Titanate Nanosheets Research Articles

2D Titanate Nanosheet–Supported NiMoOx Core@shell Nanospikes for Overall Electrocatalytic Water-Splitting Reactions

2D Titanate Nanosheet–Supported NiMoO_<i>x</i> Core@shell Nanospikes for Overall Electrocatalytic Water-Splitting Reactions

Mechanical-energy-driven HCHO purification with lattice distortion engineering and surface grafting

Formaldehyde (HCHO) is a typical indoor air pollutant with high toxicity and wide distribution. It is of great significance to use clean energy for efficient catalytic oxidation of HCHO. In this work, Fe-doped bismuth titanate (Bi4Ti3O12) nanosheets with polyethyleneimine (PEI) grafting were prepared, exhibiting a remarkable complete elimination of HCHO under ultrasonic vibration. Piezocatalytic mechanism analysis revealed that Fe3+ doping induced lattice distortion and accelerated the transfer of electrons through valence change. Additionally, the abundant amino groups in PEI efficiently gathered formaldehyde molecules on the surface of the catalysts for next catalytic reaction as well as accelerate the separation of carriers by trapping holes as strong electron donors. It showed an effective strategy for degrading organic pollutants in the air with adsorption-enhanced piezocatalysts driven by mechanical energy.

Optical manipulation of graphene oxide nanosheets toward arbitrary hetero-stacking of graphene and niobate and titanate nanosheets

Optical manipulation of graphene oxide nanosheets toward arbitrary hetero-stacking of graphene and niobate and titanate nanosheets

Tunable and Non-Invasive Printing of Transmissive Interference Colors with 2D Material Inks.

Interference colors hold significant importance in optics and arts. Current methods for printing interference colors entail complex procedures and large-scale printing systems for the scarcity of inks that exhibit both sensitivity and tunability to external fields. The production of highly transparent inks capable of rendering transmissive colors has presented ongoing challenges. Here, a type of paramagnetic ink based on 2D materials that exhibit polychrome in one magnetic field is invented. By precisely manipulating the doping ratio of magnetic elements within titanate nanosheets, the magneto-optical sensitivity named Cotton-Mouton coefficient is engineerable from 728 to a record high value of 3272 m-1 T-2, with negligible influence on its intrinsic wide optical bandgap. Combined with the sensitive and controllable magneto-responsiveness of the ink, modulate and non-invasively print transmissive interference colors using small permanent magnets are precised. This work paves the way for preparing transmissive interference colors in an energy-saving and damage-free manner, which can expand its use in widespread areas.

Monodisperse nanosheet mesophases.

Self-assemblies of anisotropic colloidal particles into colloidal liquid crystals and well-defined superlattices are of great interest for hierarchical nanofabrications that are applicable for various functional materials. Inorganic nanosheets obtained by exfoliation of layered crystals have been highlighted as the intriguing colloidal units; however, the size polydispersity of the nanosheets has been preventing precise design of the assembled structures and their functions. Here, we demonstrate that the anionic titanate nanosheets with monodisperse size reversibly form very unusual superstructured mesophases through finely tunable weak attractive interactions between the nanosheets. Transmission electron microscopy, polarizing optical microscopy, small-angle x-ray scattering, and confocal laser scanning microscopy clarified the reversible formation of the mesophases (columnar nanofibers, columnar nematic liquid crystals, and columnar nanofiber bundles) as controlled by counter cations, nanosheet concentration, solvent, and temperature.

Efficient Electrocatalytic Ammonia Synthesis via Theoretical Screening of Titanate Nanosheet-Supported Single-Atom Catalysts.

The electrocatalytic nitrogen reduction reaction (NRR) for synthesizing ammonia holds promise as an alternative to the traditional high-energy-consuming Haber-Bosch method. Rational and accurate catalyst design is needed to overcome the challenge of activating N2 and to suppress the competitive hydrogen evolution reaction (HER). Single-atom catalysts have garnered widespread attention due to their 100% atom utilization efficiency and unique catalytic performance. In this context, we constructed theoretical models of metal single-atom catalysts supported on titanate nanosheets (M-TiNS). Initially, density functional theory (DFT) was employed to screen 12 single-atom catalysts for NRR- and HER-related barriers, leading to the identification of the theoretically optimal NRR catalyst, Ru-TiNS. Subsequently, experimental synthesis of the Ru-TiNS single-atom catalyst was successfully achieved, exhibiting excellent performance in catalyzing NRR, with the highest NH3 yield rate reaching 15.19 μmol mgcat-1 h-1 and a Faradaic efficiency (FE) of 15.3%. The combination of experimental results and theoretical calculations demonstrated the efficient catalytic ability of Ru sites, validating the effectiveness of the constructed theoretical screening process and providing a theoretical foundation for the design of efficient NRR catalysts.

Enhancing the Photocatalytic Activity of Halide Perovskite Cesium Bismuth Bromide/Hydrogen Titanate Heterostructures for Benzyl Alcohol Oxidation.

Halide perovskite Cs3Bi2Br9 (CBB) has excellent potential in photocatalysis due to its promising light-harvesting properties. However, its photocatalytic performance might be limited due to the unfavorable charge carrier migration and water-induced properties, which limit the stability and photocatalytic performance. Therefore, we address this constraint in this work by synthesizing a stable halide perovskite heterojunction by introducing hydrogen titanate nanosheets (H2Ti3O7-NS, HTiO-NS). Optimizing the weight % (wt%) of CBB enables synthesizing the optimal CBB/HTiO-NS, CBHTNS heterostructure. The detailed morphology and structure characterization proved that the cubic shape of CBB is anchored on the HTiO-NS surface. The 30 wt% CBB/HTiO-NS-30 (CBHTNS-30) heterojunction showed the highest BnOH photooxidation performance with 98% conversion and 75% benzoic acid (BzA) selectivity at 2 h under blue light irradiation. Detailed optical and photoelectrochemical characterization showed that the incorporating CBB and HTiO-NS widened the range of the visible-light response and improved the ability to separate the photo-induced charge carriers. The presence of HTiO-NS has increased the oxidative properties, possibly by charge separation in the heterojunction, which facilitated the generation of superoxide and hydroxyl radicals. A possible reaction pathway for the photocatalytic oxidation of BnOH to BzH and BzA was also suggested. Furthermore, through scavenger experiments, we found that the photogenerated h+, e- and •O2- play an essential role in the BnOH photooxidation, while the •OH have a minor effect on the reaction. This work may provide a strategy for using HTiO-NS-based photocatalyst to enhance the charge carrier migration and photocatalytic performance of CBB.

Preferential growth and electron trap synergistically promoting photoreduction CO2 of Tm ion doping bismuth titanate nanosheets

In this study, we prepared two-dimensional Bi4Ti3O12 nanosheets doped with rare earth ions. The experimental results show that Bi4-xTmxTi3O12 exhibits the highest reduction performance among various rare earth doped Bi4Ti3O12 materials, with a CO yield of 7.25 μmol g−1h−1. Furthermore, a delayed reaction in Bi3.97Tm0.03Ti3O12 is observed upon a cessation of light irradiation. Theoretical calculations reveal that the introduction of Tm ion not only reduces the surface energy of (001) plane and make it preferential growth in Bi4Ti3O12, but also brings the intervening energy level of Tm ion (4f and 4d mixed orbital), which is closer to the conduction band of Bi4Ti3O12 and facilitates charge carrier accumulation in trap states. The electrons retained in the shallow traps promote the hysteresis reaction following a cessation of illumination. This work provides further insights into elucidating precise reduction reaction mechanisms underlying rare earth dopant on photocatalysts. This research provides enhanced insights into unraveling the precise reduction reaction mechanisms influenced by rare earth dopants in photocatalysts.

Synthesis of Titanate Nanosheets from Indigenous Indonesian Ilmenite Minerals

Titanate nanosheets are a type of 2-dimensional nanomaterial with vast applications in electronics, energy storage, and photocatalysis due to their superior properties, such as their large specific surface area and excellent electrical conductivity. Titanate nanosheets are expected to be the material precursor of TiO2 nanostructures with further treatment. The current research aims to synthesize titanate nanosheets using the natural mineral ilmenite from Indonesia through the hydrothermal method. X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunaeur-Emmett-Teller (BET) analysis were used to characterize the chemical composition, crystal structure, shape, size, and specific surface area of the prepared samples. The structure phase of the as-synthesized sample is known to be layered titanate. The as-synthesized nanosheet sample has a diameter ranging from 2.5 to 4 μm and BET surface areas of approximately 40 m2/g. This concise hydrothermal method could create 2-dimensional structured nanomaterials from Indonesian local minerals.

Construction of in situ C/N/S co-doped mesoporous Li4Ti5O12 nanosheets for high-rate and large-capacity lithium-ion batteries

The low capacity of Li4Ti5O12 (LTO) under high-rate charging/discharging limits its development in energy applications. Two-dimensional (2D) nanosheets equipped with mesopores offer promising opportunities to realize high-rate and long-term lithium-ion batteries. This paper successfully synthesized C/N/S co-doped lithium titanate nanosheets with rich oxygen vacancy concentration (CNSLTO) in a single step. C, N and S are doped into the LTO bulk phase, providing bulk oxygen vacancies and active sites. Partial Ti4+ conversion to Ti3+ is promoted by co-doping and introducing rich oxygen vacancies, improving the electrical conductivity. In addition, the effect of CTAB concentration on the morphology and electrochemical properties of the materials was studied experimentally. The optimized CNSLTO nanosheets have a relatively high specific surface area (99.38 m2 g−1) and numerous mesoporous, achieving outstanding performance and excellent cycling stability at high-rate as lithium-ion anode materials. The CNSLTO exhibits excellent rate capacity (171.7–152.6 mA h g−1 at 0.5–20 C) and cycling performance (97.6 % after 1000 cycles at 10 C). Additionally, the discharge-specific capacity of the LFP//CNSLTO full battery at 10 C (122.2 mA h g−1) was superior to the LFP//LTO (77.8 mA h g−1).

Highly Efficient Liquid-Phase Exfoliation of Layered Perovskite-like Titanates HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd) into Nanosheets

Nanosheets of layered perovskite-like oxides attract researchers as building blocks for the creation of a wide range of demanded nanomaterials. However, Ruddlesden–Popper phases are difficult to separate into nanosheets quantitatively via the conventional liquid-phase exfoliation procedure in aqueous solutions of bulky organic bases. The present study has considered systematically a relatively novel and efficient approach to a high-yield preparation of concentrated suspensions of perovskite nanosheets. For this, the Ruddlesden–Popper titanates HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd) have been intercalated by n-alkylamines with various chain lengths, exposed to sonication in aqueous tetrabutylammonium hydroxide (TBAOH) and centrifuged to separate the nanosheet-containing supernatant. The experiments included variations of a wide range of conditions, which allowed for the achievement of impressive nanosheet concentrations in suspensions up to 2.1 g/L and yields up to 95%. The latter were found to strongly depend on the length of intercalated n-alkylamines. Despite the less expanded interlayer space, the titanates modified with short-chain amines demonstrated a much higher completeness of liquid-phase exfoliation as compared to those with long-chain ones. It was also shown that the exfoliation efficiency depends more on the sample stirring time in the TBAOH solution than on the sonication duration. Analysis of the titanate nanosheets obtained by means of dynamic light scattering, electron and atomic force microscopy revealed their lateral sizes of 30–250 nm and thickness of 2–4 nm. The investigated exfoliation strategy appears to be convenient for the high-yield production of perovskite nanosheet-based materials for photocatalytic hydrogen production, environmental remediation and other applications.

Lead-Free Piezoelectric Energy Harvester Based on 2D Bismuth Titanate.

The use of two-dimensional (2D) layered materials with a noncentrosymmetric structure dramatically increases the potential of nanoscale electromechanical systems and electronic devices. In this work, liquid-phase exfoliation of bulk bismuth titanate was employed to synthesize atomically thin 2D sheets and fabricate a high-performance piezoelectric energy harvester. The structural and morphological properties of the 2D sheets were analyzed, confirming their phase purity and layer formation. Piezoelectric properties of the 2D sheets were evaluated using Piezoresponse Force Microscopy (PFM), demonstrating a high d33 piezoelectric coefficient of 40 pm/V in a few-layer bismuth titanate nanosheet. A prototype energy harvesting device was fabricated with 2D bismuth titanate as the active material. The piezoelectric response of the fabricated device was recorded at different frequencies and forces, which yielded a maximum d33 of 57.8 pC/N at 1 Hz. Such a solid electromechanical performance at a relatively infinitesimal input response indicates that 2D bismuth titanate can be useful for piezoelectric energy harvesting applications.

Designed Synthesis of Cu2O Quantum Dots/TiO2 Nanotubes Heterostructure as a Photocatalyst for Converting CO2 to CH4

Herein, H+ in oxalic acid is used instead of Na+ to obtain titanate nanosheets through P200 hydrolysis, which further curls to form a multilayer TiO2 nanotubes (NTs) structure. Then, Cu2O quantum dots (QDs) are successfully loaded on TiO2 NTs via a hydrothermal method using fructose as a reducing agent. The optical, impedance, and photocurrent tests indicate that the composite structure improves its optoelectronic performance. The photocatalytic H2 production and CO2 reduction efficiency of Cu2O QDs/TiO2 NTs are lower than those of TiO2 NTs. However, the molar ratio of CH4 to CO produced by CO2 reduction of Cu2O QDs/TiO2 NTs composite catalyst is greater than that of pure TiO2 NTs. The CH4 production accounts for 97%, indicating that the composite catalyst has a high CH4 selectivity. The experimental and density functional theory calculation results prove that the Z‐scheme heterojunction accelerates the separation and transfer of photogenerated carriers, and broadens the absorption range of visible light.

Reversible Pd Catalysts Supported on Hierarchical Titanate Nanosheets for an N-Methylindole-Based Liquid Organic Hydrogen Carrier

Reversible Pd Catalysts Supported on Hierarchical Titanate Nanosheets for an <i>N</i>-Methylindole-Based Liquid Organic Hydrogen Carrier

Water flow promoted charge separation in piezoelectric Bi4Ti3O12 for the enhanced photocatalytic degradation of antibiotic

Addressing the issue of antibiotic residues in the environment is key to improving the quality of aquatic environments and reducing human health risks. In this study, piezoelectric bismuth titanate (Bi4Ti3O12) nanosheets are synthesized and employed to conduct antibiotic degradation. The piezoelectric potential induced by the water flow shear force is utilized to facilitate charge separation and migration in the photocatalytic process and enhance the catalytic degradation of antibiotic wastewater. As a result, 85% of tetracycline hydrochloride (TC) is degraded within 90 min. The piezo-photocatalytic process exhibits a 2.4 times faster reaction rate and a 15% higher mineralization rate than photocatalysis. Different environmental factors are investigated for their effects on the catalytic activity in piezo-photocatalysis. In situ electrochemical measurement and photoluminescence (PL) spectroscopy under stress demonstrated that the piezoelectric potential shifted the energy band of Bi4Ti3O12 and promoted the charge migration and separation, which produce more active species that favor the efficient catalytic degradation. Finally, the intermediate products of the tetracycline hydrochloride degradation process are analyzed and possible degradation pathways are suggested. This study elucidates the degradation mechanism of Bi4Ti3O12 as a piezo-photocatalyst for antibiotic pollutants, and meticulously investigates the charge transfer mechanism of the catalyst material in response to micro-stress. Hence, it provides an efficient solution for organic wastewater treatment and can potentially provide theoretical support for the development and performance optimization of catalyst materials applied in natural environments.

Gentle, Spontaneous Delamination of Layered Titanate Yielding New Types of Lithium Titanate Nanosheets

Gentle, Spontaneous Delamination of Layered Titanate Yielding New Types of Lithium Titanate Nanosheets

Ultra‐high power density in poly(arylene ether nitrile)‐based composites containing barium titanate and boron nitride nanosheets

AbstractBarium titanate (BT) nanoparticles were surface coated by a silane coupling agent (KH550) and core–shell structured nanoparticles (named KH550@BT) were obtained. Similarly, BT nanoparticles coated by polydopamine (PDA) were named as PDA@BT. Meanwhile, boron nitride (BN) nanosheets (BNNS) were successfully unstripped from block BN. Then, two kinds of ternary poly(arylene ether nitrile) (PEN)‐based composites are prepared using the solution casting method. Composites with 30 wt% KH550@BT and 12 wt% BNNS were named as KH550@BT/BNNS/PEN. Composites with 30 wt% PDA@BT and 12 wt% BNNS were named as PDA@BT/BNNS/PEN. The microstructure, dielectric properties, and energy storage properties of the ternary composites were studied in detail. PEN embedded with either BNNS or BT were prepared and studied for comparison. As a result, the introduction of BT will improve the dielectric constant (εr) and energy storage density (W), but it will reduce the breakdown strength (Eb) and charge–discharge efficiency (η) of composites. BNNS not only improves Eb and W but also improves η of composites. Although the introduction of BT and BNNS simultaneously may reduce η, it will improve εr, Eb, and W of composites. Most importantly, the fast discharge speed and high power density demonstrate that the BT/BNNS/PEN composites are potential candidates to be used in high power pulsed capacitors fields.Highlights Boron nitride nanosheets improve the breakdown strength of composites. The composites achieve simultaneous increment of εr and Eb. The power density of the BT/BNNS/PEN composites was higher than 70 MW cm−3.

Structural, optical, and electrical properties of cellulose/titanate nanosheets composite with enhanced protection against gamma irradiation

Two-dimensional (2D) materials have emerged as a promising functional filler in nanocomposites due to their unique anisotropy and resilience to harsh conditions. We report herein the use of Ti0.91O2 nanosheets as a protective component against γ-irradiation to cellulose paper. The titanate nanosheets were prepared via a sequence of solid-state synthesis of lepidocrocite-type Cs0.7Ti1.825O4, proton exchange to H0.7Ti1.825O4·H2O, and exfoliation with tetrabutylammonium hydroxide. The nanosheets were incorporated into the commercial cellulose filter paper by a simple dip coating up to 0.6 mg cm−2, equivalent to 10 wt% TiO2. The nanosheets distribution was demonstrated by energy dispersive X-ray (EDX) mapping, synchrotron radiation X-ray tomographic microscopy (SRXTM), and atomic force microscopy (AFM). It is found that γ-irradiation (up to 50 kGy) destroyed the cellulose Iβ crystallinity of uncoated paper, but this is less pronounced in the cellulose/titanate nanosheets composite. This was also confirmed by the lack of a 235 nm-absorption characteristics of irradiation-induced decomposition product(s) in nanosheets-containing papers, which also exhibit UVA shielding property. The coated samples remained white while the uncoated ones were darkened with γ-irradiation. In addition, the nanosheets-coated papers showed dielectric permittivity, loss tangent, and AC conductivity which were invariant of the γ-dose, unlike those from the uncoated ones. Our work demonstrates the use of lead-free Ti0.91O2 nanosheets as a γ-shielding component to slow down/prevent structural, optical, and electrical properties damages in cellulose paper, which could extend to other nature-derived materials.

Facile synthesis of polydopamine-interlinked titanate nanosheets and copper hexacyanoferrate for highly efficient removal of Cs(I)

Facile synthesis of polydopamine-interlinked titanate nanosheets and copper hexacyanoferrate for highly efficient removal of Cs(I)

Photoactive nano-confined Pt in titania nanotubes (Pt-TiNT) via microwave-assisted flow synthesis

Pt-TiNT with PtO nanoparticles dispersed within the lumen and interlayer spaces of titania nanotubes (TiNT) were prepared by a new process involving titanate nanosheets (TiNS) synthesis in an optimized microwave-assisted flow reactor, followed by ion-exchange with a Pt precursor, before triggering the titanate layer rolling to trap the Pt precursor clusters inside the titania nanotubes, followed by a thermal treatment. TEM, XRD, and Raman analyses confirm the total conversion of TiO2 into TiNS in 15 min at 120 °C and 4 bar, and the TiNS transformation into 181 nm-long TiNT with 10 and 6 nm outer and inner diameter, respectively. The 2% Pt-TiNT comprises 0.7 nm PtO clusters (according to XPS), causing slight distortions of the interlayer spaces, while a few larger 2–3 nm Pt clusters reside within the lumen. As a result, Pt-TiNT is 14-fold more active than TiNT for visible light (400–780 nm) photocatalytic oxidation of diclofenac under 2136 μW·cm−2 irradiation, and>1000-fold better than the uncatalyzed photoconversion reaction under 100 mW·cm−2 artificial solar lighting. In addition, nano-confinement of PtO clusters narrowed the bandgap of the TiNT, which, combined with its excellent absorptivity to harvest light, allowed a broader spectral range of photon energies to activate the photocatalyst.