Enhanced charge extraction for all-inorganic perovskite solar cells by graphene oxide quantum dots modified TiO2 layer

All-inorganic cesium lead bromide (CsPbBr₃) perovskite solar cells have been attracting growing interest due to superior performance stability and low cost. However, low light absorbance and large charge recombination at TiO₂/CsPbBr₃ interface or within CsPbBr₃ film still prevent further performance improvement. Herein, we report devices with high power conversion efficiency (9.16%) by introducing graphene oxide quantum dots (GOQDs) between TiO₂ and perovskite layers. The recombination of interfacial radiation can be effectively restrained due to enhanced charge transfer capability. GOQDs with C-rich active sites can involve in crystallization and fill within the CsPbBr₃ perovskite film as functional semiconductor additives. This work provides a promising strategy to optimize the crystallization process and boost charge extraction at the surface/interface optoelectronic properties of perovskites for high efficient and low-cost solar cells.     

Highly porous TiO2 films from anodically deposited titanate hybrids and their photoelectrochemical and photocatalytic activity

Hybrid films of TiO₂ and benzoquinone, its derivative 2-methyl-benzoquinone or the dye 2,9,16,23-tetrasulfophthalocyaninatonickel(II) were prepared by anodic electrodeposition from titanium alkoxide solutions. Calcination of the films at 450 °C led to removal of the organics and the formation of crystalline and highly porous TiO₂ films as seen in XRD and Kr adsorption measurements, respectively. In dye-sensitized solar cells the films achieved an overall light-to-electricity conversion efficiency of 0.8% despite a low film thickness of 0.55 μm. In the photocatalytic decomposition of methylene blue the films showed photonic efficiencies of up to 0.09% for film thicknesses around 0.5 μm, which is much higher than those of comparable TiO₂ films prepared by sol–gel method.     

无皂乳液聚合法合成聚苯乙烯微球应用于准固态电解质染料敏化太阳能电池

制备了一种提高染料敏化太阳能电池短路电流和电池光电转化效率的准固态凝胶电解质,该电解质含有5%高聚物PVDF-HFP和2% TiO₂纳米颗粒。另外,通过乙醇相无皂乳液聚合法合成了大小均一的聚苯乙烯微球,并用于制备染料敏化太阳能电池的多孔光阳极。研究了准固态电解质和液态电解质应用于不同光阳极染料敏化太阳能电池的规律。结果表明,与液态电解质相反,准固态电解更适用于孔洞较多的光阳极,在相同测试条件下,电池的短路电流由12.80 mA·cm^-2提高到13.53 mA·cm^-2,效率比液态提高11.43%,达到6.63%。     

CO2 absorption and regeneration of alkali metal-based solid sorbents

Potassium-based sorbents were prepared by impregnation with potassium carbonate on supports such as activated carbon (AC), TiO₂, Al₂O₃, MgO, SiO₂ and various zeolites. The CO₂ capture capacity and regeneration property were measured in the presence of H₂O in a fixed-bed reactor, during multiple cycles at various temperature conditions (CO₂ capture at 60 °C and regeneration at 130–400 °C). Sorbents such as K₂CO₃/AC, K₂CO₃/TiO₂, K₂CO₃/MgO, and K₂CO₃/Al₂O₃, which showed excellent CO₂ capture capacity, could be completely regenerated above 130, 130, 350, and 400 °C, respectively. The decrease in the CO₂ capture capacity of K₂CO₃/Al₂O₃ and K₂CO₃/MgO, after regeneration at temperatures of less than 200 °C, could be explained through the formation of KAl(CO₃)₂(OH)₂, K₂Mg(CO₃)₂, and K₂Mg(CO₃)₂·4(H₂O), which did not completely converted to the original K₂CO₃ phase. In the case of K₂CO₃/AC and K₂CO₃/TiO₂, a KHCO₃ crystal structure was formed during CO₂ absorption, unlike K₂CO₃/Al₂O₃ and K₂CO₃/MgO. This phase could be easily converted into the original phase during regeneration, even at a low temperature (130 °C). Therefore, the formation of the KHCO₃ crystal structure after CO₂ absorption is an important factor for regeneration, even at the low temperature. The nature of support plays an important role for CO₂ absorption and regeneration capacities. In particular, the K₂CO₃/TiO₂ sorbent showed excellent characteristics in CO₂ absorption and regeneration in that it satisfies the requirements of a large amount of CO₂ absorption (mg CO₂/g sorbent) and fast and complete regeneration at a low temperature condition (1 atm, 150 °C).     

响应曲面法优化碳酸锂反应结晶工艺

碳酸锂是制备各种锂化合物的基础锂盐,碳酸锂的制备是锂产业链当中的承前启后的关键技术。以察尔汗盐湖老卤为原料,采用响应曲面法中的central composite design（CCD）设计实验,分别考察了温度、碳酸钠加料速度、碳酸钠浓度和锂离子浓度4个因素及交互作用对反应结晶工艺中碳酸锂的收率和粒度的影响,并分别建立了响应值与影响因素之间的回归方程。响应预测最佳值为：碳酸锂收率93.68%、粒径（d₅₀）16.73 μm;相应的实验值分别为94.01%和16.91 μm。预测值与实验值接近,误差较小,说明响应曲面法建立的预测碳酸锂反应结晶的模型可靠,在最佳工艺条件下分析所制得的产品,用ICP-AES分析纯度为99.52%,用XRD分析基本无杂峰,说明反应结晶生成Li₂CO₃晶体,其主要晶面为（-1 1 0）、（-2 2 0）和（0 0 2）。     

SO2 resistant antimony promoted V2O5/TiO2 catalyst for NH3-SCR of NOx at low temperatures

To get the low temperature sulfur resistant V₂O₅/TiO₂ catalysts quantum chemical calculation study was carried out. After selecting suitable promoters (Se, Sb, Cu, S, B, Bi, Pb and P), respective metal promoted V₂O₅/TiO₂ catalysts were prepared by impregnation method and characterized by X-ray diffraction (XRD) and Brunner Emmett Teller surface area (BET-SA). Se, Sb, Cu, S promoted V₂O₅/TiO₂ catalysts showed high catalytic activity for NH₃ selective catalytic reduction (NH₃-SCR) of NO_x carried at temperatures between 150 and 400 °C. The conversion efficiency followed in the order of Se > Sb > S > V₂O₅/TiO₂ > Cu but Se was excluded because of its high vapor pressure. An optimal 2 wt% ‘Sb’ loading was found over V₂O₅/TiO₂ for maximum NO_x conversion, which also showed high resistance to SO₂ in presence of water when compared to other metal promoters. In situ electrical conductivity measurement was carried out for Sb(2%)/V₂O₅/TiO₂ and compared with commercial W(10%)V₂O₅/TiO₂ catalyst. High electrical conductivity difference (ΔG) for Sb(2%)/V₂O₅/TiO₂ catalyst with temperature was observed. SO₂ deactivation experiments were carried out for Sb(2%)/V₂O₅/TiO₂ and W(10%)/V₂O₅/TiO₂ at a temperature of 230 °C for 90 h, resulted Sb(2%)/V₂O₅/TiO₂ was efficient catalyst. BET-SA, X-ray photoelectron spectroscopy (XPS) and carbon, hydrogen, nitrogen and sulfur (CHNS) elemental analysis of spent catalysts well proved the presence of high ammonium sulfate salts over W(10%)/V₂O₅/TiO₂ than Sb(2%)/V₂O₅/TiO₂ catalyst.     

Reactivity of V2O5-WO3/TiO2 catalysts in the selective catalytic reduction of nitric oxide by ammonia

The physico-chemical characteristics and the reactivity of sub-monolayer V₂O₅-WO₃/TiO₂ deNO_x catalysts is investigated in this work by EPR, FT-IR and reactivity tests under transient conditions. EPR indicates that tetravalent vanadium ions both in magnetically isolated form and in clustered, magnetically interacting form are present over the TiO₂ surface. The presence of tungsten oxide stabilizes the surface V^IV and modifies the redox properties of V₂O₅/TiO₂ samples. Ammonia adsorbs on the catalysts surface in the form of molecularly coordinated species and of ammonium ions. Upon heating, activation of ammonia via an amide species is apparent. V₂O₅-WO₃/TiO₂ catalysts exhibits higher activity than the binary V₂O₅/TiO₂ and WO₃/TiO₂ reference sample. This is related to both higher redox properties and higher surface acidity of the ternary catalysts. Results suggest that the catalyst redox properties control the reactivity of the samples at low temperatures whereas the surface acidity plays an important role in the adsorption and activation of ammonia at high temperatures.     

V2O5-WO3-MoO3/TiO2催化剂用于NH3选择性还原减排NOx的性能（英文）

The V2O5-WO3-MoO3/TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction (XRD), scanning electron micrograph (SEM) and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass percentage of V:W:Mo:TiO2 :fiber glass= 1:4.5:4.5:72:18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to rutile by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3 . The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615-1640 mg·m-3 . Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.     

TiO2-GO/LDHs复合光催化剂的制备和表征

将钛酸四丁酯与氧化石墨烯/镁铝层状双金属氢氧化物(GO/LDHs)通过水热合成原位生长法制备二氧化钛-氧化石墨烯/镁铝层状双金属氢氧化物(TiO2-GO/LDHs)复合光催化剂,对TiO2、TiO2-GO和TiO2-GO/LDHs的物相结构和表面形态进行表征。模拟太阳光条件下催化剂对有机染料罗丹明B和抗生素四环素的光催化降解效果。结果显示,GO的加入使TiO2颗粒分散的更加均匀,不易团聚。TiO2-GO对罗丹明B的降解效果优于单一TiO2,表明GO的加入扩展了TiO2的光响应范围,抑制了电子-空穴对的复合。TiO2-GO/LDHs的降解效果优于TiO2-GO,表明LDH捕获光生空穴,加速氧化反应,生成更多的强氧化性羟基,可以更好地降解污染物。     

柔性钙钛矿太阳能电池的制备及性能研究

采用钛箔作为衬底,原位生长二氧化钛薄膜,然后制备有机钙钛矿吸收层及固态空穴传输层,组装成太阳能电池。通过电压-电流曲线测试,结果表明,这种钙钛矿太阳能电池的光生电压达到0.8 V、光生电流达到16 mA/cm²、光电转化效率为10.2%。进一步对电池进行弯折试验,弯折20次后,光电转化效率能达到初始值的85%,表现出良好的柔性特征。     

An efficient and low-cost TiO2 compact layer for performance improvement of dye-sensitized solar cells

A TiO₂ organic sol was synthesised for the preparation of a compact TiO₂ layer on fluorine-doped tin oxide (FTO) glass by a dip-coating technique. The resultant thin film was used for the fabrication of dye-sensitized solar cells (DSSCs). The compact layer typically has a thickness of ca. 110 nm as indicated by its SEM, and consists of anatase as confirmed by the XRD pattern. Compared with the traditional DSSCs without this compact layer, the solar energy-to-electricity conversion efficiency, short-circuit current and open-circuit potential of the DSSCs with the compact layer were improved by 33.3%, 20.3%, and 10.2%, respectively. This can be attributed to the merits brought by the compact layer. It can effectively improve adherence of TiO₂ to FTO surface, provide a larger TiO₂/FTO contact area, and reduce the electron recombination by blocking the direct contact between the redox electrolyte and the conductive FTO surface.     

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。     

烧结剂对新疆粉煤灰中锂浸出的作用特性

以新疆燃煤电站典型粉煤灰为研究对象,应用不同烧结剂与粉煤灰分别混合高温煅烧,通过盐酸和硫酸浸出锂,研究了烧结剂种类、煅烧温度、烧结剂添加量、浸出剂种类对锂浸出的影响。另外本文将微波技术应用于锂的浸出,对比研究了微波加热及传统水浴加热对锂浸出的效果。结果表明：碳酸钾、碳酸钠、乙酸钠、氯化钠作为烧结剂活化粉煤灰使锂的浸出效果较好;对于碳酸钠和碳酸氢钠等浸出效果较好的烧结剂,800℃较适宜作为其煅烧温度;盐酸比硫酸溶液更适合作为浸出剂浸出粉煤灰中的锂;微波加热对锂浸出有非常大的优势,微波4min比水浴4h 锂浸出量增加了55%;碳酸钠与碳酸钾混合烧结剂比单一烧结剂表现出更好的活化性能,应用30%碳酸钠和70%碳酸钾混合烧结剂煅烧活化粉煤灰后使灰中锂的浸出率达93%。     

TiO2纳米管阵列的制备改性及应用研究进展

TiO₂纳米管阵列作为一种新型的三维立体纳米材料,因其大的比表面积及特殊的几何结构而受到了广泛的关注与研究。本文回顾了近年来阳极氧化法在Ti基底上原位生成TiO₂纳米管阵列所用电解液的发展趋势,介绍了TiO₂纳米管阵列的特性,如晶型结构、光学和电学特性以及催化活性,阐述了TiO₂纳米管阵列的金属离子掺杂、非金属离子掺杂、金属沉积、导电聚合物复合、半导体复合以及其他等多种改性手段,探讨了TiO₂纳米管阵列在光电催化降解污染物、光解水制氢、染料敏化太阳能电池和传感器以及其他多个领域的应用研究进展。最后,展望了TiO₂纳米管阵列的主要研究方向是对其形貌调控与表面改性等方面作进一步研究,以期为后续研究提供参考依据。     

The effect of the hydrothermal treatment with aqueous NaOH solution on the photocatalytic and photoelectrochemical properties of visible light-responsive TiO2 thin films

The effect of the hydrothermal treatment with aqueous NaOH solution on the photoelectrochemical and photocatalytic properties of visible light-responsive TiO₂ thin films prepared on Ti foil substrate (Vis-TiO₂/Ti) by a radio-frequency magnetron sputtering (RF-MS) deposition method has been investigated. The hydrothermally treated Vis-TiO₂/Ti electrodes exhibited a significant increase in their photocurrent under UV and visible light irradiation as compared to untreated Vis-TiO₂/Ti electrode. SEM investigations revealed that the surface morphology of Vis-TiO₂/Ti are drastically changed from the assembly of the TiO₂ crystallites to the stacking of nanowires with diameters of 30–50 nm with increasing hydrothermal treatment time (3–24 h), accompanying the increase in their surface area. The separate evolution of H₂ and O₂ from water under solar light irradiation was successfully achieved using the Vis-TiO₂/Ti/Pt which is hydrothermally treated for 5 h, while the H₂ evolution ratio was 15 μmol h⁻¹ in the early initial stage, corresponding to a solar energy conversion efficiency of 0.23%.     

碳酸银光催化性能研究

银系光催化剂制备方法简单且带隙较窄,在可见光照射下具有良好的光催化效果,因此受到人们的广泛关注。以罗丹明B为降解物,在模拟可见光条件下利用碳酸银进行光催化降解实验,比较同等条件下碳酸银和二氧化钛的光催化性能,探究了碳酸银在不同pH、降解物质量浓度和催化剂投加量条件下的光催化活性,并利用总有机碳（TOC）分析矿化程度。通过X射线衍射仪（XRD）、激光拉曼光谱仪（RRS）、傅里叶变换红外光谱仪（FT-IR）和紫外吸收光谱仪（UV-Vis）对碳酸银进行表征并分析其晶相组成。结果表明,在同等条件下碳酸银对罗丹明B的光催化降解速率远大于二氧化钛,并且在溶液pH小于7、碳酸银投加量为 1 g/L条件下催化剂对质量浓度为5 mg/L的罗丹明B染料的光催化降解效果最好,紫外灯照射100 min后罗丹明B染料降解率达到98%以上,最终矿化率达到66%。     

Large-area TiO2 nanotube dye-sensitized solar cells using thermal-sprayed Ti layers on stainless steel

This work presents large-scale dye-sensitized solar cells and methods for their manufacture. A dye-sensitized solar cell device contains a photosensitive dye adsorbed on a large surface of the anode, and a transparent conductive cathode disposed opposite the anode, wherein platinum nano-catalytic particles adhere to its surface, and an electrolytic solution is sealed between the anode and the transparent conductive cathode. A titania nanotube film was fabricated by thermo-spraying titanium film on 304 stainless-steel substrate. The photo-current conversion efficiency was tested under an AM 1.5 solar simulator. The dye-sensitized solar cell device has a short current density of 8.22 mA cm^–2, open voltage of 0.71 V, fill factor of 0.59, and conversion efficiency of 3.4%. The internal impedance of the dye-sensitized solar cell was detected and simulated using an electrical impedance spectra technique with inductance, resistance, and capacitance characteristics. The stainless-steel/titania, titania/electrolyte, electrolyte, and electrolyte/(platinum/indium tin oxide) interfaces were simulated using an resistor–capacitor parallel circuit, and bulk materials such as stainless steel, tin doped indium oxide, and conducting wire were simulated by using a series of resistors and inductance.     

Unravelling the bottleneck of phosphonic acid anchoring groups aiming toward enhancing the stability and efficiency of mesoscopic solar cells

Novel near-infrared sensitizers with different anchoring groups aiming toward improved stability and efficiency of dye-sensitized solar cells were synthesized. Adsorption of these dyes on the mesoporous TiO₂ surface revealed the dye adsorption rate of –CH=CH–COOH (SQ-139)>–CH=C(CN)COOH (SQ-140)>–PO₃H₂ (SQ-143)>–CH=C(CN)PO₃H₂ (SQ-148)>–CH=C(CN)PO₃H–C₂H₅ (SQ-157)>–PO₃H–C₂H₅ (SQ-151)> –CH=CH–COOH(–PO₃H₂) (SQ-162). The binding strength of these dyes on mesoporous TiO₂ as investigated by dye desorption studies follows SQ-162>SQ-143>SQ-148>SQ-139≫SQ-157~SQ-151≫SQ-140 order. The acrylic acid anchoring group was demonstrated to be an optimum functional group owing to its fast dye adsorption rate and better binding strength on TiO₂ along with good photoconversion efficiency. Results of dye binding on TiO₂ surface demonstrated that SQ-162 bearing double anchoring groups of phosphonic and acrylic acid exhibited>550 times stronger binding as compared to dye SQ-140 having cyanoacrylic acid anchoring group. SQ-140 exhibited the best photovoltaic performance with photon harvesting mainly in the far-red to near-infrared wavelength region having short circuit current density, open-circuit voltage and fill factor of 14.28 mA·cm^–2, 0.64 V and 0.65, respectively, giving the power conversion efficiency of 5.95%. Thus, dye SQ-162 not only solved the problem of very poor efficiency of dye bearing only phosphonic acid while maintaining the extremely high binding strength opening the path for the design and development of novel near-infrared dyes with improved efficiency and stability by further increasing the π-conjugation.     

TPR and infrared measurements with cu/zno/al2o3 based catalysts for the synthesis of methanol and higher alcohols from co + h2

The influence of different promoters (CeO₂, MnO_x, K₂CO₃) on various properties of a standard coprecipitated Cu/ZnO/Al₂O₃ catalyst has been examined. The catalysts prepared were characterized by Cu surface area, PTIR and TPR measurements. It was found that addition of K₂CO₃ reduced the Cu surface area by about 30%, whereas the Cu surface area did not decrease with addition of the other promoters. The reduction behaviour was affected by the addition of K₂CO₃ as well as by MnO_x, but not by CeO₂. The cause of these effects is possibly an electronic interaction between the promoter and Cu ions.The effect of the different promoters on the activity and selectivity has also been studied. The K₂CO₃ promoted catalyst has an optimum selectivity to higher alcohols at 280 °C; addition of Mn made the catalyst more selective towards methanol. At 300 °C, the Ce promoted catalyst had a high selectivity to methanol and iso-butanol. The promoting effect of the additives may be caused by stabilization of the surface intermediates leading to alcohols. Infrared measurements of adsorbed CO or adsorbed methanol on materials with and without K did not, however, provide any evidence for a difference in reaction mechanism.     

C2H2 oxidation by plasma/TiO2 combination: Influence of the porosity, and photocatalytic mechanisms under plasma exposure

Plasma/catalyst combination is an active solution to reach high conversion rates at low energetic cost. TiO₂ is one of the catalysts frequently used in dielectric barrier discharges. Plasma/TiO₂ synergy was already exhibited but the mechanisms still have to be understood. This work distinguishes three main effects involved in the synergy: (a) effect of catalyst on the injected power, (b) the effect of porosity on C₂H₂ oxidation, and (c) the photocatalytic degradation of C₂H₂ on TiO₂ under plasma exposure. Different glass fibres-based catalytic materials coated with SiO₂ and/or TiO₂ nano-particles are used to separate these three contributions regarding to C₂H₂ conversion. It is reported that at constant voltage the injected power is mainly increased by the presence of glass fibres. C₂H₂ oxidation is mainly enhanced by the macroporosity of glass fibres and in a minor way by the nano-particles. The production of O atoms close to the surface is probably responsible for the higher C₂H₂ removal efficiency with porous material. The photocatalytic activity of TiO₂ is negligible in the plasma except if additional UV lamps are used to activate TiO₂. With external UV, photocatalytic activity is more efficient in the plasma phase than in a neutral gas phase. This plasma/photocatalysis synergy is due to the use of O atoms in photocatalytic mechanisms.