Nanosized Anatase TiO2 Single Crystals with Tunable Exposed (001) Facets for Enhanced Energy Conversion Efficiency of Dye‐Sensitized Solar Cells

This paper reports the synthesis of nanosized TiO₂ single crystals with different percentages of exposed (001) facets in the presence of HF solution. Various characterizations are conducted to understand the correlation between particle morphology, exposed (001) facets and photo‐conversion efficiency of the nanosized anatase TiO₂ single crystals. An enhancement in dye‐sensitized solar cells (DSSCs) overall conversion efficiency is observed for the photoanode consisting of nanosized TiO₂ single crystals with higher percentage of exposed (001) facets, increasing from 7.47%, 8.14% to 8.49% for the TiO₂ single crystals with ca. 10%, 38%, and 80% percentage of exposed (001) facets. Experimentally confirmed by dark current potential and open‐circuit voltage decay scans, such highly exposed (001) facets are not only favorable for more dye adsorption but also effectively retard the charge recombination process in DSSCs.     

Oxygen Vacancies Evoked Blue TiO2(B) Nanobelts with Efficiency Enhancement in Sodium Storage Behaviors

Oxygen vacancies (OVs) dominate the physical and chemical properties of metal oxides, which play crucial roles in the various fields of applications. Density functional theory calculations show the introduction of OVs in TiO₂(B) gives rise to better electrical conductivity and lower energy barrier of sodiation. Here, OVs evoked blue TiO₂(B) (termed as B‐TiO₂(B)) nanobelts are successfully designed upon the basis of electronically coupled conductive polymers to TiO₂, which is confirmed by electron paramagnetic resonance and X‐ray photoelectron spectroscopy. The superiorities of OVs with the aid of carbon encapsulation lead to higher capacity (210.5 mAh g^?1 (B‐TiO₂(B)) vs 102.7 mAh g^?1 (W‐TiO₂(B)) at 0.5 C) and remarkable long‐term cyclability (the retention of 94.4% at a high rate of 10 C after 5000 times). In situ X‐ray diffractometer analysis spectra also confirm that an enlarged interlayer spacing stimulated by OVs is beneficial to accommodate insertion and removal of sodium ions to accelerate storage kinetics and preserve its original crystal structure. The work highlights that injecting OVs into metal oxides along with carbon coating is an effective strategy for improving capacity and cyclability performances in other metal oxide based electrochemical energy systems.     

Shape‐ and Size‐Controlled Synthesis of Uniform Anatase TiO2 Nanocuboids Enclosed by Active {100} and {001} Facets

Uniform anatase TiO₂ nanocuboids enclosed by active {100} and {001} facets over a wide size range (60–830 nm in length) with controllable aspect ratios were solvothermally synthesized through hydrolysis of titanium tetraisopropoxide (TTIP) using acetic acid (HAc) as the solvent and the ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim][BF₄]) as the capping agent. The size and aspect ratio of the anatase TiO₂ nanocuboids can be readily adjusted by changing the composition parameters including the contents of [bmim][BF₄], water, and HAc in the quaternary solution system. It was revealed that [bmim][BF₄] played an important role in stabilizing both the {100} and {001} facets of the anatase TiO₂ nanocuboids. On the one hand, [bmim][BF₄] acted as a fluoride source to release F^? ions for stabilizing the {001} facets; on the other hand, the [bmim]⁺ ions acted as effective capping ions to preferentially stabilize the {100} facets. The obtained near‐monodisperse anatase TiO₂ nanocuboids exhibited an interesting self‐assembly behavior during deposition. These single‐crystalline anatase nanocuboids showed extremely high crystalline phase stability, retaining the pure phase of anatase as well as the morphology even after being calcined at 900 °C. Moreover, the anatase nanocuboids exhibited considerably enhanced photocatalytic activity owing the wholly exposed active {100} and {001} facets.     

Trifunctional TiO2 Nanoparticles with Exposed {001} Facets as Additives in Cobalt‐Based Porphyrin‐Sensitized Solar Cells

In this study, highly mesoporous TiO₂ composite photoanodes composed of functional {001}‐faceted TiO₂ nanoparticles (NPs) and commercially available 20 nm TiO₂ NPs are employed in efficient porphyrin‐sensitized solar cells together with cobalt polypyridyl‐based mediators. Large TiO₂ NPs (approximately 50 nm) with exposed {001} facets are prepared using a fast microwave‐assisted hydrothermal (FMAH) method. These unique composite photoanodes favorably mitigate the aggregation of porphyrin on the surface of TiO₂ NPs and strongly facilitate the mass transport of cobalt‐polypyridyl‐based electrolytes in the mesoporous structure. Linear sweep voltammetry reveals that the transportation of Co(polypyridyl) redox is a diffusion‐controlled process, which is highly dependent on the porosity of TiO₂ films. Electrochemical impedance spectroscopy confirms that the FMAH TiO₂ NPs effectively suppress the interfacial charge recombination toward [Co(bpy)₃]³⁺ because of their oxidative {001} facets. In an optimal condition of 40 wt% addition of FMAH TiO₂ NPs in the final formula, the power conversion efficiency of the dye‐sensitized cells improves from 8.28% to 9.53% under AM1.5 (1 sun) conditions.     

Improved Photocatalytic Performance of Heterojunction by Controlling the Contact Facet: High Electron Transfer Capacity between TiO2 and the {110} Facet of BiVO4 Caused by Suitable Energy Band Alignment

Charge separation at the interface of heterojunctions is affected by the energy band alignments of the materials that compose the heterojunctions. Controlling the contact crystal facets can lead to different energy band alignments owing to the varied electronic structures of the different crystal facets. Therefore, BiVO₄‐TiO₂ heterojunctions are designed with different BiVO₄ crystal facets at the interface ({110} facet or {010} facet), named BiVO₄‐110‐TiO₂ and BiVO₄‐010‐TiO₂, respectively, to achieve high photocatalytic performance. Higher photocurrent density and lower photoluminescence intensity are observed with the BiVO₄‐110‐TiO₂ heterojunction than those of the BiVO₄‐010‐TiO₂ heterojunction, which confirms that the former possesses higher charge carrier separation capacity than the latter. The photocatalytic degradation results of both Rhodamine B and 4‐nonylphenol demonstrate that better photocatalytic performance is achieved on the BiVO₄‐110‐TiO₂ heterojunction than the BiVO₄‐010‐TiO₂ heterojunction under visible light (≥422 nm) irradiation. The higher electron transfer capacity and better photocatalytic performance of the BiVO₄‐110‐TiO₂ heterojunction are attributed to the more fluent electron transfer from the {110} facet of BiVO₄ to TiO₂ caused by the smaller interfacial energy barrier. This is further confirmed by the selective deposition of Pt on the TiO₂ surface as well as the longer lifetime of Bi⁵⁺ in the BiVO₄‐110‐TiO₂ heterojunction.     

High Reversible Pseudocapacity in Mesoporous Yolk–Shell Anatase TiO2/TiO2(B) Microspheres Used as Anodes for Li‐Ion Batteries

As an anode material for lithium‐ion batteries, titanium dioxide (TiO₂) shows good gravimetric performance (336 mAh g^?1 for LiTiO₂) and excellent cyclability. To address the poor rate behavior, slow lithium‐ion (Li⁺) diffusion, and high irreversible capacity decay, TiO₂ nanomaterials with tuned phase compositions and morphologies are being investigated. Here, a promising material is prepared that comprises a mesoporous “yolk–shell” spherical morphology in which the core is anatase TiO₂ and the shell is TiO₂(B). The preparation employs a NaCl‐assisted solvothermal process and the electrochemical results indicate that the mesoporous yolk–shell microspheres have high specific reversible capacity at moderate current (330.0 mAh g^?1 at C/5), excellent rate performance (181.8 mAh g^?1 at 40C), and impressive cyclability (98% capacity retention after 500 cycles). The superior properties are attributed to the TiO₂(B) nanosheet shell, which provides additional active area to stabilize the pseudocapacity. In addition, the open mesoporous morphology improves diffusion of electrolyte throughout the electrode, thereby contributing directly to greatly improved rate capacity.     

Heterojunction of SrTiO3/TiO2 nanotubes with dominant (001) facets: Synthesis,formation mechanism and photoelectrochemical properties

Controllable growth of anatase TiO₂ with dominant high reactive crystal facets has attracted intense interest in the past few years due to their unique structure-dependent properties. In this work, SrTiO₃/TiO₂ heterostructure nanotubes (SrT) arrays films with high reactive dominant (001) facets of anatase TiO₂ were successfully prepared through the part conversion of TiO₂ by a hydrothermal method. Various characterizations were used to investigate the morphologies, crystal phases and chemical compositions of the prepared samples. Structure analyses using X-ray diffraction and a high-resolution transmission electron microscope revealed that, the treatment sequence of hydrothermal reaction and annealing was a crucial influence factor on controlling the growth of preferred orientation of (001) facets of TiO₂ in SrTiO₃/TiO₂ heterojunction, whereas the inverse treatment sequence yielded randomly oriented facets. The formation mechanism of dominant (001) facets of TiO₂ in the heterojunction was related to crystal structures of TiO₂ and SrTiO₃. The heteroepitaxial growth on (001) plane of SrTiO₃ led to dominant (001) facets of anatase TiO₂ attributing to their excellent surface lattices match. The photoelectric performances of pure TiO₂ nanotubes and SrT were investigated by photoluminescence, UV–visible diffuse reflectance, photocurrent and current–voltage response. The semiconductor characteristics of them were studied by electrochemical impedance spectroscopy and Mott–Schottky analysis in detail. The results demonstrated that the heterostructure of SrT not only increased light absorption, but also effectively shifted the Fermi level and promoted charge transfer. Among all the samples, the SrTiO₃/TiO₂ heterojunction prepared by 1 h hydrothermal treatment (1SrT) exhibited the best photoelectrochemical performances due to the synergetic contributions of the high active (001) facets of anatase TiO₂ and the charge transport properties of the heterostructure.     

草酸氧钛酸分解法制备纳米金红石型TiO_2粉体

用硫酸钛与草酸按比例配合 ,析出草酸氧钛酸晶体 ,将其洗涤后在 75 0～ 82 0℃焙烧 ,因草酸氧钛酸分解时 ,其分子中较大部分成分以气体 :CO2 、CO、水蒸气形式挥发到空气中 ,从而固态产物成为纳米级的金红石型二氧化钛粉体。用透射电子显微镜 (TEM)测定 ,其粒径范围为 10～ 35 nm;用 X射线衍射 (XRD)测定 ,其晶型为金红石型。     

TiO_2(Ag)纳米半导体薄膜的制备及其光催化性能

对热解Ｔｉ（ＯＣ４Ｈ９）４＋ＡｇＮＯ３溶胶制备的ＴｉＯ２（Ａｇ）纳米半导体薄膜光催化特性与其结构的关系进行了研究。薄膜对二卡基砜的光催化降解结果表明,热解温度显著影响薄膜的光催化作用,这与ＴｉＯ２微粒的长大和晶相转变有关;适量的Ａｇ作活性剂可以显著改善薄膜的光催化性能。     

低阻钛酸锶钡基PTC材料的制备与电性能

BaTiO3正温度系数(PTC)陶瓷因其具有较高的室温电阻率而使其在低压领域中的应用受到限制,因此,有必要降低其室温电阻率.低阻化的一个途径是将金属与BaTiO3基PTC陶瓷复合来制备复合PTC材料.采用传统陶瓷工艺制备Ni/(Ba,Sr)TiO3复合PTC材料.为避免金属Ni被氧化,复合材料在弱还原气氛下烧成.为排除烧结气氛的影响而讨论金属Ni的影响,(Ba,Sr)TiO3 PTC陶瓷也在同一弱还原气氛下烧成.PbO-B2O3-ZnO-SiO2系玻璃料的加入改善了复合材料的两相分布,优化了复合材料的性能.     

新型无铅压电陶瓷NBT-NBSN的研究

采用传统陶瓷制备方法,制备出一种钙钛矿结构无铅新压电陶瓷材料(1-x)(Na1/2Bi1/2)TiO3-x(Na1/2Bi1/2)(Sb1/2Nb1/2)O3(x=0~1.4%,摩尔分数)。研究了(Na1/2Bi1/2)TiO3(NBT)陶瓷B位复合离子(Sb1/2Nb1/2)4 取代对介电和压电性能的影响。X-射线衍射分析表明,所研究的组成均能形成纯钙钛矿(ABO3)型固溶体。陶瓷材料的介电常数-温度曲线显示陶瓷在升温过程中存在两个介电常数温度峰,不同频率下陶瓷材料的介电常数-温度曲线显示该体系材料具有明显的弛豫铁电体特征。检测了不同组成陶瓷的压电性能,发现材料的压电常数d33、厚度机电耦合系数kt和介电常数rε随着x值的增加先增加后降低,在x=0.8%时,陶瓷的d33=97 pC/N,kt=0.50,为所研究组成中的最大值,介电损耗tanδ则随x值的增加而增加。     

真空度对VO2(B)型薄膜制备及光电特性的影响

对不同真空度下得到的VO2(B)型薄膜的结品状况、组分、电学性质 和光学性质进行测试和分析,以探讨退火真空度对VO2(B)型薄膜的影响.以高纯五氧化二钒(V2O3)粉末(纯度高于99.99%,质量分数)为原料,采用真 空蒸发——还原工艺,分别在高、低真空度下还原出VO2(B)型(空间群为C2m)薄膜.利用X射线衍射(XRD)仪,X射线光电子能谱仪(XPS),电阻温度关系(TCR)测试仪和紫外可见分光光度计对薄膜进行测试,讨论了退火真空度对VO2(B)刑薄膜的结品状况、组分、电学性质和光学性质的影响.结果显示,在高、低真空度下退火,VO2(B)型薄膜出现的温度范围是不同的,在低真空度下退火出现的范围在400～480℃,而在高真空度下退火出现的范围只有400～440 C;高真空度退火得到薄膜的晶粒较大,透过率较低真空度得到的薄膜高7%～8%;但在低真空度下退火,薄膜中的V更易被还原,电阻温度系数绝对值更大,最大可达-2.4%/K.     

功能晶体材料NaEr（WO4）2单晶的生长与性能研究

首次生长具有白钨结构的NaEr（WO4）2晶体。测量得晶体在UV波段的截止波长为326nm,此NaY(WO4)2(321nm)晶体要长。这是由于Er^3 具有较大的极化力造成的。测量了NaEr(WO4)2红外透过光谱和喇曼光谱,并对晶格振动模式进行了分析。所有这些性质和同结构的NaY（WO4)2晶体进行了比较。     

复合添加ZnO/V_2O_5对(Zr_(0.8)Sn_(0.2))TiO_4陶瓷性能的影响

讨论了复合添加Zn O/V2O5对(Zr0.8Sn0.2)Ti O4介质陶瓷烧结机制和微波介电性能的影响。结果表明:Zn O/V2O5对(Zr0.8Sn0.2)Ti O4的烧结有一定的促进作用,但Zn O/V2O5添加量的增大会造成晶格缺陷和残留气孔增多,从而导致材料的密度和Q×f降低。在1 320℃保温4 h并添加了0.6 wt%Zn O/V2O5的试样具有相对较好的介电性能:εr=36.48,Q×f=16 800 GHz。     

VO2(B)薄膜的制备及特性优化研究

采用直流磁控溅射法,在纯氩气氛中溅射V2O5靶材,在覆盖有氮化硅薄膜的P(100)硅基片表面沉积氧化钒薄膜.对沉积的薄膜进行了后续高真空高温退火处理.利用XRD对薄膜的晶相进行了分析,结果表明退火处理前和退火处理后的薄膜都具有VO2各晶面的取向,XPS分析证明了XRD的物相分析结果.对薄膜的方阻特性的测试表明生成的薄膜是典型的VO2(B)薄膜,退火后的薄膜方阻减小,方阻温度系数也降低.在此基础上,利用薄膜晶界散射理论,通过改变薄膜沉积时间和沉积温度使薄膜的方阻和方阻温度系数随薄膜厚度和晶粒大小而变化,从而使薄膜的电性能达到优化.     

Zn(SCN)_2·2H_2O晶体结构和喇曼光谱的研究

本文报道了一种新的非线性光学晶体Zn(SCN)_2·2H_2O的结构和喇曼光谱。对结构和喇曼光谱的关系进行了讨论。     

Formation of uniform GaAs multi-atomic steps with 20–30 nm periodicity and related structures on vicinal (111)B planes by MBE

We studied morphology of GaAs surfaces and the transport properties of two-dimensional electron gas (2DEG) on vicinal (111)B planes. Multi-atomic steps (MASs) are found on the vicinal (111)B facet grown by molecular beam epitaxy, which will affect electron transport on the facet. We also studied how the morphology of GaAs epilayers on vicinal (111)B substrates depends on growth conditions, especially on the As₄ flux. The uniformity of MASs on the substrates have been improved and smooth surfaces were obtained when the GaAs was grown with high As₄ flux, providing step periodicity of 20 nm. The channel resistance of the 2DEG perpendicular to the MASs is reduced drastically with this smooth morphology. These findings are valuable not only for fabricating quantum devices on the (111)B facets but also those on the vicinal (111)B substrates.