TiO2光催化剂的光谱研究

采用sol-gel法制备了纳米TiO2光催化剂,运用FTIR,FT－Ranam,DSR等光谱技术对催化剂进行了表征,以光催化解油酸作为模型反应考察光催化活性。实验结果表明,催化剂的烧结温度对催化剂的晶相结构、半导体能带结构、光吸收性能及光催化活性均产生显著的影响,当烧结温度为400℃时,TiO2光催化剂具有最好的表观吸光度,最大的吸收带边,以及最佳的光催化活性。     

Cu-Fe-TiO2/膨润土复合光催化剂的表征及性能

以膨润土为载体,用溶胶-凝胶法制备了不同焙烧温度的Cu-Fe双金属掺杂的TiO2/膨润土复合光催化剂,采用XRD、TG-DSC和N2吸附技术对其结构进行了表征,通过光催化降解直接天蓝染料废水,考察了焙烧温度对催化剂光催化性能的影响.结果表明,当焙烧温度高于300℃时,催化剂中出现了锐钛矿型TiO2,掺杂的Cu2+、Fe3+可能进入了TiO2晶格取代了部分Ti4+,使其晶格产生了一定程度的畸变,形成了复合半导体,拓宽了TiO2的光谱响应范围,并且Cu2+、Fe3+掺杂的TiO2复合半导体进入了蒙脱石层间,与膨润土成功复合,增大了催化剂的比表面积并改善了催化剂的孔体积,提高了光催化剂活性和再生性.     

SO2-4/CeO2-TiO2光催化材料的制备与光谱表征

采用溶胶-凝胶法结合硫酸浸渍法制备了SO2-4/CeO2-TiO2复合氧化物.利用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、吡啶吸附红外光谱(Py-FTIR)、紫外-可见光漫反射光谱(UV-Vis)、X射线光电子能谱价带谱(VB-XPS)及荧光光谱(PL)技术对样品的结构、性质进行了表征,以光催化分解水制氢为模型反应,评价了样品的光催化性能.XRD,FTIR结合PL结果表明CeO2与TiO2的复合形成了异质结构,有利于提高光生电子与光生空穴的分离效率,对催化剂活性的提高有促进作用;Py-FTIR谱图证明SO2-4/CeO2-TiO2复合氧化物在表面具有Lewis酸性,Lewis酸性位的产生是由于SO2-4在样品表面的配位吸附所致,S O— 的诱导效应增强了表面金属得电子能力,从而进一步提升光生载流子的分离效率;UV-Vis及XPS价带谱分析说明,半导体氧化物复合能够缩减带隙,拓宽光响应范围,Lewis酸性影响复合氧化物的能带结构,使其导带底位置向负向移动,利于光催化还原能力的提高,进而促进其光催化制氢活性.光催化分解水制氢实验结果表明,SO2-4/CeO2-TiO2复合氧化物具有优于纯氧化物CeO2,TiO2及未经硫酸浸渍的CeO2-TiO2复合氧化物的催化活性,5 h的产氢速率为1934.1μmol·g-1·h-1.光谱分析结果结合光催化制氢活性评价结果表明,SO2-4/CeO2-TiO2复合氧化物的异质结构与酸浸渍是影响样品光催化性能的主要因素.     

TiO2/SnO2复合氧化物的制备和光谱特性

为了研究TiO2/SnO2复合氧化物的光学特性,用胶体化学方法制备了以SnO2为内核的TiO2/SnO2复合氧化物,并且用紫外-可见光吸收光谱、X射线衍射和红外光谱对TiO2/SnO2复合氧化物的特性进行了分析.结果显示TiO2和TiO2/SnO2的能带宽度分别为4.13和3.86 eV,表现出量子尺寸效应;TiO2/SnO2在紫外区域具有宽的强吸收带.X射线衍射中TiO2的(110)衍射峰的位置移动了1.6°,强度也发生了变化;与TiO2红外光谱相比,TiO2/SnO2中Ti-O键的伸缩振动由500cm-1移到了656 cm-1,并有560 cm-1的肩峰,与吸附水相应的1650 cm-1附近的吸收峰和3420 cm-1的吸收峰均有所增加.     

Pt／TiO2粉末的结构和性能

TiO2半导体光催化技术是一种新型的环境污染物净化技术。传统的TiO2光催化剂太阳能利用率和光量子利用率低，限制了光催化技术的工业化应用。因此缩短催化剂的禁带宽度使吸收光谱向可见光谱扩展和抑制TiO2光生电子与空穴的复合是提高太阳能利用率的技术关键。掺杂可在半导体表面引入缺陷位置或改变结晶度，影响电子与空穴的复合或拓展光的吸收波段，从而影响TiO2的光催化活性。由于金属元素掺杂TiO2的催化活性强烈地依赖于TiO2的价态、结构以及金属元素与TiO2之间的细微作用，文中采用溶胶凝胶法制备纳米Pt/TiO2粉末，     

Ag负载WO3/TiO2光催化剂的合成及其催化性能

以钛酸丁酯、无水乙醇、钨酸铵为原料,采用溶胶-凝胶法合成了WO3/TiO2复合光催化剂;采用光还原技术制备了Ag负载WO3/TiO2光催化剂,借助X射线粉末衍射(XRD)和UV-Vis光谱等技术对样品的组成和光吸收性能进行了表征,并以罗丹明B为模型污染物考察样品的光催化活性。XRD分析表明,所得粉体均为锐钛矿型纳米TiO2,且与WO3复合后,纳米TiO2特征衍射峰宽化,强度降低;UV-Vis光谱分析表明,载银使得催化剂在400—700nm的可见光区域对光响应,且在紫外光区吸收显著增强,对光具有更高的利用率;以罗丹明B为降解物的光催化实验表明,WO3复合对纳米TiO2光催化活性有显著的影响,而载Ag后其光催化活性进一步提高,将该光催化剂用于炼油厂废水的处理,效果较好。     

不同干燥法制备纳米TiO2光催化剂的光谱研究

本文分别用常态、超临界乙醇和超临界CO2干燥法干燥钛酸正丁酯的醇凝胶，制备纳米TiO2光催化剂。应用XRD，FTIR，FT－Raman和Fluorescent spectrum(FS)等光谱技术对催化剂进行了表征。以光催化降解罗丹明B为模型反应，比较所得样品光催化活性。实验结果表明，不同干燥方法对催化剂的晶相结构、半导体能带结构、光吸收性能、表面性质及光催化活性均产生显著的影响，用超临界CO2干燥法制备的TiO2光催化剂具有较好的光催化活性。     

CO2和C2H4光催化合成丙烯酸的Cu/ZnO-TiO2催化剂

采用溶胶凝胶法制备了金属负载的复合型固体材料Cu/ZnO TiO2,并用X射线衍射、透射电子显微术、BET比表面测试、红外吸收光谱、紫外可见漫反射光谱以及光催化反应等实验技术对固体材料的表面结构、光响应性能、化学吸附性能以及光反应性能进行了表征和评价.实验结果表明,制得的固体材料粒径约为10nm,晶体结构以锐钛矿型TiO2 为主; ZnO和TiO2 复合后部分地形成了Zn-O-Ti键联,提高了对250~400nm光的吸收强度;金属Cu的负载扩展了材料在可见光范围的吸收,且使其紫外吸收限发生蓝移;反应物在固体材料表面的吸附态是影响光反应结果的主要因素; CO2 卧式吸附态和C2H4 非解离双点吸附态是光合成丙烯酸的有效吸附态,100℃以下合成丙烯酸的选择性大于87%.     

TiO2/SnO2复合光催化剂的制备及性能

采用特殊液相沉淀法制备纳米级的TiO2/SnO2复合粒子,对制备的纳米TiO2/SnO2采用XRD、TEM等手段进行了表征。用它做催化剂在日光下对甲基橙溶液进行了光催化实验。结果表明,纳米级TiO2/SnO2复合催化剂比纯TiO2的催化活性好,当SnO2摩尔百分数为20%时效果最佳,在60min内对10mg/L的甲基橙水溶液的降解率高达90.2%,具有较好的光催化活性。     

负载型复合半导体MoO3-TiO2/SiO2的结构与吸光性能

采用表面改性法制备了负载型复合半导体材料MoO3TiO2/SiO2,用X射线衍射、比表面测定、透射电子显微镜、红外光谱、拉曼光谱、紫外可见漫反射等技术对固体材料的结构进行了表征,并从固体材料的光响应性能和化学吸附性能方面进行了评价.结果表明,MoO3TiO2/SiO2表面存在着高度分散的MoO3和TiO2微晶,它们之间有一定的复合和键联作用,形成了Mo-O-Ti键;MoO3TiO2/SiO2复合材料表面对丙烷分子有化学吸附性能,Mo=O键上的端氧是C3H8的活性吸附位;与本体MoO3和TiO2相比,复合后MoO3TiO2/SiO2的能隙值有所增加,在紫外光区的吸光强度也明显加强,使得光生载流子的复合效率得到抑制,并产生了一定的量子尺度效应.     

光电变色器件用纳米晶氧化钛薄膜的微结构与特性

纳米晶TiO2薄膜在光电变色器件中具有很重要的作用。它的微结构直接影响染料的吸附、光的散射以及电荷输运的特性。因此，探索TiO2薄膜的微结构(如粒径、表面形貌和厚度等)及光电性能是非常有意义的。采用电子束蒸发工艺制备了光电变色器件用纳晶TiO2薄膜，利用原子力显微镜、X射线衍射、俄歇电子能谱等手段对纳米晶TiO2薄膜的表面形貌、结晶状态及组分进行了分析。从理论上研究和讨论了纳米晶TiO2薄膜晶粒尺寸对光电性能的影响，并用量子限制效应解释了吸收光谱峰值波长随粒径减小而发生蓝移的现象。     

Ti1-xCexO2体系纳米粉体的制备及其结构表征

 采用溶胶凝胶法制备了纳米Ti_1-xCe_xO₂系列样品。利用X射线衍射（XRD）、透射电子显微镜（TEM）、高分辨电子显微镜（HRTEM）对纳米Ti_1-xCe_xO₂系列样品颗粒尺寸、形貌以及固溶区范围和物相组成进行了研究；同时，采用Rietveld结构精修的方法研究了Ce的不同掺杂量对TiO₂晶体结构的影响。实验结果表明，Ce掺杂TiO₂能够形成Ti_1-xCe_xO₂固溶体，Ti_1-xCe_xO₂的固溶区范围在x=0～0.06之间，Ti_1-xCe_xO₂的晶粒度为5～10 nm，平均颗粒粒度约35 nm，且粒度均匀。     

Enhanced Laser Cooling of Rare-Earth-Ion-Doped Composite Material

We predict enhanced laser cooling performance of rare-earth-ions-doped glasses containing nanometre-sized ultrafine particles, which can be achieved by the enhanucement of locai field around rare earth ions, owing to the surface plasma resonance of small metallic particles. The influence of energy transfer between ions and the particle is theoretically discussed. Depending on the particle size and the ion emission quantum efficiency, the enhancement of the absorption is predicted. It is concluded that the absorption are greatly enhanced in these composite materials, the cooling power is increased as compared to the bulk material.     

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.     

Enhanced Laser Cooling of Rare-Earth-Ion-Doped Glass Containing Nanometer-Sized Metallic Particles

The enhanced laser cooling performance ofrare-earth-ions-doped glasses containing small particles is predicted. Thisis achieved by the enhancement of local field around rare earth ions, owingto the surface plasmon resonance of small metallic particles. The role ofenergy transfer between ions and the particle is theoretical discussed.Depending on the particle size and the ion emission quantum efficiency, theenhancement of the absorption and the fluorescence is predicted. Moreover,taking Yb³⁺-doped ZBLAN as example, the cooling power and heat-lightconverting efficiency are calculated. It is finally concluded that theabsorption and the fluorescence are greatly enhanced in these compositematerials, the cooling power is increased compared to the bulk material.     

ZnS∶Cu-罗丹明B的荧光共振能量转移性质

为了解决现有的基于量子点荧光共振能量转移体系的生物毒性问题,选用无毒的ZnS∶Cu量子点与罗丹明B构建新型荧光共振能量转移体系。通过共沉淀法成功制备了形貌均一的ZnS∶Cu纳米晶量子点。在此基础上,测试了不同掺杂浓度的ZnS∶Cu量子点及罗丹明B的荧光光谱。然后,通过对ZnS∶Cu量子点的表面修饰构建了以ZnS∶Cu量子点为供体、罗丹明B为受体的荧光共振能量转移体系。实验结果表明:ZnS∶2%Cu量子点的发光光谱与罗丹明B的吸收光谱在481 nm处有较大重合,说明构建荧光共振能量转移的最佳铜掺杂摩尔分数为2%。通过计算发现以ZnS∶2%Cu量子点为供体、罗丹明B为受体的荧光共振能量转移体系的能量转移效率为25.8%。进一步实验结果表明,罗丹明B浓度也能够影响能量转移。     

Visible-light-induced degradation of formaldehyde over titania photocatalyst co-doped with nitrogen and nickel

Titanium isopropoxide, ammonium carbonate and nickelous nitrate were used as the sources of titanium, nitrogen, and nickel to prepare titania photocatalyst co-doped with nitrogen and nickel by means of the modified sol-gel method. The photocatalyst was characterized by X-ray diffraction (XRD), UV-vis diffusive reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). The prepared N-Ni co-doped photocatalyst showed optical absorption in the visible light area and exhibited excellent photocatalytic ability for the degradation of formaldehyde under visible light irradiation. The effects of annealing temperature and component on the phase composition and photocatalytic activity were investigated. The results demonstrated that nitrogen atoms was weaved into the structure of titania and led to the response to visible light. However, nickel atoms existed in the form of Ni₂O₃, dispersed on the surface of TiO₂, suppressed the recombination of photo-induced electron-hole pairs, raised the photo quantum efficiency, and led to the enhancement of photocatalytic performance. The increase of photoactivity was attributed to the synergistic effects of co-doping.     

生物质碳量子点的绿色制备及对Cu2+的检测

向日葵作为我国主要的油料作物之一,其秸秆是天然的纤维素材料,具有绿色无毒,成本低廉的优势,是制备生物质碳量子点的理想材料之一。近年来,由于含铜农药和化学肥料的不规范使用,大量含铜污染物被排放导致农田土壤和水环境中的铜含量远高于环境背景值。因此,迫切需要开发出一种选择性好、灵敏性强且对环境友好的Cu²⁺检测方法。碳量子点(CDs)是一种粒径小于10 nm的准球形荧光碳纳米材料,因其表面含有丰富的极性官能团,具有良好的水溶性而被广泛研究。与传统的半导体量子点(CdSe, CdTe)相比,CDs具有合成原料广泛、生物相容性好等优点。主要应用于生物成像、光催化、光电转化以及传感检测等领域。然而目前用于碳化合成CDs的前驱体大多为昂贵的化学品,且合成过程复杂污染环境,限制了CDs的大规模生产与应用。开发出一种生态友好,简单、廉价的CDs合成方法是很有意义的。本研究以废弃的向日葵秸秆为碳源,采用简便的水热法合成生物质碳量子点(S-CDs)作为荧光探针,用于检测识别Cu²⁺。通过对S-CDs的一系列光学性质分析与表征,鉴定出其表面官能团主要包括O—H, N...     

Atomically thin MoS₂: a new direct-gap semiconductor

The electronic properties of ultrathin crystals of molybdenum disulfide consisting of N=1,2,…,6 S-Mo-S monolayers have been investigated by optical spectroscopy. Through characterization by absorption, photoluminescence, and photoconductivity spectroscopy, we trace the effect of quantum confinement on the material's electronic structure. With decreasing thickness, the indirect band gap, which lies below the direct gap in the bulk material, shifts upwards in energy by more than 0.6 eV. This leads to a crossover to a direct-gap material in the limit of the single monolayer. Unlike the bulk material, the MoS? monolayer emits light strongly. The freestanding monolayer exhibits an increase in luminescence quantum efficiency by more than a factor of 10? compared with the bulk material.