纳米Fe2O3/膨润土复合催化剂的制备及光催化活性

在合成过程中使用表面活性剂聚乙烯醇 (PVA) ,通过铁盐与膨润土浆液反应制备纳米Fe2 O3 /膨润土复合催化剂 .XRD分析结果表明 ,该复合物主要是由α Fe2 O3 构成 ;并以橙二为目标污染物 ,对催化剂的催化活性进行了比较 ,复合催化剂的催化活性要远大于α Fe2 O3 的催化活性 ;不同催化剂 (含有相同质量的α Fe2 O3 )的催化活性为 :Fe A >Fe B >Fe C >Fe D .此外 ,对于复相光催化反应和均相光催化反应进行了比较 ,结果表明 ,复相光催化降解速率要远大于均相光催化降解速率 .     

镍钒复合光催化剂的光谱特征及其光催化性能

以SiO2、活性炭(AC)和Al2O3为载体,采用浸渍法制备了Ni-V-O系负载光催化剂.考察了样品的光谱特征,并在紫外光下评价了样品在甲醇和CO2光催化反应巾的性能;通过吡啶吸附FIIR和UV-Vis分析,结合反应测试结果,比较了催化剂载体对产物选择件的影响.XRD结果表明,在系列催化剂中,SiO2载体上的镍、钒粒子分散程度最高.吡啶吸附FIIR结果显示,系列催化剂表面存在L酸中心;相同的活性组分由于载体不同,所得到的负载催化剂表面酸度不同.负载催化剂表面L酸强度顺序为:Ni-V-O/SiO2>Ni-V-O/Al2O3>Ni-V-O/AC.不同酸度的催化剂,其上的羰基化产物甲酸甲酯(MF)和碳酸二甲酯(DMC)的选择性也不同.催化剂的表面酸强度是影响羰基产物选择性的主要因素.     

Ag-TiO_2/KIT-6复合纳米光催化剂的研究

以有序介孔SiO2(简称KIT-6)为载体,采用钛酸丁酯水解法将纳米TiO2与KIT-6复合,并通过沉积沉淀法将纳米Ag粒子负载于其上,首次制得Ag-TiO2/KIT-6复合光催化剂,并采用相同的方法制备了一系列相关的催化剂.以光催化降解甲基橙来评价其催化性能,光催化活性顺序为Ag-TiO2/KIT-6＞Ag/TiO2＞TiO2/KIT-6＞TiO2＞Ag/KIT-6.利用XRD、N2物理吸附、XPS、UV-Vis DRS和TEM对系列催化剂进行表征,结果表明Ag-TiO2之间形成的异质结和催化剂的大比表面积是Ag-TiO2/KIT-6具有最高光催化活性的重要原因.其中Ag-TiO2之间的异质结结构,有效抑制了光生电子和光生空穴在TiO2表面和体相内部的复合,提高了光催化活性;此外Ag-TiO2/KIT-6的大比表面积大大提高了催化剂的吸附能力,增加了催化剂与污染物的接触,达到快速光催化降解污染物的目的.     

有机种子对异戊二烯光氧化反应形成二次有机气溶胶的粒谱演化和形成速率的影响

基于室内烟雾箱实验平台,研究了在有机种子气溶胶下,来自OH启动异戊二烯光氧化反应形成的二次有机气溶胶的动力学. 探究了二次有机气溶胶的粒谱分布分别与来自室内大气中痕量碳氢化合物光氧化反应产生的种子颗粒物浓度以及前体物异戊二烯浓度的依赖关系. 研究结果表明在高浓度种子气溶胶和低浓度异戊二烯条件下(对应于典型城市大气条件),光化学反应形成的二次有机产物凝聚到种子颗粒物表面而造成的颗粒物增长起主导作用;而在低浓度种子气溶胶和相对高浓度异戊二烯条件下(对应于典型偏远地区大气条件),二次有机气溶胶粒谱分布出现双模式结构,分别对应于来自均相成核的新粒子生成和二次有机产物在种子颗粒物上的凝聚增长. 此外,还研究了有机种子颗粒物浓度对二次有机气溶胶形成的影响,评估了在不同种子浓度下二次有机气溶胶粒谱分布的演化和相应新粒子的形成速率.     

粉末活性炭吸附对氨基苯酚模拟废水的效果

在静态条件下,研究了活性炭吸附对氨基苯酚模拟废水的效果,确定了处理废水的pH值、活性炭用量、振荡时间、温度、废水中对氨基苯酚浓度、振荡速率以及电解质对吸附效果的影响.实验表明L活性炭在pH值为6.4,用量4.5g,温度35C,振荡2.5h的条件下,对100mL质量浓度为50mg/L的对氨基苯酚模拟废水处理效果最佳.     

基于Er3+：YAlO3/TiO2的可见光催化降解室内甲醛

为使TiO2能够在可见光下发挥其于紫外激发的高光催化活性降解室内甲醛,采用水热处理法将TiO2与掺杂稀土离子Er3+的上转换发光剂Er3+∶YAlO3结合,制备具有可见光响应的Er3+∶YAlO3/TiO2光催化剂,并对其进行了表征分析。结果表明,TiO2以锐钛矿为主,且Er3+∶YAlO3可有效地将可见光上转换至可激发TiO2的紫外光。在箱式反应器中进行光催化降解气态甲醛,研究了甲醛初始浓度与催化剂用量对甲醛降解效率的影响。结果表明,该光催化反应的假一级反应速率常数( kapp )与甲醛初始浓度成正相关,而随催化剂用量的增加先升高后降低。当甲醛初始浓度为0.058 mg/m3、催化剂用量为0.1224 g/L时,kapp最大为3.65×10-3 min-1。该反应符合Langmuir-Hinshelwood模型,反应速率常数为5×10-8 mg/( L·min)。     

粉末活性炭对模拟对苯二酚废水吸附研究

在静态条件下,研究了不同条件下活性炭对对苯二酚废水的吸附效果,确定了处理废水的pH值、活性炭用量、振荡时间、温度、废水中对苯二酚浓度、振荡速率以及电解质对吸附效果的影响。实验表明：活性炭在pH值为6.5,用量3.5g,温度35℃,振荡3.5h的条件下,对100mL质量浓度为100mg/L的对苯二酚模拟废水处理效果最佳。     

碳纳米管制备条件探索及对亚甲基蓝的吸附性能

探索了用气相沉积法制备碳纳米管时,不同温度、催化剂浓度、反应时间对碳纳米管定向性、径向管径、表面性能的影响,结果表明,反应温度750℃、催化剂浓度5g/100mL、反应时间30min是制备碳纳米管的最佳实验条件。在最佳条件下制备碳纳米管并进行对亚甲基蓝吸附的研究,探索了吸附时间、pH、吸附浓度、温度对吸附结果的影响。     

甲醇催化燃烧动力学及铂催化剂结构选择性研究

在严格的动力学控制下研究了甲醇催化燃烧反应动力学本征特性。铂催化剂上甲醇催化燃烧由氧气在催化剂上的活化过程控制,催化燃烧速率受限于铂表面的活性氧原子浓度;甲醇催化燃烧速率等于氧气在催化剂表面上的活化速率,随氧气分压增加而线性增加而不依赖于甲醇的分压。催化燃烧反应速率常数随催化剂颗粒直径减小而降低,随铂原子配位数减小而降低,由于少部分活性组分更容易吸附在铂催化中低配位数的原子上限制了氧气的活化过程。在微量催化剂的协助下甲醇就能实现稳定的低温催化燃烧,因而能有效地改善微细燃烧器内燃烧特性。     

原位核磁共振技术研究反应环境对光催化甲醇重整过程的影响

本文利用原位核磁共振技术，系统研究了在真实反应体系中反应环境（气氛、压强、气体量等）对甲醇光催化重整反应产物的影响.发现不同气氛对甲醇光催化重整的反应产物有着不同的抑制作用，而环境压强及气体量对于甲醇光催化重整反应产物产率的影响较小.在此基础上，本文进一步讨论了气体在催化剂表面的吸附方式和环境气氛影响甲醇光催化重整反应产物的机理.     

空气电极/AC作载体对TiO2光催化性能的影响

研究了空气电极和活性碳 (AC)作载体对TiO2 光催化氧化活性艳红 (K 2BP)性能的影响 .实验结果表明 ,用空气电极 /AC作载体能显著提高TiO2 的光催化反应速度 ;空气电极不仅具有良好的合成H2 O2 的性能 ,而且对TiO2 光催化剂可产生大约 +0 .5V的偏压作用 ,大大减小了TiO2 光生电荷的复合几率 ;AC对有机物分子良好的吸附作用提高了有机物分子在TiO2 表面及周围的富集浓度 ,其含量在 2 1%左右可使光催化剂达到最佳的催化效果 .复合电极工作电流密度对活性艳红的氧化脱色速度有影响 ,i=15mA/cm2 ,速度达到最大 ;活性艳红分子在复合电极表面的吸附受溶液pH值的影响 ;提出了复合电极的工作原理 .     

FTIR-ATR技术考察TiO2膜对油酸的光催化氧化性能

采用Sol-Gel和PVD法在玻璃、陶瓷、铝片表面制备出TiO2膜,直接将食用油中的主成分油酸用溶剂稀释后均匀涂在膜表面,采用FTIR-ATR技术实现了对膜样品光催化自清洁性能的快速准确评价,并通过测量水的接触角评价了膜的亲水性。结果表明,Sol-Gel法和PVD法制备的TiO2/玻璃膜都具有较好的光致亲水性和光催化降解油酸性能,两者的亲水性没有明显差别,但前者的光催化活性稍优于后者。比较Sol-Gel法制备的TiO2/玻璃、TiO2/陶瓷和TiO2/铝片膜对油酸的光催化降解性能发现,光照3·5h后3个样品的降解率分别为92%,85%和46%,表明基底材料性质对TiO2膜的光催化活性有明显影响,镀在非导电性玻璃和陶瓷表面的TiO2膜比镀在导电性金属铝表面的TiO2膜对油酸有更高的光催化降解能力。     

Interfacial properties of g-C_3N_4/TiO_2 heterostructures studied by DFT calculations

Constructing the hetrostructure is a feasible strategy to enhance the performances of photocatalysts. However, there are still some fundamental details and mechanisms for the specific design of photocatalysts with heterostructure,which need further confirming and explain.In this work,g-C₃N₄-based heterostructures are constructed with TiO₂ in different ways,and their intrinsic factors to improve the photocatalytic activity are systematically studied by density functional theory(DFT).When g-C₃N₄ combines horizontally with TiO₂ to form a heterostructure,the interaction between them is dominated by van der Waals interaction.Although the recombination of photo-generated electron-hole pair cannot be inhibited significantly,this van der Waals interaction can regulate the electronic structures of the two components,which is conducive to the participation of photo-generated electrons and holes in the photocatalytic reaction.When the g-C₃N₄ combines vertically with TiO₂ to form a heterostructure,their interface states show obvious covalent features,which is very beneficial for the photo-generated electrons’ and holes’ transport along the opposite directions on both sides of the interface.Furthermore,the built-in electric field of g-C₃N₄/TiO₂ heterostructure is directed from TiO₂ layer to g-C₃N₄ layer under equilibrium,so the photo-generated electron-hole pairs can be spatially separated from each other.These calculated results show that no matter how g-C₃N₄ and TiO₂ are combined together,the g-C₃N₄/TiO₂ heterostructure can enhance the photocatalytic performance through corresponding ways.     

微波场辅助银掺杂TiO2薄膜光催化降解甲基橙溶液的实验研究

用紫外-可见吸收光谱仪和原子力显微镜(AFM)表征了制备的TiO2和Ag/TiO2薄膜的光谱特性和表面形貌,研究了掺杂改性、微波场辅助作用以及两者相结合的光催化降解方法的薄膜催化活性.结果表明:催化剂的掺杂改性与微波场辅助作用相结合的光催化降解效果优于微波场辅助光催化方法和银掺杂光催化方法.     

Importance of ligands on TiO_2 nanocrystals for perovskite solar cells

The fabrication of high-quality electron-selective layers at low temperature is a prerequisite to realizing efficient flexible and tandem perovskite solar cells(PSCs). A colloidal-quantum-dot ink that contains TiO_2 nanocrystals enables the deposition of a flat film with matched energy level for PSCs; however, the selection of ligands on the TiO_2 surface is still unexplored. Here, we systematically studied the effect of the titanium diisopropoxide bis(acetylacetonate)(TiAc_2)ligand on the performance of PSCs with a planar n-i-p architecture. We prepared TiO_2 nanocrystals from TiCl4 and ethyl alcohol with Cl~- ligands attached on its surface and we found that a tiny amount of TiAc_2 treatment of as-prepared TiO_2 nanocrystals in a mixed solution of chloroform and methyl alcohol can enhance PSC power conversion efficiency(PCE)from 14.7% to 18.3%. To investigate the effect of TiAc_2 ligand on PSCs, TiO_2 samples with different TiAc_2 content were prepared by adding TiAc_2 into the as-obtained TiO_2 nanocrystal solution. We use x-ray photoelectron spectroscopy to identify the content of Cl so as to reveal that Cl ligands can be substituted by TiAc_2. We speculate that the improvement in PCE originates from amorphous TiO_2 formation on the TiO_2 nanocrystal surface, whereby a single-molecule layer of amorphous TiO_2 facilitates charge transfer between the perovskite film and the TiO_2 electronic transport layer, but excessive TiAc_2 lowers the PSC performance dramatically. We further prove our hypothesis by x-ray diffraction measurements. We believe the PCE of PSCs can be further improved by carefully choosing the type and changing the content of surface ligands on TiO_2 nanocrystal.     

新型复合电极对偶氮染料分子的光催化降解

介绍了具有合成H2 O2 和光催化性能的双功能新型复合电极 ,并用X射线衍射、扫描电镜等方法进行了表征 .双功能复合电极是将TiO2 光催化剂负载在活性碳 (AC)和具有合成H2 O2 性能的新型载体空气电极上形成的 .在复合电极作阴极的光反应器中 ,·OH和TiO2 光催化剂的存在实现了光化学氧化与光催化氧化在同一电极 /溶液界面上的联合作用 .实验结果表明 ,复合电极对提高偶氮染料分子活性艳红 (K 2BP)的氧化降解速度起了重要作用 ,仅反应 3min ,脱色率可达 4 9% ;反应 80min ,偶氮染料分子COD去除率可达 4 7% .     

Carbon-nanodot-coverage-dependent photocatalytic performance of carbon nanodot/TiO_2 nanocomposites under visible light

Carbon nanodots(CDs) with visible absorption band and TiO_2 are integrated to enhance the photosensitivity of TiO_2.The CD/TiO_2 nanocomposites show obvious CD-coverage-dependent photocatalytic performance. The CD/TiO_2 nanocomposites with moderate CD coverge exhibit the highest photocatalytic activity after being irradiated with visible light, which is more excellent than that of TiO_2. Too little CD coverage could result in poor visible light absorption, which limits the photocatalytic performance of CD/TiO_2 nanocomposites. While, too much CD coverage weakens the photocatalytic activity of CD/TiO_2 nanocomposites by restraining the extraction of conduction band electrons within TiO_2 to generate active oxygen radicals and the electron transfer(ET) process from CDs to TiO_2. These results indicate that rational regulation of CD coverage and the realization of efficient ET process are important means to optimize the photocatalytic performance of CD/TiO_2 nanocomposites.     

Solar light decomposition of DFP on the surface of anatase and rutile TiO2 prepared by hydrothermal treatment of microemulsions

The photocatalytic decomposition of diisopropylfluorophosphate (DFP) over nanostructured anatase and rutile TiO₂ powder was investigated by FTIR and XPS. Upon irradiation with artificial solar light DFP decomposed on both polymorphs as evidenced by FTIR. For both crystalline structures acetone and subsequently coordinated formate and carbonate were observed on the surface during the photocatalytic reaction as the isopropyl groups dissociated from DFP. XPS revealed that small amounts of phosphates and inorganic fluoride (TiF) gradually built up on both TiO₂ surfaces, while organic F was present only on the rutile phase. From repeated cycles of intermittent DFP adsorption and irradiation measurements, the decomposition rates and formation of residuals on the surface were deduced. It was found that the overall oxidation yield is higher on anatase than rutile. The oxidation rate decreases with increasing irradiation time, an effect that is more pronounced on rutile. We find that both the difference between the polymorphs and the initial decrease of the oxidation yield can largely be explained by variations in surface area rather than poisoning by PO_x or F species. In particular, we observe a dramatic decrease of the specific area of rutile as a function of photocatalytic oxidation cycle.     

PbO对V_2O_5/TiO_2催化剂NH_3选择性催化还原NO的影响

基于铅在中国燃煤和MSW焚烧烟气中的特点,采用静态N_2物理吸附、NH_3化学吸附、程序升温表面反应、傅里叶变换红外光谱和催化剂活性评价的方法,研究了PbO对1 wt.%V_2O_5/TiO_2催化剂NH_3选择性催化还原NO的影响.结果表明,PbO使SCR催化剂活性降低.对于燃煤锅炉,PbO对V_2O_5/TiO_2催化剂的影响可以忽略不计;对于MSW焚烧炉,PbO是使V_2O_5/TiO_2催化剂失活的重要铅化合物.Pb覆盖在TiO_2表面上,与V活性位覆盖在TiO_2表面上的方式类似.催化剂的失活主要是由于PbO中和了催化剂表面Brφnsted酸性位的酸性,Brφnsted酸性位对于NH_3的吸附和活化起重要作用.     

Improvement in sonochemical degradation of 4-chlorophenol by combined use of Fenton-like reagents

Studies on the sonolysis of a wide range of organic compounds have demonstrated that ultrasonic irradiation has potential for decomposition of organic pollutants in hazardous wastewater. However, the ultrasonic irradiation alone cannot provide high enough rate of decomposition to be used practically. One of the solutions to increase the degradation efficiency is to combine the ultrasound application with other advanced chemical oxidation processes (AOPs). In this study, in order to increase the efficiency of ultrasonically assisted degradation of organic pollutants in water, we examined effects of three kinds of solid Fe-containing catalysts, namely iron powder, basic oxygen furnace (BOF) slag and mill scale on the degradation rate of 4-CP (4-chlorophenol) in aqueous solutions containing hydrogen peroxide. In the experiments, 4-CP was considered as a model organic compound. All three Fe-containing matters when react with hydrogen peroxide are involved in the Fenton-like reaction system, which is one of the promising AOPs. The results showed that both the iron powder and mill scale additions can accelerate the degradation of 4-CP, although the effect is dependent on the solution pH. All 4-CP could be decomposed for 2 min at pH=3 and for 1h at pH=5.6. On the other hand, the BOF slag had no catalysis effect on the 4-CP degradation because of higher concentration of calcium and lower concentration of iron.