Homojunction of Oxygen and Titanium Vacancies and its Interfacial n–p Effect

The homojunction of oxygen/metal vacancies and its interfacial n–p effect on the physiochemical properties are rarely reported. Interfacial n–p homojunctions of TiO₂ are fabricated by directly decorating interfacial p‐type titanium‐defected TiO₂ around n‐type oxygen‐defected TiO₂ nanocrystals in amorphous–anatase homogeneous nanostructures. Experimental measurements and theoretical calculations on the cell lattice parameters show that the homojunction of oxygen and titanium vacancies changes the charge density of TiO₂; a strong EPR signal caused by oxygen vacancies and an unreported strong titanium vacancies signal of 2D ¹H TQ‐SQ MAS NMR are present. Amorphous–anatase TiO₂ shows significant performance regarding the photogeneration current, photocatalysis, and energy storage, owing to interfacial n‐type to p‐type conductivity with high charge mobility and less structural confinement of amorphous clusters. A new “homojunction of oxygen and titanium vacancies” concept, characteristics, and mechanism are proposed at an atomic‐/nanoscale to clarify the generation of oxygen vacancies and titanium vacancies as well as the interface electron transfer.     

Biodegradable Polysilsesquioxane Nanoparticles as Efficient Contrast Agents for Magnetic Resonance Imaging

Polysilsesquioxane (PSQ) nanoparticles are crosslinked homopolymers formed by condensation of functionalized trialkoxysilanes, and provide an interesting platform for developing biologically and biomedically relevant nanomaterials. In this work, the design and synthesis of biodegradable PSQ particles with extremely high payloads of paramagnetic Gd(III) centers is explored, for use as efficient contrast agents for magnetic resonance imaging (MRI). Two new bis(trialkoxysilyl) derivatives of Gd(III) diethylenetriamine pentaacetate (Gd‐DTPA) containing disulfide linkages are synthesized and used to form biodegradable Gd‐PSQ particles by base‐catalyzed condensation reactions in reverse microemulsions. The Gd‐PSQ particles, PSQ‐ 1 and PSQ‐ 2 , carry 53.8 wt% and 49.3 wt% of Gd‐DTPA derivatives, respectively. In addition, the surface carboxy groups on the PSQ‐ 2 particles can be modified with polyethylene glycol (PEG) and the anisamide (AA) ligand to enhance biocompatibility and cell uptake, respectively. The Gd‐PSQ particles are readily degradable to release the constituent Gd(III) chelates in the presence of endogenous reducing agents such as cysteine and glutathione. The MR relaxivities of the Gd‐PSQ particles are determined using a 3T MR scanner, with r₁ values ranging from 5.9 to 17.8 mMs^?1 on a per‐Gd basis. Finally, the high sensitivity of the Gd‐PSQ particles as T₁‐weighted MR contrast agents is demonstrated with in vitro MR imaging of human lung and pancreatic cancer cells. The enhanced efficiency of the anisamide‐functionalized PSQ‐ 2 particles as a contrast agent is corroborated by both confocal laser scanning microscopy imaging and ICP‐MS analysis of Gd content in vitro.     

A Brown Mesoporous TiO2‐x/MCF Composite with an Extremely High Quantum Yield of Solar Energy Photocatalysis for H2 Evolution

A brown mesoporous TiO_2‐x/MCF composite with a high fluorine dopant concentration (8.01 at%) is synthesized by a vacuum activation method. It exhibits an excellent solar absorption and a record‐breaking quantum yield (Φ = 46%) and a high photon–hydrogen energy conversion efficiency (η = 34%,) for solar photocatalytic H₂ production, which are all higher than that of the black hydrogen‐doped TiO₂ (Φ = 35%, η = 24%). The MCFs serve to improve the adsorption of F atoms onto the TiO₂/MCF composite surface, which after the formation of oxygen vacancies by vacuum activation, facilitate the abundant substitution of these vacancies with F atoms. The decrease of recombination sites induced by high‐concentration F doping and the synergistic effect between lattice Ti³⁺–F and surface Ti³⁺–F are responsible for the enhanced lifetime of electrons, the observed excellent absorption of solar light, and the photocatalytic production of H₂ for these catalysts. The as‐prepared F‐doped composite is an ideal solar light‐driven photocatalyst with great potential for applications ranging from the remediation of environmental pollution to the harnessing of solar energy for H₂ production.     

Solar photocatalysts from Gd–La codoped TiO2 nanoparticles

Gd–La codoped TiO₂ nanoparticles with diameter of 10 nm were successfully synthesized via a sol–gel method. The photocatalytic activity of the Gd–La codoped TiO₂ nanoparticles evaluated by photodegrading methyl orange has been significantly enhanced compared to that of undoped or Gd or La monodoped TiO₂. Ti⁴⁺ may substitute for La³⁺ and Gd³⁺ in the lattices of rare earth oxides to create abundant oxygen vacancies and surface defects for electron trapping and dye adsorption, accelerating the separation of photogenerated electron–hole pairs and methyl orange photodegradation. The formation of an excitation energy level below the conduction band of TiO₂ from the binding of electrons and oxygen vacancies decreases the excitation energy of Gd–La codoped TiO₂, resulting in versatile solar photocatalysts. The results suggest that Gd–La codoped TiO₂ nanoparticles are promising for future solar photocatalysts.     

Preparation and structure of nanostructured Ti–Ni–O with modified low temperature sol–gel route

A series of nanoscaled Ti–Ni–O samples doped with different TiO₂ content are prepared by modified low temperature sol–gel route at 400 °C. BET data reveals that the content of dopant TiO₂ influences the grain size. XRD analysis indicates that the lattice parameter of particles increased with the TiO₂ content. XPS results show that the surface state of nickel and titanium ion changed. Both of the latter two results suggest that there is an interaction takes place between TiO₂ and NiO.     

Preparation,characterization and photocatalytic activity of TiO2 codoped with yttrium and nitrogen

Nanocrystalline photocatalysts of TiO₂ codoped with yttrium and nitrogen were prepared by the sol–gel method and investigated by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), the Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS), respectively. Slight red-shifts of the Raman peak at 144 cm^?1 were observed in the doped samples after the incorporation of Y³⁺ and N^3? into the lattice of TiO₂. The N doping caused the improvement of visible light absorption because of the formation of the N 2p states isolated above the valence band maximum of TiO₂. Whereas, the absorption property of the pure or N doped TiO₂ was depressed after the introduction of Y. The photocatalytic activities of the samples were evaluated by monitoring the degradation of methylene blue (MB) solution. The codoped sample with N and 0.05 at.% Y exhibited an enhanced photocatalytic efficiency. It is suggested that the charge trapping due to the Y doping and the visible light response due to the N doping are responsible for the enhanced photocatalytic performance in this sample. However, the photocatalytic activity of the codoped TiO₂ was suppressed step by step as the Y doping level increased, which could be attributed to the formation of photogenerated charge carriers recombination centers at the Y substituting sites.     

Dotted Core–Shell Nanoparticles for T1‐Weighted MRI of Tumors

Gd‐based T ₁‐weighted contrast agents have dominated the magnetic resonance imaging (MRI) contrast agent market for decades. Nevertheless, they are reported to be nephrotoxic and the U.S. Food and Drug Administration has issued a general warning concerning their use. In order to reduce the risk of nephrotoxicity, the MRI performance of the Gd‐based T ₁‐weighted contrast agents needs to be improved to allow a much lower dosage. In this study, novel dotted core–shell nanoparticles (FeGd‐HN3‐RGD2) with superhigh r ₁ value (70.0 mM^?1 s^?1) and very low r ₂/r ₁ ratio (1.98) are developed for high‐contrast T ₁‐weighted MRI of tumors. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay and histological analyses show good biocompatibility of FeGd‐HN3‐RGD2. Laser scanning confocal microscopy images and flow cytometry demonstrate active targeting to integrin α_vβ₃ positive tumors. MRI of tumors shows high tumor ΔSNR for FeGd‐HN3‐RGD2 (477 ± 44%), which is about 6‐7‐fold higher than that of Magnevist (75 ± 11%). MRI and inductively coupled plasma results further confirm that the accumulation of FeGd‐HN3‐RGD2 in tumors is higher than liver and spleen due to the RGD2 targeting and small hydrodynamic particle size (8.5 nm), and FeGd‐HN3‐RGD2 is readily cleared from the body by renal excretion.     

The abnormal grain growth and dielectric properties of (Nb,Ba) doped TiO2 ceramics

The effect of consolidation pressure and crystallite size of powders crystal phases of TiO₂ on sintered microstructure of TiO₂ ceramics doped with 0.25 mol % Nb and 1.0 mol % Ba were investigated. Also, the development sequence of abnormal grain growth of (niobium, barium) doped TiO₂ ceramics was proposed. The second phases of as-sintered surface were determined. The dielectric properties of Ag-electroded samples were correlated with the resistivity of the bulk (Nb, Ba) doped TiO₂ ceramics. Abnormal grain growth lowered the resistivity of bulk material of (Nb, Ba) doped TiO₂ ceramics, and moved the relaxation frequency of fan δ to high frequency region over 10⁵ Hz. Controlling the sintered microstructures can obtain reasonably good dielectric properties.     

Core–Satellite Polydopamine–Gadolinium‐Metallofullerene Nanotheranostics for Multimodal Imaging Guided Combination Cancer Therapy

Integration of magnetic resonance imaging (MRI) and other imaging modalities is promising to furnish complementary information for accurate cancer diagnosis and imaging‐guided therapy. However, most gadolinium (Gd)–chelator MR contrast agents are limited by their relatively low relaxivity and high risk of released‐Gd‐ions‐associated toxicity. Herein, a radionuclide‐⁶⁴Cu‐labeled doxorubicin‐loaded polydopamine (PDA)–gadolinium‐metallofullerene core–satellite nanotheranostic agent (denoted as CDPGM) is developed for MR/photoacoustic (PA)/positron emission tomography (PET) multimodal imaging‐guided combination cancer therapy. In this system, the near‐infrared (NIR)‐absorbing PDA acts as a platform for the assembly of different moieties; Gd₃N@C₈₀, a kind of gadolinium metallofullerene with three Gd ions in one carbon cage, acts as a satellite anchoring on the surface of PDA. The as‐prepared CDPGM NPs show good biocompatibility, strong NIR absorption, high relaxivity (r ₁ = 14.06 mM^?1 s^?1), low risk of release of Gd ions, and NIR‐triggered drug release. In vivo MR/PA/PET multimodal imaging confirms effective tumor accumulation of the CDPGM NPs. Moreover, upon NIR laser irradiation, the tumor is completely eliminated with combined chemo‐photothermal therapy. These results suggest that the CDPGM NPs hold great promise for cancer theranostics.     

Structural and dielectric studies of Eu3+/Ag nanocrystallites: SiO2–TiO2 matrices

Silver nanocrystallites/Eu³⁺ doped SiO₂–TiO₂ matrices were synthesised through sol–gel route and the structural and dielectric properties of the matrices were studied. Structural characterizations were done using EDX, XRD, FTIR, AFM and TEM measurements. The TEM and XRD measurements confirm the presence of Ag and TiO₂ nanocrystals. The dielectric and electrical conductivity studies of the samples were done for a frequency range of 100 Hz–2 MHz. The conductivity variation with the Ag content in the Eu³⁺ doped SiO₂–TiO₂ system has been explained by correlating the presence of ionic contribution to the electrical conductivity process. Also, the frequency dependence of dielectric constant and conductivity were studied. The Cole–Cole parameters were calculated and the semicircles observed in the plots indicate a single relaxation process. This behaviour can be modelled by an equivalent parallel RC circuit.     

Synthesis and characterization of aluminum diboride products using <Superscript>27</Superscript>Al, <Superscript>11</Superscript>B NMR and ab initio studies

Understanding different bonding environments in various metal borides provides insight into their structures and physical properties. Polycrystalline aluminum diboride (AlB₂) samples have been synthesized and compared both with a commercial sample and with the literature. One issue that arose is the relative ease with which boron-rich and aluminum deficient phases of aluminum borides can be presented in AlB₂. Here, we report ²⁷Al, ¹¹B nuclear magnetic resonance (NMR) spectroscopy and first-principles calculations on AlB₂ in order to shed light on these different bonding environments at the atomic level and compare the structural and electronic properties of the products of different preparations. Along with the aforementioned, the present study also takes an in-depth look at the nature of the ¹¹B and ²⁷Al nuclear spin–lattice relaxation recovery data for the AlB₂ and other superhard materials. The nuclear spin–lattice relaxation has been measured for a static sample and with magic-angle spinning. The combination of NMR and band structure calculations highlights the synthetic challenges with superhard materials.     

Nanocrystalline sol–gel TiO2–SnO2 coatings: Preparation,characterization and photo-catalytic performance

In this study, preparation of SnO₂ (0–30 mol% SnO₂)–TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process has been investigated. The effects of SnO₂ on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Surface topography and surface chemical state of thin films were examined by atomic force microscopy and X-ray photoelectron spectroscopy. XRD patterns showed an increase in peak intensities of the rutile crystalline phase by increasing the SnO₂ content. The prepared Sn doped TiO₂ photo-catalyst films showed optical absorption in the visible light area exhibited excellent photo-catalytic ability for the degradation of methylene blue under visible light irradiation. Best photo-catalytic activity of Sn doped TiO₂ thin films was measured in the TiO₂–15 mol% SnO₂ sample by the Sn⁴⁺ dopants presented substitution Ti⁴⁺ into the lattice of TiO₂ increasing the surface oxygen vacancies and the surface hydroxyl groups.     

Magnetic properties of RRh3B2(R=La,Ce, Nd,Gd) compounds

The¹¹Bnmr results on RRh₃B₂(R=La, Ce, Nd and Gd) are reported. For CeRh₃B₂, specific heat and electrical resistivity are reported. From a comparative study of the¹¹Bnmr Knight shifts and the spin lattice relaxation times of these compounds it is shown that in CeRh₃B₂, there is strong hybridization of 4f states with the conduction electrons. A local moment on Ce with admixture of 4f and 5d–6s orbitals is suggested.     

Effect of novel (Gd,Cu) substitution on the electrical properties and magnetoelectric coupling of bismuth ferrite ceramics

The influence of Gd dopant and (Gd, Cu) dopants on the ferroelectric, dielectric and magnetoelectric properties of single phase BiFeO₃ (BFO) were investigated. Nanoparticles of undoped BiFeO₃, Bi_0.95Gd_0.05FeO₃ and Bi_1?xGd_xFe_0.98Cu_0.02O₃ (x?=?1, 2, 3, 4 and 5%) were prepared by sol–gel method. X-ray diffraction reveals that all the samples crystallize in rhombohedral phase. The simultaneous Gd and Cu doping at BFO lattice has significantly enhanced the ferroelectric properties of BFO compared to that of BFO. Substitution of Gd alone at the Bi site, gave rise to attractively enhanced remnant polarization. Though the (Gd, Cu) doped BFO samples exhibit relatively less enhancement, their values of remnant polarization are appreciable. Doping of (Gd, Cu) in the BFO lattice leads to an appreciable dielectric properties. An effective magnetoelectric coupling has been recorded for doped BFO when compared to BFO.     

Mesoporous and Nanostructured TiO2 layer with Ultra‐High Loading on Nitrogen‐Doped Carbon Foams as Flexible and Free‐Standing Electrodes for Lithium‐Ion Batteries

A simple and green method is developed for the preparation of nanostructured TiO₂ supported on nitrogen‐doped carbon foams (NCFs) as a free‐standing and flexible electrode for lithium‐ion batteries (LIBs), in which the TiO₂ with 2.5–4 times higher loading than the conventional TiO₂‐based flexible electrodes acts as the active material. In addition, the NCFs act as a flexible substrate and efficient conductive networks. The nanocrystalline TiO₂ with a uniform size of ≈10 nm form a mesoporous layer covering the wall of the carbon foam. When used directly as a flexible electrode in a LIB, a capacity of 188 mA h g^?1 is achieved at a current density of 200 mA g^?1 for a potential window of 1.0–3.0 V, and a specific capacity of 149 mA h g^?1 after 100 cycles at a current density of 1000 mA g^?1 is maintained. The highly conductive NCF and flexible network, the mesoporous structure and nanocrystalline size of the TiO₂ phase, the firm adhesion of TiO₂ over the wall of the NCFs, the small volume change in the TiO₂ during the charge/discharge processes, and the high cut‐off potential contribute to the excellent capacity, rate capability, and cycling stability of the TiO₂/NCFs flexible electrode.     

Effects of Gd2O3 on structure and magnetic properties of Ni-Mn ferrite

The emulsion method was used to prepare nanocrystalline Ni_0.7Mn_0.3Gd _x Fe_2-x O₄ ferrites. The growth of particles, the structure and the magnetic properties were investigated by X-ray diffraction (XRD), Mössbauer spectroscopy and vibrating sample magnetometer (VSM). Furthermore, the influence of Gd₂O₃ on magnetic properties of Ni-Mn ferrite powders has been investigated in detail. When the crystallite sizes are about 30–40 nm, all the samples have the similar Ms values. The variational rules of saturation magnetization (Ms) and coercivity (Hc) along with doped-Gd contents at different sintering temperatures show that the maximum Gd ions content doped into ferrite lattices is x = 0.06. When Gd-doped content x is larger than 0.06, the doped Gd ions can’t enter into the ferrite lattice totally but reside at grain boundary, as the ionic radii of the Gd³⁺ ions are larger than that of Fe³⁺ ions. The ferrimagnetism have not disappeared completely, even if the crystallite size is 7.8 nm.     

Dielectric properties and relaxation behavior of Sm substituted SrTiO3 ceramics

Sr_1–1.5xSm_xTiO₃ (x = 0–0.025) ceramics were fabricated by the conventional solid-state reaction method. Experimental results show that all ceramics are pure cubic perovskite structure, and the lattice parameters and average grain sizes of the ceramics decrease with the Sm concentration increasing. Compared with the pure SrTiO₃ ceramics, the relative dielectric constant could be enhanced to 3,681 (at 1 kHz and room temperature)with dielectric loss less than 0.02 when x = 0.02. The good stability of ε _r under 0–20 kV/cm is beneficial to applying in high voltage conditions. Two sets of relaxation peaks of Sm doped SrTiO₃ ceramics are observed which are all related to the oxygen vacancies. The medium-temperature relaxation is ascribed to the coupling of oxygen vacancies with strontium vacancies and the origin of high-temperature relaxation is the motion of oxygen vacancies.     

Epitaxial Growth of Lattice‐Mismatched Core–Shell TiO2@MoS2 for Enhanced Lithium‐Ion Storage

Core–shell structured nanohybrids are currently of significant interest due to their synergetic properties and enhanced performances. However, the restriction of lattice mismatch remains a severe obstacle for heterogrowth of various core–shells with two distinct crystal structures. Herein, a controlled synthesis of lattice‐mismatched core–shell TiO₂@MoS₂ nano‐onion heterostructures is successfully developed, using unilamellar Ti_0.87O₂ nanosheets as the starting material and the subsequent epitaxial growth of MoS₂ on TiO₂. The formation of these core–shell nano‐onions is attributed to an amorphous layer‐induced heterogrowth mechanism. The number of MoS₂ layers can be well tuned from few to over ten layers, enabling layer‐dependent synergistic effects. The core–shell TiO₂@MoS₂ nano‐onion heterostructures exhibit significantly enhanced energy storage performance as lithium‐ion battery anodes. The approach has also been extended to other lattice‐mismatched systems such as TiO₂@MoSe₂, thus suggesting a new strategy for the growth of well‐designed lattice‐mismatched core–shell structures.     

Formation of TiO2 nano-fiber doped with Gd3+ and its photocatalytic activity

Titanium dioxide (TiO₂) nano-fibers doped with Gd³⁺ were synthesized by two-step synthesis method. The formed fibers were visualized from transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results showed that the average diameter of the TiO₂ nano-fibers was 60–80 nm and the length of fibers was in the range of 6–7 μm. The TiO₂ nano-fibers doped with Gd³⁺ heat treated in glycerol solvent had smaller crystal size than those without heat treatment. However, the size of TiO₂ nano-fibers decreased with increasing the heating temperature. The results obtained in the photocatalytic degradation of methyl orange indicated that the photocatalytic activity of the TiO₂ nano-fibers doped with Gd³⁺ appeared a little reduction relative to that of TiO₂ nanopowders.     

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

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