SnO2 highly sensitive CO gas sensor based on quasi-molecular-imprinting mechanism design.

Response of highly sensitive SnO2 semiconductor carbon monoxide (CO) gas sensors based on target gas CO quasi-molecular-imprinting mechanism design is investigated with gas concentrations varied from 50 to 3000 ppm. SnO2 nanoparticles prepared via hydrothermal method and gas sensor film devices SC (exposed to the target gas CO for 12 h after the suspension coating of SnO2 film to be fully dried, design of quasi-molecular-imprinting mechanism, the experiment group) and SA (exposed to air after the suspension coating of SnO2 film to be fully dried, the comparison group) made from SnO2 nanoparticles are all characterized by XRD, SEM and BET surface area techniques, respectively. The gas response experimental results reveal that the sensor SC demonstrates quicker response and higher sensitivity than the sensor SA does. The results suggest that in addition to the transformation of gas sensor materials, surface area, and porous membrane devices, the Molecular Imprinting Theory is proved to be another way to promote the performance of gas sensors.

3D carbon/cobalt-nickel mixed-oxide hybrid nanostructured arrays for asymmetric supercapacitors.

The electrochemical performance of supercapacitors relies not only on the exploitation of high-capacity active materials, but also on the rational design of superior electrode architectures. Herein, a novel supercapacitor electrode comprising 3D hierarchical mixed-oxide nanostructured arrays (NAs) of C/CoNi3 O4 is reported. The network-like C/CoNi3 O4 NAs exhibit a relatively high specific surface area; it is fabricated from ultra-robust Co-Ni hydroxide carbonate precursors through glucose-coating and calcination processes. Thanks to their interconnected three-dimensionally arrayed architecture and mesoporous nature, the C/CoNi3 O4 NA electrode exhibits a large specific capacitance of 1299 F/g and a superior rate performance, demonstrating 78% capacity retention even when the discharge current jumps by 100 times. An optimized asymmetric supercapacitor with the C/CoNi3 O4 NAs as the positive electrode is fabricated. This asymmetric supercapacitor can reversibly cycle at a high potential of 1.8 V, showing excellent cycling durability and also enabling a remarkable power density of ∼13 kW/kg with a high energy density of ∼19.2 W·h/kg. Two such supercapacitors linked in series can simultaneously power four distinct light-emitting diode indicators; they can also drive the motor of remote-controlled model planes. This work not only presents the potential of C/CoNi3 O4 NAs in thin-film supercapacitor applications, but it also demonstrates the superiority of electrodes with such a 3D hierarchical architecture.

Enhanced ethylene photodegradation performance of g-C3N4-Ag3PO4 composites with direct Z-scheme configuration.

Photocatalytic oxidation of ethylene continues to be a challenge at the frontier of chemistry. In a previous report, a simple Ag3 PO4 semiconductor material was shown to have strong photooxidative properties and efficiently oxidised water and decomposed organics in aqueous solution under visible-light illumination. Herein, its effects on the photo-oxidation of gaseous C2 H4 were investigated by fabricating graphitic C3 N4-Ag3 PO4 composite semiconductors with direct Z-scheme configuration. It was found that both the ethylene photo-oxidative activity and the stability of Ag3 PO4 are considerably improved by fabrication of Z-scheme composites. Moreover, stable C2 H4 photo-oxidation activity could be obtained by treating the composite at 450 °C for 3 h after long-term operation. From the point of view of environmental pollutant cleanup, the present technique avoids the side reaction of oxidising water and will be valuable for further investigations on both Ag3 PO4 and CH degradation.

Fabrication of a SnO2-based acetone gas sensor enhanced by molecular imprinting.

This work presents a new route to design a highly sensitive SnO2-based sensor for acetone gas enhanced by the molecular imprinting technique. Unassisted and acetone-assisted thermal synthesis methods are used to synthesis SnO2 nanomaterials. The prepared SnO2 nanomaterials have been characterized by X-ray powder diffraction, scanning electron microscopy and N2 adsorption-desorption. Four types of SnO2 films were obtained by mixing pure deionized water and liquid acetone with the two types of as-prepared powders, respectively. The acetone gas sensing properties of sensors coated by these films were evaluated. Testing results reveal that the sensor coated by the film fabricated by mixing liquid acetone with the SnO2 nanomaterial synthesized by the acetone-assisted thermal method exhibits the best acetone gas sensing performance. The sensor is optimized for the smooth adsorption and desorption of acetone gas thanks to the participation of acetone both in the procedure of synthesis of the SnO2 nanomaterial and the device fabrication, which results in a distinct response-recovery behavior.

The three-dimensional coordination network in poly[di-µ3-cyanido-µ5-[5-(pyridin-4-yl)tetrazolato]-tricopper(I)].

In the title three-dimensional tetrazolate-based coordination polymer, poly[bis(µ(3)-cyanido-κ(3)N:C:C)[µ(5)-5-(pyridin-4-yl)tetrazolato-κ(5)N:N':N'':N''':N'''']tricopper(I)], [Cu(3)(C(6)H(4)N(5))(CN)(2)](n), there are two types of coordinated Cu(I) atoms. One type exhibits a tetrahedral environment and the other, residing on a twofold axis, adopts a trigonal coordination environment. The closest Cu···Cu distance is only 2.531 (2) Å, involving a bridging cyanide C atom. All four tetrazolate and the pyridine N atom of the 4-(pyridin-4-yl)-1H-tetrazolate anion are coordinated to these Cu(I) atoms and exhibit a µ(5)-bridging mode. The three-dimensional coordination network can be topologically simplified as a rarely observed (3,3,4,5)-connected network with the Schläfli symbol (4.6.8(4))(2).(4(2).6.8(7)).(6.8(2))(3).

Wide Concentration Range of Tb3+ Doping Influence on Scintillation Properties of (Ce, Tb, Gd)3Ga2Al3O12 Crystals Grown by the Optical Floating Zone Method.

To obtain a deeper understand of the energy transfer mechanism between Ce3+ and Tb3+ ions in the aluminum garnet hosts, (Ce, Tb, Gd)3Ga2Al3O12 (GGAG:Ce, Tb) single crystals grown by the optical floating zone (OFZ) method were investigated systematically in a wide range of Tb3+ doping concentration (1-66 at.%). Among those, crystal with 7 at.% Tb reached a single garnet phase while the crystals with other Tb3+ concentrations are mixed phases of garnet and perovskite. Obvious Ce and Ga loss can be observed by an energy dispersive X-ray spectroscope (EDS) technology. The absorption bands belonging to both Ce3+ and Tb3+ ions can be observed in all crystals. Photoluminescence (PL) spectra show the presence of an efficient energy transfer from the Tb3+ to Ce3+ and the gradually quenching effect with increasing of Tb3+ concentration. GGAG: 1% Ce3+, 7% Tb3+ crystal was found to possess the highest PL intensity under excitation of 450 nm. The maximum light yield (LY) reaches 18,941 pho/MeV. The improved luminescent and scintillation characteristics indicate that the cation engineering of Tb3+ can optimize the photoconversion performance of GGAG:Ce.

Cu@C composite nanotube array and its application as an enzyme-free glucose sensor.

We report a novel hydrothermal method for the synthesis of a Cu@C nanotube array on a centimeter-scale substrate for the first time. In this hydrothermal reaction process, employing the carbon coated ZnO nanorod array as an inexpensive and partially sacrificial template, along with the ZnO dissolving in the alkaline atmosphere, the formed Cu particles deposit and grow on the carbon surface gradually. Importantly, the carbon shell of the template is not only essential to the preservation of the array configuration, but also makes a significant contribution to the final nanostructure. Such a method provides a morphology-reservation transformation when various shaped carbon-containing templates are adopted. Moreover, this designed Cu@C array has been demonstrated as an excellent electrode material for an enzyme-free glucose sensor in terms of sensitivity (1200 µA mM( - 1) cm( - 2)) and significantly lower applied potential (-0.2 V). Our results present the first preparation of the Cu@C composite nanotube array and may open up an opportunity for rational design of advanced electrode materials for enzyme-free glucose sensors.

Binder-free Cu-supported Ag nanowires for aqueous rechargeable silver-zinc batteries with ultrahigh areal capacity.

As one of the most mature battery systems, the silver-zinc battery holds huge promise in the field of aqueous rechargeable batteries due to superior performance, high safety and environmental friendliness. It is urgent to improve the areal capacity of silver-zinc batteries so far. This study reports a novel Cu-supported Ag Nanowires (Cu@AgNAs1-5: abbreviation of Cu@AgNAs1, Cu@AgNAs2, Cu@AgNAs3, Cu@AgNAs4 and Cu@AgNAs5) as binder-free cathodes for high performance rechargeable aqueous silver-zinc batteries. Cu@AgNAs1-5 are successfully prepared by two steps of electrochemical nanoengineering and mild galvanic replacement between Cu and [Ag(NH3)2]+ chelate ions under green solution. With ultrahigh Ag loading of above 81 mg cm-2, the Cu@AgNAs5 cathode achieves ultrahigh areal capacity of above 36 mAh cm-2 at current density of 10 mA cm-2. Benefiting from synergistic effect of Ag and Cu, multiply twinned structure accompanied by lattice defections (such as lattice distortion, mismatch and dislocation) and heterostructures, the Cu@AgNAs1-5 cathodes achieve excellent Ag utilization and cycling stability. Furthermore, the aqueous rechargeable Cu@AgNAs5-Zn battery demonstrates an excellent areal capacity of 36.80 mAh cm-2 at 10 mA cm-2. This work offers a promising pathway to greatly enhance areal capacity of bimetallic nanostructure-based electrodes and the Cu@AgNAs1-5-Zn batteries are attractive for large-scale energy-storage application.

In Situ Engineering of the Core-Shell Ag@Cu Structure on Porous Nanowire Arrays for High Energy and Stable Aqueous Ag-Bi Batteries.

There is an urgent need to design practical aqueous rechargeable batteries (ARBs) with high energy density and long cycle life, using state-of-the-art cathode materials with low toxicity and environmental friendly nature. In virtue of the stable discharge potential and high energy density, silver (Ag) presents a huge perspective in the field of aqueous batteries. Herein, the paradigm of a novel core-shell Ag@Cu structure in situ Cu porous nanowire array skeleton (Ag@Cu NWA) is designed as the efficient cathode of an ARB. Benefiting from the ultrathin metal Ag shell (∼7 nm) and the high-conductivity metal Cu core, along with the robust porous nanowire framework, the as-obtained Ag@Cu NWA cathode integrates the features of maximal utilization of the active material, superior charge transfer, and exceptional electrolyte accessibility, exhibiting a considerable capacity of 1.79 mA h cm-2 (458 mA h g-1: 92.3% of theoretical capacity) and remarkable cycling stability (83.6% retention after 5000 cycles). Furthermore, a well-designed aqueous rechargeable Ag//Bi full cell is fabricated using the Ag@Cu NWA cathode, achieving high capacity (1.57 mA h cm-2 at 2 mA cm-2) with excellent rate performance (92.9% at 20 mA cm-2) and an admirable energy density of 16.96 mW h cm-3. This work puts forward a prospective strategy to construct viable new types of ARB materials based on multimetal nanocomposites, showing great potential for practical electronic devices.

Self-assembly of Bi2WO6 square nanoplates into hierarchical structures.

Bi2WO6 hierarchical structures constructed by a number of square nanoplates of average approximately 70 nm in side length and approximately 25 nm in thickness have been synthesized by a hydrothermal method at 180 degrees C. The single-crystal subunit nanoplates with (002) as their two-dimensional (2D) surfaces assembled orderly using both their edges and faces into free-standing films. It was found that the self-assembled growth of these hierarchical structures strongly depended on surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), the amounts of the starting materials and the molar ratio of precursors (Bi3+ to WO4(2-)), etc. The growth mechanism was discussed based on the comparative experimental results.

Solution-based growth and optical properties of self-assembled monocrystalline ZnO ellipsoids.

Self-assembled unusual ZnO ellipsoids have been grown by a facile low-temperature (60 degrees C) solution process on a large scale. FESEM and TEM reveal that these ellipsoids have an average horizontal axis of 1.5 microm and a longitudinal axis of 0.6 microm. Experimental results obtained from the early growth stage demonstrate that the ZnO ellipsoidal structures are single crystals and formed from direct "oriented attachment" of two types of building blocks, that is, nanorods and nanoparticles. It is further found that the existence of poly(ethylene glycol) (PEG-10 000) is vital to the formation of the complex microparticles. Raman spectrum, room-temperature photoluminescence, and UV-vis absorption spectra are also discussed. This work presents a simple and effective route for large-scale fabrication of single-crystal ZnO ellipsoids with micrometer-scale sizes and 3D self-assembled structures.

Facile and large-scale production of ZnO/Zn-Al layered double hydroxide hierarchical heterostructures.

ZnO/Zn-Al layered double hydroxide (ZnO/Zn-Al LDH) hierarchical architecture, a new type of ZnO-based heterostructure, has been synthesized directly on an Al substrate via a facile solution phase process. The firecracker-like heterostructures consist of uniform ZnO nanorods orderly standing at the edges of two-dimensional (2D) surfaces of Zn-Al LDH nanoplatelets. Experimental result obtained from the early growth stage indicates that the underlying Zn-Al LDH nanoplatelet arrays are well constructed with their (00l) planes perpendicular to the surface of Al substrate. We propose that the "edge effect" of Zn-Al LDH and the "lattice match" between ZnO and Zn-Al LDH are vital to the growth of such heterostructures. The effects of total solution volume and NH3.H2O concentration on the formation of heterostructures are investigated. It is found that other LDH-based complex structures can also be achieved controllably by varying the mentioned experimental factors. Our work is the first demonstration of fabricating intricate ZnO/Zn-Al LDH heterostructures as well as well-defined Zn-Al LDH arrays on an Al substrate, for which several promising applications such as optoelectronics, biosensors, and catalysis can be envisioned.

Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts.

The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation.

Encapsulation of nanoscale metal oxides into an ultra-thin Ni matrix for superior Li-ion batteries: a versatile strategy.

Li-ion batteries' (LIBs) performance proves to be highly correlated with ionic and electrical transport kinetics in electrodes. Although continual progress has been achieved in rational design of ideal electrode systems, their energy density, cyclic endurance and productivity are still far from perfect for practical use. Herein we propose an interesting, facile and versatile strategy to encapsulate various nanoscale metal oxides (covering both nanopowders and nanostructured arrays) into an ultrathin Ni matrix (metal oxide@Ni) for superior LIBs. Evolutions of such metal oxide@Ni hybrids (taking MnO@Ni and CoO@Ni as models) are thoroughly studied by monitoring their whole fabrication process. Putting "armors" on nanoscale metal oxides is thought helpful for the promotion of the LIB performance since the outer Ni matrix provides both mechanical protection against huge volume changes and effective routes for electron transfer. As a proof-of-concept demonstration, all metal oxide@Ni hybrid electrodes exhibit drastic improvements in the capacity retention (e.g. ∼452% capacity rise for the MnO@Ni case while ∼551% for CoO@Ni NWs), long-term cyclic stability and rate capabilities. This designed strategy can be further extended to make other advanced oxide@metal hybrids, not only for LIBs but also for other potential fields.

Three-dimensional Ni/SnOx/C hybrid nanostructured arrays for lithium-ion microbattery anodes with enhanced areal capacity.

The areal capacity of lithium-ion microbatteies (LIMBs) can be potentially increased by adopting a three-dimensional (3D) architectured electrode. Herein, we report the novel 3D Ni/SnOx/C hybrid nanostructured arrays that were built directly on current collectors via a facile hydrothermal method followed by a calcination-reduction process. Branched SnO2 nanorods grew uniformly on Ni2(OH)2CO3 nanowall arrays, resulting in the formation of precursors with a 3D interconnected architecture. By using ethylene glycol as the reducing agent, the glucose-coated SnO2/Ni2(OH)2CO3 precursors were evolved into an interesting 3D Ni/SnOx/C hybrid nanostructured arrays within the calcination treatment. Compared to conventional 2D SnOx/C nanorod arrays, the electrode of 3D Ni/SnOx/C hybrid nanostructured arrays exhibited enhanced lithium storage capacity per unit area, preferable rate capability and improved cycling performance when tested for LIMBs. The superior performance might be attributed to the open-up Ni frameworks that can not only serve as effective channels for electrons transport and Li+ diffusion but also help to accommodate the large volume changes upon lithiation/delithiation.

Diffusion-controlled evolution of core-shell nanowire arrays into integrated hybrid nanotube arrays for Li-ion batteries.

Controlled integration of multiple semiconducting oxides into each single unit of ordered nanotube arrays is highly desired in scientific research for the realization of more attractive applications. We herein report a diffusion-controlled solid-solid route to evolve simplex Co(CO3)0.5(OH)0.11H2O@TiO2 core-shell nanowire arrays (NWs) into CoO-CoTiO3 integrated hybrid nanotube arrays (NTs) with preserved morphology. During the evolution procedure, the decomposition of Co(CO3)0.5(OH)0.11H2O NWs into chains of CoCO3 nanoparticles initiates the diffusion process and promotes the interfacial solid-solid diffusion reaction even at a low temperature of 450 °C. The resulting CoO-CoTiO3 NTs possess well-defined sealed tubular geometries and a special "inner-outer" hybrid nature, which is suitable for application in Li-ion batteries (LIBs). As a proof-of-concept demonstration of the functions of such hybrid NTs in LIBs, CoO-CoTiO3 NTs are directly tested as LIB anodes, exhibiting both a high capacity (~600 mA h g(-1) still remaining after 250 continuous cycles) and a much better cycling performance (no capacity fading within 250 total cycles) than CoO NWs. Our work presents not only a diffusion route for the formation of integrated hybrid NTs but also a new concept that can be employed as a general strategy to fabricate other oxide-based hybrid NTs for energy storage devices.

A novel evolution strategy to fabricate a 3D hierarchical interconnected core-shell Ni/MnO2 hybrid for Li-ion batteries.

A novel evolution strategy has been put forward to build a 3D interconnected core-shell Ni/MnO(2) hybrid on a current collector, which demonstrated stable cyclic performance and good rate capabilities when applied as the anode for Li-ion batteries.

Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage.

Metal oxide nanostructures are promising electrode materials for lithium-ion batteries and supercapacitors because of their high specific capacity/capacitance, typically 2-3 times higher than that of the carbon/graphite-based materials. However, their cycling stability and rate performance still can not meet the requirements of practical applications. It is therefore urgent to improve their overall device performance, which depends on not only the development of advanced electrode materials but also in a large part "how to design superior electrode architectures". In the article, we will review recent advances in strategies for advanced metal oxide-based hybrid nanostructure design, with the focus on the binder-free film/array electrodes. These binder-free electrodes, with the integration of unique merits of each component, can provide larger electrochemically active surface area, faster electron transport and superior ion diffusion, thus leading to substantially improved cycling and rate performance. Several recently emerged concepts of using ordered nanostructure arrays, synergetic core-shell structures, nanostructured current collectors, and flexible paper/textile electrodes will be highlighted, pointing out advantages and challenges where appropriate. Some future electrode design trends and directions are also discussed.

Building one-dimensional oxide nanostructure arrays on conductive metal substrates for lithium-ion battery anodes.

Lithium ion battery (LIB) is potentially one of the most attractive energy storage devices. To meet the demands of future high-power and high-energy density requirements in both thin-film microbatteries and conventional batteries, it is challenging to explore novel nanostructured anode materials instead of conventional graphite. Compared to traditional electrodes based on nanostructure powder paste, directly grown ordered nanostructure array electrodes not only simplify the electrode processing, but also offer remarkable advantages such as fast electron transport/collection and ion diffusion, sufficient electrochemical reaction of individual nanostructures, enhanced material-electrolyte contact area and facile accommodation of the strains caused by lithium intercalation and de-intercalation. This article provides a brief overview of the present status in the area of LIB anodes based on one-dimensional nanostructure arrays growing directly on conductive inert metal substrates, with particular attention to metal oxides synthesized by an anodized alumina membrane (AAM)-free solution-based or hydrothermal methods. Both the scientific developments and the techniques and challenges are critically analyzed.

Urchinlike MnO2 nanoparticles for the direct electrochemistry of hemoglobin with carbon ionic liquid electrode.

In this paper an urchinlike MnO(2) nanoparticle was synthesized by hydrothermal method and applied to the protein electrochemistry for the first time. By using a carbon ionic liquid electrode (CILE) as the basal electrode, hemoglobin (Hb) was immobilized on the surface of CILE with chitosan (CTS) and MnO(2) nanoparticle composite materials. Spectroscopic results indicated that Hb molecules retained its native structure in the composite film. A pair of well-defined redox peaks appeared on the cyclic voltammogram with the formal peak potential as -0.180 V (vs. SCE), which indicated that direct electron transfer of Hb was realized on the modified electrode. The result can be attributed to the specific characteristic of MnO(2) nanoparticle and the advantages of CILE, which facilitated the electron transfer rate. The fabricated CTS-MnO(2)-Hb/CILE showed good electrocatalytic ability to the reduction of trichloroacetic acid (TCA). Under the optimal conditions the catalytic current was in linear to TCA concentration in the range from 0.5 to 16.0 mmol L(-1) with the detection limit calculated as 0.167 mmol L(-1) (3σ). The result indicated that urchinlike MnO(2) nanoparticle had the potential application in the third generation electrochemical biosensors.