Tuning the electronic band structure of PCBM by electron irradiation

Tuning the electronic band structures such as band-edge position and bandgap of organic semiconductors is crucial to maximize the performance of organic photovoltaic devices. We present a simple yet effective electron irradiation approach to tune the band structure of [6, 6]-phenyl-C61-butyric acid methyl ester (PCBM) that is the most widely used organic acceptor material. We have found that the lowest unoccupied molecular orbital (LUMO) level of PCBM up-shifts toward the vacuum energy level, while the highest occupied molecular orbital (HOMO) level down-shifts when PCBM is electron-irradiated. The shift of the HOMO and the LUMO levels increases as the irradiated electron fluence increases. Accordingly, the band-edge position and the bandgap of PCBM can be controlled by adjusting the electron fluence. Characterization of electron-irradiated PCBM reveals that the variation of the band structure is attributed to the molecular structural change of PCBM by electron irradiation.     

Visible-light-induced photoelectrochemical behaviors of Fe-modified TiO2 nanotube arrays

Fe-modified TiO(2) nanotube arrays (TiO(2) NTs) were prepared by annealing amorphous TiO(2) NTs whose surface was covered with Fe(3+) by a dip-coating procedure, and characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and UV-visible reflectance spectroscopy. The photoelectrochemical properties were evaluated by the photocurrent response and photoelectrocatalytic (PEC) degradation of methylene orange (MO) and 4-chlorophenol in water under visible-light irradiation (λ > 420 nm). The results showed that a Fe-modified TiO(2) NTs electrode exhibited a larger photocurrent response and higher PEC activity for the degradation of organic pollutants than a pure TiO(2) NTs electrode. At a bias potential of 0.4 V, the photocurrent response of a 0.5 M Fe-modified TiO(2) NTs electrode exceeded that of a pure TiO(2) NTs electrode by a factor of about 10, and the PEC degradation rates of MO and 4-chlorophenol on a 0.5 M Fe-modified TiO(2) NTs electrode exceeded those on a pure TiO(2) NTs electrode by a factor of about 2.5. The larger photocurrent response and higher PEC activity of Fe-modified TiO(2) NTs could be attributed to the enhancement of separation of charge-carriers at the external electric field and the extension of the light response range of TiO(2) to the visible-light region with the narrowing of the band gap.     

Surface plasmon resonance metal-coupled biomass carbon modified TiO2 nanorods for photoelectrochemical water splitting

Exploring efficient and stable photoanode materials is a necessary link to realize the practical application of solar-driven photoelectrochemical (PEC) water splitting.Hence,we prepared rutile TiO2 nanorods,with a width of 50 nm,which was growth in situ on carbon cloth (TiO2@CC) by hydrothermal reaction.And then,Ag nanoparticles (NPs) and biomass N,S-C NPs were chosen for the additional modification of the fabricated TiO2 nanorods to produce broccoli-like Ag-N,S-C/TiO2@CC nanocomposites.According to the result of ultraviolet-visible diffuse reflectance spectroscopy (UV-vis) and PEC water splitting per-formance tests,Ag-N,S-C/TiO2@CC broadens the absorption region of TiO2@CC from the ultraviolet region to the visible region.Under AM 1.5G solar light irradiation,the photocurrent density of Ag-N,S-C/TiO2@CC is 89.8 μA·cm-2,which is 11.8 times higher than TiO2@CC.Under visible light irradiation,the photocurrent density of Ag-N,S-C/TiO2@CC reaches to 12.6 μA·cm-2,which is 21.0 times higher than TiO2@CC.Moreover,Ag-N,S-C/TiO2@CC shows a photocurrent responses in full pH range.It can be found that Ag NPs and N,S-C NPs play key roles in broaden the absorption range of TiO2 nanorods to the visible light region and,promote the occurrence of PEC water oxidation reaction due to the surface plasmon resonance effect of Ag NPs and the synergistic effect of N,S-C NPs.The mechanism demonstrated that Ag-N,S-C/TiO2@CC can separate the photogenerated electron-hole pairs effectively and transfer the photogenerated electrons to the photocathode (Pt plate) in time.This research provides a new strategy for exploration surface plasma metal coupled biomass carbon materials in the field of PEC water splitting.     

Carbon-modified TiO2 for photocatalysis

ABSTRACT: Here we present a method to produce TiO2 nanocrystals coated by thin layer of graphitic carbon. The coating process was prepared via chemical vapor deposition (CVD) with acetylene used as a carbon feedstock with TiO2 used as a substrate. Different temperatures (400°C and 500°C) and times (10, 20, and 60 s) of reaction were explored. The prepared nanocomposites were investigated by means of transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy/diffuse reflectance spectroscopy and ultraviolet-vis (UV-vis)/diffuse reflectance spectroscopy. Furthermore, photocatalytic activity of the materials was investigated under visible and UV-vis light irradiation in the process of phenol decomposition. It was found that TiO2 modification with carbon resulted in a significant increase of photoactivity under visible irradiation and decrease under UV-vis light irradiation. Interestingly, a shorter CVD time and higher process temperature resulted in the preparation of the samples exhibiting higher activity in the photocatalytic process under visible light irradiation.     

Improved conversion efficiency of Ag2S quantum dot-sensitized solar cells based on TiO2 nanotubes with a ZnO recombination barrier layer

We improve the conversion efficiency of Ag2S quantum dot (QD)-sensitized TiO2 nanotube-array electrodes by chemically depositing ZnO recombination barrier layer on plain TiO2 nanotube-array electrodes. The optical properties, structural properties, compositional analysis, and photoelectrochemistry properties of prepared electrodes have been investigated. It is found that for the prepared electrodes, with increasing the cycles of Ag2S deposition, the photocurrent density and the conversion efficiency increase. In addition, as compared to the Ag2S QD-sensitized TiO2 nanotube-array electrode without the ZnO layers, the conversion efficiency of the electrode with the ZnO layers increases significantly due to the formation of efficient recombination layer between the TiO2 nanotube array and electrolyte.     

TiO_2电极制备、表征及光电催化研究

文章采用阳极氧化法制备了TiO2纳米管电极、TiO2膜电极,对其进行了SEM、XRD表征的比较。研究了电化学过程、光解、TiO2纳米管的光催化、TiO2纳米管电极的光电催化对五氯苯酚的降解,研究表明光电催化降解速度最快。此外,TiO2纳米管电极和TiO2膜电极对五氯苯酚的光电催化降解也进行了研究。结果表明,TiO2纳米管电极对五氯苯酚光电催化效果明显好于TiO2膜电极,2h二者的降解率分别为81.5%,69%。     

负载型二氧化钛光电催化降解苯酚废水的反应动力学

采用浸渍提拉法制备发泡镍载二氧化钛薄膜电极,并以其为工作电极,建立三电极光电催化体系,对该体系降解苯酚的动力学进行了研究.考察了反应液初始pH值、反应物初始浓度、催化剂用量、光辐照强度、外加直流偏压值对光电催化反应速率的影响,采用幂指数方程描述反应动力学,得到方程C=C₀exp(-0.5430 C ^-0.4241 ₀ E ^0.2968 Q ^0.5418 I ^0.5877 t).方程计算值与实验值吻合较好,误差基本在15％以内.     

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％。     

N-Ion-implanted TiO2 photoanodes in quantum dot-sensitized solar cells

Hierarchical nanostructured titanium dioxide (TiO(2)) clumps were fabricated using electrostatic spray with subsequent nitrogen-ion doping by an ion-implantation technique for improvement of energy conversion efficiency for quantum dot-sensitized solar cells (QDSCs). CdSe quantum dots were directly assembled on the produced N-ion-implanted TiO(2) photoanodes by chemical bath deposition, and their photovoltaic performance was evaluated in a polysulfide electrolyte with a Pt counter electrode. We found that the photovoltaic performance of TiO(2) electrodes was improved by nearly 145% upon N-ion implantation. The efficiency improvement seems to be due to (1) the enhancement of electron transport through the TiO(2) layer by inter-particle necking of primary TiO(2) particles and (2) an increase in the recombination resistance at TiO(2)/QD/electrolyte interfaces by healing the surface states or managing the oxygen vacancies upon N-ion doping. Therefore, N-ion-doped photoanodes offer a viable pathway to develop more efficient QD or dye-sensitized solar cells.     

气相火焰燃烧合成锌掺杂TiO2纳米晶的光催化性能

以四氯化钛和乙酰丙酮锌为原料,采用气相火焰燃烧合成锌掺杂TiO2纳米晶,利用XRD, XPS和ICP-AES研究了纳米晶结构,考察了锌掺杂TiO2纳米晶在紫外光辐照下催化降解罗丹明B(Rhodamine B)的活性,探讨了光催化机理. 研究结果表明,掺杂相锌主要分布在TiO2表相,并形成均匀分散的ZnO团簇;燃烧过程中锌掺杂对纳米TiO2的晶相组成及晶粒尺寸影响不大. 当掺杂量为0.21%(mol)时,样品具有最高的光催化活性. 光催化机理分析表明,TiO2与ZnO不同的能带位置使光生载流子能够有效分离,改善了纳米TiO2光催化活性.     

Modified microwave method for the synthesis of visible light-responsive TiO2/MWCNTs nanocatalysts

Recently, TiO₂/multi-walled carbon nanotube (MWCNT) hybrid nanocatalysts have been a subject of high interest due to their excellent structures, large surface areas and peculiar optical properties, which enhance their photocatalytic performance. In this work, a modified microwave technique was used to rapidly synthesise a TiO₂/MWCNT nanocatalyst with a large surface area. X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller measurements were used to characterise the structure, morphology and the surface area of the sample. The photocatalytic activity of the hybrid nanocatalysts was evaluated through a comparison of the degradation of methylene blue dye under irradiation with ultraviolet and visible light. The results showed that the TiO₂/MWCNT hybrid nanocatalysts degraded 34.9% of the methylene blue (MB) under irradiation with ultraviolet light, whereas 96.3% of the MB was degraded under irradiation with visible light.     

胶原纤维为模板介孔TiO_2和Pt掺杂TiO_2纤维的制备及光催化降解黑液（英文）

以胶原纤维为模板,Ti（SO4）2为钛源,合成了新型光催化剂—介孔TiO2和Pt掺杂TiO2纤维。通过场发射扫描电镜（FESEM）、比表面积和孔径分析、紫外–可见光谱和分子荧光光谱等检测手段对两种介孔TiO2纤维的结构和物理性能进行了表征。FESEM分析表明,胶原纤维的表面结构能被较好地保留在介孔TiO2和Pt掺杂TiO2纤维中。N2吸附–脱附等温线为IV型,表明TiO2和Pt掺杂TiO2纤维具有介孔结构。基于结构的特点,在可见光和UV-A激发下,介孔TiO2和Pt掺杂TiO2纤维表现出强于商品级纳米TiO2（Degussa P25）的总有机碳（TOC）脱除率。此外,Pt的掺杂能明显改善介孔TiO2的光催化活性。光催化实验表明,Pt掺杂TiO2纤维（1.0g L–1）在可见光照射420 min后,黑液的TOC脱除率为37%;UV-A（360 nm）照射300min后,TOC脱除率为51%。因此,制备的介孔TiO2和Pt掺杂TiO2纤维作为一类性能优异的光催化剂,能用于黑液的光催化降解,并在其他类似的反应条件下具有潜在的应用前景。     

TiO2纳米管电极光电催化氧化工艺对罗丹明B的脱色

在平面转盘光电液膜反应器的基础上,以纳米管TiO2代替溶胶凝胶法制备的TiO2纳米颗粒结构,以提高对染料废水的脱色效果。在0.5%HF体系和20 V电压下,采用阳极氧化法制得纳米管TiO2膜电极,根据光电响应试验的结果,选取120 min作为氧化时间。以RhB为目标污染物,应用转盘光电液膜反应器,在UV照射下进行脱色研究。结果表明在光催化和光电催化过程中,纳米管TiO2膜电极对RhB的脱色率分别达89%和94%,比溶胶凝胶电极分别提高了66%和10%。最佳脱色条件:转速为80 r/min,偏压为0.8 V。且在处理高浓度的RhB溶液时,纳米管电极的优势更加明显。     

N、F掺杂的TiO2膜电极在可见光条件下光电催化氧化诱惑红脱色效果的研究

纯TiO2光催化剂只能利用紫外光进行光催化反应,而通过金属／非金属掺杂可以扩大其波长吸收范围,实现在可见光条件下的光催化反应。该实验以NH4F作为添加剂,用溶胶一凝胶法制备N、F掺杂的TiO2粉末,并尝试用涂渍附着法制备了N、F掺杂的TiO2膜电极。选取诱惑红作为目标污染物,应用自制的斜板式液膜光电反应器,在≥400nm可见光照射下进行光电催化氧化性能的研究。考察了其可见光光电催化氧化的影响因素和光电催化的效率,确定最佳的优化条件为：偏压=1．0V,pH=1．5～2．0,Na2SO4=1000mg／L。可实现可见光条件下对30mg／L诱惑红染料溶液的脱色,其脱色率可达到40％。     

Application of a polymer heterojunction in dye-sensitized solar cells

Using a blend heterojunction consisting of a C₆₀ derivative, [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM), and poly(3-hexylthiophene) (P3HT) as a charge carrier transfer medium to replace the I₃⁻/I⁻ redox electrolyte, a novel TiO₂/dye/PCBM/P3HT dye-sensitized solar cell was fabricated and characterized. It was found that the P3HT/PCBM heterojunction widened the incident light harvest range from ultraviolet to visible light, and improved the photoelectrical response of the dye-sensitized solar cell. We investigated the influence of the PCBM/P3HT ratio and barrier layer on the photoelectric performance of the solar cell and proposed optimized preparation conditions. The optimized solar cell with a barrier layer and PCBM/P3HT ratio of 1:2 had a short circuit current density of 5.52 mA cm⁻², an open circuit voltage of 0.87 V, a fill factor of 0.640 and a light-to-electric energy conversion efficiency of 3.09% under a simulated solar light irradiation of 100 mW cm⁻².     

Degradation of dye wastewater in a thin-film photoelectrocatalytic (PEC) reactor with slant-placed TiO2/Ti anode

A thin-film photoelectrocatalytic (PEC) reactor with slant-placed TiO₂/Ti anode was developed and successfully applied to degrade Rhodamine B (RhB) and textile effluent. Using a 5–150 mg L⁻¹ RhB solution as the model system, thin-film PEC removed total color and TOC by 99–28% and 78–15%, respectively, in 1 h, which is much higher than 82–7% and 60% to zero by conventional PEC. The enhanced treatment efficiency achieved by thin-film PEC process was attributed to the significantly reduced path length of irradiation light source. The wastewater was kept circulating during the experiments to timely refresh the aqueous film on the TiO₂/Ti anode and promote the mass transfer of the target pollutants and the degradation products in the bulk solution. The thin-film PEC reactor can degrade both simulated and real dye wastewater efficiently under UV light irradiation. Results suggested that thin-film PEC was particularly superior for treating a high concentration solution. The thin-film PEC reactor was also applied to treat RhB solution efficiently under solar light irradiation. The recycle experiments demonstrated excellent stability and reliability of the slant-placed TiO₂/Ti anode. This study proposed a simple and effective method to design PEC reactor applicable for industrial dye wastewater treatment.     

A high‐efficient rotating disk photoelectrocatalytic (PEC) reactor with macro light harvesting pyramid‐surface electrode

A series of pyramid‐surface TiO₂/Ti electrodes were proposed, fabricated, and used in a rotating disk photoelectrocatalytic (PEC) reactor to treat rhodamine B (RB) solution. Compared with conventional planar electrode, pyramid‐surface electrode exhibited much lower light reflectivity, larger photocurrent, and better treatment efficiency. For samples containing 20 to 150 mg L^?1 RB, 100– 98% color removal, and 87–30% COD removal were obtained in 150 min using 1/3 (h/w) pyramid‐surface electrode, much higher than 98–77% and 48–9% obtained by a conventional planer electrode. The excellent treatment performance attributed to two major reasons: (a) enhanced light harvest resulted from multiple reflections of irradiation light on the pyramid‐surface, and (b) enlarged electrode surface area enabling the electrode to carry more TiO₂ catalyst and pollutants for treatment. Experimental results also showed that the pyramid‐surface electrode consumed less power and exhibited superior performance when treating high concentration wastewater. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2448–2455, 2012     

Effect of cooling rate of pre-annealed CdS thin film electrodes prepared by chemical bath deposition: Enhancement of photoelectrochemical characteristics

Thin films of CdS, deposited by chemical bath deposition (CBD) onto films of fluorine-doped tin oxide/glass (glass/FTO) substrates were prepared and investigated for photoelectrochemical conversion (PEC) of light into electricity. Knowing the hazardous nature of CdS, the focal theme of this work was to modify the electrodes by simple economic ways to maximize their conversion efficiency and minimize their degradation under PEC conditions. This was to avoid leaching out of hazardous Cd²⁺ ions. Different parameters have been investigated for this purpose. Multi-deposition preparation, redox couple, and electrode etching affected electrode PEC characteristics. Consistent with earlier literature, annealing the electrode enhanced its conversion efficiency and stability. On the other hand, effect of cooling rate of pre-annealed CdS electrodes, prepared by CBD, on their PEC characteristics has been investigated here for the first time. Controlling the cooling rate was one major factor that affected CdS surface morphology, conversion efficiency and stability under PEC conditions. The major recommendation coming out here is that PEC characteristics of CdS thin film electrodes can be significantly enhanced by pre-annealing the electrode at ∼250 °C followed by its slow cooling.     

Electrochemically hydrogenated TiO2 nanotubes with improved photoelectrochemical water splitting performance

One-dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as photoanode for photoelectrochemical (PEC) water splitting. In this work, we report a facile and eco-friendly electrochemical hydrogenation method to modify the electronic and PEC properties of ATO nanotube films. The hydrogenated ATO (ATO-H) electrodes present a significantly improved photocurrent of 0.65 mA/cm² in comparison with that of pristine ATO nanotubes (0.29 mA/cm²) recorded under air mass 1.5 global illumination. The incident photon-to-current efficiency measurement suggests that the enhanced photocurrent of ATO-H nanotubes is mainly ascribed to the improved photoactivity in the UV region. We propose that the electrochemical hydrogenation induced surface oxygen vacancies contribute to the substantially enhanced electrical conductivity and photoactivity.     

Organic-skinned inorganic nanoparticles: surface-confined polymerization of 6-(3-thienyl)hexanoic acid bound to nanocrystalline TiO2

There are many practical difficulties in direct adsorption of polymers onto nanocrystalline inorganic oxide surface such as Al2O3 and TiO2 mainly due to the insolubility of polymers in solvents or polymer agglomeration during adsorption process. As an alternative approach to the direct polymer adsorption, we propose surface-bound polymerization of pre-adsorbed monomers. 6-(3-Thienyl)hexanoic acid (THA) was used as a monomer for poly[3-(5-carboxypentyl)thiophene-2,5-diyl] (PTHA). PTHA-coated nanocrystalline TiO2/FTO glass electrodes were prepared by immersing THA-adsorbed electrodes in FeCl3 oxidant solution. Characterization by ultraviolet/visible/infrared spectroscopy and thermal analysis showed that the monolayer of regiorandom-structured PTHA was successfully formed from intermolecular bonding between neighbored THA surface-bound to TiO2. The anchoring functional groups (-COOH) of the surface-crawling PTHA were completely utilized for strong bonding to the surface of TiO2.