LED可见光下Au/TiO_2光催化氧化甲醛表观动力学

甲醛是室内空气中典型的挥发性有机化合物(VOCs)之一。等离子激元型光催化剂可吸收可见光,可在室温常压下利用太阳光驱动光催化氧化脱除室内空气中甲醛的反应,其表观反应动力学研究对设计等离子激元型光催化剂及应用于脱除VOCs等污染物具有重要意义。研究了LED可见光下等离子激元型Au/TiO2光催化脱除气相中甲醛的表观反应动力学,考察不同波长的可见光源、光强及反应气相对湿度对表观反应动力学的影响,根据对实验数据的分析求得LED可见光催化氧化甲醛表观反应速率常数k(I,H)。结果表明,在13%相对湿度、蓝光光强为38.5mW·cm-2的条件下,光反应的甲醛转化率达77%,是暗反应的近5倍。在LED红、绿、蓝、白光照射下,随着光强增加,甲醛转化率快速增加后缓慢增至基本不变。相同光强(低于42 mW·cm-2)和湿度条件下,红、绿、蓝光源的甲醛转化率相近,白光略低于其他光源。干气氛下,光反应和暗反应的甲醛转化率几乎为0。湿气氛下,光反应和暗反应均有甲醛转化率,光反应的甲醛转化率更高。不同光源条件下甲醛转化率随相对湿度变化规律相似。相对湿度为21.9%时甲醛转化率最高,而后保持不变,基本在80%左右。通过对红、绿、蓝、白光的数据拟合计算,得到表观动力学参数k(I)H、k(H)I、k(I,H)以及速率方程。     

PEMFC用Pt纳米线阴极催化剂的制备及在电堆中的应用

采用无模板法制备了用于质子交换膜燃料电池（PEMFC）的碳载铂纳米线（Pt NWs/C）阴极催化剂,使用透射电镜（TEM）和X射线衍射图谱技术（XRD）对催化剂的微观结构和形貌进行了表征。研究结果表明,制备的铂催化剂具有纳米线的结构,平均截面直径为（4.0±0.2）nm,线长为15～25 nm。利用循环伏安（CV）法和线性伏安扫描法（LSV）表征催化剂的电化学活性和氧还原反应（ORR）特性,结果表明制备的Pt NWs/C催化剂电化学特性良好。利用Pt NWs/C和Pt/C作为阴极催化剂制备膜电极（MEA）,并进行测试,最大功率密度分别为705.6 mW·cm^-2和674.4 mW·cm^-2。然后以Pt NWs/C和Pt/C为阴极催化剂组装了18片和20片的电堆,并进行性能测试,电堆的最大功率密度分别为409.2 mW·cm^-2和702.7 mW·cm^-2,单电池电压差异系数（C_v）分别为16.1%和4.36%,这表明Pt NWs/C作为阴极催化剂在放大后的膜电极组件（MEA）里表现出较好的催化活性,但与商业催化剂相比其性能与均一性还有待提高。该研究可为Pt NWs/C催化剂放大制备提供依据,同时可为后续的基于Pt NWs/C的电堆的耐久性测试和车载应用奠定基础。     

高压气体氛围中的聚氨酯非等温固化动力学

采用高压DSC对0.1~6 MPa压力范围二氧化碳（CO₂）及氮气（N₂）氛围中的聚氨酯非等温固化动力学进行了研究。利用Kissinger法及两种不同积分形式的等转化率法求取了聚氨酯固化过程的表观活化能E_a,在此基础上采用Málek法确定了固化反应的机理函数及动力学参数,得到固化反应动力学方程,并分析了高压CO₂及N₂的存在对固化过程的影响。研究结果表明,该聚氨酯体系的活化能随着反应转化率的增加呈现出典型的先减小后增加的S型反应特征,由于高压气体的静压作用及溶剂效应,体系的表观活化能随着气体压力的升高而逐渐降低,CO₂的溶剂效应明显强于N₂;利用Sestak-Berggren模型进行拟合,发现在不同压力的气体氛围中该模型与非等温测试得到的DSC曲线较为吻合,表明该体系在常压及高压气体存在下均符合自催化模型。     

樟脑醌／乙二醇-3-吗啡啉基丙酸酯甲基丙烯酸酯引发牙科复合树脂的光聚合动力学研究

采用Photo-DSC研究了樟脑醌（CQ）／乙二醇-3-吗啡啉基丙酸酯甲基丙烯酸酯（EGMPM）可见光引发牙科复合树脂聚合的动力学过程．考察了CQ浓度、EGMPM浓度以及光强对牙科修复复合树脂光聚合动力学的影响．结果表明：增加引发体系的浓度和增加光强都可以增加反应速率和转化率；同时实验结果验证了Rp∝（I0[CQ][EGMPM]）^1／2的动力学关系．     

3种紫细菌天然光合色素敏化DSSC光电转化性能

基于自然界光合作用机理的DSSC研究备受关注。不产氧光合细菌中的紫细菌是研究光合作用机理的良好模式生物。从3种典型紫细菌中获得了7种具有不同吸光范围、极性和结构的细菌叶绿素a（BChl a）和类胡萝卜素（Car）以及3种改性BChl a。在此基础上,较系统地比较了天然与改性BChl a、多组分与单一组分Car、BChl a色素浓度、BChl a和Car共敏对DSSC光电性能的影响,并对色素与半导体材料的相互作用进行了表征。结果表明：100 mW·cm^-2入射光强下,在不添加任何分散剂（spacer）的条件下,具有近红外吸收的天然BChl a光电转化性能较优,光电转换效率为1.26%。单一组分Car比多组分Car具有较高的光电性能,玫红品Car光电转换效率最佳。BChl a敏化TiO₂薄膜电极,吸收光谱红移,800 nm特征荧光淬灭。BChl a与Car共敏TiO₂薄膜电极,拓宽了可见光吸收光谱,短路电流和光电转换效率比BChl a提高了12%和7.3%。紫细菌天然色素廉价易得、环境友好,不仅能吸收可见光,而且能有效利用红外光,这对研制响应可见光-近红外的太阳能电池光电器件具有重要参考价值。     

羟基新戊醛合成工艺及其动力学

羟基新戊醛是合成多种精细化学品的重要中间体。以叔胺溶液为催化剂,利用正交实验法优化了甲醛异丁醛缩合制备羟基新戊醛的工艺条件,并考察了缩合反应动力学。由正交实验结果得到最佳反应条件为:催化剂的用量为3%质量分数,反应温度75℃,甲醛与异丁醛的物质的量之比为1.1:1,反应压力0.3 MPa,反应时间80 min,在此条件下产物收率可达98.33%。动力学的研究结果表明:缩合主副反应的表观活化能分别为40.801 k J/mol和64.088 k J/mol;主反应对异丁醛、甲醛反应级数分别为1和1.2,副反应对羟基新戊醛的反应级数为2。通过残差分析和统计检验,表明动力学模型是适定的。     

咪唑类酸性离子液体催化合成双酚F反应动力学研究

提出了苯酚、甲醛经酸性离子液体[Hmim]HSO₄催化的反应机理和三步骤反应模式,推导出了其反应动力学方程。结果表明：反应速率常数与反应温度和离子液体浓度有关。在酚、醛物质的量比6∶1和充分搅拌条件下,在反应温度80～100℃及酸、醛物质的量比2∶1～1∶2范围内,采用滴加甲醛方式,进行了双酚F合成反应的动力学实验,实验结果与动力学模型拟合良好。在n(酚)∶n(醛)∶n(酸)为6∶1∶1及80～90℃最佳反应条件下,双酚F收率可达79%以上,反应表观活化能E_a=19.92 kJ/mol。     

改性活性半焦脱除烟气中SO2的反应动力学

在固定床反应器中，研究用改性活性半焦来脱除烟气中SO₂的动力学问题。考察半焦粒径、反应温度和空速对SO₂转化率的影响，建立了本征动力学方程。反应级数为一级，表观活化能为10.058 kJ·mol^-1，指前因子为69.622 2。     

酸性低共熔溶剂四乙基氯化铵/三氟乙酸高效催化氧化脱除模拟油中的硫化物

将适量四乙基氯化铵（TEAC）和三氟乙酸（TFA）通过简单搅拌加热（70℃）的方式合成一系列新型低共熔溶剂TEAC/nTFA（n=0.5,1,1.5,2）,并对其结构进行红外光谱和核磁共振氢谱表征分析。以TEAC/nTFA为催化剂和萃取剂,H₂O₂为氧化剂研究其对模拟油中硫化物的脱除效果。并考察了n_（TEAC（/n_（TFA（、温度、O/S、不同硫化物等反应条件对脱硫效率的影响。在最佳反应条件下,TEAC/TFA对二苯并噻吩（DBT（,苯并噻吩（BT（和噻吩（TH（的脱除率分别达到95.4%,56.2%和23.4%。基于一级动力学和Arrhenius方程,估算出氧化脱除DBT所需的活化能约为56.8 kJ·mol^-1。反应活化能较低,氧化反应较易进行。TEAC/TFA回收利用5次之后活性无明显降低。     

辉钼矿氧化焙烧动力学研究

通过热重-差热实验,采用气-固多相反应的未反应收缩核模型研究了辉钼矿氧化焙烧的动力学.结果表明,辉钼矿氧化焙烧是强放热反应,温度越高,辉钼矿氧化速率越快;350~500℃辉钼矿转化率较低,Arrhenius方程计算的表观活化能为80.14k J/mol,反应由内扩散控制;540~630℃时转化率明显增高,表观反应活化能为90.42 k J/mol,反应由界面化学反应控制;升温速率对辉钼矿氧化焙烧过程影响显著,升温速率越低,辉钼矿氧化越充分、转化率越高,氧化放出的总热量越多.     

Plasmonic Au nanoparticles supported on both sides of TiO2 hollow spheres for maximising photocatalytic activity under visible light

A strategy of intensifying the visible light harvesting ability of anatase TiO₂ hollow spheres (HSs) was developed, in which both sides of TiO₂ HSs were utilised for stabilising Au nanoparticles (NPs) through the sacrificial templating method and convex surface-induced confinement. The composite structure of single Au NP yolk-TiO₂ shell-Au NPs, denoted as Au@Au(TiO₂, was rendered and confirmed by the transmission electron microscopy analysis. Au@Au(TiO₂ showed enhanced photocatalytic activity in the degradation of methylene blue and phenol in aqueous phase under visible light surpassing that of other reference materials such as Au(TiO₂ by 77% and Au@P25 by 52%, respectively, in phenol degradation.     

Au/TiO2复合物的制备、表征及其增强光催化灭菌活性

为提升TiO₂光催化活性克服其可见光响应能力差的问题,采用沉积-沉淀法制备了Au/TiO₂复合物光催化剂,利用X射线衍射（XRD）、傅里叶红外光谱（FTIR）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-vis DRS）、荧光发射光谱等对样品进行了表征。XRD、FTIR和XPS结果表明,Au/TiO₂中TiO₂为锐钛矿相且Au成功沉积至TiO₂。UV-vis DRS和荧光发射光谱结果表明,适量Au修饰不仅能提高TiO₂对可见光的吸收,还可促进TiO₂光生电子-空穴对分离,有利于增强其光催化活性。自由基捕获实验证实,形成?OH的数量与光照时间成正比且?OH生成量越多,光催化活性越高。对比考察了Au/TiO₂和TiO₂在氙灯光源照射下对大肠杆菌的光催化杀灭作用,并探讨了Au负载量、光照时间、光照强度、光催化剂浓度等因素对灭菌性能的影响。结果表明：Au/TiO₂的光催化灭菌活性优于TiO₂,且与光照时间和光照强度均成正比;Au的适宜负载量为3%（质量分数）;3%Au/TiO₂在光照时间60min、光照强度7mW/cm²、光催化剂浓度100μg/mL的条件下,对大肠杆菌的杀灭效率高达91.3%。     

Au@TiO2纳米管阵列的制备及光催化性能

利用一种简单易行、可控的方法制备了均匀的Au@TiO₂纳米管阵列。首先在室温下通过阳极氧化的方法形成TiO₂纳米管，再在氧化后的TiO₂纳米管上用磁控溅射沉积不同厚度的Au膜，最后将沉积Au膜后的TiO₂纳米管在空气中450℃退火2h。热处理过程导致了Au向TiO₂纳米管的扩散，在纳米管表面形成了Au“岛”包裹的Au@TiO₂纳米管。对制备的Au@TiO₂纳米管的微观结构利用了扫描电子显微镜、能谱、X射线衍射和透射电子显微镜进行表征。并且用光电流、紫外可见光光漫反射光谱、荧光光谱和降解亚甲基蓝溶液的方法分析测量了Au@TiO₂纳米管的光电性能及光催化性能。结果表明：当可见光照射含Au@TiO₂纳米管催化剂的亚甲基蓝水溶液时，其光催化性能远远高于纯TiO₂纳米管，这是由于Au颗粒表面等离子体共振效应（LSPR）增加了电子-空穴对的分离并且延缓了其重组所致。     

二氧化钛纳米结构形貌可控合成及光催化性能

以不同方法制备棒状、球状和花状3种形貌的TiO_2纳米粒子,采用X粉末衍射、扫描电子显微镜、荧光光谱和紫外-可见漫反射等对TiO_2纳米粒子进行结构及形貌分析。以亚甲基蓝为降解模型,分别在紫外光与可见光条件下对TiO_2纳米粒子进行光催化性能研究,分析TiO_2的形貌结构影响光催化性能的机理。结果表明,花状TiO_2纳米粒子光催化性能最好,其中高能晶面与微观形貌尺寸对TiO_2光催化性能具有重要影响。     

侧光光纤引导的内源可见光催化降解亚甲基蓝(英文)

The side-glowing optical fibers (SOFs) were chosen as the conducting medium of endogenous light; and 20 mg·L-1 methylene blue was chosen as the target to be degraded. The SOF is made up of quartz core with a silicon cladding, which can emit light through side surface more uniformly and transmit light for longer distance to avoid attenuation of light by liquid medium. The filament lamp was chosen as visible light source. Different reaction conditions, such as the presence of optical fiber or not, the quantity of SOF, light irradiation intensity were tested by measuring the methylene blue degradation of methylene blue. The results show that suitable reaction conditions were 1.167 g·L-1 Ag + /TiO 2 with 7% (by mass) of Ag + doped in TiO 2 , and 500 roots of SOF (30 cm length in solution). The photocatalytic degradation efficiency under 300W lamp irradiation for 8h was about 97%. And the photocatalytic degradation efficiency of methylene blue degradation was proportional to SOF quantity, light irradiation intensity and catalytic dosage within a certain range. Compared with general UV and visible light SOFs could save a huge amount of energy and cost, in the potential applications in dealing with organic pollutants on a large scale.     

Photocatalytic activation of TiO2 under visible light using Acid Red 44

The activation of TiO₂ photocatalyst for photocatalysis under the visible light using Acid Red 44 (C₁₀H₇N=NC₁₀H₃(SO₃Na)₂OH) is described. Adjustment of the pH enhanced the photocatalytic activation of TiO₂ in the presence of visible light. This confirms that the adsorption of a dye on TiO₂ surface is an important factor in dye-photosensitization. The differences in the photocatalytic activation mechanism under visible irradiated conditions with that of UV irradiated condition are proposed. The dye-sensitized photocatalysis under visible light was applied to the decomposition of phenol, is a toxic chemical used in industry and frequently discharged into water.     

B掺杂对负载型TiO_2光催化剂脱硝性能的影响

采用超声辅助溶胶-凝胶法制备活化半焦负载B掺杂TiO_2光催化剂,即B-TiO_2/ASC。在相同实验条件下,分别在紫外和可见光下研究其对模拟烟气的光催化氧化脱硝性能。结果表明,在紫外和可见光下,B掺杂光催化剂的活性得到提高,在可见光下的活性增加更加显著,反应180 min后仍可保持80%以上的脱硝率。结合XRD和FT-IR分析,可以看出B以取代掺杂的方式存在于TiO_2中并且导致TiO_2表面缺陷。表面缺陷有助于光生载流子的分离,从而延长光生电子的寿命并增加参与光催化反应的光生电子数量,从而产生更多的羟基自由基氧化NO,最终提高光催化脱硝率。     

纳米N掺杂TiO2的制备及可见光催化活性研究

N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.     

Photocatalytic degradation of organic compounds diluted in water using visible light-responsive metal ion-implanted TiO2 catalysts: Fe ion-implanted TiO2

The application of metal ion-implantation method has been made to improve the electronic properties of the TiO₂ photocatalyst to realize the utilization of visible light. The photocatalytic properties of these unique TiO₂ photocatalysts for the purification of water have been investigated. By the metal ion-implantation method, metal ions (Fe⁺, Mn⁺, V⁺, etc.) are accelerated enough to have the high kinetic energy (150 keV) and can be implanted into the bulk of TiO₂. TiO₂ photocatalysts which can absorb visible light and work as a photocatalyst efficiently under visible light irradiation were successfully prepared using this advanced technique. The UV-Vis absorption spectra of these metal ion-implanted TiO₂ photocatalysts were found to shift toward visible light regions depending on the amount and the kind of metal ions implanted. They were found to exhibit an effective photocatalytic reactivity for the liquid-phase degradation of 2-propanol diluted in water at 295 K under visible light (λ>450 nm) irradiation. The investigation using XAFS analysis suggested that the substitution of Ti ions in TiO₂ lattice with implanted metal ions is important to modify TiO₂ to be able to adsorb visible light.     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.