Dual Heterogeneous Structures Promote Electrochemical Properties and Photocatalytic Hydrogen Evolution for Inverse Opal ZnO/ZnS/Co3O4 Crystals.

Potocatalytic hydrogen evolution represnets a promising way to achieve renewable energy sources. Dual heterojunctions with an inverse opal structure are proposed for addressing fundamental challenges (low surface area, inefficient light absorption, and poor charge separation) in photocatalytic water splitting. Inverse opal structure and Co3O4 were introduced to design and synthesize a ZnO/ZnS/Co3O4 (IO-ZnO/ZnS/Co3O4) photocatalyst. Morphology characterizations and photoelectric measurements reveal that the introduction of three-dimensional (3D) structures and dual heterojunctions improves light utilization efficiency and accelerates charge separation, greatly promoting photoelectric performance. The as-prepared IO-ZnO/ZnS/Co3O4 manifests superior photocurrent density (0.49 mA/cm2), which is 4 times higher than that of IO-ZnO/ZnS due to the existence of dual heterojunctions. The result is further confirmed by an enhanced H2 production rate (153.01 µmol/g/h) in pure water. Notably, excellent cycling stability is achieved in pure water because Co3O4 can rapidly capture photogenerated holes to inhibit severe photocorrosion of ZnO/ZnS. Therefore, this work presents a new insight into inhibiting photocorrosion of metal sulfides and promoting their photoelectric performance by combining 3D structures and dual heterojunctions.

Three-Dimensional Porous Cu/Cu2+1O Nanosheet Arrays Promote Electrochemical Nitrate-to-Ammonia Conversion.

The efficiency of electrochemical nitrate (NO3-) reduction to ammonia (NH3) still remains a challenge due to the sluggish kinetics of the complex eight-electron reduction process and competitive hydrogen evolution reaction (HER). Herein, we designed new three-dimensional (3D) porous Cu/Cu2+1O nanosheet arrays (Cu/Cu2+1O NSA) by coupling a template-directed method with in situ electroreduction. Thanks to the 3D porous structure and in-plane heterojunctions, Cu/Cu2+1O NSA can provide abundant active sites and a good interfacial effect, obtaining the maximum Faradaic efficiency (FE) of ammonia (88.09%) and high yield rate of 0.2634 mmol h-1 cm-2, which is higher than that of CuO nanosheets (77.81% and 0.2188 mmol h-1 cm-2) and CuO nanoparticles (34.60% and 0.0692 mmol h-1 cm-2). Experimental results and DFT simulations show that the interface effect of Cu/Cu2+1O can decrease the reaction energy barrier of the key step (*NO to *NOH) and can greatly inhibit the competitive hydrogen evolution reaction, thereby achieving excellent electrocatalytic performance for nitrate-to-ammonia conversion.

Bi2O3-Sensitized TiO2 Hollow Photocatalyst Drives the Efficient Removal of Tetracyclines under Visible Light.

The complete removal of tetracycline residuals under visible light still is a challenging task because of their robust ring structure. To tackle this issue, we explore a novel Bi2O3-sensitized TiO2 visible-light photocatalyst by combining p-n heterojunction with hollow structure. The hollow TiO2/Bi2O3 photocatalyst manifests excellent photocatalytic performance and recyclability toward the complete degradation (100%) of antibiotics under visible light (λ > 420 nm) because of the synergistic effect of p-n heterojunction and hollow structure, successfully overcoming the challenge of the incomplete removal of antibiotics over almost all of the reported visible-light photocatalysts. Additionally, the effects of inorganic ions, pH value, water matrix, and outdoor light on the degradation of tetracyclines were investigated with many details. Notably, the degradation pathways and mechanism of tetracycline were revealed according to trapping experiments, HPLC-MS, and photoelectrochemical characterizations. Therefore, this work provides a new insight into developing visible-light photocatalysts with excellent photocatalytic performances for the complete removal of other refractory contaminants.

Design and synthesis of 'single-crystal-like' C-doped TiO2 nanorods for high-performance supercapacitors.

Although TiO2 is widely used as a promising electrode material for supercapacitors, its potential application suffers from a critical limitation due to its poor electrical conductivity and low rate capability. Here, we report a cost-effective hydrothermal strategy to design and construct a novel 'single-crystal-like' C-doped TiO2 electrode material. The as-synthesized electrode material combines the advantages of TiO2, 'single-crystal-like' features and carbon doping, considerably improving the electrical conductivity of TiO2. The electrochemical measurements demonstrate that the C-doped TiO2 material presents an excellent specific capacitance (449.8 F g-1 at 1 A g-1), which approaches six times more than the value (77.3 F g-1 at 1 A g-1) of P25 electrodes, and far beyond the value of many previously reported TiO2 electrodes. Therefore, this work explores a new method to design high performance electrochemical TiO2 electrode materials by incorporating other dopants into the TiO2 lattice.

Activated carbon modified titanium dioxide/bismuth trioxide adsorbent: One-pot synthesis, high removal efficiency of organic pollutants, and good recyclability.

Considerable endeavors have focused on tightly combining adsorption with photocatalysis in designing composite materials for environmental pollution treatment. Recent advances in coupling titanium dioxide/bismuth trioxide (TiO2/Bi2O3) with activated carbon (AC) show significantly enhanced photocatalytic performance but face critical limitations including low adsorption capacity and multi-step synthesis. In this work, we introduce a one-pot synthesis of activated carbon modified TiO2/Bi2O3 composite materials (TiO2/Bi2O3/AC). Thanks to the integrated adsorbent/photocatalyst system, TiO2/Bi2O3/AC shows a drastically enhanced removal efficiency for sulfamethazine (>81%), far beyond the corresponding value of the reported AC/TiO2/Bi2O3 adsorbent (<40%). Notably, the removal rates of other typical pollutants including tetracyclines, methyl orange, and rhodamine B are as high as >98%. Furthermore, TiO2/Bi2O3/AC obtains >80% of its adsorption rate for the fifth cycle after simple photo-regeneration without any other post-treatments. Kinetic analysis and photoelectric characterization are carried out to provide insight into adsorption mechanism. Therefore, this work demonstrates a considerable potential to design and construct other multifunctional adsorbents with advanced performance.

A temperature-responsive nanoreactor.

An originally designed temperature-responsive nanoreactor is reported. The nanoreactor is made of Ag nanoparticles and a functional polymer composite of poly(acrylamide) (PAAm) and poly(2-acrylamide-2-methylpropanesulfonic acid) (PAMPS). At a relatively low temperature (e.g., 20 °C), this nanoreactor displayed weak reactivity because of the interpolymer complexation between PAAm and PAMPS, which largely restricted the access of reactants to the encapsulated Ag nanoparticles. On the contrary, at a relatively high temperatures (e.g., 40 °C), the nanoreactor demonstrated significant catalytic activity resulting from the dissociation of the interpolymer complexation between PAAm and PAMPS, which allowed reactants to get access to the encapsulated Ag nanoparticles. By taking account of previously reported PNIPAm-based nanoreactors, which show inverse temperature response, i.e., reactivity decreases whilst temperature increases, this temperature-responsive nanoreactor would greatly facilitate and enrich the increasing studies on smart nanomaterials, generating numerous applications in a wide range of areas, such as catalysis and sensing.

Metal Nanoparticles Confined within an Inorganic-Organic Framework Enable Superior Substrate-Selective Catalysis.

The search for catalysts with a perfect substrate selectivity toward the hydrogenation of nitroarenes is a goal of high importance, which still remains a significant challenge. Here, we designed a new type of catalyst with superior substrate selectivity by combining a space-confined effect and a hydrogen-bonding network, in which metal nanoparticles (MNPs) were confined in hierarchical hollow silica (HHS) with a poly(N-isopropylacrylamide) (PNIPA) coating. Given the strong induced properties of hydrogen-bond donors and acceptors in the HHS support and PNIPA coating, the as-synthesized catalyst would achieve perfect substrate selectivity for the hydrogenation of various nitroarenes and their mixture by thoroughly impeding the reduction of nitroarenes with any hydroxyl or carboxyl groups, which is typically very difficult to be realized over almost all of the reported supported-metal catalysts. Notably, the hydrogenation of nitroarenes can produce almost quantitative yields of anilines over the as-synthesized catalyst. Furthermore, density functional theory and experimental evidence are also provided for the hierarchical structure of HHS and PNIPA coating associated with substrates to demonstrate how a substrate could have access or be blocked into the confined active centers (MNPs). Therefore, this work would open a new window to design efficient catalysts for a wide variety of substrate-selective catalyses.

Hierarchically-structured SiO2-Ag@TiO2 hollow spheres with excellent photocatalytic activity and recyclability.

A new protocol for constructing sandwich-like SiO2-Ag@TiO2 hollow spheres (SAT) is introduced, in which SiO2 acts as an efficient support for the Ag nanoparticles (Ag NPs) immobilization, while TiO2 maintains its hierarchical structure and prevents the aggregation of Ag NPs during the photocatalytic reaction. As a photocatalytic agent, the inner and outer surfaces of TiO2 can be fully occupied by pollutants molecules because of its unique structure, which faster boosts the photo-generated electrons to transfer the substrates, leading to an enhanced photocatalytic performance. Compared with Ag NPs deposited on the surface of SiO2@TiO2 (STA), the as-synthesized SAT exhibits a markedly enhanced visible-light and UV light activity than STA for degrading tetracycline and traditional dyes. The excellent photocatalytic performances are ascribed to the enhanced transport paths of photo-generated electrons, reduced recombination probability of e-/h+ pairs, and decreased threat of oxidation and corrosion. Especially, the SAT still maintains its photocatalytic efficiency after five consecutive runs even though the sample is recovered under visible-light irradiation, far beyond the reusability of STA under the same conditions. Therefore, the outstanding photocatalytic activity and excellent recyclability make SAT more potential to purify aquatic contaminants and to meet the demands of future environmental issues.

Design and Synthesis of Hierarchical SiO2@C/TiO2 Hollow Spheres for High-Performance Supercapacitors.

TiO2 has been widely investigated as an electrode material because of its long cycle life and good durability, but the relatively low theoretical capacity restricts its practical application. Herein, we design and synthesize novel hierarchical SiO2@C/TiO2 (HSCT) hollow spheres via a template-directed method. These unique HSCT hollow spheres combine advantages from both TiO2 such as cycle stability and SiO2 with a high accessible area and ionic transport. In particular, the existence of a C layer is able to enhance the electrical conductivity. The SiO2 layer with a porous structure can increase the ion diffusion channels and accelerate the ion transfer from the outer to the inner layers. The electrochemical measurements demonstrate that the HSCT-hollow-sphere-based electrode manifests a high specific capacitance of 1018 F g-1 at 1 A g-1 which is higher than those for hollow TiO2 (113 F g-1) and SiO2/TiO2 (252 F g-1) electrodes, and substantially higher than those of all the previously reported TiO2-based electrodes.

High photocatalytic activity of hierarchical SiO2@C-doped TiO2 hollow spheres in UV and visible light towards degradation of rhodamine B.

Ongoing research activities are targeted to explore high photocatalytic activity of TiO2-based photocatalysts for the degradation of environmental contaminants under UV and visible light irradiation. In this work, we devise a facile, cost-effective technique to in situ synthesize hierarchical SiO2@C-doped TiO2 (SCT) hollow spheres for the first time. This strategy mainly contains the preparation of monodisperse cationic polystyrene spheres (CPS), sequential deposition of inner SiO2, the preparation of the sandwich-like CPS@SiO2@CPS particles, and formation of outer TiO2. After the one-step removal of CPS templates by calcination at 450°C, hierarchical SiO2@C-doped TiO2 hollow spheres are in situ prepared. The morphology, hierarchical structure, and properties of SCT photocatalyst were characterized by TEM. SEM, STEM Mapping, BET, XRD, UV-vis spectroscopy, and XPS. Results strongly confirm the carbon doping in the outer TiO2 lattice of SCT hollow spheres. When the as-synthesized SCT hollow spheres were employed as a photocatalyst for the degradation of Rhodamine B under visible-light and ultraviolet irradiation, the SCT photocatalyst exhibits a higher photocatalytic activity than commercial P25, effectively overcoming the limitations of poorer UV activity for many previous reported TiO2-based photocatalysts due to doping.

Core/shell particles containing 3-(methacryloxypropyl)-trimethoxysilane in the shell: synthesis, characterization, and application.

In comparison to the corresponding single-component counterparts, core/shell particles are widely used due to their better physical and chemical properties. The surface properties of core/shell particles evidently play an important role in the process of application. It is easy to deduce that surface properties mostly depend on the properties of the component in the shell. Therefore, desirable materials of shell are very significant for the study of composite materials, especially in core/shell field. It is well known that polysiloxane has excellent properties, such as the water repellency, high flexibility, low surface energy, and biocompatibility. Its application, however, is limited due to poor cohesiveness and poor film-forming properties. Recently, much endeavor has been made to overcome such flaws. It is found that polyacrylate is commonly considered for its good cohesiveness and excellent film-forming property. The combination of polysiloxane and polyacrylate has been shown to be important in the composite material field, especially as core/shell particles. Unfortunately, their hydrophobicity is considerably different and thus, the core/shell particles consisting of polyacrylate (PA)/polysiloxane (PSi) are hard to prepare by general seeded emulsion polymerization, and are also scarcely available in the literature. In this study, the new core/shell PA/PSi particles with poly(butyl methacrylate) (PA) as the core and poly(3-(methacryloxypropyl)-trimethoxysilane) (PSi) as the shell were prepared by dispersion polymerization under the kinetically controlled conditions. The characterization of the particles by TEM, DSC, particle size analyzer as well as static contact angle confirmed the formation of core/shell structure. The application of core/shell (PA/PSi) particles also has been considered and discussed here.TEM micrographs of core/shell (PA/PSi) particles.

A self-switchable Ag nanoreactor exhibiting outstanding catalytic properties.

A highly efficient nanoreactor that contains silver nanoparticles in hollow silica spheres and an interpolymer network as a gate-keeper has been developed following a facile procedure. The fast "signal-triggered" switch of the smart network results in a high reactivity and a high response rate, yielding improved potential for many practical applications.

Stimuli-responsive controlled release and molecular transport from hierarchical hollow silica/polyelectrolyte multilayer formulations.

The smart designing of polymer hybrid carriers with a selective property will play a pivotal role in improving patient care and simplifying treatment regimes in the clinic. The controlled drug release of biomolecules from thin film coatings provides a simple pathway to offer complex localized in vivo dosing. In this investigation, we showed that it is possible to take advantage of the structure of hierarchically structured hollow silica/polymer hybrid system to control drug release. Drug-loaded polyelectrolyte multilayer films were developed using layer-by-layer assembly, incorporating the surface of the hierarchically structured hollow silica spheres. In comparison to the conventional hollow silica system, the synthesized formulation exhibited an enhanced stability, higher drug loading and better residual capacity of biomolecules. This rationally integrated architecture was demonstrated to be a very effective and controllable carrier for the drug release by changing the pH value. In addition, the developed system presented a highly selective molecular transport of doxorubicin hydrochloride (DOX), a model anti-cancer agent, at different pH values; moreover, it could be further applied to tailor cell viability, making it more promising for advanced drug therapy.

Preparation and antibacterial activities of hollow silica-Ag spheres.

Hollow silica spheres with round mesoporous shells were synthesized by core-shell template method, using monodispersed cationic polystyrene particles as core, and TEOS (tetraethoxysilane) as the silica source to form shell. After calcination at 550°C, uniform spheres with a thin shell of silica and hollow interior structures. Transmission electron microscopy results showed that the size of the spheres is about 700 nm in diameter with narrow distribution. In addition, the spheres have a high surface area of 183 m(2)/g. The spheres were subsequently used as silver-loading substrates and the silver loaded spheres were tested in antimicrobial study against gram negative bacteria Eschrichia coli in vitro. The hollow silica-Ag spheres proved significantly higher antibacterial efficacy against E. coli as compared to that of the common silica-Ag particles.

The preparation and enzyme immobilization of hydrophobic polysiloxane supports.

Enzymes are versatile biocatalysts and find increasing applications in many areas. The major advantages of using enzymes in biocatalytic transformations are their chemo-, regio-, and stereospecificity, as well as the mild reaction conditions that can be used. However, even when an enzyme is identified as being useful for a given reaction, its application is often hampered by its lack of long-term stability under process conditions, and also by difficulties in recovery and recycling. For ease of application and stabilization purposes, enzymes are often immobilized on solid supports. Among support matrices, hydrophobic biomaterials have been extensively used as supports for enzyme immobilization because the hydrophobic interactions not only can effectively increase the amount of enzyme immobilization, but also exhibit higher activity and retention of activity compared with hydrophilic supports. On the other hand, polysiloxane can evidently increase the amount of enzyme immobilization because of its hydrophobicity and strong affinity with enzyme. Therefore, this research details the first preparation and use of a hydrophobic polysiloxane support for enzyme immobilization in which the structural and functional characteristics of new supports have been investigated by using glucose oxidase (GOD) and a simple Fenton's assay method, and extremely interesting features were revealed. The results showed that the amount of GOD immobilization and the stability of GOD loaded, which are fundamental properties for enzyme separation and purification, can be significantly improved by adsorption. Moreover, the results indicated that hydrophobic polysiloxane supports can effectively increase the enzymatic affinity and durability of GOD, and decrease the rate of GOD desorbed.