Zhengyi Fu

Influence of hot pressing sintering temperature and time on microstructure and mechanical properties of TiB2 ceramics

Abstract In this paper, a titanium diboride ceramic was produced by the hot pressing sintering method. The effects of hot pressing parameters on the TiB 2 ceramic microstructure and mechanical properties were studied. The bending strength and fracture toughness were measured by three point bending testing and single edge notched bending tests (SENB), respectively. The microstructure features of the TiB 2 sintered material were revealed by means of SEM and TEM. The results show that the TiB 2 grain size increases quickly with the increasing temperature and time during hot pressing sintering. The density and the TiB 2 grain size have a great influence on the mechanical properties. The bending strength decreases with increasing TiB 2 grain size, whilst the fracture toughness increases.

Sintering boron carbide ceramics without grain growth by plastic deformation as the dominant densification mechanism.

A new ceramic sintering approach employing plastic deformation as the dominant mechanism is proposed, at low temperature close to the onset point of grain growth and under high pressure. Based on this route, fully dense boron carbide without grain growth can be prepared at 1,675–1,700 °C and under pressure of (≥) 80 MPa in 5 minutes. The dense boron carbide shows excellent mechanical properties, including Vickers hardness of 37.8 GPa, flexural strength of 445.3 MPa and fracture toughness of 4.7 MPa•m0.5. Such a process should also facilitate the cost-effective preparation of other advanced ceramics for practical applications.

Enhanced photocatalytic activity of S-doped BiVO4 photocatalysts

S-doped BiVO4 photocatalysts were synthesized using a surfactant-free hydrothermal method without any further treatments and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma atomic emission spectrometry (ICP-AES), ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), photoluminescence spectroscopy (PL) techniques, and transient photocurrent responses. The results show that S2− ions can be doped into the BiVO4 crystal lattices and substitute the O2− ions, which can increase the BiVO4 lattice parameters, increase the number of V4+ species and oxygen vacancies, and cause a red shift of the reflectance spectra. Compared with the pure BiVO4 photocatalyst, S-doped BiVO4 photocatalysts exhibit much higher photocatalytic activity in the degradation of methylene blue (MB) under visible light irradiation, because an appropriate amount of S2− ions can improve the separation efficiency of photogenerated electron–hole pairs, and hinder their recombination. The photo-stability of the S-doped BiVO4 photocatalysts, and the effects of the active species involved in the photocatalytic process from which we deduced a possible mechanism for MB photocatalytic degradation were also examined.

SBA-15 mesoporous silica coated with macrocyclic calix[4]arene derivatives: Solid extraction phases for heavy transition metal ions

A layer of macrocyclic calix[4]arene derivatives has been grafted on the internal surface of the mesochannels of the ordered mesoporous SBA-15 to develop highly efficient trap for heavy transition metal (HTM) ions. To ensure the successful anchoring of calix[4]arene derivatives on the surface of SBA-15, two different types of calix[4]arene derivatives, one with one trimethoxysilane functional group and another with two trimethoxysilane functional groups have been explored. XRD, N(2) adsorption and TEM results provide strong evidence that the mesoporous structure of the supporting materials retain their long range ordering throughout the grafting process. Solid-state NMR, TG and FT-IR spectroscopy indicate that both types of calix[4]arene derivatives can be well-anchored on the surface of the wall of SBA-15. Calix[4]arene derivative with only one trimethoxysilane functional group showed high grafting efficiency compared to that with two trimethoxysilane functional groups due to the intramolecular and intermolecular polycondensation between two trimethoxysilane functional groups. The HTM ions extraction capacity in aqueous solution of macrocycle functionalized SBA-15 nanohybrides for a series of HTM ions has been studied. The obtained materials demonstrated very high HTM ions extraction capacity up to 96% for Pb(2+) in aqueous solution.

Template-free synthesis of hierarchical porous calcium carbonate microspheres for efficient water treatment

A uniform, hierarchical porous vaterite calcium carbonate microsphere stacked from nanoparticles is synthesized in dimethylformamide–water (DMF–H2O) mixed solvent without template. We propose a solvent-reaction assisted synthesis of the product by a mesoscale growth pathway. The product shows large removal capacity towards Pb2+, Cd2+ and Zn2+, of 1960 mg g−1, 1040 mg g−1 and 587.3 mg g−1, respectively. It also exhibits efficient and selective adsorption of Congo red (272 mg g−1, 5 min for equilibrium), which is reported for the first time on calcium carbonate. The removal mechanism is demonstrated to be the precipitation transformation for the heavy metal ion sequestration, and adsorption mechanism for the removal of the organic dyes. The good performance of the product is ascribed to the large amount of active adsorption sites provided by the nanoscale building blocks and mesopores, and the short pathway provided by the sunken poles and the hierarchical structure with enhanced mass transfer and decreased blocking of channels.

Calcium Carbonate Nanoplate Assemblies with Directed High-Energy Facets: Additive-Free Synthesis, High Drug Loading, and Sustainable Releasing

Developing drug delivery systems (DDSs) with high drug-loading capacity and sustainable releasing is critical for long-term chemotherapeutic efficacy, and it still remains challenging. Herein, vaterite CaCO3 nanoplate assemblies with exposed high-energy {001} facets have been synthesized via a novel, additive-free strategy. The product shows a high doxorubicin-loading capacity (65%); the best of all the CaCO3-based DDSs so far. Also, the products sustainable releasing performance and its inhibition of the initial burst release, together, endow it with long-term drug efficacy. The work may shed light on exposing directed high-energy facets for rationally designing of a drug delivery system with long-term efficacy.

Fl―DFO molecules@mesoporous silica materials: Highly sensitive and selective nanosensor for dosing with iron ions

Highly sensitive and selective nanosensor for labile iron pool (LIP) determination, has been designed and prepared by immobilization of Fluoresceine-Desferrioxamine (Fl-DFO), a bifunctional fluoro-siderophore probe molecule with great affinity for iron ions (pKf=30.7), into highly ordered mesoporous silica structure. Different immobilization methods of Fl-DFO molecules, such as their encapsulation in surfactant micelles used as templating agents for the synthesis of mesoporous silica, direct impregnation into the mesochannels of as-synthesized mesoporous silica and their surface anchoring by covalent binding with propylamine groups implanted by post-synthesis on the internal surface of mesochannels, have been explored. Each nanohybrid has been fully characterized by small angle XRD, TEM, SEM, solid state (29)Si and (13)C MAS NMR and N(2) adsorption-desorption. The fluorescence properties of nanohybrids obtained have been correlated with the immobilization methods, generating interesting information concerning the localization of Fl-DFO molecules in the channels of mesoporous silica. The leaching of Fl-DFO molecules from mesoporous materials has been investigated. The nanosensor prepared by surface anchoring of Fl-DFO at the internal surface of mesochannels showed high performances with no leaching effect and high sensitivity in regards to its responses to ferric ions. Its fluorescence intensity decreased as soon as first Fe(III) ions are in contact with this nanosensor. A linear relationship between the fluorescence intensity and the ferric ions concentration was observed in low micromolar range. The selectivity of this nanosensor towards other metal ions has also been tested and shown its high affinity to ferric ions. This study can allow the design of a stable, portable, simple, regenerable and cost-effective nanosensor highly sensitive and selective for iron ions with detection limits in the range of cellular LIP in cells, e.g. lower micromolar range.

Organized intrafibrillar mineralization, directed by a rationally designed multi-functional protein

Taking lessons from the structure-forming process of biominerals in animals and plants, one can find tremendous inspirations and ideas for developing advanced synthesis techniques, which is called bio-process inspired synthesis. Bone, as a typical representative of biominerals, is constituted of mineralized collagen fibrils, which are formed under the functions of non-collagenous proteins (NCPs). Intrafibrillar mineralization is the consequence of a synergy among several NCPs. In the present study, we have designed a multi-functional protein, named (MBP)-BSP-HAP, based on bone sialoprotein (BSP) and hydroxyapatite binding protein (HAP), to mimic the intrafibrillar mineralization process in vitro. The three functional domains of (MBP)-BSP-HAP provide the artificial protein with multiple designated functions for intrafibrillar mineralization including binding calcium ions, binding collagen, and binding hydroxyapatite. Platelet-like hydroxyapatite crystals periodically arranged inside the collagen fibrils have been achieved under the function of (MBP)-BSP-HAP. The mechanism of intrafibrillar mineralization directed by the multi-functional protein was proposed. This work may not only shed light on bio-process inspired approaches for more economic and efficient biomimetic synthesis, but also be helpful in understanding the natural process of bone formation for bone regeneration and tissue repair.

Synthesis, Characterization, and Photocatalytic Activity of Zn-Doped SnO2/Zn2SnO4 Coupled Nanocomposites

Zn-doped SnO2/Zn2SnO4 nanocomposites were prepared via a two-step hydrothermal synthesis method. The as-prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), UV-vis diffuse reflection spectroscopy, and adsorption-desorption isotherms. The results of FESEM and TEM showed that the as-prepared Zn-doped SnO2/Zn2SnO4 nanocomposites are composed of numerous nanoparticles with the size ranging from 20 nm to 50 nm. The specific surface area of the as-prepared Zn-doped SnO2/Zn2SnO4 nanocomposites is estimated to be 71.53 m2/g by the Brunauer-Emmett-Teller (BET) method. The photocatalytic activity was evaluated by the degradation of methylene blue (MB), and the resulting showed that Zn-doped SnO2/Zn2SnO4 nanocomposites exhibited excellent photocatalytic activity due to their higher specific surface area and surface charge carrier transfer.

Photo-assisted synthesis of Au@PtAu core–shell nanoparticles with controllable surface composition for methanol electro-oxidation

Surface composition control plays a crucial role in electrocatalytic reactions for Pt-based bimetallic materials. However, strategies for controlling their surface composition always require extreme conditions including the use of harsh agents, the need for high temperatures, and the necessity of complex procedures. Here we develop a photo-assisted method to fabricate Au@PtAu core–shell nanoparticles (NPs) with well-tuned surface composition at ambient temperatures. It was found that their surface composition can be continuously regulated by the addition amount of HAuCl4 under photo-irradiation. By incorporating Au atoms, the synthesized Au@PtAu NPs show significantly improved properties for methanol electro-oxidation, owing to the reduced CO formation and the weakened binding strength of CO on Pt. The catalytic activity and durability vary with the relative active surface area of Pt or Au (PtSurf. or AuSurf.), and the optimal PtSurf. was found to be ∼64% (AuSurf. ∼36%). The present work highlights the “photo-assisted method” as a green and effective method to synthesize advanced materials with optimized functional properties.