Preparation of TiO₂ nanowires/nanotubes using polycarbonate membranes and their uses in dye-sensitized solar cells

Track-etched polycarbonate (PC) membranes were used as a soft template to synthesize mesoporous TiO(2) for use in dye-sensitized solar cells (DSSCs). The Ti precursor infiltrated into the cylindrical confined spaces of PC membranes. Upon calcination at 500 °C, TiO(2) nanowires (15TNW) were obtained from PC with a 15 nm pore diameter, whereas TiO(2) nanotubes (50TNT and 100TNT) were generated from PC with 50 and 100 nm diameter pores, respectively. TNW and TNT were used as photoelectrodes in DSSCs employing a polymer electrolyte. The ranking of the cell efficiencies of the 200 nm thick TiO(2) films was 50TNT (1.1%) > 15TNW (0.8%) ? 100TNT (0.7%), which was mostly attributed to different amounts of dye adsorption due to different surface areas. These TNW and TNT films were further coated with the graft copolymer-directed mesoporous TiO(2) and were used as interfacial layers between the FTO glass and the 4 μm thick nanocrystalline TiO(2) film. As a result, the order of energy conversion efficiency was 15TNW (5.0%) ? 50TNT (4.8%) > 100TNT (4.1%). The improved performance of 15TNW was due to a higher transmittance through the electrode and a longer electron lifetime for recombination. The DSSC performance was systematically investigated in terms of interfacial resistance and charge recombination using electrochemical impedance spectroscopy.     

Amorphous SiCNO hollow nanofibers with mesoporous walls

In this work, for the first time, we reported the fabrication of polymer-derived amorphous SiCNO ceramics via electrospinning of tetraethoxysilane (TBOS), polyvinylpyrrolidone (PVP), cetrimonium bromide (CTAB), and urea combined with subsequent air calcination. The resultant products exhibited a well-defined one-dimensional (1D) hollow fiber nanostructure with mesoporous walls. The BET surface area of SiCNO hollow nanofibers is ~95.6 m²/g, and the average pore diameter is sized in ~9 nm. The movement of urea within the core of the as-spun polymeric fibers accounted for the formation of hollow nanofibers, and the thermal decomposition of polymers such as PVP, TEOS, and urea responded for the formation of mesopores within the walls. In addition, it was found that the contents of urea within the raw materials played a critically important role in the formation of SiCNO mesoporous hollow nanofibers, making their growth in a controlled manner.     

A facile method to prepare SnO2 nanotubes for use in efficient SnO2-TiO2 core-shell dye-sensitized solar cells

A high-efficiency photoelectrode for dye-sensitized solar cells (DSSCs) should combine the advantageous features of fast electron transport, slow interfacial electron recombination and large specific surface area. However, these three requirements usually cannot be achieved simultaneously in the present state-of-the-art research. Here we report a simple procedure to combine the three conflicting requirements by using porous SnO(2) nanotube-TiO(2) (SnO(2) NT-TiO(2)) core-shell structured photoanodes for DSSCs. The SnO(2) nanotubes are prepared by electrospinning of polyvinyl pyrrolidone (PVP)/tin dichloride dihydrate (SnCl(2)·2H(2)O) solution followed by direct sintering of the as-spun nanofibers. A possible evolution mechanism is proposed. The power conversion efficiency (PCE) value of the SnO(2) NT-TiO(2) core-shell structured DSSCs (～5.11%) is above five times higher than that of SnO(2) nanotube (SnO(2) NT) DSSCs (～0.99%). This PCE value is also higher than that of TiO(2) nanoparticles (P25) DSSCs (～4.82%), even though the amount of dye molecules adsorbed to the SnO(2) NT-TiO(2) photoanode is less than half of that in the P25 film. This simple procedure provides a new approach to achieve the three conflicting requirements simultaneously, which has been demonstrated as a promising strategy to obtain high-efficiency DSSCs.     

New dye-sensitized solar cells obtained from extracted bracts of bougainvillea glabra and spectabilis betalain pigments by different purification processes

The performance of a new dye-sensitized solar cell (DSSC) based in a natural dye extracted from the Bougainvillea spectabilis' bracts, is reported. The performance of this solar cell was compared with cells prepared using extract of the Bougainvillea glabra and mixture of both extracts; in both cases the pigments were betalains, obtained from Reddish-purple extract. These dyes were purified to different extents and used for the construction of solar cells that were electrically characterized. The materials were characterized using FTIR and UV-Vis. Solar cells were assembled using TiO(2) thin film on indium tin oxide (ITO)-coated glass; a mesoporous film was sensitized with the Bougainvillea extracts. The obtained solar energy conversion efficiency was of 0.48% with a current density J(SC) of 2.29 mA/cm(2) using an irradiation of 100 mW/cm(2) at 25 °C.     

大小颗粒Ti02复合制备纳晶薄膜电极及其性能研究

选用大小粒径分别为200nm和21nm的TiO2颗粒,采用刮涂法制备了几种不同条件的TiOz薄膜电极,研究了大小颗粒Ti02的复合方式和质量比对其所组装染料敏化太阳能电池光电性能的影响。应用红外吸收光谱仪和扫描电子显微镜对Ti02薄膜电极进行了表征,在100mW／cm^2（AM1．5G）光照下,测试了电池的光电性能。结果表明：将大颗粒Ti02作为光散射层,且大颗粒Ti02和小颗粒Ti02质量比为1：3时,所制薄膜不但可以保持纳米粉体高比表面积的优点,同时可以提高对太阳光的散射率,用其组装的电池光电性能最好,转换效率达到2．46％。     

静电纺丝制备TiO2纳米纤维的光催化性能

纳米TiO2材料在光催化、抗菌等方面有着广泛应用。采用尺寸为20～30nm的TiO2颗粒与聚乙烯吡咯烷酮（PVP）的醇溶液混合制得纺丝液,通过静电纺丝技术与烧结工艺,制得TiO2纳米纤维。采用能谱仪、X射线衍射、扫描电子显微镜和投射电子显微镜等分析手段对样品进行了表征,与采用溶胶–凝胶结合静电纺丝技术得到的TiO2纳米纤维进行了形貌对比,并通过亚甲基蓝降解实验研究其光催化性能。结果表明：以TiO2纳米颗粒为原料通过静电纺丝技术制备的TiO2纳米纤维,主要为多晶相的锐钛矿结构,直径为150～250 nm,长度大于20μm,与溶胶–凝胶结合静电纺丝技术制得的TiO2纳米纤维相比,直径分布更为均匀。在紫外光照射90min时,对浓度为4mg/L的亚甲基蓝溶液的分解率为72%,具有较好的光催化效率。     

染料敏化太阳电池TiO2光阳极研究进展

纳米TiO2是目前性能最为优良的染料敏化太阳电池(DSSC)光阳极材料。文章系统综述了优化纳米TiO2光阳极的染料吸附、电子传输、再生染料等性能的技术和方法,主要包括纳米TiO2光阳极薄膜微结构的调控、TiO2光阳极的离子/元素掺杂、TiO2光阳极的表面包覆、TiO2光阳极的表面处理等方面的国内外研究进展,并分析了目前TiO2光阳极存在的主要问题及未来的发展方向。     

Aqueous Colloidal Stability Evaluated by Zeta Potential Measurement and Resultant TiO2 for Superior Photovoltaic Performance

Controlling the morphological structure of titanium dioxide (TiO₂) is crucial for obtaining superior power conversion efficiency for dye‐sensitized solar cells. Although the sol–gel‐based process has been developed for this purpose, there has been limited success in resisting the aggregation of nanostructured TiO₂, which could act as an obstacle for mass production. Herein, we report a simple approach to improve the efficiency of dye‐sensitized solar cells (DSSC) by controlling the degree of aggregation and particle surface charge through zeta potential analysis. We found that different aqueous colloidal conditions, i.e., potential of hydrogen (pH), water/titanium alkoxide (titanium isopropoxide) ratio, and surface charge, obviously led to different particle sizes in the range of 10–500 nm. We have also shown that particles prepared under acidic conditions are more effective for DSSC application regarding the modification of surface charges to improve dye loading and electron injection rate properties. Power conversion efficiency of 6.54%, open‐circuit voltage of 0.73 V, short‐circuit current density of 15.32 mA/cm², and fill factor of 0.73 were obtained using anatase TiO₂ optimized to 10–20 nm in size, as well as by the use of a compact TiO₂ blocking layer.     

Mesoporous TiO<Subscript>2</Subscript> microspheres synthesized via a facile hydrothermal method for dye sensitized solar cell applications

Mesoporous TiO₂ microspheres were successfully synthesized by a facile hydrothermal process and the obtained product was sintered at 450 °C. The sintered TiO₂ powder was characterised by powder X-ray diffraction pattern and the result shows pure anatase phase with good crystalline nature. The morphological image of field emission scanning electron microscopy and high resolution transmission electron microscopy shows spherical shape and size of the particles is around 100 to 300 nm. The Brunauer–Emmett–Teller surface area of synthesized TiO₂ material was 56.32 m² g^?1 and average pore width of synthesized materials was 7.1 and 9.3 nm. Bimodal pore structure of TiO₂ microspheres has been very effective for electrolyte diffusion into photoanode in dye sensitized solar cells. The synthesized anatase TiO₂ microsphere based dye sensitized solar cells have high surface area with light scattering effect to enhance the photocurrent and conversion efficiency than the commercial P25 photoanode material. The power conversion efficiency of synthesized mesoporous TiO₂ microspheres and commercial P25 material is 4.2 and 2.7 % respectively. Therefore bimodal mesoporous anatase TiO₂ microsphere appears to be a promising and potential candidate for dye sensitized solar cells (DSSC) application.     

Polyvinyl pyrrolidone aided preparation of TiO2 films used in flexible dye-sensitized solar cells

Polyvinyl pyrrolidone (PVP) is introduced to low temperature preparation of a good quality TiO₂ film used in flexible dye-sensitized solar cells (DSSCs). The samples are characterized by scanning electron microscopy and UV–vis absorption spectra, the photovoltaic performance of the DSSC is measured. It is found that PVP can improve the dispersion of TiO₂ particles and the adherence of TiO₂ particles to flexible substrate, as well as the adsorption of sensitized dye to TiO₂ film. Additionally, ultraviolet light irradiation can eliminate organics remained on the surface the TiO₂ film and improve the surface state of TiO₂ film. Under an optimal condition, a flexible DSSC using TiO₂ film doped PVP and UV irradiation treated achieves a light-to-electric energy conversion efficiency of 3.02% under irradiation with a simulate solar light intensity of 100 mW cm⁻².     

A combination of hard and soft templating for the fabrication of silica hollow microcoils with nanostructured walls

Hollow silica microcoils have been prepared by using functionalized carbon microcoils as hard templates and surfactant or amphiphilic dye aggregates as soft templates. The obtained materials have been characterized by electron and optical microscopy, nitrogen sorption and small angle X-ray scattering. The obtained hollow microcoils resemble the original hard templates in shape and size. Moreover, they have mesoporous walls (pore size ≈ 3 nm) with some domains where pores are ordered in a hexagonal array, originated from surfactant micelles. The obtained silica microcoils also show preferential adsorption of cationic fluorescent dyes. A mechanism for the formation of silica microcoils is proposed.     

The influence of anatase-rutile mixed phase and ZnO blocking layer on dye-sensitized solar cells based on TiO2nanofiberphotoanodes

High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO₂ nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO₂ DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO₂ electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO₂ nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6?wt.% rutile) TiO₂ nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3?mA?cm^?2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO₂ nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies.     

含异靛单元染料的合成及在DSSC中的研究

我们以三苯胺为电子给体,氰基丙烯酸为电子受体和锚定基团,首次使用窄带隙共轭单元异靛设计合成了一个D-π-A型全有机染料TPAID1,对其进行在染料敏化太阳能电池中的性能进行了一些列的表征,测定了染料在氯仿溶剂中的紫外-可见吸收光谱,并对其进行了DSSC器件表征,在AM 1.5 G,100 mW/cm2下,染料TPAID1的电池能量转换效率为0.59%(Jsc=1.59 mA/cm2,Voc=0.55 V,FF=0.69)。     

以ZIF-8为前驱体制备ZnO-TiO2复合材料及其敏化太阳能电池性能的研究

通过硝酸锌与2-甲基咪唑反应制备沸石咪唑酯骨架结构材料(ZIF-8),利用钛酸正四丁酯在ZIF-8表面水解得到ZIF/TiO2复合材料。在空气气氛中于不同温度条件下对ZIF/TiO2复合材料进行热处理得到不同的ZnO/TiO2复合材料,并应用于DSSC的光阳极,测试电池的光电流-光电压特征曲线,对测试结果进行分析。结果表明:不同ZnO/TiO2复合材料为光阳极材料制备的DSSC,光电转换效率与直接热处理制备的ZnO单相材料相比有了显著提高,其中热处理温度为600℃时,材料具备最高的光电转换效率,为3.69%,比直接热处理制备的ZnO单相材料0.78%的光电转换效率提高了373%,说明加入TiO2制备复合材料可以大幅度提高ZnO基DSSC的光电性能。     

用于染料敏化太阳能电池的苊并吡嗪类染料的设计与合成，

以吡嗪环作为吸电子基团,单羧基为连接基团,选用不同的芳环供电基团设计合成了3个苊并吡嗪类染料敏化太阳能电池(DSSC)染料。其中,以二苯胺为供电基的染料Va性能最好,主要吸光范围是400~500 nm,ELUMO为-1.10 eV,远负于TiO2的导带能级-0.5 eV,说明染料的激发态电子注入到纳米TiO2的导带在热力学上是可行的;EHOMO为1.31 eV,远正于I-/I3-的氧化还原电位0.4 eV,说明处于氧化态的染料分子从氧化还原电对得到电子再生。光电转换效率最高为3.06%,达到经典染料N719效率的43%。     

介孔TiO_2中空微球的制备及其光催化性能研究

采用双模板辅助,在水热条件下制备出TiO_2@C复合微球,高温煅烧除去模板后得到介孔TiO_2中空微球。利用XRD、SEM、TEM和氮气吸脱-脱附仪对所制备样品的晶体结构、形貌及孔结构进行表征。所制备的介孔TiO_2中空微球属于锐钛矿型,是由大量直径为15.31 nm的介孔初级微球堆积而成,整体微球直径约为360 nm,加入葡萄糖作为模板剂能使孔道结构变得有序。以罗丹明B为模拟污染物,探讨了介孔TiO_2中空微球光催化降解罗丹明B的性能。结果表明,在20 W紫外光照射下,50 mg介孔TiO_2中空微球在30 min内可使初始质量浓度为10 mg/L的罗丹明B完全降解,重复使用11次,在50 min时的降解率仍可达89.5%。     

Hollow TiO2 containing multilayer nanofibers with enhanced photocatalytic activity

Hollow titania containing multilayer nanofibers was fabricated through the combination of electrospinning with layer-by-layer technique. Two different solvents, methylbenzene and THF were used to remove the template. The morphology of the obtained hollow multilayer nanofibers confirmed that THF is better than methylbenzene. The obtained hollow multilayer fiber has a diameter of about 700 nm and its shell thickness is about 140 nm. FTIR spectra show the fabrication of multilayer nanofibers. XPS measurement indicates that TiO₂ nanoparticles can be assembled successfully. The obtained multilayer hollow nanofibers have highest photocatalytic activity to degrade methylene blue solution comparing with the TiO₂ film due to their unique hollow structure.     

Carbon nanotubes-polyethylene oxide composite electrolyte for solid-state dye-sensitized solar cells

Novel carbon nanotubes (CNTs)-polyethylene oxide (PEO) composite electrolyte for dye-sensitized solar cell (DSSC) was prepared and characterized for the first time. The strong bonding and interaction between CNTs and PEO in CNTs-PEO composites was observed by the characterization of X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and Raman spectra. The introduction of CNTs into PEO matrix significantly improved the electrolyte properties of DSSC such as roughness, amorphicity and ionic conductivity. The solid-state DSSC fabricated with the optimum composite electrolyte (added 1% CNTs in PEO matrix, 1%CNT-PEO) achieved maximum conversion efficiency of 3.5%, an open circuit voltage (V_OC) of 0.589 V, short circuit current density (J_SC) of 10.64 mA/cm² and fill factor (FF) of 56%. The highest IPCE in the DSSC fabricated with 1%CNT-PEO electrolyte is ascribed to the improved ionic conductivity of composite electrolytes and enhanced interfacial contact between electrode and electrolyte.     

Soft-template synthesized ordered mesoporous carbon counter electrodes for dye-sensitized solar cells

Ordered mesoporous carbon (OMC) with a high surface area (∼1575 m²/g) and bimodal pores (2.5 and 6.1 nm) was synthesized using a soft-template method employing triblock copolymer F127 as the structure directing agent and then applied as a low-temperature processable counter electrode for dye-sensitized solar cell (DSSC). The OMC counter electrode-based DSSC shows an energy conversion efficiency of 7.46%, whereas that of a Vulcan counter electrode is 4.30%. Electrochemical impedance spectroscopy analysis reveals decreased charge transfer resistance at the OMC counter electrode–electrolyte interface, thus improved fill factor and energy conversion efficiency.     

TiO_2/SiO_2复合纳米纤维的GQDs改性及其对甲醛的可见光催化降解性能

采用静电纺丝法合成了TiO_2/SiO_2柔性复合纳米纤维膜,而后对其进行石墨烯量子点(GQDs)改性,制备了GQDs/TiO_2-SiO_2复合纳米纤维,其中GQDs用水热法合成。用X射线衍射仪(XRD)、电子万能材料试验机、扫描电子显微镜(SEM)、紫外-可见分光光度计(UV-Vis)对其物相组成、力学性能、微观形貌以及光催化性能进行了表征。结果表明:尺寸在7 nm~15 nm之间的GQDs松散沉积在直径为200 nm~400 nm的TiO_2/SiO_2纳米纤维上,纤维连续性好,复合薄膜有较好的力学性能;TiO_2的结晶较好,为锐钛矿相;GQDs复合后将TiO_2的本征吸收从390 nm左右延伸到了420 nm左右,拓宽了TiO_2的吸收范围。在可见光催化降解中,初始浓度为0.32 mg/m~3的甲醛气体110 min后的降解效率达到70%。