Black Titania Research Articles

Characterization of titania self-aligned nanotubes prepared under various conditions for the photoelectrochemical water splitting

TiO2 nanotubes were grown by anodization of Ti sheets in an ethylene glycol solution. The then prepared nanotubes were tested with and without heat treatment at 450 ºC, for the water splitting process. The heat treatment produced increased photocurrent from 4.9 µA cm−2 to 56.8 µA cm−2 under illumination at 0.7 V vs. SHE. Modification of the nanotubes was carried out by electroreduction on both heat treated and untreated samples and its photoactivity evaluated. The spectral response showed increased photocurrent for the reduced material (black titania), although no appreciable change was detected in the absorbed spectra for the visible wavelengths. Finally, high-purity (> 99.6%) and commercially pure (99%) Ti sheets were used to grow TiO2 nanotubes with no clear difference in photocurrents (61.5 µA cm−2 vs. 65.4 µA cm−2 while illuminated at 0.7 V vs. SHE) showing the potential for cheap commercialization.

Black titanium oxide: synthesis, modification, characterization, physiochemical properties, and emerging applications for energy conversion and storage, and environmental sustainability.

Since its advent in 2011, black titanium oxide (B-TiOx) has garnered significant attention due to its exceptional optical characteristics, notably its enhanced absorption spectrum ranging from 200 to 2000 nm, in stark contrast to its unmodified counterpart. The escalating urgency to address global climate change has spurred intensified research into this material for sustainable hydrogen production through thermal, photocatalytic, electrocatalytic, or hybrid water-splitting techniques. The rapid advancements in this dynamic field necessitate a comprehensive update. In this review, we endeavor to provide a detailed examination and forward-looking insights into the captivating attributes, synthesis methods, modifications, and characterizations of B-TiOx, as well as a nuanced understanding of its physicochemical properties. We place particular emphasis on the potential integration of B-TiOx into solar and electrochemical energy systems, highlighting its applications in green hydrogen generation, CO2 reduction, and supercapacitor technology, among others. Recent breakthroughs in the structure-property relationship of B-TiOx and its applications, grounded in both theoretical and empirical studies, are underscored. Additionally, we will address the challenges of scaling up B-TiOx production, its long-term stability, and economic viability to align with ambitious future objectives.

A novel kind of hollow SiO2@g-C3N4@TiO2 microspheres for rapid removal of dyes and antibiotics in water under sunlight

In this paper, using PVP-modified polystyrene microspheres as template, tetrabutyl titanate (TEOT), tetraethyl orthosilicate (TEOS) and melamine as precursor, we developed a facile one-pot two-step method to preparing a novel kind of mesoporous hollow SiO2@TiO2@g-C3N4 ternary composite microspheres with plush surface, in which highly active black titanium dioxide (TiO2) was formed by simple calcination without further chemical reduction treatment. The structure and morphology of the composite microspheres were detailed characterized for understanding the formation mechanism. Research results indicated that the hollow SiO2 microspheres can promote the formation of oxygen vacancies in TiO2, and the ternary combination narrowed the bandgap width of the black hollow composite microspheres to 1.43 eV, thus endowing it with excellent broad-spectrum catalytic performance for rapid photo-degradation of persistent organic pollutants (POPs) such as dyes and antibiotics in water under sunlight. The removal rates of dyes reached more than 70 %, as well as that of antibiotics more than 50 % within one hour. Finally, a plausible catalytic degradation mechanism was discussed.

Tuning Stark effect by defect engineering on black titanium dioxide mesoporous spheres for enhanced hydrogen evolution

Defects can strongly affect the lattice, strain, and electronic structures of nanomaterials photocatalysts, like a double-edged sword of both positive significance and negative influence on photocatalytic performances. To date, most studies into defects only partially elucidated their beneficial or detrimental roles in photocatalysis. However, a quantitative understanding of the photocatalytic performances modulated by defect concentration still needs to be discovered. Here, a series of TiO2−X mesoporous spheres (MS) with different oxygen vacancy concentrations for photocatalytic applications were prepared by high-temperature chemical reduction. The link between oxygen vacancy concentration and photocatalytic performance was successfully established. The localization of carriers dominated by the Stark effect is first enhanced and then weakened with increasing oxygen vacancy concentration, which is a crucial factor in explaining the double-edged sword role of defect concentration in photocatalysis. As the reduction temperature rises to 300 °C, carrier localization dominated by the quantum-confined Stark effect maximizes the separation ability of photo generated electron hole pairs, thus exhibiting the best catalytic performance for photocatalytic hydrogen production and the degradation of organic pollutants, as demonstrated by a hydrogen evolution rate of 523.7 µmol g-1 h-1 and a ninefold higher RhB photodegradation rate compared to TiO2 MS. The work offers excellent flexibility for precisely constructing high-performance photocatalysts by understanding vacancy engineering.

Synthesis, Characterisation, and Applications of TiO and Other Black Titania Nanostructures Species (Review)

Black titania, a conductive ceramic material class, has garnered significant interest due to its unique optical and electrochemical properties. However, synthesising and properly characterising these structures pose a considerable challenge. This diverse material family comprises various titanium oxide phases, many of them non-stoichiometric. The term “black TiO2” was first introduced in 2011 by Xiaobo Chen, but Arne Magneli’s groundbreaking discovery and in-depth investigation of black titania in 1957 laid the foundation for our understanding of this material. The non-stoichiometric black titanium oxides were then called the Magneli phases. Since then, the science of black titania has advanced, leading to numerous applications in photocatalysis, electrocatalysis, supercapacitor electrodes, batteries, gas sensors, fuel cells, and microwave absorption. Yet, the literature is rife with conflicting reports, primarily due to the inadequate analysis of black titania materials. This review aims to provide an overview of black titania nanostructures synthesis and the proper characterisation of the most common and applicable black titania phases.

Black Titanium Oxide/Activated TaS2 Flakes Photoelectrode for Plasmon Assisted Hydrogen Evolution at Neutral pH at High Current Density.

A heterojunction photo-electrode(s) consisting of porous black titanium oxide (bTiO2) and electrochemically self-activated TaS2 flakes is proposed and utilized for hydrogen evolution reaction (HER). The self-activated TaS2 flakes provide abundant catalytic sites for HER and the porous bTiO2, prepared by electrochemical anodization and subsequent reduction serves as an efficient light absorber, providing electrons for HER. Additionally, Au nanostructures are introduced between bTiO2 and TaS2 to facilitate the charge transfer and plasmon-triggering ability of the structure created. After structure optimization, high HER catalytic activity at acidic pH and excellent HER activity at neutral pH are achieved at high current densities. In particular, with the utilization of bTiO2@TaS2 photoelectrode (neutral electrolyte, sunlight illumination) current densities of 250 and 500mA cm-2 are achieved at overpotentials of 433, and 689mV, respectively, both exceeding the "benchmark" Pt. The addition of gold nanostructures further reduces the overpotential to 360 and 543mV at 250 and 500mA cm-2, respectively. The stability of the prepared electrodes is investigated and found to be satisfying within 24 h of performance at high current densities. The proposed system offers an excellent potential alternative to Pt for the development of green hydrogen production on an industrial scale.

Black TiO2-based nanoparticles as Toll-like receptor stimulator delivery system for enhanced photothermal-immunotherapy of pancreatic cancer

BackgroundThe tumor-specific immune responses, essential for removing residual lesions and preventing tumor metastases, can be stimulated by tumor-associated antigens (TAAs) released following photothermal therapy (PTT). However, due to the immunosuppressed microenvironment of pancreatic ductal adenocarcinoma (PDAC), the TAAs released by PTT are difficult to induce an effective immune response. In this work, we prepared the mesoporous silica (mSiO2) coated black titanium dioxide (bTiO2) photothermal nanoparticles (NPs) for enhanced photothermal-immunotherapy toward PDAC, in which resiquimod (R848) was loaded and DOTA-Gd was conjugated. The NPs are specified as bTiO2@mSiO2@Gd/R848 and abbreviated to NPs/R848. R848 as a kind of Toll-like receptor 7/8 agonist can remodel the tumor microenvironment (TME) in PDAC and induce a strong immune response. Furthermore, DOTA-Gd serves as a magnetic resonance imaging (MRI) contrast agent to improve the T1-weighted MRI performance of the NPs.ResultsIn vitro results of this study show that NPs/R848 could thermally ablate tumor cells and efficiently trigger dendritic cell (DC) maturation. The results of in vivo investigations demonstrate that the combined use of photothermal-immunotherapy exhibits a significant inhibitory effect on tumor growth. Besides, it promoted maturation of DCs and enhanced infiltration of CD8 + , CD4 + T cells to improve the TME in PDAC.ConclusionsOur study anticipates that by encouraging the maturation of DCs, this strategy will improve the TME and enable the successful photothermal-immunotherapy of PDAC.

Advancements in black titanium dioxide nanomaterials for solar cells: a comprehensive review

AbstractOver the past decade, black titanium dioxide (B-TiO2) has garnered considerable attention within the scientific community due to its exceptional properties in optoelectronic and photovoltaic applications. This review offers a thorough examination of the synthesis, characteristics, and utilization of B-TiO2 nanomaterials in solar cell technologies. It underscores the pivotal role played by B-TiO2 in bolstering light absorption, facilitating charge separation, and optimizing charge transport mechanisms within solar cell architectures. Notable research endeavors are highlighted, showcasing the strides made in enhancing solar cell efficiency through the incorporation of B-TiO2. Furthermore, this review delves into the challenges inherent in the utilization of B-TiO2, including considerations of stability, scalability, and manufacturing methodologies, thereby stressing the imperative for refined synthesis techniques. Environmental concerns related to B-TiO2 are also addressed, underscoring the significance of evaluating its ecological footprint and advocating for sustainable deployment practices. Moreover, the review elucidates the future prospects of B-TiO2 in solar energy conversion, emphasizing innovations in device design and novel applications while championing environmentally conscious utilization practices. Serving as a comprehensive resource, this review is poised to empower researchers and practitioners alike, fostering deeper insights and facilitating advancements in the realm of B-TiO2 nanomaterials within the domain of solar cells.

Co-Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO2 for Catalytic Hydrogenation of Cinnamaldehyde.

Transition-metal-doped black titania, primarily in the anatase phase, shows promise for redox reactions, water splitting, hydrogen generation, and organic pollutant removal, but exploring other titania phases for broader catalytic applications is underexplored. This study introduces a synthetic approach using a Co-Ti bimetallic complex bridged by a 1,10-phenanthroline-5,6-dione ligand as a precursor for the synthesis of cobalt-doped black titania [Co@L2N@b-TiO2]. The synthesis involves precise control of pyrolysis conditions, yielding a distinct structure dominated by the rutile phase over anatase, with active cobalt encapsulated within a nitrogen-doped graphitic layer, primarily as Co0 rather than CoII and CoIII. The synthesized material is employed for the selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) under industrially viable conditions. The efficiency and selectivity of Co@L2N@b-TiO2 was compared with other catalysts, including cobalt-doped rutile TiO2 (Co@r-TiO2), anatase TiO2 (Co@a-TiO2), and black titania (Co@b-TiO2) as well as materials pyrolyzed under different atmospheres and temperatures, materials with phenanthroline ligands, and materials lacking any ligands. The superior performance of Co@L2N@b-TiO2 is attributed to its high surface area, stable Co0 within the nitrogen-doped graphitic layer, and composition of rutile and anatase phases of TiO2 and Ti2O3 (referred to as RAT), along with the synergistic interaction between RAT and Co0. These factors significantly influence the efficiency and selectivity of COL over hydrocinnamaldehyde (HCAL) and hydrocinnamyl alcohol (HCOL), indicating potential for broader applications beyond catalysis, particularly in designing of black titania-based materials.

Black Titania Janus Mesoporous Nanomotor for Enhanced Tumor Penetration and Near-Infrared Light-Triggered Photodynamic Therapy.

Thanks to their excellent photoelectric characteristics to generate cytotoxic reactive oxygen species (ROS) under the light-activation process, TiO2 nanomaterials have shown significant potential in photodynamic therapy (PDT) for solid tumors. Nevertheless, the limited penetration depth of TiO2-based photosensitizers and excitation sources (UV/visible light) for PDT remains a formidable challenge when confronted with complex tumor microenvironments (TMEs). Here, we present a H2O2-driven black TiO2 mesoporous nanomotor with near-infrared (NIR) light absorption capability and autonomous navigation ability, which effectively enhances solid tumor penetration in NIR light-triggered PDT. The nanomotor was rationally designed and fabricated based on the Janus mesoporous nanostructure, which consists of a NIR light-responsive black TiO2 nanosphere and an enzyme-modified periodic mesoporous organosilica (PMO) nanorod that wraps around the TiO2 nanosphere. The overexpressed H2O2 can drive the nanomotor in the TME under catalysis of catalase in the PMO domain. By precisely controlling the ratio of TiO2 and PMO compartments in the Janus nanostructure, TiO2&PMO nanomotors can achieve optimal self-propulsive directionality and velocity, enhancing cellular uptake and facilitating deep tumor penetration. Additionally, by the decomposition of endogenous H2O2 within solid tumors, these nanomotors can continuously supply oxygen to enable highly efficient ROS production under the NIR photocatalysis of black TiO2, leading to intensified PDT effects and effective tumor inhibition.

Cellulose-based materials in tailoring a novel defective titanium‑carbon‑phosphorus hybrid composites for highly efficient photocatalytic activity

Until now, black titania has attracted much interest as a potential photocatalyst. In this contribution, we report the first demonstration of the effective strategy to fundamentally improve the photocatalytic performance using a novel sustainable defective titanium‑carbon-phosphorous (TCPH) hybrid nanocomposite. The prepared TCPH was used for photocatalytic degradation of the main organic pollutants, which is methyl orange (MO) dye. The physico-chemical properties of as-prepared samples were characterized by various techniques to observe the transformations after carbonization and the interaction between different composite phases. The existence of Ti+3 and oxygen vacancies at the surface, and a notable increase in surface area, are all demonstrated by TCPH, together with the distinct core-shell structure. These unique properties exhibit excellent photocatalytic performance due to the boosted charge transport and separation. The highest degradation efficiency of methyl orange (MO) was attained in the case of TCPH when compared with titanium-cellulose-phosphorous (TCeP) and titanium‑carbon-phosphorous (TCPN). Accordingly, the highest degradation efficiency was achieved by applying the optimal operational conditions of 1 g/L of TCPH catalyst, 10 mg/L of MO, pH of 7 and the temperature at 25 ± 3 °C after 3 min under LED lamp (365 nm) with light intensity 100 mW/cm2. The degradation mechanism was investigated, and the trapping tests showed the dominance of hydroxyl radicals in the degradation of MO. TCPH showed high stability under a long period of operation in five consecutive cycles, which renders the highly promising on an industrial scale. The fabrication of highly active defective titanium‑carbon-phosphorous opens new opportunities in various areas, including water splitting, and CO2 reduction.

Black titania coated glass fiber as a photo absorber in interfacial solar steam generation under harsh condition

Interfacial solar steam generation (ISSG) is one of the promising solutions in the field of water filtration, desalination, and solvent recovery. For the industrial applications of the technology, there is a need for developing highly durable, thermally stable, and inert light absorbers. Therefore, this work addresses this issue by synthesizing black Titania (B–TiO2) via vacuum annealing and depositing it on glass fiber (GF) via vacuum filtration with an ethyl cellulose binder. According to the characterization techniques analyses, the change of colour is attributed to the occurrence of oxygen vacancies in the surface layers of TiO2 nanoparticles during vacuum annealing. The deposition parameters were optimized for achieving a maximum solar-weighted light absorptance of 95.7%. The optimized B–TiO2 GF was applied for the steam generation experiments and achieved the evaporation rate of 1.53 kg m−2 h−1, which corresponds to solar-steam conversion efficiency of 97.7 % under standard measurements condition of AM 1.5 G sun and ambient temperature and relative humidity of 20 °C and 40% respectively. Thanks to the high durability and chemical inertness of B–TiO2 GF it was applied for water filtration in extreme conditions of acidic/alkaline water and high-sun illumination (up to 35-sun). Worth noting that for high-sun experimentation there is a need to use a binder to improve particle attachment to the glass fibers.

Analysis of the Inhomogeneous Growth of Sputtered Black TiO2 Thin Films.

Black titanium dioxide (B-TiO2) is a highly active photoelectrochemical material compared to pure titanium dioxide due to its increased light absorption properties. Recently, we presented the deposition of thin-film B-TiO2 using an asymmetric bipolar reactive magnetron sputter process. The resulting samples exhibit excellent photoelectrochemical properties, which can be fine-tuned by varying the process parameters. In this article, results of morphological, electrical, and photoelectrochemical measurements are discussed to better understand the surprisingly high electrochemical activity of the films. In order to study the influence of the dynamic process on film formation, we use static sputtering with a fixed substrate covering the entire chamber area in front of the two targets. This allows the material composition of the sputtered film to be analyzed depending on its relative position to the targets. The results lead to the conclusion that the asymmetric bipolar sputtering mainly produces two phases, a transparent, nonconductive crystalline phase and a black, conductive amorphous phase. As a consequence, the dynamically sputtered samples are multilayers of these two materials. We discuss that the significantly better electrical and photoelectrochemical properties emerge from the inhomogeneous nature of the laminates, like also found in core-shell nanoparticles of B-TiO2.

Black TiO2-infused polydimethylsiloxane composites for efficient solar-assisted water evaporation and thermoelectric energy generation

Solar assisted interfacial water evaporation through the strategic localization of solar- thermal energy conversion by relying on the air–water interface has garnered significant interest owing to its enhanced efficiency in a variety of applications, from water purification to energy generation. Nevertheless, achieving utterly improved thermal management to enhance the efficiency of solar heat consumption is still quite complex. Herein, we created special composites of black titanium dioxide and polydimethylsiloxane (B-TiO2/PDMS) aiming effectively harvest a broad range of spectrum of solar radiation for the benefit of improving energy production and aid for water purification. The B-TiO2/PDMS sponge possesses an impressive optical to thermal transformation as an outcome, keeping a constant surface temperature of 66 °C, as opposed to 41.6 °C for PDMS sponge at typical 1 sun intensity for 10 min. This solar evaporation system constitutes a greater evaporation rate of 1.39 Kg m−2h−1 with a photothermal conversion efficiency of 70.8 % under 1 sun illumination. To accomplish integrated thermoelectric power generation during solar evaporation, the thermoelectric (TE) module is used as an insulating medium, succeeding an optimal yield of 30 mV under 1 sun. Furthermore, the as prepared B-TiO2/PDMS sponge achieved notable mechanical resilience and incredible adaptability, offering a viable approach for thermal management and cooperative way to utilize solar powered evaporation to produce potable water and energy.

Superior Performances of Q-Switched and Mode-Locked Erbium-doped Fiber Laser using Black Titanium Dioxide Thin-film Saturable Absorbers

This work reports on the improved Q-switched and mode-locked performances of black titanium dioxide (BTiO2-x) nanoparticles embedded in thin-film composite material as a saturable absorber compared to TiO2 in an erbium-doped fiber laser. The thin-film saturable absorbers were prepared by mixing the nanoparticles with polyvinyl alcohol (PVA) as a host. BTiO2-x has a better nonlinear absorption coefficient, β of -12.46 x 10-7 m/W compared to -7.15x 10-7 m/W for TIO2 determined using z-scan measurement. The laser performance was evaluated in the 85.21 mW – 126.48 mW pump power range. Upon inserting TiO2 and BTiO2-x SA in a laser cavity, the peaks of the output spectrum shifted from 1566.62 nm to 1563.24 nm and 1565.75 nm, respectively. Regarding Q-switched performances, BTiO2-x SA generates a shorter pulse width of 16.00 µs than TiO2 SA. The slope efficiency of the TiO2 SA was 11.72 %, which is higher than the slope efficiency of the BTiO2-x SA. The maximum average and peak power generated by the BTiO2-x SA were 55.67 % and 54.83 % higher than the TiO2 SA. As for mode-locked outputs, BTiO2-x SA can generate pulsed laser at a low threshold power of 62.29 mW compared to TiO2 SA. Furthermore, BTiO2-x SA produced a shorter pulse width of 5.04 ps, whereas TiO2 is 9.20 ps. This study demonstrates that BTiO2-x SA has the potential to produce ultrashort pulse width using the mode-locked technique.

Revealing the Impact of Alkaline Agents on the Photocatalytic Characteristics of Black Titanium Dioxide (TiO2)

Revealing the Impact of Alkaline Agents on the Photocatalytic Characteristics of Black Titanium Dioxide (TiO₂)

Three-in-one: Saturated, UV-protective and anti-bacterial structural colored textiles

Structural color based textiles have attracted significant attention owing to their potential in facilitating environmentally-friendly and durable coloration processes. However, the improvement of color saturation in textiles based on structural color is still under continuous investigation. Additionally, there is a rising demand for textiles featuring specialized functionalities such as anti-bacteria and anti-ultraviolet properties in daily life. In this study, a “three-in-one” amorphous photonic structure (APS) and multi-functional textile design is performed to achieve high structural color saturation, UV protection, and anti-bacteria properties. In this system, poly(styrene-butyl acrylate-methacrylate) (P(St-BA-MAA)) colloidal particles are used as building blocks, black titanium dioxide (TiO2) is used as black dopant, and water-soluble polyurethane (WPU) is used as the binder. The WPU demonstrates a significant capability to enhance the color fastness of APS/TiO2 textiles. The strong absorption of incoherent scattered light by black TiO2 in the visible range plays a crucial role in achieving a highly saturated APS-based textile. In addition, the doped black TiO2 possesses strong UV–visible light absorption and anti-bacterial capabilities, thereby supporting the development of textiles functionalized with UV protection and anti-bacteria. Our proposed simplified approach to fabricating high color saturation and functionalized APS/TiO2 textiles demonstrates significant potential for eco-textile coloring in line with market demands.

Intensifying heat using AgCu core-shell-based black titania with highly efficient photothermal conversion performance for solar-driven seawater desalination

A novel photoreceiver composed of black titania (BT) matrix with biochar for efficient steam production was investigated to measure the desalination efficiency under the illumination of one sun (1 kW m−2). The density of localized hotspots on the surface of the photothermal system is enhanced by the incorporation of AgCu core-shell that promotes photothermal activity and improves the degradation of methyl orange (MO) dye. Assemblages of AgCu nanoparticles on the surface of BT generated a strong stochastic plasmonic coupling and therefore broad-band absorption for much better solar energy consumption. The nanocomposite exhibited an excellent vaporization flux of 1.4 kg m−2 h−1 with high efficiency reaching 95.7 % under the illumination of one sun. AgCu@BT/BC exhibited an excellent surface temperature of 41 °C after only 5 min compared to other prepared photothermal systems. Furthermore, the prepared composites revealed superb degradation of MO dye under UV–vis light with a percentage of 96 %. The band gap energy of white titania decreased from 3.2 eV to 1.86 eV in the case of AgCu@BT/BC nanocomposite. Moreover, the crystalline AgCu@BT/BC demonstrates outstanding photocatalytic performance because of boosted charge migration, reduced electron-hole pair recombination rate, and identifiable shift to the red region.

Black Titanium Oxide Nanotubes Deposited with Fe (III) Oxide Nanoparticles for Electrochemical Sensing of Dopamine

Black Titanium Oxide Nanotubes Deposited with Fe (III) Oxide Nanoparticles for Electrochemical Sensing of Dopamine

Effects of micro and nano fillers on the mechanical and thermal properties of hydroxyl‐terminated polybutadiene‐polyurethane based rocket motor liner

AbstractCase bonded solid rocket motors hold significant importance in both the defense and aerospace industries which typically consist of an insulating layer, a solid propellant, and a liner layer serving as an adhesive between the insulator and solid propellant. In this investigation, the aim was to assess the critical mechanical properties of five different HTPB based liner formulations under ambient conditions, as well as at elevated and reduced temperatures. The liner formulations incorporated micro carbon black, nano carbon black, nano silica, and nano titania as fillers. A comprehensive characterization study encompassing mechanical and thermal properties was conducted to evaluate the performance of these potential rocket motor liners. Mobility reduction of polymer chains and bond strengthening at lower temperatures led to the enhancement in mechanical properties of all filled and unfilled liners with decline in temperature. All mechanical properties of filled liner formulations increased significantly compared to unfilled formulation at all temperatures. Enhancements in mechanical properties were more pronounced with carbon blacks as fillers. Thermal analyses of each formulation revealed that there were improvements in the thermal properties of filled liners compared to unfilled one.