Facile Synthesis of Organic-Inorganic Hybrid Heterojunctions of Glycolated Conjugated Polymer-TiO2-X for Efficient Photocatalytic Hydrogen Evolution.

The utilization of the organic-inorganic hybrid photocatalysts for water splitting has gained significant attention due to their ability to combine the advantages of both materials and generate synergistic effects. However, they are still far from practical application due to the limited understanding of the interactions between these two components and the complexity of their preparation process. Herein, a facial approach by combining a glycolated conjugated polymer with a TiO2-X mesoporous sphere to prepare high-efficiency hybrid photocatalysts is presented. The functionalization of conjugated polymers with hydrophilic oligo (ethylene glycol) side chains can not only facilitate the dispersion of conjugated polymers in water but also promote the interaction with TiO2-X forming stable heterojunction nanoparticles. An apparent quantum yield of 53.3% at 365 nm and a hydrogen evolution rate of 35.7 mmol h-1 g-1 is achieved by the photocatalyst in the presence of Pt co-catalyst. Advanced photophysical studies based on femtosecond transient absorption spectroscopy and in situ, XPS analyses reveal the charge transfer mechanism at type II heterojunction interfaces. This work shows the promising prospect of glycolated polymers in the construction of hybrid heterojunctions for photocatalytic hydrogen production and offers a deep understanding of high photocatalytic performance by such heterojunction photocatalysts.

Photoelectrochemical performance of a nanostructured BiVO4/NiOOH/FeOOH-Cu2O/CuO/TiO2 tandem cell for unassisted solar water splitting.

An unassisted solar water splitting tandem cell is fabricated using FeOOH/NiOOH-coated BiVO4 nanostructures as a photoanode and a TiO2-protected heterojunction Cu2O/CuO thin film as a photocathode. The individual photoelectrochemical (PEC) performance of the nanostructured BiVO4/NiOOH/FeOOH photoanode produces a photocurrent of 2.05 mA cm-2 at 1.23 V vs. RHE, while the Cu2O/CuO/TiO2 photocathode delivers -1.61 mA cm-2 at 0 V vs. RHE under an AM 1.5 filtered illumination of 100 mW cm-2. The operating point of tandem cell photocurrent is found to be 0.273 mA cm-2 at 0.56 V vs. RHE. From two-electrode linear sweep voltammetry, the tandem cell (BiVO4/NiOOH/FeOOH-Cu2O/CuO/TiO2) delivers an unassisted current density of 0.201 mA cm-2 at 0 V. The chronoamperometry test further demonstrates the stable nature of the tandem cell, which retains a current density of 0.187 mA cm-2 during a testing duration of 3000 seconds. The proposed tandem cell provides optimized solutions to designing a cost-effective and stable solar water splitting system for the fulfillment of the future energy needs.

A Multiscale, Dynamic Elucidation of Li Solubility in the Alloy and Metallic Plating Process.

Li-containing alloys and metallic deposits offer substantial Li+ storage capacities as alternative anodes to commercial graphite. However, the thermodynamically in sequence, yet kinetically competitive mechanism between Li solubility in the solid solution and intermediate alloy-induced Li deposition remains debated, particularly across the multiple scales. The elucidation of the mechanism is rather challenging due to the dynamic alloy evolution upon the non-equilibrium, transient lithiation processes under coupled physical fields. Here, influential factors governing Li solubility in the Li-Zn alloy are comprehensively investigated as a demonstrative model, spanning from the bulk electrolyte solution to the ion diffusion within the electrode. Through real-time phase tracking and spatial distribution analysis of intermediate alloy/Li metallic species at varied temperatures, current densities and particle sizes, the driving force of Li solubility and metallic plating along the Li migration pathway are probed in-depth. This study investigates the correlation between kinetics (pronounced concentration polarization, miscibility gap in lattice grains) and rate-limiting interfacial charge transfer thermodynamics in dedicating the Li diffusion into the solid solution. Additionally, the lithiophilic alloy sites with the balanced diffusion barrier and Li adsorption energy are explored to favor the homogeneous metal plating, which provides new insights for the rational innovation of high-capacity alloy/metallic anodes.

Enhanced rate capability and high-voltage cycling stability of single-crystal nickel-rich cathode by surface anchoring dielectric BaTiO3.

The single-crystal Ni-rich Li(NixCoyMn1-x-y)O2 cathode (NCM) demonstrates better cycle performance, enhanced tap density and improved mechanical structure stability, compared with polycrystalline NCM.However, limited Li+ transports, (003) plane slips and microcracks in large single particles hinder rate capability and cycle performance. To overcome these shortcomings,single-crystal NCM cathodes have been modified by nanosized tetragonal BaTiO3. Due to the dielectric properties, BaTiO3 particles induce electric field concentration at the BaTiO3-NCM-electrolyte interface. Thus, a large amount of lithium vacancies can be formed, providing sufficient sites for the hopping diffusion of lithium ions, thereby significantly enhancing the diffusion coefficient of Li+. Moreover, the redistribution of charges can inhibit the formation and accumulation of cathode-electrolyte-interface. Owing to the synergetic effect of BaTiO3, the BT-modified single-crystal NCM with the optimized loading shows a remarkable initial discharge capacity of 138.5 mAh g-1 and maintains 53.8% of its initial discharge capacity after 100 cycles under 5C at 4.5 V cut-off voltage. Overall, the proposed dielectric cathode-electrolyte-interface strategy can enhance Li+ ion transport and stabilize the interface structure, leading to improved rate performance. Meanwhile, the diffusion-induced state of charge gradient can also be inhibited, resulting in high structure stability of single-crystal NCMs under high rate and cut-off voltage cycling.

Ultraviolet-cured polyethylene oxide-based composite electrolyte enabling stable cycling of lithium battery at low temperature.

The room and low-temperature performances of solid-state lithium batteries are crucial to expand their practical application. Polyethylene oxide (PEO) has received great attention as the most representative polymer electrolyte matrix. However, most PEO-based solid-state batteries need to operate at high temperature due to low room temperature ionic conductivity. Improving the ionic conductivity by adding plasticizers or reducing the crystallinity of PEO often compromises its mechanical strength. Here, an amorphous PEO-based composite solid-state electrolyte is obtained by ultraviolet (UV) polymerizing PEO and methacryloyloxypropyltrimethoxy silane (KH570)-modified SiO2 which demonstrates both satisfactory mechanical performance and high ionic conductivity at room (3.37 × 10-4 S cm-1) and low temperatures (1.73 × 10-4 S cm-1 at 0 °C). In this electrolyte, the crystallinity of PEO is reduced through cross-linking, and therefore provides a fast Li+ ions transfer area. Moreover, the KH570-modified SiO2 inorganic particles promote the dissociation of lithium salts by Lewis acid centers to increase the ionic conductivity. Importantly, this kind of cross-linking networks endows the final electrolyte much higher mechanical strength than the pure PEO polymer electrolyte or PEO-inorganic filler blended systems. The solid-state LiFePO4/Li cell assembled with this electrolyte exhibits excellent cycling performance and high capacity at room and low temperatures.

Recent Progress in the Synthesis and Biomedical Properties of Natural Biopolymer Composites.

BACKGROUND: Natural biopolymers have drawn extensive attention because of their great biocompatibility, biodegradability, renewability, and the availability of various reactive functional groups for modifying and introducing novel components. In the last few years, numerous natural biopolymer composites have been exploited to improve their physical and chemical properties and add new functionalities. METHODS: Herein, we summarize the current progress in three common classes of natural biopolymer-based composites, including alginate, chitosan, and gelatin. RESULTS: The morphology characteristics, preparation methods, and unique functionalities of these biopolymer composites are also analyzed and discussed. CONCLUSION: Finally, the article offers an overview of recent progress in the main biomedical applications such as tissue engineering, wound-healing, and drug delivery, which inspires further progress in biopolymer composites with tailored mechanical property and stable characteristics for pharmaceutical and biomedical applications.

Redox Dual-Cocatalyst-Modified CdS Double-Heterojunction Photocatalysts for Efficient Hydrogen Production.

Cadmium sulfide (CdS) as one of the most common visible-light-responsive photocatalysts has been widely investigated for hydrogen generation. However, its low solar-hydrogen conversion efficiency caused by fast carrier recombination and poor catalytic activity hinders its practical applications. To address this issue, we develop a novel and highly efficient nickel-cobalt phosphide and phosphate cocatalyst-modified CdS (NiCoP/CdS/NiCoPi) photocatalyst for hydrogen evolution. The dual-cocatalysts were simultaneously deposited on CdS during one phosphating step by using sodium hypophosphate as the phosphorus source. After the loading of the dual-cocatalysts, the photocurrent of CdS significantly increased, while its electrical impedance and photoluminescence emission dramatically decreased, which indicates the enhancement of charge carrier separation. It was proposed that the NiCoP cocatalyst accepts electrons and promotes hydrogen evolution, while the NiCoPi cocatalyst donates electrons and accelerates the oxidation of sacrificial agents (e.g., lactic acid). Consequently, the visible-light-driven hydrogen evolution of this composite photocatalyst greatly improved. The dual-cocatalyst-modified CdS with a loading content of 5 mol % showed a high hydrogen evolution rate of 80.8 mmol·g-1·h-1, which was 202 times higher than that of bare CdS (0.4 mmol·g-1·h-1). This is the highest enhancement factor for metal phosphide-modified CdS photocatalysts. It also exhibited remarkable stability in a continuous photocatalytic test with a total reaction time of 24 h.

Gel Polymer Electrolyte with High Li+ Transference Number Enhancing the Cycling Stability of Lithium Anodes.

Lithium anodes suffer from severe safety problems in liquid electrolyte systems that result from an unstable Li plating/stripping process and Li dendrite growth, leading to rapid degradation of Li metal batteries. A polyethylene (PE)-supported gel polymer electrolyte (GPE) with excellent electrolyte uptake/retention capability was simply prepared in this paper by the construction of cross-linked polymer networks (PNs) on the surface of a poly(ethylenimine)-primed PE separator to stabilize the lithium anode. The highly delocalized negative charge of p-styrene sulfonate groups on PNs plays a role in regulating the Li+ and anion transport, giving rise to a high Li+ transference number. This GPE extended the electrochemical stability to 4.8 V and improved the stability of interface between the electrolyte and lithium metal anode (reduced overpotential and suppressed lithium dendrites) during storage and repeated lithium plating/stripping cycling. The Li metal anode-based battery employing this GPE exhibits excellent cycling stability and C-rate capability.

New Insight into Ethylenediaminetetraacetic Acid Tetrasodium Salt as a Sacrificing Sodium Ion Source for Sodium-Deficient Cathode Materials for Full Cells.

Sacrificing sodium supply sources is needed for sodium-deficient cathode materials to achieve commercialization of sodium-ion full cells using sodium-ion intercalation anode materials. Herein, the potential of ethylenediaminetetraacetic acid tetrasodium salt (EDTA-4Na) as a sacrificing sodium supply source was investigated by intimately blending it with sodium-deficient P2-type Na0.67[Al0.05Mn0.95]O2. The EDTA-4Na/Na0.67[Al0.05Mn0.95]O2 composite electrode unexpectedly exhibited an improved charge capacity of 177 mA h (g-oxide)-1 compared with the low charge capacity of 83 mA h (g-oxide)-1 for bare Na0.67[Al0.05Mn0.95]O2. The reversible capacity of an EDTA-4Na/Na0.67[Al0.05Mn0.95]O2//hard carbon full-cell system increased to 152 mA h (g-oxide)-1 at the first discharge with a Coulombic efficiency of 89%, whereas the Na0.67[Al0.05Mn0.95]O2 without EDTA-4Na delivered a discharge capacity 51 mA h g-1 because of the small charge capacity. The EDTA-4Na sacrificed itself to generate Na+ ions via oxidative decomposition by releasing four sodium ions and producing C3N as a decomposition resultant on charge. It is thought that the slight increase in discharge capacity is associated with the electroconducting nature of the C3N deposits formed on the surface of the Na0.67[Al0.05Mn0.95]O2 electrode. We elucidated the reaction mechanism and sacrificial activity of EDTA-4Na, and our findings suggest that the addition of EDTA-4Na is beneficial as an additional source of Na+ ions that contribute to the charge capacity.

On the Stability of NaO2 in Na-O2 Batteries.

Na-O2 batteries are regarded as promising candidates for energy storage. They have higher energy efficiency, rate capability, and chemical reversibility than Li-O2 batteries; in addition, sodium is cheaper and more abundant compared to lithium. However, inconsistent observations and instability of discharge products have inhibited the understanding of the working mechanism of this technology. In this work, we have investigated a number of factors that influence the stability of the discharge products. By means of in operando powder X-ray diffraction study, the influence of oxygen, sodium anode, salt, solvent, and carbon cathode were investigated. The Na metal anode and an ether-based solvent are the main factors that lead to the instability and decomposition of NaO2 in the cell environment. This fundamental insight brings new information on the working mechanism of Na-O2 batteries.

Cellulose-based Nanocarriers as Platforms for Cancer Therapy.

Cellulose is an important environmentally-friendly renewable polymer on the earth. Cellulose has been widely used as feedstocks for the synthesis of biomaterials, biofuels and biochemicals. Recently, cellulose and cellulose derivatives have received intense attention in biomedical applications, such as tissue engineering, scaffold, artificial blood vessel, skin grafts, artificial skin, drug carrier, and chronic skin diseases, many of which are somehow related to cancer therapy. In this mini-review, we focus on the up-to-date development of cellulosebased nanocarriers used for cancer therapy. Various cellulose-based nanocarriers such as bacterial cellulose (BC), cellulose acetate, microcrystalline cellulose, carboxymethyl cellulose, cellulose nanocrystals, cellulose nanofibrills, etc, are reviewed in terms of being used in drug delivery systems for cancer treatment. Different strategies for the synthesis of cellulose-based nanocarriers are summarized. Special attention is paid on the structure and properties of cellulose-based drug carriers for cancer therapy via some representative examples. Finally, the problems and future developments of these promising polymeric nanocarriers are raised and proposed.

In Situ Synthesis of Tungsten-Doped SnO2 and Graphene Nanocomposites for High-Performance Anode Materials of Lithium-Ion Batteries.

The composite of tungsten-doped SnO2 and reduced graphene oxide was synthesized through a simple one-pot hydrothermal method. According to the structural characterization of the composite, tungsten ions were doped in the unit cells of tin dioxide rather than simply attaching to the surface. Tungsten-doped SnO2 was in situ grown on the surface of graphene sheet to form a three-dimensional conductive network that enhanced the electron transportation and lithium-ion diffusion effectively. The issues of SnO2 agglomeration and volume expansion could be also avoided because the tungsten-doped SnO2 nanoparticles were homogeneously distributed on a graphene sheet. As a result, the nanocomposite electrodes of tungsten-doped SnO2 and reduced graphene oxide exhibited an excellent long-term cycling performance. The residual capacity was still as high as 1100 mA h g-1 at 0.1 A g-1 after 100 cycles. It still remained at 776 mA h g-1 after 2000 cycles at the current density of 1A g-1.

Towards an Understanding of Li2 O2 Evolution in Li-O2 Batteries: An In†Operando Synchrotron X-ray Diffraction Study.

One of the major challenges in developing high-performance Li-O2 batteries is to understand the Li2 O2 formation and decomposition during battery cycling. In this study, this issue was investigated by synchrotron radiation powder X-ray diffraction. The evolution of Li2 O2 morphology and structure was observed under actual electrochemical conditions of battery operation. By quantitatively tracking Li2 O2 during discharge and charge, a two-step process was suggested for both growth and oxidation of Li2 O2 owing to different mechanisms during two stages of both oxygen reduction reaction and oxygen evolution reaction. From an observation of the anisotropic broadening of Li2 O2 in XRD patterns, it was inferred that disc-like Li2 O2 grains are formed rapidly in the first step of discharge. These grains can stack together so that they facilitate the nucleation and growth of toroidal Li2 O2 particles with a LiO2 -like surface, which could cause parasitic reactions and hinder the formation of Li2 O2 . During the charge process, Li2 O2 is firstly oxidized from the surface, followed by a delithiation process with a faster oxidation of the bulk by stripping the interlayer Li atoms to form an off-stoichiometric intermediate. This fundamental insight brings new information on the working mechanism of Li-O2 batteries.

Homogeneous Cobalt/Vanadium Complexes as Precursors for Functionalized Mixed Oxides in Visible-Light-Driven Water Oxidation.

The heterometallic complexes (NH4 )2 [Co(H2 O)6 ]2 [V10 O28 ]⋅4 H2 O (1) and (NH4 )2 [Co(H2 O)5 (ß-HAla)]2 [V10 O28 ]⋅4 H2 O (2) have been synthesized and used for the preparation of mixed oxides as catalysts for water oxidation. Thermal decomposition of 1 and 2 at relatively low temperatures (<500 °C) leads to the formation of the solid mixed oxides CoV2 O6 /V2 O5 (3) and Co2 V2 O7 /V2 O5 (4). The complexes (1, 2) and heterogeneous materials (3, 4) act as catalysts for photoinduced water oxidation. A modification of the thermal decomposition procedure allowed the deposition of mixed metal oxides (MMO) on a mesoporous TiO2 film. The electrodes containing Co/V MMOs in TiO2 films were used for electrocatalytic water oxidation and showed good stability and sustained anodic currents of about 5 mA cm-2 at 1.72 V versus relative hydrogen electrode (RHE). This method of functionalizing TiO2 films with MMOs at relatively low temperatures (<500 °C) can be used to produce other oxides with different functionality for applications in, for example, artificial photosynthesis.

ZnO based heterojunctions and their application in environmental photocatalysis.

As an alternative to TiO2 photocatalysts, ZnO exhibits a large potential for photocatalytic (PC) applications in environmental treatments, such as degradation of wastewater, sterilization of drinking water, and air cleaning. However, the efficiency achieved with ZnO to date is far from that expected for commercialization, due to rapid charge recombination, photo-corrosion as well as poor utilization of solar energy. Fortunately, in recent years, a great number of breakthroughs have been achieved in PC performance (including activity and stability) of micro-/nano- structured ZnO by forming heterojunctions (HJs) with metal nanoparticles (NPs), carbon nanostructures and other semiconductors. In most cases, the improvement of PC performance was ascribed to the better charge separation at the interfaces between ZnO and the other components. Sometimes, the formation of hybrids is also in favor of visible light harvesting. This review summarizes recent advances in the fields of environmental photocatalysis by ZnO based HJs, and especially emphasizes their abilities in degradation of organic pollutants or harmful substances in water. We aim to reveal the mechanism underlying the enhanced PC performance by constructing HJs, and extend the potential of ZnO HJ photocatalysts for future trends, and practical, large-scale applications in environment-related fields.

Porous cellulose diacetate-SiO2 composite coating on polyethylene separator for high-performance lithium-ion battery.

The developments of high-performance lithium ion battery are eager to the separators with high ionic conductivity and thermal stability. In this work, a new way to adjust the comprehensive properties of inorganic-organic composite separator was investigated. The cellulose diacetate (CDA)-SiO2 composite coating is beneficial for improving the electrolyte wettability and the thermal stability of separators. Interestingly, the pore structure of composite coating can be regulated by the weight ratio of SiO2 precursor tetraethoxysilane (TEOS) in the coating solution. The electronic performance of lithium ion batteries assembled with modified separators are improved compared with the pristine PE separator. When weight ratio of TEOS in the coating solution was 9.4%, the composite separator shows the best comprehensive performance. Compared with the pristine PE separator, its meltdown temperature and the break-elongation at elevated temperature increased. More importantly, the discharge capacity and the capacity retention improved significantly.

Microwave-Assisted Hydrothermal Synthesis of Cellulose/Hydroxyapatite Nanocomposites.

In this paper, we report a facile, rapid, and green strategy for the synthesis of cellulose/hydroxyapatite (HA) nanocomposites using an inorganic phosphorus source (sodium dihydrogen phosphate dihydrate (NaH2PO4·2H2O)), or organic phosphorus sources (adenosine 5'-triphosphate disodium salt (ATP), creatine phosphate disodium salt tetrahydrate (CP), or D-fructose 1,6-bisphosphate trisodium salt octahydrate (FBP)) through the microwave-assisted hydrothermal method. The effects of the phosphorus sources, heating time, and heating temperature on the phase, size, and morphology of the products were systematically investigated. The experimental results revealed that the phosphate sources played a critical role on the phase, size, and morphology of the minerals in the nanocomposites. For example, the pure HA was obtained by using NaH2PO4·2H2O as phosphorus source, while all the ATP, CP, and FBP led to the byproduct, calcite. The HA nanostructures with various morphologies (including nanorods, pseudo-cubic, pseudo-spherical, and nano-spherical particles) were obtained by varying the phosphorus sources or adjusting the reaction parameters. In addition, this strategy is surfactant-free, avoiding the post-treatment procedure and cost for the surfactant removal from the product. We believe that this work can be a guidance for the green synthesis of cellulose/HA nanocomposites in the future.

Fluorine-Doped Tin Oxide Nanocrystal/Reduced Graphene Oxide Composites as Lithium Ion Battery Anode Material with High Capacity and Cycling Stability.

Tin oxide (SnO2) is a kind of anode material with high theoretical capacity. However, the volume expansion and fast capability fading during cycling have prevented its practical application in lithium ion batteries. Herein, we report that the nanocomposite of fluorine-doped tin oxide (FTO) and reduced graphene oxide (RGO) is an ideal anode material with high capacity, high rate capability, and high stability. The FTO conductive nanocrystals were successfully anchored on RGO nanosheets from an FTO nanocrystals colloid and RGO suspension by hydrothermal treatment. As the anode material, the FTO/RGO composite showed high structural stability during the lithiation and delithiation processes. The conductive FTO nanocrystals favor the formation of stable and thin solid electrolyte interface films. Significantly, the FTO/RGO composite retains a discharge capacity as high as 1439 mAhg(-1) after 200 cycles at a current density of 100 mAg(-1). Moreover, its rate capacity displays 1148 mAhg(-1) at a current density of 1000 mAg(-1).

Layer-by-Layer Deposition of Organic-Inorganic Hybrid Multilayer on Microporous Polyethylene Separator to Enhance the Electrochemical Performance of Lithium-Ion Battery.

A simple layer-by-layer (LbL) self-assembly process of poly(acrylic acid) (PAA) and ZrO2 was applied to construct functional ultrathin multilayers on polyethylene (PE) separators without sacrificing the excellent porous structure of separators. Such PAA/ZrO2 LbL-modified PE separators possess good electrolyte wettability, excellent electrolyte uptake, high ionic conductivity and large Li(+) transference number. More importantly, the top layer of LbL self-assembly would affect the dissociation of electrolyte and the formation of solid electrolyte interphase (SEI) layer in half-cells. Compared with the pristine and (PAA/ZrO2)1PAA-modified PE separators, (PAA/ZrO2)3-modified PE separator shows a larger Li(+) transference number (0.6) and a faster tendency to form a stable SEI layer, endowing half-cells with excellent capacity retention at high C-rates and superior cycling performance. These fascinating characteristics will provide the LbL self-assembly with a promising method to improve the surface property of PE separators for high performance lithium-ion batteries.