Highly Functional TNTs with Superb Photocatalytic,Optical, and Electronic Performance Achieving Record PV Efficiency of 10.1% for 1D‐Based DSSCs

Different nanostructures of TiO₂ play an important role in the photocatalytic and photoelectronic applications. TiO₂ nanotubes (TNTs) have received increasing attention for these applications due to their unique physicochemical properties. Focusing on highly functional TNTs (HF‐TNTs) for photocatalytic and photoelectronic applications, this study describes the facile hydrothermal synthesis of HF‐TNTs by using commercial and cheaper materials for cost‐effective manufacturing. To prove the functionality and applicability, these TNTs are used as scattering structure in dye‐sensitized solar cells (DSSCs). Photocatalytic, optical, Brunauer‐Emmett‐Teller (BET), electrochemical impedance spectrum, incident‐photon‐to‐current efficiency, and intensity‐modulated photocurrent spectroscopy/intensity‐modulated photovoltage spectroscopy characterizations are proving the functionality of HF‐TNTs for DSSCs. HF‐TNTs show 50% higher photocatalytic degradation rate and also 68% higher dye loading ability than conventional TNTs (C‐TNTs). The DSSCs having HF‐TNT and its composite‐based multifunctional overlayer show effective light absorption, outstanding light scattering, lower interfacial resistance, longer electron lifetime, rapid electron transfer, and improved diffusion length, and consequently, J _SC, quantum efficiency, and record photoconversion efficiency of 10.1% using commercial N‐719 dye is achieved, for 1D‐based DSSCs. These new and highly functional TNTs will be a concrete fundamental background toward the development of more functional applications in fuel cells, dye‐sensitized solar cells, Li‐ion batteries, photocatalysis process, ion‐exchange/adsorption process, and photoelectrochemical devices.     

Enhanced efficiency of tri-layered dye solar cells with hydrothermally synthesized titania nanotubes as light scattering outer layer

In the present study dye sensitized solar cells (DSSCs) have been fabricated with a tri-layer photo anode consisting of hydrothermally prepared titania nano tubes (TNT) having a diameter of 9-10 nm and length of several micrometers as outer layer, P25 TiO₂ powder as transparent light absorbing middle layer and a compact TiO₂ inner layer to improve the adhesion of different layers on a transparent conducting oxide coated substrate. In comparison to cells fabricated using TNTs or P25 alone, the tri-layer DSSCs exhibit an enhanced efficiency of 7.15% with a current density of 17.12 mA cm^− 2 under AM 1.5 illumination. The enhancement is attributed to the light scattering generated by TNTs aggregates, reduction in electron transport resistance at the TiO₂/dye/electrolyte interface and an improvement in electron life-time.     

Sulphur,nitrogen-doped TiO2/graphene oxide composites as a high performance photocatalyst

Sulphur (S), nitrogen (N)-doped TiO₂/graphene oxide (GO) composites were environmentally friendly synthesised using thiourea (CS(NH₂)₂) as a binary-element doping reagent by a simple colloidal blending method. The S, N-doped TiO₂/GO composites show higher photocatalytic degradation rates on methyl orange (MO) compared to TiO₂. The average value of k (the apparent rate constant) for the S, N-doped TiO₂/5%GO (k?=?0.035?min^?1) was found to be eight times higher than that of TiO₂ grown in solution (k?=?0.0038?min^?1) and four times higher than that of P25 (k?=?0.008?min^?1). The investigation showed that the contribution of GO to the high photocatalytic activities of the composites come from its high specific surface area, oxygen-containing functional groups and large aromatic domains that were inclined to be bound by conjugated MO molecules via π–π stacking. The doping of S and N can increase the numbers of photo-generated electrons and holes, which produce more charge carriers to form reactive species, and thus promote the degradation of MO. This work could offer a route to improve the photocatalytic activities of TiO₂ and facilitate their application in reality.     

Au Nanoclusters Sensitized Black TiO2−x Nanotubes for Enhanced Photodynamic Therapy Driven by Near‐Infrared Light

The low reactive oxygen species production capability and the shallow tissue penetration of excited light (UV) are still two barriers in photodynamic therapy (PDT). Here, Au cluster anchored black anatase TiO_2?x nanotubes (abbreviated as Au₂₅/B‐TiO_2?x NTs) are synthesized by gaseous reduction of anatase TiO₂ NTs and subsequent deposition of noble metal. The Au₂₅/B‐TiO_2?x NTs with thickness of about 2 nm exhibit excellent PDT performance. The reduction process increased the density of Ti³⁺ on the surface of TiO₂, which effectively depresses the recombination of electron and hole. Furthermore, after modification of Au₂₅ nanoclusters, the PDT efficiency is further enhanced owing to the changed electrical distribution in the composite, which forms a shallow potential well on the metal–TiO₂ interface to further hamper the recombination of electron and hole. Especially, the reduction of anatase TiO₂ can expend the light response range (UV) of TiO₂ to the visible and even near infrared (NIR) light region with high tissue penetration depth. When excited by NIR light, the nanoplatform shows markedly improved therapeutic efficacy attributed to the photocatalytic synergistic effect, and promotes separation or restrained recombination of electron and hole, which is verified by experimental results in vitro and in vivo.     

Crystal structure and photocatalytic properties of titanate nanotubes prepared by chemical processing and subsequent annealing

Anatase TiO₂ nanoparticles were synthesized from sol–gel processing, and they were used as a precursor for titanate nanotubes (TNT) formation. TNT were synthesized under reflux heating of anatase TiO₂ in concentrated NaOH solution followed by repeated washing with distilled water and 0.1 M HCl. The nanotubular structure was preserved till 450 °C, above which nanorod formation started. The as-synthesized nanotubes were found to have mixed crystal structure of anatase and Na _x H_2?x Ti₃O₇·nH₂O (where 0 < x <  2), contrary to what has been reported before. The XRD peaks of titanate were slightly shifted to higher angles upon calcination along with prominent anatase peaks. Complete transformation to nanorods occurred at 600 °C and crystal structure was transformed to Na₂Ti₆O₁₃ and anatase. Sodium presence in TNT was confirmed by EDX, and Na–O and H–O–H along with Ti–OH vibrations were found by FTIR. Ti–OH/H–O–H vibrations were less prominent for samples calcined at 500 °C and above, which confirms structural water loss is associated with morphological change. The as-synthesized TNTs had a specific surface area of 157 m² g^?1, and it decreased by increasing calcination temperature. TNTs were applied to methylene blue aqueous solution to observe their decolorization capability under UV irradiation. The as-synthesized TNTs showed enhanced photocatalytic decolorization as compared to anatase titania nanoparticles due to presence of Ti–OH groups and higher specific surface area. The photocatalytic activity reduced when TNTs were annealed at high temperatures. The changes in the photocatalytic activity are related to the existence of hydroxyl groups in the structure, decrease in specific surface area of annealed nanotubes, change in morphology from nanotubes to nanorods, and bandgap shift to visible light when TNTs were calcined at higher temperatures.     

Successive nucleation and a rodlike growth of SiOx nanoparticles into the pore bottoms of an anodic alumina template

Although the SiO_x nanoparticles were previously reported to electrochemically nucleate from the bottoms of the pore array formed in the AAO/Ti/Si system, new applications of anodic aluminum oxide templates, i.e., successive nucleation and a rodlike growth of SiO_x nanoparticles, were observed utilizing the subsequent annealing technique after the nanoparticle precipitation. Tailoring the pore bottom profile by doping type and level of wafers also critically affected to nucleate the SiO_x nanoparticles from the pore bottoms. By anodization, as previously reported, only one nanoparticle per each pore was generally precipitated from the pyramid-shaped Si-containing TiO_x nanopillars; however, subsequent annealing under a low pressure of hydrogen enabled the successive precipitation of nanoparticles. Annealing under atmospheric pressure with H₂ and N₂ resulted in the rodlike growth of a single nanoparticle without successive nanoparticle precipitation.     

Substitutional Carbon‐Modified Anatase TiO2 Decahedral Plates Directly Derived from Titanium Oxalate Crystals via Topotactic Transition

Changing the composition and/or structure of some metal oxides at the atomic level can significantly improve their performance in different applications. Although many strategies have been developed, the introduction of heteroatoms, particularly anions to the internal part of metal oxide particles, is still not adequate. Here, an effective strategy is demonstrated for directly preparing polycrystalline decahedral plates of substitutional carbon‐doped anatase TiO₂ from titanium (IV) oxalate by a thermally induced topotactic transition in an inert atmosphere. Because of the carbon concentration gradient introduced in side of the plates, the carbon‐doped TiO₂ (TiO_2–xC_x) shows an increased visible light absorption and a two orders of magnitude higher electrical conductivity than pure TiO₂. Consequently, it can be used as a photocatalyst and an active material for lithium storage and shows much superior activity in generating hydroxyl radicals under visible light and greatly increased electrical‐specific capacity at high charge–discharge rates. The strategy developed could also be applicable to the atomic‐scale modification of other metal oxides.     

Preparation and characterization of titanate nanotubes/carbon composites

Titanate nanotubes/carbon composites(TNT/CCs) were synthesized by allowing carbon-coated TiO₂ (CCT) powder to react with a dense aqueous solution of NaOH at 120 °C for a proper period of time. As-prepared CCT and TNT/CCs were characterized by means of transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectrometry. The processes for formation of titanate nanotubes/carbon composites were discussed. It was found that the TiO₂ particles in TiO₂-carbon composite were enwrapped by a fine layer of carbon with a thickness of about 4 nm. This carbon layer functioned to inhibit the transformation from anatase TiO₂ to orthorhombic titanate. As a result, the anatase TiO₂ in CCT was incompletely transformed into orthorhombic titanate nanotubes upon 24 h of reaction in the dense and hot NaOH solution. When the carbon layers were gradually peeled off along with the formation of more orthorhombic titanate nanotubes at extended reaction durations (e.g., 72 h), anatase TiO₂ particles in CCT were completely transformed into orthorhombic titanate nanotubes, yielding TNT/CCs whose morphology was highly dependent on the reaction time and temperature.     

Microstructure and Optical Properties of Tantalum Modified TiO<Subscript>2</Subscript> Thin Films Prepared by the Sol–Gel Process

Tantalum doped TiO₂ thin films ((TiO₂)_1−x (Ta₂O₅) _x , x=0, 0.1%, 0.3%, 0.5%, 0.8%) were prepared on ITO-coated substrates by means of the sol–gel method and spin coating technology followed by rapid thermal annealing treatment (RTA). The effects of various processing parameters, including Ta content (x=0–0.8%) and annealing temperature, on the growth and properties of thin films were investigated. Structural characteristics by X-ray diffraction analysis indicated that the doping of Ta₂O₅ in the TiO₂ without change the anatase structure of TiO₂ thin films. The optical transmittance of (TiO₂)_1−x (Ta₂O₅) _x thin films decrease from 50% down to 20% with increasing the Ta₂O₅ concentrations from x=0.00 to x=0.8%. The absorption coefficient shows energy gap were decreased with increasing Ta₂O₅ content from 2.932 eV for x=0.00 to 2.717 eV for x=0.8%. Doping TiO₂ with Ta₂O₅ can lower its band gap and shift its optical response to the visible region.     

Synthesis of TiO2 nanotube films via pulsed laser deposition followed by a hydrothermal treatment

Titanium dioxide nanotube (TNT) films were prepared by pulsed laser deposition (PLD) of P25 and P90 TiO₂ nanoparticles onto stainless steel foils followed by a hydrothermal treatment (HT). Heating the PLD films in a TNT precursor solution at 150°C resulted in a well-adhered dense mat of TNTs that were ～10?nm in diameter with a pore size of ～4?nm. The TiO₂ nanotube films were characterised by SEM, TEM, XRD and Raman spectroscopy.     

Plasma‐Induced Amorphous Shell and Deep Cation‐Site S Doping Endow TiO2 with Extraordinary Sodium Storage Performance

Structural design and modification are effective approaches to regulate the physicochemical properties of TiO₂, which play an important role in achieving advanced materials. Herein, a plasma‐assisted method is reported to synthesize a surface‐defect‐rich and deep‐cation‐site‐rich S doped rutile TiO₂ (R‐TiO_2–x‐S) as an advanced anode for the Na ion battery. An amorphous shell (≈3 nm) is induced by the Ar/H₂ plasma, which brings about the subsequent high S doping concentration (≈4.68 at%) and deep doping depth. Experimental results and density functional theory calculations demonstrate greatly facilitated ion diffusion, improved electronic conductivity, and an increased mobility rate of holes for R‐TiO_2?x‐S, which result in superior rate capability (264.8 and 128.5 mAh g^?1 at 50 and 10 000 mA g^?1, respectively) and excellent cycling stability (almost 100% retention over 6500 cycles). Such improvements signify that plasma treatment offers an innovative and general approach toward designing advanced battery materials.     

Ultrafast Flame Annealing of TiO2 Paste for Fabricating Dye‐Sensitized and Perovskite Solar Cells with Enhanced Efficiency

Mesoporous TiO₂ nanoparticle (NP) films are broadly used as electrodes in photoelectrochemical cells, dye‐sensitized solar cells (DSSCs), and perovskite solar cells (PSCs). State‐of‐the‐art mesoporous TiO₂ NP films for these solar cells are fabricated by annealing TiO₂ paste‐coated fluorine‐doped tin oxide glass in a box furnace at 500 °C for ≈30 min. Here, the use of a nontraditional reactor, i.e., flame, is reported for the high throughput and ultrafast annealing of TiO₂ paste (≈1 min). This flame‐annealing method, compared to conventional furnace annealing, exhibits three distinct benefits. First, flame removes polymeric binders in the initial TiO₂ paste more completely because of its high temperature (≈1000 °C). Second, flame induces strong interconnections between TiO₂ nanoparticles without affecting the underlying transparent conducting oxide substrate. Third, the flame‐induced carbothermic reduction on the TiO₂ surface facilitates charge injection from the dye/perovskite to TiO₂. Consequently, when the flame‐annealed mesoporous TiO₂ film is used to fabricate DSSCs and PSCs, both exhibit enhanced charge transport and higher power conversion efficiencies than those fabricated using furnace‐annealed TiO₂ films. Finally, when the ultrafast flame‐annealing method is combined with a fast dye‐coating method to fabricate DSSC devices, its total fabrication time is reduced from over 3 h to ≈10 min.     

Synthesis of H2Ti2O3·H2O nanotubes and their effects on the flame retardancy of bamboo fiber/high-density polyethylene composites

H₂Ti₂O₃·H₂O nanotubes (TNTs) were prepared through hydrothermal synthesis and dispersed in bamboo fiber/HDPE (BH) composites to improve the flame retardancy of the composites. TEM observation showed that TiO₂ particles were transformed into TNTs through hydrothermal treatment at 120 °C for 12 h in 8 M NaOH solution. Then, a cone calorimeter and a limiting oxygen index chamber were used to evaluate the effects of the TNTs on the flame retardancy of the BH composites. Results demonstrated that TNTs definitely improved the flame retardancy of BH composites by absorbing decomposition products from combustion due to its large specific area and tubular structure. Additionally, the TNTs reduced the free volume in the microzone, strengthened the molecular chain rigidity, and then contributed to the thermostability and flame retardancy of the BH composites.     

Nano Titanium Monoxide Crystals and Unusual Superconductivity at 11 K

Nano TiO₂ is investigated intensely due to extraordinary photoelectric performances in photocatalysis, new‐type solar cells, etc., but only very few synthesis and physical properties have been reported on nanostructured TiO or other low valent titanium‐containing oxides. Here, a core–shell nanoparticle made of TiO core covered with a ≈5 nm shell of amorphous TiO_1+x is newly constructed via a controllable reduction method to synthesize nano TiO core and subsequent soft oxidation to form the shell (TiO_1+x). The physical properties measurements of electrical transport and magnetism indicate these TiO@TiO_1+x nanocrystals are a type‐?? superconductor of a recorded T_c^onset = 11 K in the binary Ti–O system. This unusual superconductivity could be attributed to the interfacial effect due to the nearly linear gradient of O/Ti ratio across the outer amorphous layer. This novel synthetic method and enhanced superconductivity could open up possibilities in interface superconductivity of nanostructured composites with well‐controlled interfaces.     

Selective Growth of Metal‐Free Metallic and Semiconducting Single‐Wall Carbon Nanotubes

A major obstacle for the use of single‐wall carbon nanotubes (SWCNTs) in electronic devices is their mixture of different types of electrical conductivity that strongly depends on their helical structure. The existence of metal impurities as a residue of a metallic growth catalyst may also lower the performance of SWCNT‐based devices. Here, it is shown that by using silicon oxide (SiO_x) nanoparticles as a catalyst, metal‐free semiconducting and metallic SWCNTs can be selectively synthesized by the chemical vapor deposition of ethanol. It is found that control over the nanoparticle size and the content of oxygen in the SiO_x catalyst plays a key role in the selective growth of SWCNTs. Furthermore, by using the as‐grown semiconducting and metallic SWCNTs as the channel material and source/drain electrodes, respectively, all‐SWCNT thin‐film transistors are fabricated to demonstrate the remarkable potential of these SWCNTs for electronic devices.     

Supercapacitor Electrodes Based on Hierarchical Mesoporous MnOx/Nitrided TiO2 Nanorod Arrays on Carbon Fiber Paper

Metal nitride nanoarrays are attractive to electrochemical energy storage and in this work, hierarchical mesoporous manganese oxide (MnO_x) nanoflakes and nitrided TiO₂ nanorod arrays (NTNA) are prepared on carbon fiber paper (CFP) by hydrothermal synthesis and electrodeposition. The MnO_x/NTNA/CFP electrode delivers outstanding electrochemical performance such as high areal capacitance of 327 mF cm⁻² at a current density of 0.25 mA cm⁻² and good cycling stability with 96% retention after 5000 cycles. Compared to the MnO_x/TiO₂/CFP and MnO_x/CFP electrodes, the MnO_x/NTNA/CFP electrode possesses better electrochemical properties such as higher areal capacitance, better electrochemical activity, and cycling life. The enhanced performance can be attributed to the nitrided TiO₂ nanorod arrays with higher conductivity offering low electrochemical impedance and fast ion/electron transfer. The MnO_x/NTNA/CFP electrode is a promising candidate in high‐performance supercapacitor applications.     

Aerosol‐Assisted Heteroassembly of Oxide Nanocrystals and Carbon Nanotubes into 3D Mesoporous Composites for High‐Rate Electrochemical Energy Storage

Nanostructured composites built from ordinary building units have attracted much attention because of their collective properties for critical applications. Herein, we have demonstrated the heteroassembly of carbon nanotubes and oxide nanocrystals using an aerosol spray method to prepare nanostructured mesoporous composites for electrochemical energy storage. The designed composite architectures show high conductivity and hierarchically structured mesopores, which achieve rapid electron and ion transport in electrodes. Therefore, as‐synthesized carbon nanotube/TiO₂ electrodes exhibit high rate performance through rapid Li⁺ intercalation, making them suitable for ultrafast energy storage devices. Moreover, the synthesis process provides a broadly applicable method to achieve the heteroassembly of vast low‐dimensional building blocks for many important applications.     

Rational Design of Three‐Layered TiO2@Carbon@MoS2 Hierarchical Nanotubes for Enhanced Lithium Storage

Here we demonstrate the rational design and synthesis of three‐layered TiO₂@carbon@MoS₂ hierarchical nanotubes for anode applications in lithium‐ion batteries (LIBs). Through an efficient step‐by‐step strategy, ultrathin MoS₂ nanosheets are grown on nitrogen‐doped carbon (NC) coated TiO₂ nanotubes to achieve the TiO₂@NC@MoS₂ tubular nanostructures. This smart design can effectively shorten the diffusion length of Li⁺ ions, increase electric conductivity of the electrode, relax volume variation of electrode materials upon cycling, and provide more active sites for electrochemical reactions. Owing to these structural and compositional features, the hierarchical TiO₂@NC@MoS₂ nanotubes manifest remarkable lithium storage performance with good rate capability and long cycle life.     

Metal Cation‐Assisted Synthesis of Amorphous B,N Co‐Doped Carbon Nanotubes for Superior Sodium Storage

Nearly inexhaustible sodium sources on earth make sodium ion batteries (SIBs) the best candidate for large‐scale energy storage. However, the main obstacles faced by SIBs are the low rate performance and poor cycle stability caused by the large size of Na⁺ ions. Herein, a universal strategy for synthesizing amorphous metals encapsulated into amorphous B, N co‐doped carbon (a‐M@a‐BCN; M = Co, Ni, Mn) nanotubes by metal cation‐assisted carbonization is explored. The methodology allows tailoring the structures (e.g., length, wall thickness, and metals doping) of a‐M@a‐BCN nannotubes at the molecular level. Furthermore, the amorphous metal sulfide encapsulated into a‐BCN (a‐MS_x@a‐BCN; MS_x: CoS, Ni₃S₂, MnS) nanotubes are obtained by one‐step sulfidation process. The a‐M@a‐BCN and a‐MS_x@a‐BCN possess the larger interlayer spacing (0.40 nm) amorphous carbon nanotube rich in heteroatoms active sites, making them exhibit excellent Na⁺ ions diffusion kinetics and capacitive storage behavior. As SIBs anodes, they show high capacity, excellent rate performance, and long cycle stability.     

Scalable production of ultra small TiO2 nano crystal/activated carbon composites by atomic layer deposition for efficient removal of organic pollutants

A high surface area photo-catalytic composite material is synthesized by depositing thin films of titanium dioxide (TiO₂) on activated carbon (AC) particles using atomic layer deposition (ALD). A rotary ALD reactor is developed for scalable fabrication of powder and grams of the catalyst is prepared in each batch. The processes of TiO₂ ALD are monitored by mass spectrometry. Saturated ALD surface reactions are confirmed so that the entire surface of the AC support is covered by conformal coatings of TiO₂. For composites fabricated by 3 or more ALD cycles of TiO₂, the amorphous oxide layers can be converted to crystalline films by high temperature annealing. The as-prepared TiO₂/AC composites are highly reactive in photo-catalyzed degradation of methyl orange. The excellent catalytic performance is attributed to the abundant and uniformly dispersed active phase, formation of very active ultra small (<5 nm) TiO₂ crystals, and easy accessibility of the active sites.