基于光微热量-荧光光谱联用技术研究光催化热力学和动力学的温度效应

利用光微热量-荧光光谱联用技术,对光催化过程的热谱和光谱信息同步监测,获取了五个温度下,g-C_3N_4@Ag@Ag_3PO_4光催化降解罗丹明B的原位热动力学、光谱动力学信息,探究了温度对相关参数的影响。结果表明,催化降解反应分为三个阶段:(i)污染物和催化剂的光响应过程;(ii)光响应吸热和污染物降解放热的竞争过程;(iii)保持稳定的放热率。吸热和放热的竞争过程符合一级动力学,降解速率随着温度的升高而增大;稳定放热阶段为拟零级反应,在283.15 K、288.15 K、293.15 K、298.15 K、303.15 K下的放热速率分别为0.4668±0.3875μJ·s~(-1)、0.5314±0.3379μJ·s~(-1)、0.5064±0.3234μJ·s~(-1)、0.5328±0.3377μJ·s~(-1)、0.5762±0.3452μJ·s~(-1)。本研究为探究光催化过程的原位热力学、热动力学及光谱信息及机理的推测提供科学依据。     

g-C_3N_4@Ag_3PO_4光催化降解罗丹明B过程的原位光-微热量-荧光光谱研究

采用光-微热量-荧光光谱联用系统获取了g-C_3N_4@Ag_3PO_4光降解罗丹明B(RhB)的原位热/动力学信息和三维荧光光谱信息,并结合热力学和光谱学结果探究了光催化降解罗丹明B的微观机制.结果表明,光催化降解过程主要分为表观吸热、热平衡以及稳定放热3个阶段.在g-C_3N_4@Ag_3PO_4存在下,可见光照射10 min后,罗丹明B的三维荧光特征发射峰强度降低至初始值的7.1%,罗丹明B的降解脱色率达92.9%,是相同条件下以纯g-C_3N_4为催化剂时的2.06倍.随着光照时间的延长,光-微热量计显示10 min后以降解及矿化非荧光中间产物为主,并保持热焓变化率为-(0.226±0.0916)mJ/s稳定放热,为拟零级反应过程,并且该阶段为光催化反应的决速步骤.     

光量热法初探甲基橙光催化原位降解过程

通过在室温下还原前驱体制备了Ag@AgCl催化剂, 并利用X射线粉末衍射仪(XRD)和场发射扫描电子显微镜(FE-SEM)对产物进行表征. 设计了新型光化学-微热量系统, 用该系统获得了Ag@AgCl光催化降解甲基橙实时、 在线的热力学和动力学瞬态信息. 研究结果表明, 该降解过程首先经历吸热再迅速进入放热阶段, 最后曲线恒定于一个长的放热平台, 计算得到ab, ac和ad段的热效应分别为-0.2609, 2.5845和40.7289 J, 放热平台cd的平均速率为2.581 mJ/s, 并详细探讨了该过程的微观降解机制.     

微波助离子液体中Y掺杂TiO_2光催化剂制备及微波强化光催化活性

在微波助离子液体介质中制备稀土元素Y掺杂改性TiO_2光催化剂,以提高催化剂的光催化降解活性,用XRD、SEM和BET等测试手段对催化剂结构进行表征;以甲基橙溶液和苯酚溶液为模拟污染物,分别在紫外光照(UV)和微波辐射-紫外光照(MW-UV)条件下考察TiO_2-Y催化剂的光催化活性;以对苯二甲酸作为荧光探针利用荧光技术检测TiO_2-Y催化剂表面所产生的羟基自由基,并对光催化降解反应进行动力学分析,探索了光催化降解反应机理.实验结果表明,通过优化反应条件后制得的TiO_2-Y催化剂具有较高光催化活性和热稳定性,在UV和UV-MW条件下降解甲基橙和苯酚溶液1.5h后,甲基橙降解率分别为98.3%和99.5%,苯酚降解率分别为97.5%和98.2%.荧光光谱分析表明,TiO_2-Y在MW-UV条件下产生的羟基自由基比UV条件下要多,因而微波辐照具有强化TiO_2-Y降解模拟污染物的作用;反应动力学数据分析表明,TiO_2-Y光催化降解甲基橙溶液反应呈现一级反应动力学规律,其表观速率常数K最大值为0.051 9min-1.     

微波超声强化银掺杂TiO_2催化剂光催化活性的研究

在[Bmim]PF6离子液体介质中,用溶胶凝胶-微波干燥法制备银掺杂TiO_2光催化剂TiO_2-Ag.以甲基橙为有机污染物,用微波超声组合仪分别在微波(MW)、紫外(UV)、紫外-微波(UV-MW)和超声-紫外-微波(UT-UV-MW)4种条件下降解甲基橙溶液,考察银掺杂对催化剂降解甲基橙的影响,以提高催化剂光催化性能.分别用X射线衍射分析(XRD)、扫描电子显微镜(SEM)、能谱分析(EDS)、热重-差示扫描量热分析(TG-DSCDTG)、固体紫外可见分析(Uv-vis)和红外分析(IR)对TiO_2-Ag催化剂进行测试表征.结果表明,优化条件下制备TiO_2-Ag催化剂在UV、UV-MW和UT-UV-MW条件下降解甲基橙35 min后,甲基橙的降解率分别为88.05%、93.98%和99.84%;降解甲基橙55min后,甲基橙的降解率分别为98.79%、99.05%和99.90%.在UTUV-MW条件下降解25min后,降解率接近100%.表明TiO2-Ag催化剂具有较高的光催化降解活性,微波超声协同作用加快光催化降解反应进行.催化剂的结构分析表明,银掺杂抑制了二氧化钛晶相的转变,使相变温度升高,稳定性增强;同时,催化剂向可见光区扩宽了光响应范围,提高了量子效率,从而光催化性能得以提高.     

TiO_2光电化学电池催化氧化甲基红

以钛基TiO2薄膜为光阳极,研究了光电化学电池中阳极光催化降解偶氮染料甲基红的动力学.结果表明,短接光电化学电池分隔了光催化过程的阴、阳极反应,有利于抑制光生载流子的复合,提高光催化氧化速率.相同实验条件下短路光电流越大,则甲基红降解速率越高.在基底和TiO2薄膜之间夹层SnO2得到组装电极Ti/SnO2/TiO2,进一步提高了光生载流子的分离效率;同时采用电化学阻抗谱(EIS)评价了电极的光催化性能.     

光催化-膜分离集成反应器及其应用

 设计了一种新型光催化-陶瓷膜分离集成反应器,在反冲条件下利用此集成反应器进行了甲基橙光催化氧化反应,分别考察了陶瓷膜对光催化剂TiO2微粉的截留率、膜的渗透通量、光催化氧化脱色率以及不同膜分离压力下的光催化反应速率常数. 结果表明,TiO2-甲基橙悬浆液体系中TiO2微粉的截留率可达到99.9%, 经集成反应器完成一个反应周期后甲基橙氧化脱色率达到10%, 光催化氧化脱色效果高于圆柱式反应器.     

海绵状纳米结构TiO2膜的制备及其光催化活性

采用电化学阳极氧化法在钛表面构筑了海绵状纳米结构TiO2膜. 应用扫描电子显微镜(SEM)和X射线衍射(XRD)对膜层的形貌和晶型进行了分析和表征, 考察了阳极氧化时间对膜层厚度的影响, 并通过海绵状纳米结构TiO2膜对甲基橙的光催化降解研究了膜层厚度与光催化活性的关系. 结果表明, 海绵状纳米结构TiO2膜对甲基橙具有光催化降解作用, 而且随着膜层厚度的增加, 光催化降解速率显著增大, 厚度为2.2 μm的海绵状纳米结构TiO2膜对甲基橙的光催化降解速率是厚度为480 nm的6.4倍.     

不同形貌Ag_3PO_4光催化过程热力学、动力学及表面热力学效应

室温条件下,采用离子交换法制备了四足状、立方体、十二面体和块体Ag3PO4.采用自主设计的新型光化学-微热量系统获取了LED白光下不同形貌Ag3PO4光催化降解甲基橙原位过程热力学和动力学信息,以此关联Ag3PO4的催化降解速率和催化机理.通过光量热系统外模拟实验证明Ag3PO4光催化活性规律,分别在405 nm激光和模拟日光下,对该规律进行了验证.利用微热量技术获取了不同形貌Ag3PO4的摩尔表面Gibbs自由能,并将其与催化活性相关联.结果表明,不同形貌Ag3PO4光催化活性由强到弱依次为立方体、四足状、十二面体和块体Ag3PO4,其光催化降解甲基橙原位过程的热效应分别为?885.63,?320.78,?238.5和?161.78 k J/mol;热焓变化率分别为?0.59,?0.21,?0.16和?0.11 mJ/s,该变化规律与催化降解速率具有一致性,Ag3PO4的表面结构和摩尔表面Gibbs自由能是导致其催化性能产生形貌效应的主要原因.     

CaMoO4微晶生长过程的原位微量热法研究

在碱性条件下采用原位微量热法对CaMoO4微晶的构建进行了研究. 首次呈现了CaMoO4微晶生长过程能量变化的特征热谱曲线; 该特征热谱曲线由一个反映最初反应成核的典型吸热曲线和随后晶体生长的两个相对较弱的不连续放热曲线组成. 在导向机制的基础上, 结合CaMoO4微晶生长过程的形貌演变, 简要地讨论了CaMoO4微晶生长过程的热动力学信息. 反应成核过程、晶化过程及微晶的二次生长过程的速率常数分别为1.54×10-4、1.09×10-4和0.71×10-4 s-1. 由于晶体的聚集和扩散二者之间强烈的相互作用, 使得反应速率下降, 从而呈现出一个相对较平坦的第二次放热曲线.     

碳自掺杂g-C3N4光催化性能的原位光微量热-荧光光谱研究

通过在尿素前驱体中添加单宁酸, 原位缩聚形成碳自掺杂石墨相氮化碳(g-C₃N₄). 利用X射线光电子能谱(XPS)、 场发射扫描电子显微镜(FESEM)、 X射线衍射(XRD)仪和同步热分析(TG-DSC)等方法对碳自掺杂 g-C₃N₄的形貌、 物相结构和能带价态组分进行表征分析, 结合紫外-可见吸收光谱(UV-Vis)和原位光微量热-荧光光谱联用仪获得碳自掺杂g-C₃N₄降解罗丹明B的原位热/动力学信息和三维荧光光谱信息, 探讨了光催化降解罗丹明B的微观机制. 结果表明, 单宁酸浓度≤10 mg/mL时, 碳会取代七嗪单元结构的氮原子形成g-C₃N₄骨架碳自掺杂; 单宁酸浓度≥ 20 mg/mL时, 碳以无定形形式沉积负载在g-C₃N₄表面上形成无定形碳自掺杂. 骨架碳自掺杂g-C₃N₄形成的π电子有效缩短了禁带宽度, 减小了光生电子-空穴复合几率, 比无定形C掺杂g-C₃N₄显示出更优异的光催化性能, 催化主要活性物种为h⁺和·O{}_{\mathrm{2}}^{-}. 碳自掺杂g-C₃N₄光催化降解过程可分为光响应吸热、 降解污染物放热平衡过程和稳定放热3个过程. 其中骨架碳自掺杂g-C₃N₄(C/N摩尔比为0.844)在光照1000 s内, 三维荧光光谱检测的RhB降解率锐减, 光照1000 s后, 其RhB降解率为87.6%, 分别是原始g-C₃N₄和无定形碳自掺杂g-C₃N₄的3.13倍和1.95倍. 光照1000 s后, 光微量热计显示以矿化和降解非荧光发色中间产物为主, 并保持以热变速率为(0.9799±0.5356) μJ/s稳定放热, 为拟零级反应过程, 是光催化反应的决速步骤.     

Photodegradation of aqueous methyl orange on MnTiO<Subscript>3</Subscript> powder at different initial pH

The photodegradation of aqueous methyl orange on MnTiO₃ powder was studied in this work. The effects of initial pH and H₂O₂ on the photodegradation of aqueous methyl orange were studied. Single-phase MnTiO₃ powder was synthesized by a sol–gel method. X-ray diffraction analysis shows powders have a particle size of 43.7 nm and rhombohedral pyrophanite structure. The photocatalysis experiments revealed that the efficiency of decolorization of the aqueous methyl orange (1 × 10⁻⁵ M) on the MnTiO₃ powder is very fast in sunlight. The rate of decolorization appears larger at initial pH 5 and 9 than at pH 7. H₂O₂ (2%) can remarkably accelerate the decolorization at low initial pH.     

Ag@AgCl embedded on cellulose film: a stable,highly efficient and easily recyclable photocatalyst

In this work, cellulose–Ag@AgCl composite films have been fabricated directly through a one-step coagulation of a cellulose/1-butyl-3-methylimidazolium chloride (BmimCl) solution with AgNO₃ and PVP. The AgCl was formed upon the addition of AgNO₃ to a cellulose/BmimCl solution, and underwent further reaction with excess Cl^?, leading to the complete dissolution of AgCl. The AgCl crystals were regenerated on the cellulose matrix during the coagulation process. The AgCl was partial decomposed to Ag⁰ and formed Ag@AgCl under visible light irradiation. The morphology of Ag@AgCl in the cellulose matrix was controlled by varying the concentration of PVP. The addition of PVP enabled the formation of stable cellulose films embedded with Ag@AgCl. The composite film demonstrated efficient photodegradation of methyl orange, which was retained upon recycling. This work thus provides a simple pathway for the preparation of Ag@AgCl embedded on a polymer support via one-step coagulation.     

Preparation and photocatalytic activity of carbon dot/Ag/AgCl

CD (carbon dot)/Ag/AgCl compound photocatalysts with different compounding degrees were prepared via a precipitation method, and their physiochemical properties were characterized by X‐ray diffraction, FE‐SEM, UV–vis and the like. Through the degradation experiment of methyl orange (MO), the effects of different compounding amount and methyl orange concentration on photocatalytic degradation were investigated to find the best ratio. It was found the photocatalytic activity of CD/Ag/AgCl was significantly higher than Ag/AgCl, and the best compounding dosage was 6 mg/l carbon dot. The degradation rate of CD/Ag/AgCl was lower when the initial MO concentration was higher. Five repeated experiments were conducted to test the stability of the catalysts, and showed the MO degradation rates were all above 85%, indicating the CD/Ag/AgCl compound photocatalysts all showed high stability and repeatability. The reaction mechanism of CD/Ag/AgCl photocatalyst was studied by electrochemical experiments and ESR experiments. The results show that the doping of CD effectively improves the photocatalytic degradation ability of MO.     

Fe-Ni 共掺杂 ZnO 的制备及其光催化降解甲基橙活性

 采用溶液法制备了 Fe-Ni 共掺杂 ZnO 光催化剂, 并运用 X 射线衍射、扫描电镜和原子发射光谱等对催化剂进行了表征. 以甲基橙 (MO) 为模型污染物, 评价了样品的光催化活性, 考察了甲基橙初始浓度及其 pH 值, 以及催化剂用量等对光催化反应性能的影响. 结果表明, Fe-Ni 共掺杂降低了 ZnO 的结晶度, 并促进了晶粒的长大. 光催化降解反应表明, Fe-Ni 共掺杂显著提高了 ZnO 光催化降解甲基橙的活性, 当催化剂用量为 0.6 g/L, 经 120 min 紫外光照射时, 可使甲基橙溶液 (10 mg/L) 降解率达到 93.5%. 关键词：铁; 镍; 共掺杂; 氧化锌; 光催化; 甲基橙; 降解     

Fabrication,characterization, and photocatalytic performance of TiO<Subscript>2</Subscript> hybridized with SiO<Subscript>2</Subscript>

Nanostructures TiO₂–SiO₂ photocatalysts were successfully synthesized using the sol-gel method, hydro-calcination, co-precipitation and room-temperature solid-phase synthesis technology. X-ray powder diffraction pattern (XRD), Fourier transform infrared spectrum (FTIR), photoluminescence (PL) spectra, thermal analyses (TG–DTA), scanning electron micrographs (SEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) were used to characterize the as-synthesized catalysts. Photocatalytic performances of the catalysts were evaluated by the degradation of methyl orange (MO) under s imulated natural light and the degradation rate of MO is 97.2%. The composites showed a good stability: after five recycling runs there are no significant decreases in the photocatalytic activity. The photodegradation of methylene blue, rhodamine B, methyl violet, naphthol green B, basic fuchsin, malachite green, and methyl red were also tested, and the degradation rate of dyes could reach over 94.2 %. A possible mechanism for the photocatalysis with the TiO₂–SiO₂ was proposed.     

Fe_3O_4/SrTiO_3复合光催化剂降解甲基橙

用共沉淀法制备了SrTiO3光催化剂及Fe3O4/SrTiO3复合光催化剂.通过紫外-可见漫反射光谱、XRD、SEM-EDX对其进行表征,以甲基橙为探针分子考察其光催化性能.结果表明,适量Fe3O4的掺入可明显提高Sr-TiO3光催化剂对可见光的吸收,从而增强其光催化性能;在光降解甲基橙的反应中,掺杂10%Fe3O4的SrTiO3光催化剂其催化活性是纯SrTiO3光催化剂的两倍.