Search

A novel catalyst, TiO2 nanoparticles dispersed in silicate, were used to photodegrade sulforhodamine B (SRB) under UV–VIS irradiation. With good photocatalytic activity and the ability to be readily separated from the reaction system, this novel catalyst exhibits the potential to be effective in the treatment of dye pollutants in aqueous systems. [Copyright &y& Elsevier]

Lithium-oxygen (Li–O 2) batteries can exhibit high theoretical energy density and be surely suitable for potential energy storage. However, they suffer from early discharge termination and consequently low practical capacity, which has been regarded as the blockage of the diffusion of oxygen and the electron transfer on cathode surface. Herein, based on experimental results and theoretical simulation, it is confirmed that the discharge termination is largely caused by the surface adsorption of oxygen and the corresponding reaction intermediates. A TiO 2 -coated binder-free carbon paper has been prepared and used as cathode for Li–O 2 battery. During the first discharge, the discharge plateau at ca. 2.55 V has not been observed due to the weak adsorption of oxygen on TiO 2 surface, indicative of an early discharge termination of Li–O 2 battery. It is further identified that the formed vacancies on TiO 2 surface during lithiation/delithiation prevents the early discharge termination. Therefore, the interaction between oxygen and electrode surface plays a key role in discharge termination mechanism of Li–O 2 batteries. [ABSTRACT FROM AUTHOR]

• Sulfur intercalated hierarchical hydrotalcite with large surface area synthesized. • Adsorption capability towards heavy metal ions improved significantly by sulfur. • Both cationic and anionic heavy metal pollutants simultaneously removed. • Heavy metal ions are efficiently purified from simulating electroplating effluent. Hydrotalcite materials are generally utilized for anionic pollutants due to its interlayered anion exchange ability. Their potentiality for cationic contaminants is rarely explored. In this study, disulfide (S 2 -) intercalated LDH material demonstrated capability to remove both heavy metal cations and oxyanions simultaneously from water. The S 2 - intercalation of LDH significantly improved its adsorption capability towards both heavy metal cations (C o 2 + and N i 2 +) and oxyanion (C r O 4 2 -). The adsorption amount of S-LDH towards C o 2 + and N i 2 + reached 88.6mg/g and 76.2mg/g, which are 405% and 281% higher than that of pristine LDH. For C r O 4 2 - removal, the adsorption amount reached 34.7mg/g, 402% higher than that of pristine LDH. The cations capture mechanism mainly depends on the novel layer sheet cation substitution mechanism based on irreversible precipitation and the generation of metal sulfide precipitates. Meanwhile, the interlayered S 2 - can be easily replaced by C r O 4 2 - to realize the simultaneous removal of both heavy metal cations and oxyanions. In the fixed-bed column experiments, 448 bed volume (BV) (672 mL) of simulating electroplating wastewater can be efficiently treated by yielding only 1 BV(15 mL) of chemical sludge, which is practically acceptable. This work provided a highly practical adsorption technology based on the S 2 - modification hydrotalcite material for the purification of heavy metal ions contaminated wastewater. [ABSTRACT FROM AUTHOR]

A facile one-pot two-stage photochemical synthesis of aromatic azoxy compounds and imines has been developed by coupling the selective reduction of nitroaromatic compounds with the selective oxidation of amines in an aqueous solution. In the first stage (light illumination, Ar atmosphere), the light excited nitroaromatic molecule abstract H from amine to form ArNO2H and amine radical, which then form nitrosoaromatic, hydroxylamine and imine compounds. Water acts as a green solvent for the dispersion of the reactants and facilitates the formation of nitrosoaromatic and hydroxylamine intermediate compounds. In the second stage (no light, air atmosphere), the condensation of nitrosoaromatic and hydroxylamine compounds yields aromatic azoxy product with the aid of molecular oxygen in air. This photochemical synthesis achieved both high conversion and high product selectivity (>99%) at room temperature. [ABSTRACT FROM AUTHOR]

Antimony (Sb) decontamination in water is necessary owing to the worsening pollution which seriously threatens human life safety. Designing bismuth-based photocatalysts with hydroxyls have attracted growing interest because of the broad bandgap and enhanced separation efficiency of photogenerated electron/hole pairs. Until now, the available photocatalysis information regarding bismuth-based photocatalysts with hydroxyls has remained scarce and the contemporary report has been largely limited to Bi 3 O(OH)(PO 4 ) 2 (BOHP). Herein, Bi 3 O(OH)(AsO 4 ) 2 (BOHAs), a novel ultraviolet photocatalyst, was fabricated via the co-precipitation method for the first time, and developed to simultaneous photocatalytic oxidation and adsorption of Sb(III). The rate constant of Sb(III) removal by the BOHAs was 32.4, 3.0, and 4.3 times higher than those of BiAsO 4 , BOHP, and TiO 2 , respectively, indicating that the introduction of hydroxyls could increase the removal of Sb(III). Additionally, the crucial operational parameters affecting the adsorption performance (catalyst dosage, concentration, pH, and common anions) were investigated. The BOHAs maintained 85% antimony decontamination of the initial yield after five successive cycles of photocatalysis. The Sb(III) removal involved photocatalytic oxidation of adsorbed Sb(III) and subsequent adsorption of the yielded Sb(V). With the acquired knowledge, we successfully applied the photocatalyst for antimony removal from industrial wastewater. In addition, BOHAs could also be powerful photocatalysts in the photodegradation of organic pollutants studies of which are ongoing. It reveals an effective strategy for synthesizing bismuth-based photocatalysts with hydroxyls and enhancing pollutants' decontamination., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

A majority of clay minerals contain Fe, and the redox cycling of Fe(III)/Fe(II) in clay minerals has been extensively studied as it may fuel the biogeochemical cycles of nutrients and govern the mobility, toxicity and bioavailability of a number of environmental contaminants. There are three types of Fe in clay minerals, including structural Fe sandwiched in the lattice of clays, Fe species in interlayer space and adsorbed on the external surface of clays. They exhibit distinct reactivity towards contaminants due to their differences in redox properties and accessibility to contaminant species. In natural environments, microbially driven Fe(III)/Fe(II) redox cycling in clay minerals is thought to be important, whereas reductants (e.g., dithionite and Fe(II)) or oxidants (e.g., peroxygens) are capable of enhancing the rates and extents of redox dynamics in engineered systems. Fe(III)-containing clay minerals can directly react with oxidizable pollutants (e.g., phenols and polycyclic aromatic hydrocarbons (PAHs)), whereas structural Fe(II) is able to react with reducible pollutants, such as nitrate, nitroaromatic compounds, chlorinated aliphatic compounds. Also structural Fe(II) can transfer electrons to oxygen (O 2 ), peroxymonosulfate (PMS), or hydrogen peroxide (H 2 O 2 ), yielding reactive radicals that can promote the oxidative transformation of contaminants. This review summarizes the recent discoveries on redox reactivity of Fe in clay minerals and its links to fates of environmental contaminants. The biological and chemical reduction mechanisms of Fe(III)-clay minerals, as well as the interaction mechanism between Fe(III) or Fe(II)-containing clay minerals and contaminants are elaborated. Some knowledge gaps are identified for better understanding and modelling of clay-associated contaminant behavior and effective design of remediation solutions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The iron mineral-catalyzed degradation of cephalosporin antibiotics with H 2 O 2 occurs ubiquitously in nature. Despite numerous studies, the effects of environmental conditions on reactive species production and degradation processes of cephalosporins remain unclear. Here, we report the iron mineral of goethite as the efficient and heterogenous catalyst for the degradation of cefradine (CRD) via H 2 O 2 activation under different conditions involving pH and visible light irradiation. Results show that the CRD removal rate is highly dependent on pH and visible light irradiation. Interestingly, when the pH ranges from 4.0 to 7.0, the degradation intermediates of CRD under dark are the same as under visible light conditions in the goethite/H 2 O 2 system. And, the ratio of CRD degradation rate constant (k Light /k Dark ) reaches a maximum at pH 5.0, suggesting that CRD existing as zwitterion species is preferable for its removal with photoassistance. The mechanism investigation reveals that both •OH and ≡[Fe IV O] 2+ oxidants are generated during the reaction process, and •OH is the major oxidant at acidic pH, while ≡[Fe IV O] 2+ is more likely to be formed with photoassistance at near-neutral pH. According to UPLC-MS/MS analysis, CRD degradation likely happens via hydrogen atom abstraction from cyclohexadienyl by •OH, thioether and olefin oxidation by ≡[Fe IV O] 2+ , and Fe III -catalyzed hydrolytic cleavage of β-lactam ring. These findings highlight the vital roles of pH and photoassistance in the heterogeneously activated H 2 O 2 with goethite for CRD degradation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Surface-plasmon-mediated phenylacetylide intermediate transfer from the Cu to the Pd surface affords a novel mechanism for transmetalation, enabling wavelength-tunable cross-coupling and homo-coupling reaction pathway control. C-C bond forming Sonogashira coupling and Glaser coupling reactions in O 2 atmosphere are efficiently driven by visible light over heterogeneous Cu and Pd nanoparticles as a mixed catalyst without base or other additives. The reaction pathway can be controlled by switching the excitation wavelength. Shorter wavelengths (400-500 nm) give the Glaser homo-coupling diyne, whereas longer wavelength irradiation (500-940 nm) significantly increases the degree of cross-coupling Sonogashira coupling products. The ratio of the activated intermediates of alkyne to the iodobenzene is wavelength dependent and this regulates transmetalation. This wavelength-tunable reaction pathway is a novel way to optimize the product selectivity in important organic syntheses., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Direct photocatalytic CO 2 reduction from primary sources, such as flue gas and air, into fuels, is highly desired, but the thermodynamically favored O 2 reduction almost completely impedes this process. Herein, we report on the efficacy of a composite photocatalyst prepared by hyper-crosslinking porphyrin-based polymers on hollow TiO 2 surface and subsequent coordinating with Pd(II). Such composite exhibits high resistance against O 2 inhibition, leading to 12% conversion yield of CO 2 from air after 2-h UV-visible light irradiation. In contrast, the CO 2 reduction over Pd/TiO 2 without the polymer is severely inhibited by the presence of O 2 ( ≥ 0.2 %). This study presents a feasible strategy, building Pd(II) sites into CO 2 -adsorptive polymers on hollow TiO 2 surface, for realizing CO 2 reduction with H 2 O in an aerobic environment by the high CO 2 /O 2 adsorption selectivity of polymers and efficient charge separation for CO 2 reduction and H 2 O oxidation on Pd(II) sites and hollow TiO 2 , respectively., (© 2022. The Author(s).)

High-risk arsenic contamination found in aqueous system is reported across the world and causing severe environmental issues. In this study, the Mg-Al Layered Double Hydroxide (LDH) modified by sulphur species (LDH-S) was found exhibiting high effectivity and selectivity in As(V) removal owing to the strong interaction between embedded HS - and AsO 4 3- . The LDH-S with Mg to Al ratio 2-1 give the best performance with As(V) adsorption capacity 40.8 mg/g, which is 715% higher than that of pristine LDH (2-1). The adsorbent exhibits a high tolerance to concentrated competitive anions. In the continuous flow test, the adsorbent can reduce the As(V) concentration from 20 ppm to below-ppb-level indicating the potential in industry application. The adsorption mechanism is experimentally investigated and examined by Density Function Theory (DFT) calculation. The result illustrates that, differ from the traditional ion exchange mechanism of LDH, the enhanced removal capacity and selectivity of LDH-S for As(V) is attributed to the strong affinity between H atom from HS- ion (in the interlayer region of LDH) and the O atom from AsO 4 3- ., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier Inc.)

The practical applications of non-aqueous lithium-oxygen batteries are impeded by large overpotentials and unsatisfactory cycling durability. Reported here is that commonly encountered fatal problems can be efficiently solved by using a carbon- and binder-free electrode of titanium coated with TiO 2 nanotube arrays (TNAs) and gold nanoparticles (AuNPs). Ultraviolet irradiation of the TNAs generates positively charged holes, which efficiently decompose Li 2 O 2 and Li 2 CO 3 during recharging, thereby reducing the overpotential to one that is near the equilibrium potential for Li 2 O 2 formation. The AuNPs promote Li 2 O 2 formation, resulting in a large discharge capacity. The electrode exhibits excellent stability with about 100 % coulombic efficiency during continuous cycling of up to 200 cycles, which is due to the carbon- and binder-free composition. This work reveals a new strategy towards the development of highly efficient oxygen electrode materials for lithium-oxygen batteries., (© 2020 Wiley-VCH GmbH.)

We report a platinum nanocluster/graphitic carbon nitride (Pt/g-C 3 N 4 ) composite solid catalyst with a photocatalytic anaerobic oxidation function for highly active and selective transformation of alcohols to ketones. The desirable products were successfully obtained in good to excellent yields from various functionalized alcohols at room temperature, including unactivated alcohols. Mechanistic studies indicated that the reaction could proceed through a Pt-mediated hole oxidation initiating an α-alcohol radical intermediate followed by a two-electron oxidation pathway. The merit of this strategy offers a general approach towards green and sustainable organic synthetic chemistry.

In this study, we report a Janus- or twins-type honeycomb 3D porous nitrogen-doped carbon (NC) nanosheet array encapsulating ultrafine CoP/Co 2 P nanorods supported on Ti foil (CoP/Co 2 P@NC/Ti) as a self-supported electrode for efficient hydrogen evolution. The synthesis and formation mechanism of 3D porous NC nanosheet array assembled into a honeycomb layer with ultrafine CoP/Co 2 P single-crystal nanorods encapsulated is systematically presented. The CoP/Co 2 P@NC/Ti electrode exhibits low overpotentials (η 10 ) of 31, 49, and 64 mV at a current density of -10 mA cm -2 in 0.5 M H 2 SO 4 , 1.0 KOH, and 1.0 M PBS, respectively, exceeding the overwhelming majority of the documented transition metal phosphide-based electrocatalysts. Density functional theory calculation reveals that the superior electrocatalytic performance for hydrogen evolution reaction could be ascribed to the strong coupling effects of the reactive facets of CoP and Co 2 P with the 3D porous NC nanosheet, making it exhibit a more thermo-neutral hydrogen adsorption free energy., Competing Interests: Declaration of Interests The authors declare no competing interests., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Transition-metal-doping can improve some physical properties of titanium dioxide (TiO 2 ) nanowires (NWs), which leads to important applications in miniature devices. Here, we investigated the elastic moduli of single-crystalline pristine and Fe-doped rutile TiO 2 NWs using the three-point bending method, which is taken as a case study of impacts on the elastic properties of TiO 2 NWs caused by transition-metal-doping. The Young's modulus of the pristine rutile TiO 2 NWs decreases when the cross-sectional area increases (changing from 246 GPa to 93.2 GPa). However, the elastic modulus of the Fe-doped rutile NWs was found to increase with the cross-sectional area (changing from 91.8 GPa to 200 GPa). For NWs with similar geometrical size, the elastic modulus (156.8 GPa) for Fe-doped rutile NWs is 24% smaller than that (194.5 GPa) of the pristine rutile TiO 2 NWs. The vacancies generated by Fe-doping are supposed to cause the reduction of elastic modulus of rutile TiO 2 NWs. This work provides a fundamental understanding of the effects of transition-metal-doping on the elastic properties of TiO 2 NWs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

It is challenging but important to understand the mechanical properties of one-dimensional (1D) nanomaterials for their design and integration into nanodevices. Generally, brittle ceramic nanowires (NWs) cannot withstand a large bending strain. Herein, in situ bending deformation of titanium dioxide (TiO 2 ) NWs with a bronze/anatase dual-phase was carried out inside a transmission electron microscopy (TEM) system. An ultralarge bending strain up to 20.3% was observed on individual NWs. Through an in situ atomic-scale study, the large bending behavior for a dual-phase TiO 2 NW was found to be related to a continuous crystalline-structure evolution including phase transition, small deformation twinning, and dislocation nucleation and movements. Additionally, no amorphization or crack occurred in the dual-phase TiO 2 NW even under an ultralarge bending strain. These results revealed that an individual ceramic NW can undergo a large bending strain with rich defect activities.

A carbon electrode with low cost and high stability exhibited competitiveness for its practical application in organic-inorganic hybrid perovskite solar cells (PSCs). Nonetheless, issues such as poor interface contact with an adjacent perovskite layer and obvious hysteresis phenomenon are bottlenecks that need to be overcome to make carbon-based PSCs (C-PSCs) more attractive in practice. Herein, we report an effective method to enhance the interfacial charge transport of C-PSCs by introducing the CuSCN material into the device. Two types of CuSCN-assisted devices were studied in this work. One was based on the deposition of an ultrathin CuSCN layer between the perovskite absorber layer and the carbon cathode (PSK/CuSCN/C), and the other was by infiltrating CuSCN solution into the carbon film (PSK/C-CuSCN) by taking advantage of the macroporous structure of the carbon. We have found that the CuSCN incorporation by both methods can effectively address the hysteretic feature in planar C-PSCs. The origin for the hysteresis evolution was unraveled by the investigation of the energy alignment and the kinetics of interfacial charge transfer and hole trap-state density. The results have shown that both types of CuSCN-containing devices showed improved interfacial charge carrier extraction, suppressed carrier recombination, reduced trap-state density, and enhanced charge transport, leading to negligible hysteresis. Furthermore, the CuSCN-incorporated C-PSCs demonstrated enhanced device stability. The power conversion efficiency remained 98 and 91% of the initial performance (13.6 and 13.4%) for PSK/CuSCN/C and PSK/C-CuSCN, respectively, after being stored under a high humidity (75-85%) environment for 10 days. The devices also demonstrated extraordinary long-term stability with a negligible performance drop after being stored in air (relative humidity: 33-35%) for 90 days.

A study on the mechanical properties of one-dimensional layered titanate nanomaterials is crucial since they demonstrate important applications in various fields. Here, we conducted ex situ and in situ atomic-scale investigation on the bending properties of a kind of ceramic-layered titanate (Na2Ti2O4(OH)2) nanowire using transmission electron microscopy. The nanowires showed flexibility along the 100 direction and could obtain a maximum bending strain of nearly 37%. By analysing the defect behaviours, the unique bending properties of this ceramic material were found to correlate with a novel arrangement of dislocations, an active dislocation nucleation and movement along the axial direction resulting from the weak electrostatic interaction between the TiO6 layers and the low b/a ratio. These results provide a pioneering and key understanding on the bending behaviours of layered titanate nanowire families and potentially other one-dimensional nanomaterials with layered crystalline structures.

In situ tensile tests show atypical defect motions in the brittle Na 2 Ti 3 O 7 (NTO) nanowire (NW) within the elastic deformation range. After brittle fracture, elastic recovery of the NTO NW is followed by reversible motion of the defects in a time-dependent manner. An in situ cyclic loading-unloading test shows that these mobile defects shift back and forth along the NW in accordance with the loading-unloading cycles and eventually restore their initial positions after the load is completely removed. The existence of the defects within the NTO NWs and their motions does not lead to plastic deformation of the NW. The atypical defect motion is speculated to be the result of the glidibility of the TiO 6 layers, where weakly bonded cation layers are in between. Exploration of the above novel observation can establish new understandings of the deformation behavior of superlattice nanostructures.

Removal of the toxic selenium compounds, selenite (SeO 3 2- ) and selenate (SeO 4 2- ), from contaminated water is imperative for environmental protection in both developing and industrialized countries. Providing high selectivity adsorbents to the target ions is a big challenge. Here we report that micro sphere-like δ-Bi 2 O 3 (MS-δ-Bi 2 O 3 ) with surface oxygen vacancy defects can capture hypertoxic SeO x 2- anions from aqueous solutions with superior capacity and fast uptake rate. High capture selectivity to SeO 3 2- anions is observed, since the O atoms of SeO 3 2- anions fill the oxygen vacancies on the (111) facet of δ-Bi 2 O 3 forming a stable complex structure. This mechanism is distinctly different from other known mechanisms for anion removal, and implies that we may utilize surface defects as highly efficient and selective sites to capture specific toxic species. Thus, we present a new route here to design superior adsorbents for toxic ions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is one of the key reactions for producing chemical commodities from biomass and their derivatives. The challenge for this reaction is to develop an efficient catalytic process that can be conducted under mild conditions (room temperature and atmospheric pressure, using oxygen molecules in air as the oxidant) and a recyclable catalyst. Herein we report a photocatalyst of cobalt thioporphyrazine (CoPz) dispersed on g-C 3 N 4 (abbreviated as CoPz/g-C 3 N 4 ), which exhibits excellent catalytic activity toward the selective oxidation of HMF into FDCA under simulated sunlight using oxygen molecules in air as a benign oxidant. For example, an FDCA yield of 96.1% in an aqueous solution at pH = 9.18 is achieved at ambient temperature and air pressure. At lower pH (4.01), the product generated is 2,5-diformylfuran. Hence, it is possible to control the reaction outcome by control of the pH of the reaction system. g-C 3 N 4 itself is not a suitable catalyst for the selective oxidation because under the experimental conditions g-C 3 N 4 generates hydroxyl radicals that initiate processes that oxidize HMF directly to CO 2 and H 2 O. CoPz on the other hand activates O 2 to give singlet oxygen ( 1 O 2 ), which more controllably oxidizes HMF to FDCA albeit at a more moderate yield (36.2%). The strong interaction between the CoPz and g-C 3 N 4 in the CoPz/g-C 3 N 4 catalyst is experimentally evidenced, which not only improves accessibility of the CoPz sites and makes the catalyst recyclable but also disables the hydroxyl radical generation by g-C 3 N 4 and promotes 1 O 2 generation on the CoPz sites, significantly enhancing the catalytic performance. This study demonstrates the potential for efficient non-noble metal photocatalysts for organic transformations driven by sunlight.

Construction of nanoarchitectures requires techniques like joint formation and trimming. For ceramic materials, however, it is extremely difficult to form nanojoints by conventional methods like merging. In this work, we demonstrate that ceramic titanate nanowires (NWs) can be joined by spot melting under electron beam (e-beam) irradiation (EBI). The irradiation fuses the contacted spot of titanate NWs yielding an intact nanojoint. Nanojoints with different morphologies can be produced. The joint structures consist of titanium dioxide (TiO 2 ) rutile, anatase, and titanate phases in the direction away from the e-beam melting spot. The titanate binds to anatase via a crystallographic matching coherent interface (the oxygen atoms at the interface are shared by the two phases) and the anatase solidly binds to the rutile joint. The resulting rutile joint is stable at high temperatures. Additionally, it is demonstrated that the heat production from EBI treated rutile can be utilized to break metal NWs (Ag, Cu, and Ni) apart by spot melting. The required e-beam intensity is considerably mild (75 pA/cm 2 ) which allows visual access and control over the NW melting. Direct melting of Ag and Cu is not applicable under EBI due to their high thermal conductivity even with high current density (500 pA/cm 2 ). Our findings reveal that ceramic nanojoint formation and spot melting at nanoscale are applicable if the properties of nanomaterials are understood and properly utilized.

To achieve uniform carbon coating on TiO2 nanomaterials, high temperature (>500 °C) annealing treatment is a necessity. However, the annealing treatment inevitably leads to the strong phase transformation from TiO2(B) with high lithium ion storage (LIS) capacity to anatase with low LIS one as well as the damage of nanostructures. Herein, we demonstrate a new approach to create TiO2(B)/carbon core/shell nanotubes (C@TBNTs) using a long-chain silane polymethylhydrosiloxane (PMHS) to bind the TBNTs by forming Si-O-Ti bonds. The key feature of this work is that the introduction of PMHS onto TBNTs can afford TBNTs with very high thermal stability at higher than 700 °C and inhibit the phase transformation from TiO2(B) to anatase. Such a high thermal property of PMHS-TBNTs makes them easily coated with highly graphitic carbon shell via CVD process at 700 °C. The as-prepared C@TBNTs deliver outstanding rate capability and electrochemical stability, i.e., reversible capacity above 250 mAh g(-1) at 10 C and a high specific capacity of 479.2 mAh g(-1) after 1000 cycles at 1 C. As far as we know, the LIS performance of our sample is the highest among the previously reported TiO2(B) anode materials.

Hydrotalcite (HT)-based materials are usually applied to capture anionic pollutants in aqueous solutions. Generally considered anion exchangers, their ability to capture radioactive cations is rarely exploited. In the present work, we explored the ability of pristine and calcined HT getters to effectively capture radioactive cations (Sr(2+) and Ba(2+)) which can be securely stabilized at the getter surface. It is found that calcined HT outperforms its pristine counterpart in cation removal ability. Meanwhile, a novel anion removal mechanism targeting radioactive I(-) is demonstrated. This approach involves HT surface modification with silver species, namely, Ag2CO3 nanoparticles, which can attach firmly on HT surface by forming coherent interface. This HT-based anion getter can be further used to capture I(-) in aqueous solution. The observed I(-) uptake mechanism is distinctly different from the widely reported ion exchange mechanism of HT and much more efficient. As a result of the high local concentrations of precipitants on the getters, radioactive ions in water can be readily immobilized onto the getter surface by forming precipitates. The secured ionic pollutants can be subsequently removed from water by filtration or sedimentation for safe disposal. Overall, these stable, inexpensive getters are the materials of choice for removal of trace ionic pollutants from bulk radioactive liquids, especially during episodic environmental crisis.

Recent advances in direct-use plasmonic-metal nanoparticles (NPs) as photocatalysts to drive organic synthesis reactions under visible-light irradiation have attracted great interest. Plasmonic-metal NPs are characterized by their strong interaction with visible light through excitation of the localized surface plasmon resonance (LSPR). Herein, we review recent developments in direct photocatalysis using plasmonic-metal NPs and their applications. We focus on the role played by the LSPR of the metal NPs in catalyzing organic transformations and, more broadly, the role that light irradiation plays in catalyzing the reactions. Through this, the reaction mechanisms that these light-excited energetic electrons promote will be highlighted. This review will be of particular interest to researchers who are designing and fabricating new plasmonic-metal NP photocatalysts by identifying important reaction mechanisms that occur through light irradiation., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nitrogen-doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400-700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N-doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface-bonded N species, whereas the core remains N doped. N-Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible-light irradiation. The surface-oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N-doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N-doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible-light-driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N-doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N-doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Cerium ions (Ce(3+)) can be selectively doped into the TiO2(B) core of TiO2(B)/anatase core-shell nanofibers by means of a simple one-pot hydrothermal treatment of a starting material of hydrogen trititanate (H2Ti3O7) nanofibers. These Ce(3+) ions (≈0.202 nm) are located on the (110) lattice planes of the TiO2(B) core in tunnels (width≈0.297 nm). The introduction of Ce(3+) ions reduces the defects of the TiO2(B) core by inhibiting the faster growth of (110) lattice planes. More importantly, the redox potential of the Ce(3+)/Ce(4+) couple (E°(Ce(3+)/Ce(4+))=1.715 V versus the normal hydrogen electrode) is more negative than the valence band of TiO2(B). Therefore, once the Ce(3+)-doped nanofibers are irradiated by UV light, the doped Ce(3+) ions--in close vicinity to the interface between the TiO2(B) core and anatase nanoshell--can efficiently trap the photogenerated holes. This facilitates the migration of holes from the anatase shell and leaves more photogenerated electrons in the anatase nanoshell, which results in a highly efficient separation of photogenerated charges in the anatase nanoshell. Hence, this enhanced charge-separation mechanism accelerates dye degradation and alcohol oxidation processes. The one-pot treatment doping strategy is also used to selectively dope other metal ions with variable oxidation states such as Co(2+/3+) and Cu(+/2+) ions. The doping substantially improves the photocatalytic activity of the mixed-phase nanofibers. In contrast, the doping of ions with an invariable oxidation state, such as Zn(2+), Ca(2+), or Mg(2+), does not enhance the photoactivity of the mixed-phase nanofibers as the ions could not trap the photogenerated holes., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Emergency treatment of radioactive material leakage and safety disposal of nuclear waste is a constant concern all along with the development of radioactive materials applications. To provide a solution, titanate with large surface area (143 m(2)g(-1)) and a lamina morphology (the thickness of the lamina is in range of tens of nanometers) was prepared from inorganic titanium compounds by hydrothermal reactions at 433 K. Ag(2)O nanocrystals (5-30 nm) were deposited onto the titanate lamina. The surface of the titanate lamina has crystallographic similarity to that of Ag(2)O nanocrystals. Hence, the deposited Ag(2)O nanocrystals and titanate substrate join together at these surfaces, forming a well-matched phase coherent interface between them. Such coherence between the two phases reduces the overall energy by minimizing surface energy and anchors the Ag(2)O nanocrystals firmly on the external surface of the titanate structure. The composite thus obtained was applied as efficient adsorbent to remove radioactive iodine from water (one gram adsorbent can capture up to 3.4 mmol of I(-) anions). The composite adsorbent can be recovered easily for safe disposal. The structure changes of the titanate lamina and the composite adsorbent were monitored by various techniques. The isotherm and kinetics of iodine adsorption, competitive adsorption and column adsorption using the adsorbent were studied to assess its iodine removal abilities. The adsorbent exhibited a capacity as high as 3.4 mmol of iodine per gram of adsorbent in 1h. Therefore, Ag(2)O deposited titanate lamina is an effective adsorbent for removing radioactive iodine from water., (Copyright © 2013 Elsevier B.V. All rights reserved.)

With new photocatalysts of gold nanoparticles supported on zeolite supports (Au/zeolite), oxidation of benzyl alcohol and its derivatives into the corresponding aldehydes can proceed well with a high selectivity (99 %) under visible-light irradiation at ambient temperature. Au/zeolite photocatalysts were characterised by UV/Vis, X-ray photoelectron spectroscopy (XPS), TEM, XRD, energy-dispersive spectroscopy (EDS), Brauner-Emmet-Teller (BET) analyses, IR and Raman techniques. The surface plasmon resonance (SPR) effect of gold nanoparticles, the adsorption capability of zeolite supports and the molecular polarities of aromatic alcohols were demonstrated to have an essential correlation with the photocatalytic performances. In addition, the effects of light intensity, wavelength range and the role of molecular oxygen were investigated in detail. The kinetic study indicated that the visible-light irradiation required much less apparent activation energy for photooxidation compared with thermal reaction. Based on the characterisation data and the photocatalytic performances, we proposed a possible photooxidation mechanism., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The hydrothermal formation of branched titanate nanotubes that grow a 3D nanotubular network directly onto a titanium substrate is reported. The resultant 3D nanotubular network exhibits a unique all-dimensional uniform porous structure. The inner and outer tubular diameters of branched titanate nanotubes were found to be approximately 6 and 12 nm, respectively. For the majority of the nanotubes, the wall is formed from three layers of titanate with an approximate 7.7 A interlayer space. In terms of individual nanotubes, these characteristics are quantitatively similar to those of previously reported nonbranched nanotubes. However, in terms of how nanotubes are arranged in the film, the all-dimensional uniform nanotubular network structure obtained here is distinctively different from those of previously reported structures. The 3D nanotubular network structure was formed by the jointing of branched nanotubes. In contrast, the previously reported nanotubes tend to grow vertically on the substrate, and the resultant tubular films are formed by interwoven nonbranched nanotubes. The branched titanate nanotubes can be readily formed on titanium substrates but not in solution suspension forms. A continuous seed formation-oriented crystal growth mechanism was proposed for the branched titanate nanotubular network formation. Such a network structure could be useful for applications such as photocatalysis, membrane separation, field emission, and photovoltaic devices.

Three catalytic oxidation reactions have been studied: The ultraviolet (UV) light induced photocatalytic decomposition of the synthetic dye sulforhodamine B (SRB) in the presence of TiO(2) nanostructures in water, together with two reactions employing Au/TiO(2) nanostructure catalysts, namely, CO oxidation in air and the decomposition of formaldehyde under visible light irradiation. Four kinds of TiO(2) nanotubes and nanorods with different phases and compositions were prepared for this study, and gold nanoparticle (Au-NP) catalysts were supported on some of these TiO(2) nanostructures (to form Au/TiO(2) catalysts). FTIR emission spectroscopy (IES) measurements provided evidence that the order of the surface OH regeneration ability of the four types of TiO(2) nanostructures studied gave the same trend as the catalytic activities of the TiO(2) nanostructures or their respective Au/TiO(2) catalysts for the three oxidation reactions. Both IES and X-ray photoelectron spectroscopy (XPS) proved that anatase TiO(2) had the strongest OH regeneration ability among the four types of TiO(2) phases or compositions. Based on these results, a model for the surface OH group generation, absorption, and activation of molecular oxygen has been proposed: The oxygen vacancies at the bridging O(2-) sites on TiO(2) surfaces dissociatively absorb water molecules to form OH groups that facilitate adsorption and activation of O(2) molecules in nearby oxygen vacancies by lowering the absorption energy of molecular O(2). A new mechanism for the photocatalytic formaldehyde decomposition with the Au/TiO(2) catalysts is also proposed, based on the photocatalytic activity of the Au-NPs under visible light. The Au-NPs absorb the light owing to the surface plasmon resonance effect and mediate the electron transfers that the reaction needs.

Synergistic interactions between N and F can be used to tune the band structures of N-doped TiO(2) (see scheme). Reduction potential of conduction band electron is positively shifted to weaken unwanted O(2) reduction, but enhances the target reduction reaction in air. The tuning also enhances the oxidation ability of the valence band to oxidize water to O(2), which makes photocatalytic reduction proceed without any organic sacrificial reagents.

Niobium pentoxide reacts actively with concentrate NaOH solution under hydrothermal conditions at as low as 120 degrees C. The reaction ruptures the corner-sharing of NbO(7) decahedra and NbO(6) octahedra in the reactant Nb(2)O(5), yielding various niobates, and the structure and composition of the niobates depend on the reaction temperature and time. The morphological evolution of the solid products in the reaction at 180 degrees C is monitored via SEM: the fine Nb(2)O(5) powder aggregates first to irregular bars, and then niobate fibers with an aspect ratio of hundreds form. The fibers are microporous molecular sieve with a monoclinic lattice, Na(2)Nb(2)O(6).(2)/(3)H(2)O. The fibers are a metastable intermediate of this reaction, and they completely convert to the final product NaNbO(3) cubes in the prolonged reaction of 1 h. This study demonstrates that by carefully optimizing the reaction condition, we can selectively fabricate niobate structures of high purity, including the delicate microporous fibers, through a direct reaction between concentrated NaOH solution and Nb(2)O(5). This synthesis route is simple and suitable for the large-scale production of the fibers. The reaction first yields poorly crystallized niobates consisting of edge-sharing NbO(6) octahedra, and then the microporous fibers crystallize and grow by assembling NbO(6) octahedra or clusters of NbO(6) octahedra and NaO(6) units. Thus, the selection of the fibril or cubic product is achieved by control of reaction kinetics. Finally, niobates with different structures exhibit remarkable differences in light absorption and photoluminescence properties. Therefore, this study is of importance for developing new functional materials by the wet-chemistry process.

Hydrogen titanate nanofibers synthesized by a hydrothermal reaction, are chemically reactive, readily reacting with dilute acid. This reaction is a topochemical process in which in situ phase transition from H-titanate to anatase takes place and the product retains the fibril morphology. The extent of this reaction can be precisely controlled, allowing us to achieve a delicate composite structure at nanoscale: long titanate fibers of 40-100 nm thick and up to 30 mum long covered with anatase nanocrystals of 10-30 nm. The structure has desired photocatalytic properties and can be separated readily after use. This study demonstrates new opportunities to create delicate inorganic nanostructures with advanced functions by wet chemical reactions.