布在Ti_0.7W_0.3O₂纳米颗粒周围并构筑了稳定的p-n复合异质结构界面.Ti_0.7W_0.3O₂/BiVO₄ p-n复合异质结构界面光催化剂具有更宽的可见光响应范围和更低的能带宽度.纯BiVO₄和Ti_0.7W_0.3O₂纳米颗粒的导带位置分别为-0.62 eV和0.56 eV.优化了Ti_0.7W_0.3O₂/BiVO₄ p-n复合异质结构界面光催化剂降解苯酚的条件（即：pH值为4.5,催化剂用量为0.60 g·L^-1和苯酚初始浓度95 mg·L^-1）,质量分数为5%Ti_0.7W_0.3O₂/BiVO₄表现出最高的苯酚催化活性且初始降解速率常数（k）为0.01137 min^-1.6次连续光催化降解苯酚后,Ti_0.7W_0.3O₂/BiVO₄ p-n复合异质结构表现出良好的稳定性和可循环使用性.自由基捕获结果说明3种自由基均参加了苯酚的光催化降解过程中,且氧化能力由强到弱顺序为：羟自由基（·OH^-） > 过氧化物自由基阴离子（·O^2-） > 光生空穴（h⁺）.总有机碳结果表明苯酚在降解的过程中是先产生了中间降解产物,最后这些中间产物再矿化为无机的CO₂和H₂O.利用对苯二甲酸（TA）荧光探针证明了Ti_0.7W_0.3O₂/BiVO₄ p-n复合异质结构界面光催化剂降解苯酚为羟自由基（·OH^-）机理反应;同时,利用紫外-可见光谱（UV-Vis）和高效液相色谱-质谱联用技术（HPLC-MS）探究了苯酚的中间降解产物,推测了苯酚在Ti_0.7W_0.3O₂/BiVO₄ p-n复合异质结构界面上可能的降解机理.     

碱/抗坏血酸活化分子氧氧化水中As（III）

研究了碱/抗坏血酸（H₂A）活化分子氧体系（碱/H₂A体系）氧化水中三价砷（As（III））的过程与机理.考察了pH、H₂A浓度、As（III）初始浓度、水中常见阴离子（Cl^-、NO₃^-、HCO₃^-）和有机质富里酸对As（III）氧化效率的影响,通过自由基抑制实验及电子自旋共振（ESR）鉴定了体系中的活性氧物质（ROS）,并采用液相色谱-质谱分析技术鉴定了H₂A的降解产物.结果表明,在pH=9~12范围内,pH值越高,As（III）氧化速率越快;pH=10条件下,随着H₂A浓度从0.05 mmol·L^-1增加到1 mmol·L^-1,反应1 h后,As（III）氧化率从24%增加至92%.机理研究结果表明,H₂O₂是碱/H₂A活化分子氧体系中氧化As（III）的主要ROS,它主要来自碱性条件下H₂A与分子氧的单电子或双电子反应,同时,体系中H₂A也发生了氧化性降解.碱/H₂A体系可用于含砷废水的预处理,并与离子交换吸附方法联合,实现高效除砷.     

WO3/g-C3N4异质结光催化剂的制备和光催化活性探究

采用水热合成和煅烧法制备高催化活性的WO₃/g-C₃N₄材料,并用于酸性橙G废水的降解.同时,采用X射线衍射、漫反射光谱、傅立叶变换红外光谱、扫描电镜和氮吸附-脱附测试、X光子能谱和光致发光光谱方法对复合材料进行了表征.降解实验表明,复合材料的光催化性能比单一WO₃和g-C₃N₄高,且Z型光催化剂WO₃/g-C₃N₄在WO₃与g-C₃N₄质量比为3∶10时具有最高的光催化活性,在105 min内对20 mg·L^-1酸性橙G的光降解效率达98%,反应速率是单一g-C₃N₄的5倍.采用自由基捕获剂分别对体系中的·OH、·O₂^-和h⁺进行捕获实验,结果表明,·OH、·O₂^-和h⁺共同参与了光催化降解反应,其中,h⁺是Z型WO₃/g-C₃N₄光催化的主要活性物质.复合催化剂具有良好的重复利用性,在3次循环试验后光降解效率仍达90%.     

CuNiFe LDHs/BiO2-x异质结可见光活化过硫酸盐降解环丙沙星

采用水热法成功合成了CuNiFe LDHs/BiO_2-x复合光催化剂,并在可见光照射下用于活化过硫酸盐（PMS）降解环丙沙星（CIP）.由于光催化和PMS活化的协同作用,CIP的去除率高达88.3%.利用XRD、FT-IR、SEM、XPS和UV-Vis DRS等方法对制备的光催化剂进行了表征.确定了CuNiFe LDHs的最佳负载量,并考察了PMS用量、初始pH值和无机阴离子（Cl^-、CO₃^2-和NO₃^-）对降解的影响.电子顺磁共振和自由基捕获实验表明·OH和h⁺是CIP降解的主要活性物种,并提出了该体系可能的降解机制.     

磁性CeO2-Fe3O4复合材料光催化/吸附去除水中As(III)

原水砷污染问题严重威胁饮用水水质安全,随着生活饮用水标准的提高,致使多地饮用水中砷超标问题突显.本研究利用CeO₂半导体的光催化活性及CeO₂和Fe₃O₄对As（V）的强亲和力,合成了双组份磁性CeO₂-Fe₃O₄复合材料,并采用SEM、XRD、BET和VSM等手段进行表征,考察复合材料的光催化/吸附除砷效果;研究了初始pH值、共存离子等因素对吸附除砷效果的影响;采用等温吸附模型、吸附动力学模型等手段进行吸附特性研究.实验结果表明,在光催化过程中,·OH和·O₂^-为主要的活性氧化物种.在紫外照射下,As（Ⅲ）能完全被氧化为毒性较低的As（V）,同时将As（V）高效吸附于CeO₂-Fe₃O₄粒子表面.在中性条件下,CeO₂-Fe₃O₄粒子对砷的饱和吸附量为122.19 mg·g^-1.共存离子Cl^-和SO₄^2-对As（V）的吸附没有显著影响,而CO₃^2-、SiO₃^2-和PO₄^3-与As（V）存在明显的竞争吸附,使As（V）的吸附去除效果明显降低.吸附动力学和吸附等温线模拟分别符合准二级动力学方程和Freundlich吸附等温线,表明As（V）的吸附以化学吸附为主导.CeO₂-Fe₃O₄复合吸附剂可快速实现固液分离,容易再生且重复利用性较好,具有广泛的应用前景.     

锰氧化物负载施氏矿物去除酸性矿山废水中As(III)的性能及机理

施氏矿物是天然的砷吸附剂,但其存在酸性条件下对As(III)吸附性能较弱且无法对As(III)氧化降毒的缺陷. 采用液相沉淀法成功制备出锰氧化物负载施氏矿物(MnO_x@Sch),研究锰负载量、初始pH值和共存离子对MnO_x@Sch去除As(III)的影响,并采用吸附动力学结合XPS、FTIR及TEM等表征探究该过程的机理. 结果表明:在初始pH=3、投加量为0.5 g·L^-1、As(III)初始浓度为1 mg·L^-1的条件下,As(III)与MnO_x@Sch反应后的剩余浓度仅为2.42~3.38 μg·L^-1.MnO_x@Sch去除As(III)受初始pH影响较小,H₂PO₄^-共存时As(III)去除存在明显的抑制作用. MnO_x@Sch 去除As(III)的过程符合准二级动力学方程和颗粒内扩散方程. 液相化学组分和固相产物表征分析显示MnO_x@Sch对As(III)的去除机理可概括为As(III)氧化、静电吸附和络合配位及配体交换. 研究结果可为施氏矿物及其改性材料应用于酸性矿山废水砷污染治理提供理论依据.     

CDs-BOC复合催化剂可见光下活化过硫酸盐降解典型PPCPs

本研究通过简便的水热和煅烧两步法合成了一种新型光催化剂,该方法用碳量子点（CDs）修饰BiOCl纳米片.制备的纳米复合材料（CDs-BOC）通过X射线衍射（XRD）、扫描电子显微镜（SEM）、高分辨率透射电子显微镜（HRTEM）、紫外-可见漫反射吸收光谱（DRS）、X射线光电子能谱（XPS）和稳态荧光光谱（PL）等手段进行了表征.结果表明,此材料成功地引入了CDs.7% CDs-BOC纳米复合材料的光吸收边界被增强至可见光区域（424 nm）,并提高了光致电子-空穴对的分离效率.为了提高有机污染物降解的效果,过硫酸盐（PS）被引入了CDs-BOC光催化体系中.由于复合纳米催化剂具有出色的光催化能力,光生电子可以有效活化PS,产生更多的活性氧化物质.在可见光（λ>420 nm）照射下,20 min内可以完全去除5 mg·L^-1对-乙酰氨基酚（AAP）.通过自由基淬灭实验和电子顺磁共振波谱（EPR）,探明了此体系具有多种活性氧化物质：·OH、·SO₄^-、·O₂^-和h⁺,并提出了降解反应机制.以上结果体现出CDs-BOC/PS体系在光催化处理水污染方面具有广阔的应用前景.     

蒙脱土原位生长MoS2复合材料光催化降解罗丹明B的机理研究

通过在Na⁺-MMT表面生长MoS₂来提高窄带隙半导体光生电子分离速率及稳定性.利用阳离子填充法及水热法成功制备了复合光催化剂Na⁺-MMT/MoS₂,并通过FT-IR、SEM、TEM、Raman、XRD、TG、XPS、UV-DRS和ESR等表征进一步证明了材料的成功负载及光、电化学性能. 同时,以有机染料罗丹明B为待降解染料来评价光催化剂的催化性能,发现其在80 min可有效降解罗丹明B,降解率达96%.经过5次循环使用后,Na⁺-MMT/MoS₂复合光催化剂仍具有较好的光催化性能.因此,利用MMT的表面电负性及稳定的片层结构负载MoS₂,可形成光生电子迁移通道进一步提高电荷迁移速率及光催化剂的稳定性.本研究可为黏土材料调控窄带隙半导体制备环境友好型光催化剂提供新思路.     

菌株ZD8的分离鉴定及其异养硝化和缺氧/好氧反硝化特性研究

从稳定运行的ASBR厌氧氨氧化反应器中分离筛选出一株在缺氧和好氧条件下均具有高效反硝化能力的菌株ZD8,该菌株为假单胞属(Pseudomonas sp.),大小2 μm×0.25 μm,无鞭毛和芽孢.实验结果表明,缺氧条件下,ZD8最适合的碳源为柠檬酸钠;当C/N为10时,具有最佳的反硝化效果.菌株ZD8在缺氧条件下不具有硝化能力.在好氧条件下菌株ZD8获得最佳反硝化效果的C/N为22,最适合pH范围是7.2~9.9.菌株ZD8在好氧条件下具有高效的异养硝化能力,NH₄⁺-N平均去除速率为8.3 mg·L^-1·h^-1.当以KNO₃为氮源时ZD8的反硝化速率为13.1 mg·L^-1·h^-1;而以NaNO₂为氮源时,其反硝化速率为6.98 mg·L^-1·h^-1.在同时存在NH₄⁺-N和NO₃^--N或NH₄⁺-N和NO₂^--N的系统中,菌株ZD8均首先利用NH₄⁺-N发生硝化作用,NH₄⁺-N的存在对反硝化具有抑制作用,并且NH₄⁺-N对NO₂^--N的反硝化抑制作用更强;在同时存在NO₃^--N和NO₂^--N的系统中,菌株ZD8优先利用NO₃^--N进行好氧反硝化脱氮.     

Synthesis of novel CeO2-BiVO4/FAC composites with enhanced visible-light photocatalytic properties

To utilize visible light more effectively in photocatalytic reactions, a fly ash cenosphere （FAC）-supported CeO2-BiV04 （CeO2-BiVO4/FAC） composite photocatalyst was prepared by modified metalorganic decomposition and impregnation methods. The physical and photophysical properties of the composite have been characterized by X-ray diffraction （XRD）, scanning electron microscope （SEM） and energy dispersive X-ray spectroscopy （EDX）, X-ray photoelectron spectroscopy （XPS）, and UV-Visible diffuse reflectance spectra. The XRD patterns exhibited characteristic diffraction peaks of both BiVO4 and Ce02 crystalline phases. The XPS results showed that Ce was present as both Ce4＋ and Ce3＋ oxidation states in Ce02 and dispersed on the surface of BiV04 to constitute a p-n heterojunction composite. The absorption threshold of the CeO2-BiVO4/FAC composite shifted to a longer wavelength in the UV-Vis absorption spectrum compared to the pure Ce02 and pure BiV04. The composites exhibited enhanced photocatalytic activity for Methylene Blue （MB） degradation under visible light irradiation. It was found that the 7.5 wt.% CeO2-BiVO4/FAC composite showed the highest photocatalytic activity for MB dye wastewater treatment.     

Triton X-100 induced cuboid-like BiVO4 microsphere with high photocatalytic performance

A highly active visible light-induced BiVO₄ photocatalyst was prepared by a simple co-precipitation method using ammonia solution as a pH adjustor and Triton X-100 (TX100) as a structure directing agent. The physical properties of the prepared BiVO₄ photocatalyst were investigated by several techniques such as X-ray diffractometer (XRD), Brunauer–Emmett–Teller (BET) surface area measurement, scanning electron microscopy (SEM), energy dispersive analysis (EDS), Fourier-transformed infrared spectroscopy (FT-IR), photoluminescence (PL), and UV–Vis diffused reflectance spectroscopy (DRS). XRD results revealed the existence of a monoclinic scheelite structure in both the unmodified and the modified samples. The TX100 played a crucial role to control the cuboid-like shape morphology of BiVO₄. The DRS results showed that the as-prepared cuboid BiVO₄ possessed enhanced visible light absorption range compared with that of the unmodified BiVO₄. The photocatalytic activity was evaluated via indigo carmine (IC) degradation under visible light irradiation. The modified BiVO₄ showed higher photocatalytic efficiency than the unmodified BiVO₄ and the commercial P25-TiO₂ which could be ascribed to the better charge separation efficiency.     

Response surface methodology analysis of the photocatalytic removal of Methylene Blue using bismuth vanadate prepared via polyol route

Visible-light driven photocatalyst bismuth vanadate (BiVO₄) photocatalyst was synthesized by the polyol route using ethylene glycol. The precipitate was washed, dried and calcined at 450℃ for 3 hr. The sample was characterized by X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), zeta potential, surface area (BET method) and band gap energy via diffuse reflectance spectroscopy (DRS). The synthesized BiVO₄ has a monoclinic phase with a surface area of 4.3 m²/g and a band gap energy of 2.46 eV. A majority of the particles were in the range of 90-130 nm as obtained from the particle size distribution histrogram. The efficiency of the sample as a visible-light driven photocatalyst was examined by photodegrading Methylene Blue (MB). The effects of some operational photodegradation parameters such as mass loading, initial dye concentration and pH were also examined. Experimental design methodology was applied by response surface modeling and optimization of the removal of MB. The multivariate experimental design was employed to develop a quadratic model as a functional relationship between the percentage removal of MB and three experimental factors (BiVO₄ loading, MB initial concentration and pH). The percentage removal of MB approached 67.21% under optimized conditions. In addition, a satisfactory goodness-of-fit was achieved between the predictive and the experimental results.     

Porous FeOx/BiVO4-δS0.08：Highly efficient photocatalysts for the degradation of Methylene Blue under visible-light illumination

Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide （y wt.% FeOx/BiVO4-δS0.08, y = 0.06, 0.76, and 1.40） photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt.% FeOx/BiVO4-δS0.08 photocatalysts contained a monoclinic scheetlite BiVO4 phase with a porous olive-like morphology, a surface area of 8.8-9.2 m^2/g, and a bandgap energy of 2.38-2.42 eV. There was co-presence of surface Bi^5＋, Bi^3＋, V^5＋, V^3＋, Fe^3＋, and Fe^2＋ species in y wt.% FeOx/BiVO4-δS0.08. The 1.40 wt.% FeOx/BiVO4-δS0.08 sample performed the best for Methylene Blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and FeOx co-doping, higher oxygen adspecies concentration, and lower baudgap energy were responsible for the excellent visible-light-driven catalytic activity of 1.40 wt.% FeOx/BiVO4-δS0.08.     

负载型TiO2光电催化降解孔雀石绿的动力学研究

以钛酸四丁酯(TBOT)为钛源,硝酸镧为镧源,尿素为氮源,采用溶胶-凝胶法合成了La-N共掺杂的TiO2光催化剂,并探究了其对孔雀石绿氧化降解的性能.结果表明该反应遵循一级动力学,得到动力学模型;其中外加偏电压的反应分级数(0.935 8)高于pH的反应分级数(0.611 9)以及初始浓度的反应分级数(0.335),表明外加偏电压对反应的影响最大.模型值与实验值吻合良好(R2为0.910～0.996 1),说明该反应动力学模型能较好地描述光电催化降解孔雀石绿过程.     

Influence factors for the oxidation of pyrite by oxygen and birnessite in aqueous systems

The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments, oxygen and manganese oxides participate in the oxidation of pyrite. In this work, the oxidation processes of natural pyrite by oxygen and birnessite were studied in simulated systems, and the influence of pH, Fe(II) and Cr(III) on the intermediates and redox rate was investigated. SO₄^2 − and elemental S were formed as the major and minor products, respectively, during the oxidation processes. Ferric (hydr) oxides including Fe(OH)₃ and goethite were formed with low degree of crystallinity. Low pH and long-term reaction facilitated the formation of goethite and ferric hydroxide, respectively. The rate of pyrite oxidation by birnessite was enhanced in the presence of air (oxygen), and Fe(II) ions played a key role in the redox process. The addition of Fe(II) ions to the reaction system significantly enhanced the oxidation rate of pyrite; however, the presence of Cr(III) ions remarkably decreased the pyrite oxidation rate in aqueous systems. The introduction of Fe(II) ions to form a Fe(III)/Fe(II) redox couple facilitated the electron transfer and accelerated the oxidation rate of pyrite. The present work suggests that isolation from air and decreasing the concentration of Fe(II) ions in aqueous solutions might be effective strategies to reduce the oxidation rate of pyrite in mining soils.     

玻璃纤维负载P25光催化接触氧化活性艳红X-3B

在玻璃纤维上焙烧P25制备了负载型TiO2光催化剂,探讨了焙烧温度对催化活性的影响,设计了光催化接触氧化反应器,并以活性艳红X-3B为模型污染物,考察溶液pH值、共存阴离子(CO₃^2-、SO₄^2-、Cl-)对光催化反应的影响.结果表明,焙烧温度直接影响负载后催化剂的活性,300℃负载时活性最高,SEM照片显示此时P25与载体结合牢固、负载颗粒均匀.酸性条件对活性艳红X-3B的降解有利,当溶液初始pH由2.0上升到10.0时,活性艳红X-3B的降解率从90.06%下降至42.71%.共存的CO₃^2-、SO₄^2-对活性艳红X-3B降解的影响不大,但Cl^-对氧化过程有明显的抑制,使活性艳红X-3B的降解率下降17.03%.利用成熟的光催化剂P25,通过烧结的方法制备负载型催化剂是当前替代粉末催化剂的较为可行的方案.     

Fabrication of electrochemically-modified BiVO4-MoS2-Co3O4composite film for bisphenol A degradation

A new electrochemically-modified BiVO₄-MoS₂-Co₃O₄ (represented as E-BiVO₄-MoS₂-Co₃O₄) thin film electrode was successfully synthesized for environmental application. MoS₂ and Co₃O₄ were grown on the surface of BiVO₄ to obtain BiVO₄-MoS₂-Co₃O₄. E-BiVO₄-MoS₂-Co₃O₄ film was achieved by further electrochemical treatment of BiVO₄-MoS₂-Co₃O₄. The as-prepared E-BiVO₄-MoS₂-Co₃O₄ exhibited significantly enhanced photoelectrocatalytic activity. The photocurrent density of E-BiVO₄-MoS₂-Co₃O₄ thin film is 6.6 times that of BiVO₄ under visible light irradiation. The degradation efficiency of E-BiVO₄-MoS₂-Co₃O₄ for bisphenol A pollutant was 81.56% in photoelectrochemical process. The pseudo-first order reaction rate constant of E-BiVO₄-MoS₂-Co₃O₄ film is 3.22 times higher than that of BiVO₄. And its reaction rate constant in photoelectrocatalytic process is 14.5 times or 2 times that in photocatalytic or electrocatalytic process, respectively. The improved performance of E-BiVO₄-MoS₂-Co₃O₄ was attributed to the synergetic effects of the reduction of interfacial charge transfer resistance, the formation of oxygen vacancies and sub-stoichiometric metal oxides and higher separation efficiency of photogenerated electron-hole pairs. E-BiVO₄-MoS₂-Co₃O₄ is a promising composite material for pollutants removal.     

Catalytic oxidation effect of MnSO4 on As(III) by air in alkaline solution

The catalytic oxidation effect of MnSO₄ on As(III) by air in an alkaline solution was investigated. According to the X-ray diffraction (XRD), scanning electron microscope-energy dispersive spectrometer (SEM-EDS) and X-ray photoelectron spectroscopy (XPS) analysis results of the product, it was shown that the introduction of MnSO₄ in the form of solution would generate Na_0.55Mn₂O₄·1.5H₂O with strong catalytic oxidation ability in the aerobic alkaline solution, whereas the catalytic effect of the other product MnOOH is not satisfactory. Under the optimal reaction conditions of temperature 90°C, As/Mn molar ratio 12.74:1, air flow rate 1.0 L/min, and stirring speed 300 r/min, As(III) can be completely oxidized after 2 hr reaction. The excellent catalytic oxidation ability of MnSO₄ on As(III) was mainly attributed to the indirect oxidation of As(III) by the product Na_0.55Mn₂O₄·1.5H₂O. This study shows a convenient and efficient process for the oxidation of As(III) in alkali solutions, which has potential application value for the pre-oxidation of arsenic-containing solution or the detoxification of As(III).