Topographical and crystalline change on surface by sandblasting improve flexural and shear bond strength of niobia-modified yttria-stabilized tetragonal zirconia polycrystal.

This study aimed to investigate the effects of sandblasting on the physical properties and bond strength of two types of translucent zirconia: niobium-oxide-containing yttria-stabilized tetragonal zirconia polycrystals ((Y, Nb)-TZP) and 5 mol% yttria-partially stabilized zirconia (5Y-PSZ). Fully sintered disc specimens were either sandblasted with 125 µm alumina particles or left as-sintered. Surface roughness, crystal phase compositions, and surface morphology were explored. Biaxial flexural strength (n=10) and shear bond strength (SBS) (n=12) were evaluated, including thermocycling conditions. Results indicated a decrease in flexural strength of 5Y-PSZ from 601 to 303 MPa upon sandblasting, while (Y, Nb)-TZP improved from 458 to 544 MPa. Both materials significantly increased SBS after sandblasting (p<0.001). After thermocycling, (Y, Nb)-TZP maintained superior SBS (14.3 MPa) compared to 5Y-PSZ (11.3 MPa) (p<0.001). The study concludes that (Y, Nb)-TZP is preferable for sandblasting applications, particularly for achieving durable bonding without compromising flexural strength.

Trimetallic Chalcogenide Species: Synthesis, Structures, and Bonding.

In an attempt to isolate boron-containing tri-niobium polychalcogenide species, we have carried out prolonged thermolysis reactions of [Cp*NbCl4] (Cp* = ɳ5-C5Me5) with four equivalents of Li[BH2E3] (E = Se or S). In the case of the heavier chalcogen (Se), the reaction led to the isolation of the tri-niobium cubane-like cluster [(NbCp*)3(µ3-Se)3(BH)(µ-Se)3] (1) and the homocubane-like cluster [(NbCp*)3(µ3-Se)3(µ-Se)3(BH)(µ-Se)] (2). Interestingly, the tri-niobium framework of 1 stabilizes a selenaborate {Se3BH}- ligand. A selenium atom is further introduced between boron and one of the selenium atoms of 1 to yield cluster 2. On the other hand, the reaction with the sulfur-containing borate adduct [LiBH2S3] afforded the trimetallic clusters [(NbCp*)3(µ-S)4{µ-S2(BH)}] (3) and [(NbCp*)3(µ-S)4{µ-S2(S)}] (4). Both clusters 3 and 4 have an Nb3S6 core, which further stabilizes {BH} and mono-sulfur units, respectively, through bi-chalcogen coordination. All of these species were characterized by 11B{1H}, 1H, and 13C{1H} NMR spectroscopy, mass spectrometry, infrared (IR) spectroscopy, and single-crystal X-ray crystallography. Moreover, theoretical investigations revealed that the triangular Nb3 framework is aromatic in nature and plays a vital role in the stabilization of the borate, borane, and chalcogen units.

Release behavior and mechanism of uranium and thorium from Ta-Nb tailings under simulated rainfall in Jiangxi Province, China.

Tantalum-niobium ore belongs to associated radioactive ore, which is accompanied by a certain amount of radioactive uranium and thorium. The remaining slag is enriched with a large number of radionuclides; after weathering, natural rainfall, and surface water scouring, radioactive elements such as uranium, thorium, and some heavy metal elements are exposed or washed into the soil, which poses a threat to the ecological environment and human health. In this study, for characterization analysis during, before, and after leaching, dynamic simulation experiment was carried out on a Ta-Nb slag sample in Jiangxi, China. From SEM analysis, the soluble substances adsorbed on the slag surface dissolve into the solution after leaching in simulated rainfall, and the remained slag becomes smooth with different particle sizes. The XRD diffraction analysis of the sample showed that after leaching in simulated rainfall, the existing forms of elements are different. pH of the leachate of Ta-Nb slag is 1.79; Ta-Nb slag contains many rare metal elements, nonmetal elements, radioactive elements, and some salt compounds; and the content of thorium is higher than that of uranium by EDS analysis. The release of uranium and thorium is obviously affected by the amount of leachate and pH. Under the lower pH of leaching solution, the release of uranium and thorium is more effective. The results of Fick diffusion theory and Elovich equation show that the release and migration mode of uranium and thorium in Ta-Nb slag are mainly surface elution; under acidic conditions, the release and migration of uranium and thorium are faster. This study provides basic data and scientific information for solving the key problems of pollution control of associated radioactive waste in environmental protection.

Functionalized 2D Nb2C nanosheets for primary and recurrent cancer photothermal/immune-therapy in the NIR-II biowindow.

Near-infrared-II (NIR-II) cancer photothermal therapy (PTT) has become more and more attractive as the NIR-II light shows a higher tissue penetrating depth, which leads to better anti-cancer effects. Recently, the members of the MXene family have been reported as NIR-II photothermal agents, possessing a high specific surface area and a fascinating light-to-heat conversion rate at the same time. Herein, we reported a combination of NIR-II photothermal therapy and immune therapy based on the MXene family member niobium carbide (Nb2C). First, Nb2C nanosheets (NSs) under 50 nm were prepared. They showed a high photothermal conversion efficiency under a 1064-nm laser, and the NIR-II light showed a deeper tissue penetration depth. Then, a nanoplatform with high R837 stability and a high loading rate was obtained after modification with a polydopamine (PDA) layer on the surface of Nb2C. With the R837 modification, the percentage of mature dendritic cells (DCs) increased and the immune response enhanced, compared with the immune response caused by PTT only. Finally, a red blood cell (RBC) membrane was applied as a coat over the nanoplatform in order to avoid excessive blood clearance. During in vivo experiments, blood circulation of Nb2C@PDA-R837@RBC nanoparticles (NPs) was prolonged, and all primary tumors were eliminated. Secondary tumors were also inhibited effectively due to the strengthened immune response, proving that Nb2C@PDA-R837@RBC NPs could inhibit tumor recurrence. All the results above indicated Nb2C@PDA-R837@RBC NPs as a potential RBC camouflaged nanoplatform for the combination of effective PTT and immune therapy towards tumor treatment.

Niobium Carbide MXene Augmented Medical Implant Elicits Bacterial Infection Elimination and Tissue Regeneration.

Incurable bacterial infections, impenetrable microbial biofilm, and irreversible antibiotic resistance are among the most dangerous threats for humans. With few effective strategies available in antimicrobial and antibiofilm development, innovative methodologies inspired by the advances in other fields such as nanomedicine are becoming more and more attractive to realize innovative antibacterial agents. Herein, a 2D niobium carbide (Nb2C) MXene titanium plate (Nb2C@TP)-based clinical implant with practical multimodal anti-infection functions was developed. Such emerging modes are capable of destroying biofilms for direct bacteria elimination through down-regulating bacterial energy metabolism pathways, suppressing biofilm formation, and enhancing as-formed biofilm detachment via an activating accessory gene regulator. Another intriguing feature of this nanomedicine is the sensitization ability toward bacteria via photothermal transduction, which reduces the temperature necessary for bacteria eradication and mitigates possible normal tissue damage. Moreover, the Nb2C@TP medical implant is able to alleviate proinflammatory responses by scavenging excessive reactive oxygen species in infectious microenvironments, benefiting angiogenesis and tissue remodeling.

Photocatalytic degradation of nevirapine with a heterostructure of few-layer black phosphorus coupled with niobium (V) oxide nanoflowers (FL-BP@Nb2O5).

The degradation and removal of antiviral drugs in water has emerged remains a major challenge. This work presents, the photodegradation of nevirapine (NVP) with a novel p-n heterostructure of FL-BP@Nb2O5 nanoparticles synthesized via hydrothermal method. Several characterization techniques revealed a successful formation of the heterostructure with well aligned band positions that promoted excellent separation of charge carriers. A systematic study was conducted on the effect of initial pH, initial catalyst loading and initial concentration on the degradation kinetics of NVP. Degradation efficiency of 68% was achieved with the FL-BP@Nb2O5 after 3 h with 5 ppm initial concentration solution of NVP, at a working pH of 3 and 15 mg of photocatalyst. The stable fragment resulting from the degradation of NVP was n-butanol as evidenced by LC/MS. The successful degradation of NVP transpired with synergistic effect exhibited by the heterostructure that led to accelerated formation of reactive species that were responsible for the breaking down of NVP into smaller fragments. A TOC removal percentage of 19.03% after the photodegradation of NVP was observed, suggesting a successful break down of NVP to simpler non-toxic carbon-containing compounds.

Preparation and characterization of Pectin/Polypyrrole based multifunctional coatings on TiNbZr alloy for orthopaedic applications.

Being a natural and renewable polysaccharide, pectin (PC) is considered a polymer with promising potential for many applications. In the present investigation, novel multifunctional pectin/polypyrrole (PC/PPy) composite coatings loaded with gentamicin (GM) were electrochemically deposited on TiNbZr alloy to enhance its biocompatibility, antibacterial performance and corrosion resistance in physiological environment. Various surface and structural characterization techniques were deployed to examine the composite coatings. in vitro corrosion analysis confirmed that the composite coated TiNbZr specimen exhibited higher corrosion resistant performance in simulated body fluid (SBF). The drug release kinetics was estimated and the results corroborated the sustained release of GM from the controlled degradation of the composite matrix. The pectin composite coatings exhibited effective antibacterial performance; due to the sustained release of GM. In-vitro cell culture studies validated the improved biocompatibility of the composite coatings. Among the developed coatings, composite coatings loaded with 10 wt. % of GM exhibited the lowest corrosion rate, enhanced biocompatibility, and antibacterial performance.

Effect of ytterbium amount on LaNbO4:Tm3+,Yb3+ nanoparticles for bio-labelling applications.

PURPOSE: This work investigates how Yb3+ concentration affects the luminescent properties of LaNbO4 nanoparticles for medical imaging applications. Due to the highly transparent optical window for organic tissues in the near infrared region (650-1000 nm), upconversion fluorescence allows near infrared wavelengths to penetrate deeply into tissues, which is useful in biomedical areas such as biodetection, activated phototherapy, and screening. MATERIALS/METHOD: Upconversion nanoparticles based on LaNbO4 doped with Tm3+ and Yb3+ were prepared by the one-step industrial process called Spray Pyrolysis. Samples with different Tm3+:Yb3+ molar ratios (1:4, 1:8 and 1:16) were obtained. RESULTS: The X-ray powder diffractograms of all the samples displayed the typical peaks of a crystalline material (tetragonal phase). Emission bands emerged in the blue, red, and near infrared regions, and they corresponded to the Tm3+1G4 → 3H6 (475 nm), 1G4 → 3F4 (650 nm), 3F2,3 â†’ 3H6 (690 nm), and 3H4 → 3H6 (803 nm) transitions, which indicated a two-photon absorption process. As for bio-labelling application, the results indicated that Yb3+ concentration was directly related to signal intensity. CONCLUSIONS: The intensity of positive conversion emissions depends directly on Yb3+ concentration. The bio-labelling tests pointed to the potential application of these materials. The sample containing the highest amount of Yb3+ provided better results and was easier to detect than the standard sample.

A two-dimensional MXene potentiates a therapeutic microneedle patch for photonic implantable medicine in the second NIR biowindow.

Due to the refractory nature and recurrence of cancer, the related treatments are continuously updated and improved. Here, we designed a soluble polyvinylpyrrolidone (PVP) microneedle system loaded with a two-dimensional (2D) MXene (Nb2C nanosheets) for medical implantation and photothermal ablation of superficial tumors in the second near infrared biological window (NIR-II). In this system, 2D Nb2C nanosheets acted as high-performance photothermal nanoagents, and biocompatible PVP functioned as matrix material to maintain the structure of the needles. The microneedle system exhibited sufficient skin-penetration ability and distinctive dissolution behavior. After being inserted into the skin of the tumor site, it can be dissolved within a short period to release the loaded 2D Nb2C nanosheets. The temperature of the tumor site increased rapidly to almost 70 °C under the irradiation of a 1064 nm laser at a power density of 1 W cm-2, and this could provide sufficient conditions for photonic tumor ablation. After two weeks of treatment, the tumor growth was significantly suppressed, compared to that of the control group, and the survival rate of mice was clearly improved. In addition, the biocompatibility of the microneedle system was tested on mice, in which no significant toxicity or side effects were observed. Therefore, this kind of microneedle system with minimally invasive, safe and effective features is expected to be developed as an intriguing strategy for localized superficial cancer treatment.

Electrooxidation Using Nb/BDD as Post-Treatment of a Reverse Osmosis Concentrate in the Petrochemical Industry.

This work evaluated the performance of an electrochemical oxidation process (EOP), using boron-doped diamond on niobium substrate (Nb/BDD), for the treatment of a reverse osmosis concentrate (ROC) produced from a petrochemical wastewater. The effects of applied current density (5, 10, or 20 mA·cm-2) and oxidation time (0 to 5 h) were evaluated following changes in chemical oxygen demand (COD) and total organic carbon (TOC). Current efficiency and specific energy consumption were also evaluated. Besides, the organic byproducts generated by EOP were analyzed by gas chromatography coupled to mass spectrometry (GC⁻MS). The results show that current densities and oxidation time lead to a COD and TOC reduction. For the 20 mA·cm-2, changes in the kinetic regime were found at 3 h and associated to the oxidation of inorganic ions by chlorinated species. After 3 h, the oxidants act in the organic oxidation, leading to a TOC removal of 71%. Although, due to the evolution of parallel reactions (O2, H2O2, and O3), the specific energy consumption also increased, the resulting consumption value of 66.5 kW·h·kg-1 of COD is considered a low energy requirement representing lower treatment costs. These results encourage the applicability of EOP equipped with Nb/BDD as a treatment process for the ROC.

Conditions affecting the release of thorium and uranium from the tailings of a niobium mine.

Determinations of the mobility of metals from tailings is a critical part of any assessment of the environmental impacts of mining activities. The leaching of thorium and uranium from the tailings of different processing stages of a niobium mine was investigated for several pH, ionic strengths and concentrations of natural organic matter (NOM). The pH of the leaching solution did not have a noticeable impact on the extraction of Th, however, for pH values below 4, increased U mobilization was observed. Similarly, only a small fraction of Th (0.05%, ≤15 µg kg-1) and U (1.22%, ≤6 µg kg-1) were mobilized from the tailings in the presence of environmentally relevant concentrations of Ca, Mg or Na. However, in the presence of 10 mg L-1 of fulvic acid, much higher concentrations of ca. 700 µg kg-1 of Th and 35 µg kg-1 of U could be extracted from the tailings. Generally, colloidal forms of Th and dissolved forms of U were mobilized from the tailings, however, in the presence of the fulvic acid, both dissolved and colloidal forms of the two actinides were observed. Single Particle ICP-MS was used to confirm the presence of Th (and U) containing colloids where significant numbers (up to 107 mL-1) of Th and U containing colloids were found, even in 0.2 µm filtered extracts. Although mass equivalent diameters in the range of 6-13 nm Th and 6-9 nm for U could be estimated (based upon the presence of an oxyhydroxide), most of the colloidal mass was attributed to larger (>200 nm) heterocomposite particles.

Therapeutic mesopore construction on 2D Nb2C MXenes for targeted and enhanced chemo-photothermal cancer therapy in NIR-II biowindow.

Two-dimensional (2D) MXenes have emerged as a promising planar theranostic nanoplatform for versatile biomedical applications; but their in vivo behavior and performance has been severely influenced and hindered by a lack of necessary surface chemistry for adequate surface engineering. To solve this critical issue, this work employs versatile sol-gel chemistry for the construction of a unique "therapeutic mesopore" layer onto the surface of 2D niobium carbide (Nb2C) MXene. Methods: The in situ self-assembled mesopore-making agent (cetanecyltrimethylammonium chloride, in this case) was kept within the mesopores for efficient chemotherapy. The abundant surface saline chemistry of mesoporous silica-coated Nb2C MXene was further adopted for stepwise surface engineering including PEGylation and conjugation with cyclic arginine-glycine-aspartic pentapeptide c(RGDyC) for targeted tumor accumulation. Results: 2D Nb2C MXenes were chosen based on their photothermal conversion capability (28.6%) in the near infrared (NIR)-II biowindow (1064 nm) for enhanced photothermal hyperthermia. Systematic in vitro and in vivo assessments demonstrate targeted and enhanced chemotherapy and photothermal hyperthermia of cancer (U87 cancer cell line and corresponding tumor xenograft; inhibition efficiency: 92.37%) in the NIR-II biowindow by these mesopore-coated 2D Nb2C MXenes. Conclusion: This work not only significantly broadens the biomedical applications of 2D Nb2C MXene for enhanced cancer therapy, but also provides an efficient strategy for surface engineering of 2D MXenes to satisfy versatile application requirements.

Niobium treated by Plasma Electrolytic Oxidation with calcium and phosphorus electrolytes.

Niobium plates were electrochemically treated by Plasma Electrolytic Oxidation (PEO) with electrolytes containing phosphorous and/or calcium. Three different electrolyte and experimental parameters were used forming three different surfaces. Film morphology, thickness, and chemical composition were analyzed by scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). A profilometer and the sessile drop technique measured the average surfaces roughness (Ra) and contact angles respectively. X-ray diffraction technique (XRD) analyzed the oxide crystallinity, and scratch tests evaluated the film adhesion. All oxidized surfaces presented pores, without observed cracks. Comparing the different experimental conditions, films obtained with phosphoric acid (P100) show superficial pores, phosphorus incorporation, high hydrophilicity, non-crystalline oxide formation, and good scratch resistance. Films treated with calcium acetate electrolyte (Ca100), compared to P100 exhibit smaller size pores and film thickness, smaller hydrophilicity, and lower scratch resistance. They also demonstrated higher oxide crystallinity, calcium incorporation, and pores interconnections. When the PEO was executed with a blended electrolyte containing calcium acetate and phosphoric acid (Ca50P50) the formed films presented the highest thickness, high phosphorus incorporation, and the lowest contact angle compared with other films. In addition, the pores size, the scratch resistance, calcium incorporation, and oxide crystallinity present intermediate values compared to P100 and Ca100 films. Film crystallinity seems to be influenced by calcium incorporation, whereas, hydrophilicity is phosphorus amount dependent. The pores amount and their interconnections reduced the scratch resistance. Surface features obtained in this work are largely mentioned as positive characteristics for osseointegration processes.

A Two-Dimensional Biodegradable Niobium Carbide (MXene) for Photothermal Tumor Eradication in NIR-I and NIR-II Biowindows.

Conventionally, ceramics-based materials, fabricated by high-temperature solid-phase reaction and sintering, are preferred as bone scaffolds in hard-tissue engineering because of their tunable biocompatibility and mechanical properties. However, their possible biomedical applications have rarely been considered, especially the cancer phototherapeutic applications in both the first and second near-infrared light (NIR-I and NIR-II) biowindows. In this work, we explore, for the first time as far as we know, a novel kind of 2D niobium carbide (Nb2C), MXene, with highly efficient in vivo photothermal ablation of mouse tumor xenografts in both NIR-I and NIR-II windows. The 2D Nb2C nanosheets (NSs) were fabricated by a facile and scalable two-step liquid exfoliation method combining stepwise delamination and intercalation procedures. The ultrathin, lateral-nanosized Nb2C NSs exhibited extraordinarily high photothermal conversion efficiency (36.4% at NIR-I and 45.65% at NIR-II), as well as high photothermal stability. The Nb2C NSs intrinsically feature unique enzyme-responsive biodegradability to human myeloperoxidase, low phototoxicity, and high biocompatibility. Especially, these surface-engineered Nb2C NSs present highly efficient in vivo photothermal ablation and eradication of tumor in both NIR-I and NIR-II biowindows. This work significantly broadens the application prospects of 2D MXenes by rationally designing their compositions and exploring related physiochemical properties, especially on phototherapy of cancer.

Dynamically tuning near-infrared-induced photothermal performances of TiO2 nanocrystals by Nb doping for imaging-guided photothermal therapy of tumors.

Conventional wide bandgap semiconductors can absorb UV/visible light but have no photoabsorption band in the near-infrared (NIR) region, leading to difficulty in their use as NIR-responsive agents. With TiO2 as an example, we report the tuning from UV-responsive TiO2 nanocrystals to blue TiO2 nanocrystals with newly appeared NIR absorption band through the Nb-doping strategy. A strong NIR band should result from the localized surface plasmon resonances due to the considerable free electrons originating from the efficient incorporation of Nb5+ ions (<15.5%). Interestingly, under the irradiation of a 1064 nm laser, Nb-doped TiO2 nanocrystals can convert laser energy into heat, and higher Nb-doping content can lead to higher NIR-induced temperature elevation, highlighting that the photothermal performances of TiO2 nanocrystals can be dynamically modulated by adjusting the Nb-doping levels. After coating with PEGylated phospholipid, the resulting nanocrystals display water dispersibility, high photothermal conversion efficiency and cytocompatibility. Therefore, these Nb-doped TiO2 nanocrystals can be used as efficient and heavy-metal-free nanoagents for the simultaneous NIR/photoacoustic imaging and photothermal therapy of tumors using a 1064 nm laser in the second biological window.

A voltammetry sensor platform for baicalein and baicalin simultaneous detection in vivo based on Ta2O5-Nb2O5@CTS composite.

Baicalein and baicalin are the major flavonoids found in Scutellariae Radix, an essential herb which has had a presence in traditional Chinese medicine (TCMs) for more than two thousands of years. Owing to their similar characteristics and physiochemical properties, sensitive, it is a great challenge to detect both of them simultaneously. In this work, a novel, facile and sensitive electrochemical method was proposed based on tantalum oxide (Ta2O5), niobium oxide (Nb2O5) particles and antiseptic chitosan modified carbon paste electrode (Ta2O5-Nb2O5@CTS-CPE). Scanning electron microscope (SEM), X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV) and electrochemical impedance spectrum (EIS) were used to characterize the properties and investigate the electrochemical response of the sensor. The electrochemical behaviors and redox mechanisms of two analytes were investigated at the target electrode. Under the optimum conditions, the highly sensitive and simultaneous determination of baicalein and baicalin was successfully achieved with a linear response range of 0.08-8.0µM for both of them. The obtained detection limits for baicalein and baicalin were of 0.05 and 0.03µM (S/N=3), respectively. Furthermore, the proposed sensor displayed high sensitivity, excellent stability and satisfactory results in Scutellariae Radix samples analysis and hydrolysis process analysis of baicalin in vivo.

Uranium luminescence in La2 Zr2 O7 : effect of concentration and annealing temperature.

The speciation of a particular element in any given matrix is a prerequisite to understanding its solubility and leaching properties. In this context, speciation of uranium in lanthanum zirconate pyrochlore (La2 Zr2 O7 = LZO), prepared by a low-temperature combustion route, was carried out using a simple photoluminescence lifetime technique. The LZO matrix is considered to be a potential ceramic host for fixing nuclear and actinide waste products generated during the nuclear fuel cycle. Special emphasis has been given to understanding the dynamics of the uranium species in the host as a function of annealing temperature and concentration. It was found that, in the LZO host, uranium is stabilized as the commonly encountered uranyl species (UO22+ ) up to a heat treatment of 500 °C at the surface. Above 500 °C, the uranyl ion is diffused into the matrix as the more symmetric octahedral uranate species (UO66- ). The uranate ions thus formed replace the six-coordinated 'Zr' atoms at regular lattice positions. Further, it was observed that concentration quenching takes place beyond 5 mol% of uranium doping. The mechanism of the quenching was found to be a multipolar interaction. Copyright © 2016 John Wiley & Sons, Ltd.

Hydrophilic Nb5⁺-immobilized magnetic core-shell microsphere--A novel immobilized metal ion affinity chromatography material for highly selective enrichment of phosphopeptides.

Rapid and selective enrichment of phosphopeptides from complex biological samples is essential and challenging in phosphorylated proteomics. In this work, for the first time, niobium ions were directly immobilized on the surface of polydopamine-coated magnetic microspheres through a facile and effective synthetic route. The Fe3O4@polydopamine-Nb(5+) (denoted as Fe3O4@PD-Nb(5+)) microspheres possess merits of high hydrophilicity and good biological compatibility, and demonstrated low limit of detection (2 fmol). The selectivity was also basically satisfactory (ß-casein:BSA=1:500) to capture phosphopeptides. They were also successfully applied for enrichment of phosphopeptides from real biological samples such as human serum and nonfat milk. Compared with Fe3O4@PD-Ti(4+) microspheres, the Fe3O4@PD-Nb(5+) microspheres exhibit superior selectivity to multi-phosphorylated peptides, and thus may be complementary to the conventional IMAC materials.

Defect-meditated efficient catalytic activity toward p-nitrophenol reduction: A case study of nitrogen doped calcium niobate system.

This work reported on the synthesis of a series of nitrogen doped Ca2Nb2O7 with tunable nitrogen content that were found to be efficient and green noble-metal-free catalysts toward catalytic reduction of p-nitrophenol. XPS and ESR results indicated that the introduction of nitrogen in Ca2Nb2O7 gave rise to a large number of defective nitrogen and oxygen species. Defective nitrogen and oxygen species were found to play synergetic roles in the reduction of p-nitrophenol. The underlying mechanism is completely different from those reported for metallic nanoparticles. Moreover, the more negative conduction band edge potential enabled nitrogen doped Ca2Nb2O7 to show photo-synergistic effects that could accelerate the reduction rate toward p-nitrophenol under UV light irradiation. This work may provide a strategy for tuning the catalytic performance by modulating the chemical composition, electronic structure as well as surface defect chemistry.

Synthesis and characterisation of the uranium pyrochlore betafite [(Ca,U)2(Ti,Nb,Ta)2O7].

Betafite of composition [(Ca,U)2(Ti,Nb,Ta)2O7] was prepared via a solid state synthesis route. The synthesis was shown to be sensitive to initial reactant ratios, the atmosphere used (oxidising, neutral, reducing) and time. The optimum conditions for the synthesis of betafite were found to be heating the reactants required at 1150°C for 48 h under an inert gas atmosphere. XRD characterisation revealed that the synthesised betafite contained minor impurities. EPMA analysis of a sectioned surface showed very small regions of Ca-free betafite on grain boundaries as well as minor rutile impurities. Some heterogeneity between the Nb:Ta ratio was observed by quantitative EPMA but was generally within the nomenclature requirements stated for betafite. SEM analysis revealed the synthesised betafite was comprised mostly of hexaoctohedral crystals of ∼ 3 µm in diameter. XPS analysis of the sample showed that the uranium in the synthesised betafite was predominately present in the U(5+) oxidation state. A minor amount of U(6+) was also detected which was possibly due to surface oxidation.