A Dual Photoelectrode Photoassisted Fe-Air Battery: The Photo-Electrocatalysis Mechanism Accounting for the Improved Oxygen Evolution Reaction and Oxygen Reduction Reaction of Air Electrodes.

Effective utilization of solar energy in battery systems is a promising solution to achieve sustainable and green development. In this work, a photoassisted Fe-air battery (PFAB) with two photoelectrodes of ZnO-TiO2 heterostructure and polyterthiophene (pTTh)-coated CuO (pTTh-CuO) grown on fluorine-doped tin oxide (FTO) is proposed. The band structure of semiconductors and the charge-transfer mechanism of heterostructure are studied. The electrochemical results show that the photogenerated electrons and holes play key roles in reducing the oxygen evolution reaction (OER)/oxygen reduction reaction (ORR) overpotential in the discharging and charging processes, respectively. The short-circuit current density, the open-circuit voltage, and the maximum power output of the PFAB can reach 34.28 mA cm-2 , 1.15 V, and 5.69 mW cm-2 upon illumination, respectively. The photoassisted Fe-air battery exhibits a low charge voltage of 0.64 V for ZnO-TiO2 as photoelectrode and a discharge voltage of 1.38 V for pTTh-CuO as a photoelectrode at 0.1 mA cm-2 .

Smart Solar-Metal-Air Batteries Based on BiOCl Photocorrosion for Monolithic Solar Energy Conversion and Storage.

Herein, a BiOCl hydrogel film electrode featuring excellent photocorrosion and regeneration properties acts as the anode to construct a novel type of smart solar-metal-air batteries (SMABs), which combines the characteristics of solar cells (direct photovoltaic conversion) and metal-air batteries (electric energy storage and release interacting with atmosphere). The cyclic photocorrosion processes between BiOCl (Bi3+ ) and Bi can simply be achieved by solar light illumination and standing in the dark. Upon illumination, the device takes open-circuit configuration to charge itself from the sunlight. Notably, in this system, the converted solar energy can be stored in the SMABs without the need of external assistance. In the discharging process in the dark, Bi0 spontaneously turns back to Bi3+ producing electrons to induce the oxygen reduction reaction. With an illumination of 15 min, the battery with an electrode area of 1 cm2 can be continuously discharged for ≈3000 s. Taking elemental Bi as the calculation object, the theoretical capacity of the SMABs is 384.75 mAh g-1 , showing its potential application in energy storage. This novel type of SMABs is developed based on the unique photocorrosive and self-oxidation reaction of BiOCl to achieve photochemical energy generation and storage.

A sensitive cholesterol electrochemical biosensor based on biomimetic cerasome and graphene quantum dots.

A simple and sensitive electrochemical cholesterol biosensor was fabricated based on ceramic-coated liposome (cerasome) and graphene quantum dots (GQDs) with good conductivity. The cerasome consists of a lipid-bilayer membrane and a ceramic surface as a soft biomimetic interface, and the mild layer-by-layer self-assembled method as the immobilization strategy on the surface of the modified electrode was used, which can provide good biocompatibility to maintain the biological activity of cholesterol oxidase (ChOx). The GQDs promoted electron transport between the enzyme and the electrode more effectively. The structure of the cerasome-forming lipid was characterized by Fourier transform infrared (FT-IR). The morphology and characteristics of the cerasome and GQDs were characterized by transmission electron microscopy (TEM), zeta potential, photoluminescence spectra (PL), etc. The proposed biosensors revealed excellent catalytic performance to cholesterol with a linear concentration range of 16.0 × 10-6-6.186 × 10-3 mol/L, with a low detection limit (LOD) of 5.0 × 10-6 mol/L. The Michaelis-Menten constant (Km) of ChOx was 5.46 mmol/L, indicating that the immobilized ChOx on the PEI/GQDs/PEI/cerasome-modified electrode has a good affinity to cholesterol. Moreover, the as-fabricated electrochemical biosensor exhibited good stability, anti-interference ability, and practical application for cholesterol detection.

Synergy of Bi2 O3 and RuO2 Nanocatalysts for Low-Overpotential and Wide pH-Window Electrochemical Ammonia Synthesis.

Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is still seriously impeded by the inferior NH3 yield and low Faradaic efficiency, especially at low overpotentials. Herein, we report the synthesis of nano-sized RuO2 and Bi2 O3 particles grown on functionalized exfoliated graphene (FEG) through in situ electrodeposition, denoted as RuO2 -Bi2 O3 /FEG. The prepared self-supporting RuO2 -Bi2 O3 /FEG hybrid with a Bi mass loading of 0.70 wt% and Ru mass loading of 0.04 wt% shows excellent NRR performance at low overpotentials in acidic, neutral and alkaline electrolytes. It achieves a large NH3 yield of 4.58±0.16 µgNH3 h-1  cm-2 with a high Faradaic efficiency of 14.6 % at -0.2 V versus reversible hydrogen electrode in 0.1 M Na2 SO4 electrolyte. This performance benefits from the synergistic effect between Bi2 O3 and RuO2 which respectively have a fairly strong interaction of Bi 6p orbitals with the N 2p band and abundant supply of *H, as well as the binder-free characteristic and the convenient electron transfer via graphene nanosheets. This work highlights a new electrocatalyst design strategy that combines transition and main-group metal elements, which may provide some inspirations for designing low-cost and high-performance NRR electrocatalysts in the future.

Fe2O3/BiOI-Based Photoanode with n-p Heterogeneous Structure for Photoelectric Conversion.

We report a promising photoanode material of Fe2O3/BiOI for efficient photoelectric conversion in solar cells, which was fabricated with BiOI attached to a one-dimensional Fe2O3 nanorod array. The two semiconductors of p-type BiOI and n-type Fe2O3 formed a heterogeneous structure for efficient charge separation. The highest open circuit voltage and short circuit current of the solar cell can reach 0.41 V and 4.89 mA/cm2, respectively. This study opens an available field to develop low-cost and environmentally friendly photoelectric materials for solar cells.

Preparation and performance of crosslinked poly(arylene ether)s containing azobenzene chromophores.

A series of novel poly(arylene ether)s with crosslinked groups and different azobenzene chromophores contents (azo-CPAEs: PAE-allyl20%-azo20%, PAE-allyl20%-azo40%, PAE-allyl20%-azo60%) were synthesized from a new bisfluoro monomer, (2,6-difluorophenyl)-(4-hydroxyphenyl)methanone. Their chemical structures were characterized by means of UV-vis and FI-IR. The thermal properties of the polymers were investigated by TGA and DSC, indicating the polymers had high glass transition temperatures (Tg > 147 °C) and good thermal stability (Td5 > 360 °C) even when the contents of azobenzene chromophores was high to 60%. And the influence of thermal crosslinking on the performance of PAE-allyl20%-azo20%, a typical one of the series, was investigated. Tg of PAE-allyl20%-azo20% increased with the increase of heating time when heat-treated at 250 °C for 20, 40 and 60 min, indicating the crosslink degree of the polymer increased. After heat-treated for 60 min, Tg of PAE-allyl20%-azo20% increased to 175 °C from 147 °C before thermal crosslinking. Upon irradiation with a 532 nm neodymium doped yttrium aluminum garnet (Nd:YAG) laser beam, the remnant value of the polymer PAE-allyl20%-azo20% before and after the thermal crosslinking were 81 and 96%, respectively, meaning that the PAE-allyl20%-azo20% after thermal crosslink showed more stable photoinduced alignment than that before thermal crosslinking.

Cerasomes: Soft Interface for Redox Enzyme Electrochemical Signal Transmission.

Anionic cerasomes, which consist of a liposomal lipid bilayer and a ceramic surface, were used as a soft interface for the construction of an integrated modified electrode to achieve the transmission of chemical information from a redox enzyme through electrical signals. The morphological properties of the cerasomes were systematically compared with those of two structural analogues, namely, liposomes and silica nanoparticles. The results indicated that the cerasomes combined the advantages of liposomes and silica nanoparticles. The lipid bilayer gave excellent biocompatibility, as in the case of liposomes, and high structural stability, similar to that of silica nanoparticles, was derived from the silicate framework on the cerasome surface. The performance at the electrochemical interface created by means of a combination of cerasomes and horseradish peroxidase on a glassy carbon electrode was much better than those achieved with liposomes or silica nanoparticles instead of cerasomes. The potential use of cerasomes in the construction of supramolecular devices for mediator-free biosensing was evaluated.

Mesoporous TiO2-Based Photoanode Sensitized by BiOI and Investigation of Its Photovoltaic Behavior.

We reported a novel BiOI/mesoporous TiO2 photoanode for solar cells, which was fabricated with BiOI attached onto a three-dimensional mesoporous TiO2 film by a chemical bath deposition (CBD) method. BiOI was revealed as an efficient and environmental friendly semiconductor sensitizer to make TiO2 respond to visible light. Based on this photoanode, mesoporous TiO2-based solar cell sensitized by BiOI exhibited promising photovoltaic performance. Meanwhile, the optimization of photovoltaic performance was also achieved by varying cycles of deposition immersions. The highest open circuit voltage and short circuit current of the solar cell can reach 0.5 V and 1.5 mA/cm(2), respectively.

Photoinduced deformation behavior of poly(aryl ether)s with different azobenzene groups in the side chain.

Azobenzene-containing poly(aryl ether)s are a potential type of photoinduced deformable high-performance polymer. However, research on photoinduced deformation of azobenzene-containing poly(aryl ether)s focuses mainly on poly(aryl ether)s containing azobenzene groups in the main chain. In this paper, the photoinduced deformation of poly(aryl ether)s containing azobenzene groups in the side chain was studied for the first time. Two novel poly(aryl ether)s containing azobenzene groups in the side chain were synthesized, and their photoinduced isomerization behavior and photoinduced deformation behavior were studied. It could be seen that the match of the excitation luminescence to the maximum absorption peak of the azobenzene groups was more compatible, and the photoinduced motion of the polymers was faster. In addition, poly(aryl ether)s containing azobenzene groups in the side chain showed highly stable photoinduced deformation. The results of this work will be helpful for designing polymers which could be controlled by lasers of different wavelengths.

Novel polystyrene microspheres functionalized by imidazolium and the electrocatalytic activity towards H2O2 of its Prussian blue composite.

Copolymerization of styrene (St) and 1-vinyl-3-ethylimidazolium bromide (VEIB), novel poly(St-co-VEIB) microspheres were generated. Owing to the presence of imidazolium groups, such microspheres having an average diameter of 125 nm, behave electropositively when dispersed in aqueous solution. Furthermore, due to the presence of imidazolium groups, having a capacity of ion-exchange and weak reducibility on the surface of the PS microspheres, [Fe(CN)6]³â» was absorbed on the surface of poly(St-co-VEIB) microspheres, and simultaneously, Fe³âº was reduced to Fe²âº. Thus, in situ growth of Prussian blue (PB) nanoparticles could occur on the surface of poly(St-co-VEIB) microspheres without the addition of any other reducing agent. This methodology, utilizing the ion-exchange and weak reducibility properties of the imidazolium groups on the surface of micro-/nanostructures is a novel general method for assembling hierarchical nanostructured materials. Finally, the electrochemical property of the strawberry-like PS/PB composite microspheres was also investigated by applying a glassy carbon electrode. A good repeatability of the cyclic voltammetry responses, having a good linearity and sensitivity, for the electrocatalytic reduction of H2O2 was obtained.

Photocorrosion-Based BiOCl Photothermal Materials for Synergistic Solar-Driven Desalination and Photoelectrochemistry Energy Storage and Release.

Solar-driven interfacial evaporation is one of the most promising desalination technologies. However, few studies have effectively combined energy storage with evaporation processes. Here, a novel multifunctional interfacial evaporator, calcium alginate hydrogel/bismuth oxychloride/carbon black (HBiC), is designed, which integrates the characteristics of interfacial evaporation and direct photoelectric conversion. Under illumination, the Bi nanoparticles which were produced by photoetching of BiOCl and its reaction heat are simultaneously used for the heating of water molecules. Meanwhile, part of the solar energy is converted into chemical energy through the photocorrosion reaction and stored in HBiC. At night, Bi NPs undergo autooxidation reaction and an electric current is generated during this process (like a metal-air battery), in which the maximum current density is more than 15 µA cm-2. This scientific design cleverly combines desalination with power generation and provides a new development direction for energy collection and storage.

Asymmetric ultrathin silica nanonets as a super-performance emulsifier.

HYPOTHESIS: Pickering emulsions have been used in many fields such as catalytic synthesis, pharmaceutics and oilfield chemicals. They usually have good stability, but in some extreme conditions such as at high temperatures or in special liquid-liquid systems, poor stability is often encountered. EXPERIMENTS: Herein, ultrathin silica nanosheets with controllable morphologies were synthesized via a simple interfacial anisotropic self-assembly approach integrated with pore-forming techniques. By regulating the size, density and pattern of the apertures, three types of unique nanosheets including mesoporous nanosheets, meso/macroporous topology-nanosheets and asymmetric nanonets with hollows were obtained. FINDINGS: After a simple hydrophobic modification, the nanonets exhibited super-performance as particulate emulsifiers, owing to their two-dimensional (2D) structures of large pore volume and hierarchical pore/hollow arrangements. As a result, those silica nanonets can stabilize various emulsion systems at considerably high temperatures that are difficult to be stabilized by conventional particulate emulsifiers even at a dose of 100x higher. This work paves a promising way to develop novel 2D asymmetric nanomaterials with tunable compositions, aperture parameters and morphologies for emulsification and potential applications.

Preparation of asymmetric particles by controlling the phase separation of seeded emulsion polymerization with ethanol/water mixture.

Alcohols are discovered for the first time to tune the morphology of poly(vinyl benzyl chloride)-poly(3-methacryloxypropyltrimethoxysilane) (PVBC-PMPS) composite particles through seeded emulsion polymerization within the alcohol/water mixture. Here, monodispersed linear PVBC particles was synthesized through the dispersion polymerization and employed as the seeds. The as-obtained PVBC-PMPS composite particles could be dramatically tuned from core-shell structures to snowman-like particles, to dumbbell-shaped particles, to inverse snowman-like particles when the ethanol content in reaction mixtures is only adjusted within a narrow range. The morphology of fresh PMPS bulges was observed after removing the linear PVBC seeds with N,N'-dimethyl formamide, and their formation mechanism was studied by monitoring the free radical polymerization and sol-gel process of 3-methacryloxypropyltrimethoxysilane. It has been confirmed that the sol-gel kinetics were the main factor on the particles' morphology. In addition, morphologies of PVBC-PMPS particles were also varied by the MPS feeding amount, types of the co-solvent and pH values of alcohol/water mixtures.

Chemical coupling of manganese-cobalt oxide and oxidized multi-walled carbon nanotubes for enhanced lithium storage.

Carbonaceous materials are extensively utilized to optimize the electrochemical performance of the transition metal oxides as anode for lithium-ion batteries. However, the in-depth mechanism of the synergistic effect and the interfacial interaction between transition metal oxides and conductive carbon material has not been elucidated clearly. Herein, by using the oxidized multi-walled carbon nanotubes (oMWCNTs), an advanced MnO2/(Co, Mn)(Co, Mn)2O4/oMWCNTs (MO/CMO/oMWCNTs) nanocomposite with abundant metal-oxygen-carbon (Me-OC) bonds as linkage bridge is fabricated for the first time. The strong covalent bonds interactions can simultaneously enhance the intrinsic sluggish kinetics and structural stability of MO/CMO/oMWCNTs nanocomposite. Meanwhile, the mixed transition metal oxides featuring mix valence state can significantly promote the electrode material activity. Consequently, the newly prepared MO/CMO/oMWCNTs electrode displays superior long-term durability with the capacity of 897 mAh g-1 over 1000 cycles at 2 A g-1 and ultrafast charging/discharging capability of 673 mAh g-1 at 5 A g-1. Detailed electrochemical kinetic analysis reveals that over 70% of the energy storage of MO/CMO/oMWCNTs electrode is dominated by the pseudocapacitive behavior. This work demonstrates an easily scalable approach for constructing high-performance transition metal oxides/carbon electrode materials through interfacial regulation.

Fabrication of an electrochemical platform based on the self-assembly of graphene oxide-multiwall carbon nanotube nanocomposite and horseradish peroxidase: direct electrochemistry and electrocatalysis.

A novel hybrid nanomaterial (GO-MWNTs) was explored based on the self-assembly of multiwall carbon nanotubes (MWNTs) and graphene oxide (GO). Compared with pristine MWNTs, such a nanocomposite could be well dispersed in aqueous solution and exhibit a negative charge. Driven by the electrostatic interaction, positively charged horseradish peroxidase (HRP) could then be immobilized onto GO-MWNTs at the surface of a glassy carbon (GC) electrode to form a HRP/GO-MWNT/GC electrode under mild conditions. TEM was used to characterize the morphology of the GO-MWNT nanocomposite. UV-vis and FTIR spectra suggested that HRP was immobilized onto the hybrid matrix without denaturation. Furthermore, the immobilized HRP showed enhanced direct electron transfer for the HRP-Fe(III)/Fe(II) redox center. Based on the direct electron transfer of the immobilized HRP, the HRP/GO-MWNT/GC electrode exhibited excellent electrocatalytic behavior to the reduction of H(2)O(2) and NaNO(2), respectively. Therefore, GO-MWNTs could provide a novel and efficient platform for the immobilization and biosensing of redox enzymes, and thus may find wide potential applications in the fabrication of biosensors, biomedical devices, and bioelectronics.

Carbon Dots as an Indicator of Acid-Base Titration and a Fluorescent Probe for Endoplasm Reticulum Imaging.

In this study, carbon dots (CDs) with red color are successfully prepared via hydrothermal treatment of o-phenylenediamine and urea. The as-prepared red CDs exhibit an acidichromism feature, making them turn purple at pH 4.4 and become blue at pH 3.3. Further investigations reveal that the surface chemical bond species of CDs are responsible for the acidichromism feature. Taking advantage of the acidichromism feature, the CDs are employed as a titration indicator for analysis of alkali samples, which gives rise to satisfactory results without significant difference between the titration methods using CDs and methyl orange or a mixture of methyl red and bromocresol green as indicators. The CDs show excitation-independent fluorescence with dual-emission at 600 and 650 nm, along with a respectable quantum yield of 20.1%, which provides the CDs with deep tissue penetration and minimum autofluorescence background that is desirable in bioimaging. In addition, the CDs are found to light up endoplasm reticulum particularly, indicating their endoplasm reticulum targeting capability, which is proven by a colocalization study with other classical subcellular dyes. Endocytosis inhibiting investigations confirm that the endoplasm reticulum targeting ability is mainly attributed to the caveolin/lipid-raft-mediated endocytosis pathways of CDs. This study not only presents a facile approach for red CDs but also explores the possibility of CDs in titration analysis and in endoplasm reticulum targeting imaging.

Superhydrophobic Coating Derived from the Spontaneous Orientation of Janus Particles.

A superhydrophobic surface was achieved using a monolayer of the perpendicularly oriented epoxy-silica@polydivinylbenzene (PDVB) Janus particles (JPs) on an epoxy resin substrate. The epoxy-silica@PDVB JPs were synthesized from the silica@PDVB/polystyrene (PS) JPs through selective etching of the PDVB/PS belly and the surface modification of the silica part. The modified silica parts can be covalently bonded with the epoxy resin to make the perpendicular orientation spontaneous as well as the coating more robust. The outward PDVB bellies can constitute the micro-/nanoscale hierarchical structures for the superhydrophobic property. The superhydrophobic coating exhibits water repellence and self-cleaning properties. Moreover, the coating exhibits good chemical durability that it can keep the superhydrophobic property after long-time immersion in various aqueous solutions and organic solvents. The coating is still superhydrophobic after water flushing and mechanical wearing, showing the perfect mechanical durability.

Pickering emulsion-embedded hierarchical solid-liquid hydrogel spheres for static and flow photocatalysis.

Pickering emulsion-based photocatalysis is considered to be a promising system due to its large active surface area and water/oil spatial separation capability for enrichment of substrates and products. In this work, a novel hierarchical structure composed of calcium alginate gel sphere wrapped ionic liquid-in-water Pickering emulsion with TiO2 in the water phase, which are stabilized by graphene oxide, is prepared via a facile one-step emulsion gelation method. Such subtle combination of Pickering emulsion, hydrogel and TiO2 with a multi-stage solid-liquid assemblage structure shows enhanced degradation activity of 2-naphthol into small molecular alkanes under simulated solar irradiation. The photodegradation activity is attributed to the ionic liquid as adsorption medium for 2-naphthol, and the high-efficient charge separation at graphene oxide/TiO2 interface superior to that of pure TiO2. More importantly, the as-prepared millimeter-sized assembled gel spheres can be directly used as the column filler to construct continuous flow photocatalytic system, maintaining the promising performance in removing pollutants from water with ~100% remove ability of 2-naphthol on stream. A charge transfer mechanism of the photocatalyst is proposed, i.e. photogenerated charges are separated in TiO2/graphene oxide p-n heterostructure at the interface of Pickering emulsion droplets.

Fabrication of a biocompatible and conductive platform based on a single-stranded DNA/graphene nanocomposite for direct electrochemistry and electrocatalysis.

A novel electrochemical platform was designed by combining the biocompatibility of single-stranded DNA (ss-DNA) and the excellent conductivity of graphene (GP). This nanocomposite (denoted as ss-DNA/GP) was first used as an electrode material for the immobilization and biosensing of redox enzymes. On the basis of electrostatic interactions, horseradish peroxidase (HRP) self-assembled with ss-DNA/GP on the surface of a glassy carbon (GC) electrode to form an HRP/ss-DNA/GP/GC electrode. UV/Vis and FTIR spectra were used to monitor the assembly process and indicated that the immobilized HRP on the ss-DNA/GP matrix retained its native structure well. A pair of stable and well-defined redox peaks of HRP with a formal potential of about -0.26 V (vs. Ag/AgCl) in a pH 7.0 phosphate buffer solution were obtained at the HRP/ss-DNA/GP/GC electrode; this demonstrates direct electron transfer between the immobilized HRP and the electrode. In addition, the modified electrode showed good electrocatalytic performance towards H(2)O(2) with high sensitivity, wide linear range, and good stability. Accordingly, the ss-DNA/GP nanocomposite provides a novel and efficient platform for the immobilized redox enzyme to realize direct electrochemistry and has a promising application in the fabrication of third-generation electrochemical biosensors.

Surface modification of cerasomes with AuNPs@poly(ionic liquid)s for an enhanced stereo biomimetic membrane electrochemical platform.

A novel liposomal nanocomposite, Au@PIL-cerasome, with biocompatibility and conductivity was fabricated via the self-assembly of cerasomes and gold nanoparticles (AuNPs) stabilized by poly(ionic liquid)s (PILs). The surface charge, morphology and chemical composition of the nanocomposites were characterized by the zeta potential, UV-vis, TEM, SEM and EDS. The nanocomposites exhibited structural stability directly on the surface of solid electrodes, without fusion. Electrochemical impedance experiments demonstrated that the nanocomposites had an enhanced conductivity compared with unmodified cerasomes. Horseradish peroxidase (HRP), as a reporter, was immobilized on the nanocomposites without denaturation or inactivation. The direct electron transfer of HRP was achieved, and the HRP/Au@PIL-cerasome/GCE exhibited an amplified current and improved electrocatalytic activity. Activity towards H2O2 displayed a linear range over 10-70 µM and a detection limit of 3.3 µM. Activity towards NO2- displayed linear ranges over 1-5 mM and 5-1280 mM, and the limit of detection was 0.11 mM. In addition, the electrode was stable and reproducible, with 6% RSD. Such multi-component liposomal nanocomposites with an enhanced electrical performance pave a better way for building novel and straightforward 3D stereo biomimetic electrochemical platforms and even molecular communication systems to investigate information transduction between cells.