Large Interfacial Area Research Articles

Hydrogen absorption of Pd/ZrO2 composites prepared from Zr65Pd35 and Zr60Pd35Pt5 amorphous alloys

Metal-dispersed composites were derived from amorphous Zr65Pd35 and Zr65Pd30Pt5 alloys and their hydrogen absorption behavior was studied. X-ray diffractograms and scanning electron micrographs indicated that mixtures containing ZrO2, the metallic phase of Pd, and PdO were formed for both amorphous alloys heat-treated in air. In the composites, micron-sized Pd-based metal precipitates were embedded in a ZrO2 matrix after heat treatment at 800 °C in air. The hydrogen temperature-programmed reduction was applied to study the reactivity of hydrogen gas with the oxidized Zr65Pd35 and Zr65Pd30Pt5 materials. Rapid hydrogen absorption and release were observed on the composite derived from the amorphous alloy below 100 °C. The hydrogen pressure–concentration isotherm showed that the absorbed amount of hydrogen in materials depended on the formation of the Pd or Pt-doped Pd phase and its large interface area to the matrix in the nanocomposites. The results indicate the importance of the composite structure for the fabrication of a new type of hydrogen storage material prepared from amorphous alloys.

Simple synthesis and characterization of vertically aligned Ba0.7Sr0.3TiO3–CoFe2O4 multiferroic nanocomposites from CoFe2 nanopillar arrays

A new strategy to elaborate (1-3) type multiferroic nanocomposites with controlled dimensions and vertical alignment is presented. The process involves a supported nanoporous alumina layer as a template for growth of free-standing and vertically aligned CoFe2 nanopillars using a room temperature pulsed electrodeposition process. Ba0.70Sr0.30TiO3–CoFe2O4 multiferroic nanocomposites were grown through direct deposition of Ba0.7Sr0.3TiO3 films by radio-frequency sputtering on the top surface of the pillar structure, with in situ simultaneous oxidation of CoFe2 nanopillars. The vertically aligned multiferroic nanocomposites were characterized using various techniques for their structural and physical properties. The large interfacial area between the ferrimagnetic and ferroelectric phases leads to a magnetoelectric voltage coefficient as large as ∼320 mV cm−1 Oe−1 at room temperature, reaching the highest values reported so far for vertically architectured nanocomposite systems. This simple method has great potential for large-scale synthesis of many other hybrid vertically aligned multiferroic heterostructures.

Mechanisms and Control of Self-Emulsification upon Freezing and Melting of Dispersed Alkane Drops.

Emulsification requires drop breakage and creation of a large interfacial area between immiscible liquid phases. Usually, high-shear or high-pressure emulsification devices that generate heat and increase the emulsion temperature are used to obtain emulsions with micrometer and submicrometer droplets. Recently, we reported a new, efficient procedure of self-emulsification (Tcholakova et al. Nat. Commun. 2017, 8, 15012), which consists of one to several cycles of freezing and melting of predispersed alkane drops in a coarse oil-in-water emulsion. Within these freeze-thaw cycles of the dispersed drops, the latter burst spontaneously into hundreds and thousands of smaller droplets without using any mechanical agitation. Here, we clarify the main factors and mechanisms, which drive this self-emulsification process, by exploring systematically the effects of the oil and surfactant types, the cooling rate, and the initial drop size. We show that the typical size of the droplets, generated by this method, is controlled by the size of the structural domains formed in the cooling-freezing stage of the procedure. Depending on the leading mechanism, these could be the diameter of the fibers formed upon drop self-shaping or the size of the crystal domains formed at the moment of drop-freezing. Generally, surfactant tails that are 0-2 carbon atoms longer than the oil molecules are most appropriate to observe efficient self-emulsification. The specific requirements for the realization of different mechanisms are clarified and discussed. The relative efficiencies of the three different mechanisms, as a function of the droplet size and cooling procedure, are compared in controlled experiments to provide guidance for understanding and further optimization and scale-up of this self-emulsification process.

Intensification of oily waste waters purification by means of liquid atomization

In this research, a possibility of using liquid atomization for improving the efficiency of purification of wastewater by different methods has been studied. By the introduced method and an experimental setup for wastewater purification, saturation rate increases with its purification by means of dissolved air flotation. Liquid atomization under excess pressure allows to gain a large interfacial area between the saturated liquid and air, which may increase the rate of purified liquid saturation almost twice, compared to the existing methods of saturation. Current disadvantages of liquid atomization used for intensification of wastewater purification include high energy cost and secondary emulsion of polluting agents. It is also known that by means of liquid atomization a process of ozonizing can be intensified. Large contact surface between the purified liquid and ozone–air mixture increases the oxidizing efficiency, which allows to diminish ozone discharge. Liquid atomization may be used for purification of wastewaters by ultraviolet radiation. Small drops of liquid will be proportionally treated by ultraviolet, which makes it possible to do purification even of turbid wastewaters. High-speed liquid motion will prevent the pollution of quartz tubes of ultraviolet lamps.

Amine-Functionalized Graphene/CdS Composite for Photocatalytic Reduction of CO2

This study provides a significant enhancement in CO2 photoconversion efficiency by the functionalization of a reduced graphene oxide/cadmium sulfide composite (rGO/CdS) with amine. The amine-functionalized graphene/CdS composite (AG/CdS) was obtained in two steps. First, graphene oxide (GO) was selectively deposited via electrostatic interaction with CdS nanoparticles modified with 3-aminopropyltriethoxysilane. Subsequently, ethylenediamine (NH2C2H4NH2) was grafted by an N,N′-dicyclohexylcarbodiimide coupling reaction between the amine group of ethylenediamine and the carboxylic group of GO. As a result, a few layers of amine-functionalized graphene wrapped CdS uniformly, forming a large interfacial area. Under visible light, the photocurrent through the AG/CdS significantly increased because of enhanced charge separation in CdS. The CO2 adsorption capacity on AG/CdS was 4 times greater than that on rGO/CdS at 1 bar. These effects resulted in a methane formation rate of 2.84 μmol/(g h) under visible light...

Facile one-pot synthesis of chain-like titanium dioxide nanostructure arrays for efficient ultraviolet sensing

Hierarchical TiO2 nanostructure arrays have been successfully synthesized on FTO glass by a facile one-pot hydrothermal method. The novel nanostructure arrays are composed of nanowire trunks and epitaxial nanobranches, and covered by interconnected nanosheets. The UV sensing performance is investigated by integrated them into a photoelectrochemical cell. Benefited from the efficient transport networks and large interface area provided by the novel nanostructure array, the assembled UV sensor exhibits a high responsivity of 0.11A/W, a fast response time of 20–40ms for current signal, as well as the self-powered, visible-blind characteristic and considerable spectral response under weak irradiation. Our work has provided an efficient strategy to improve the sensing performance of photoelectrochemical UV sensors by building hierarchical chain-like nanostructures with simple method.

(Invited) Silicon Nanopillars Coated with Earth-Abundant Electrocatalysts for Enhanced Photoelectrochemical Hydrogen Production

Solar-driven photoelectrochemical (PEC) water splitting for hydrogen production promises to solve the impending energy and environmental crisis. The key to increase the efficiency of PEC hydrogen generation is developing high-performance catalysts and photocathodes. 3D p-type silicon (p-Si) nanopillar (NP) arrays are promising architectures due to the high light harvesting and the large interfacial areas. We demonstrate its enhanced PEC performance with a photocurrent density of -37.5 mA/cm2 at 0 V (vs. RHE) under simulated 100 mW/cm2 (1 Sun) with an AM 1.5 G filter, which is the highest value reported for p-type Si photocathodes. The synergic effects of the excellent light harvesting of Si NP array core and the good optical transparency, as well as excellent electrocatalytic activity of NiCoSex shell boost the production and utilization of photogenerated electrons. The Faradaic efficiency of H2 and O2 on p-Si/NiCoSex was approximately 100%, which confirmed that the photocurrent during PEC reaction was attributed to hydrogen generation. The completely enclosed core-shell structure isolated the Si NP from air and aqueous electrolyte and minimized the oxidation of silicon, leading to good stability. The design of p-Si/NiCoSex core/shell NP arrays offers a new strategy for preparing highly efficient photoelectrochemical solar energy conversion devices.

Effect of Interfacial Lithium Insertion on the Stability and Electronic Structure of Graphene/LiFePO4

Surface properties are significantly important to the high capacity and rate capability of LiFePO4 nanoparticles as cathode materials for lithium ion batteries. Using the first-principles total energy calculations, the stability and the electronic structure evolution of the graphene/LiFePO4 interface with different amounts of Li atoms inserted have been systematically investigated. It is revealed that the interfacial Li atom insertion could contribute markedly to the capacity of graphene modified or coated LiFePO4 with large specific interface area. The interfacial binding between graphene and LiFePO4 surface in parallel orientation becomes stronger with the increase of the interfacial Li atoms amount which involves more than van de Waals interaction. The electronic conductivity of the LiFePO4 surface is weakened during the Li insertion at the interface, while the Mn-doped LiFePO4 surface maintains the excellent conductivity in the early stage of lithiation. However, stable polaron forms at the semiconducting LiFePO4 surface during lithiation. Moreover, the graphene modification and the Mn doping exert positive effect on the surface oxygen stability.

Improved energy density and dielectric properties of P(VDF-HFP) composites with TiO2 nanowire clusters

Dielectric composites are of great demand in the micro-electronics industry. To enhance the energy storage density of the composites, TiO2 nanowire clusters was synthesized by a hydrothermal method and incorporated into the P(VDF-HFP) polymer matrix in this work. The microstructure, dielectric properties of the prepared film were discussed and the effects of TiO2 loading on the energy density were investigated. The results shows that the TiO2 clusters were tightly blended to the P(VDF-HFP) matrix owing to the dopamine-modified interface. The dielectric constant increased with the loading of TiO2, the maximum dielectric constant reached 12.04 with 7.5 vol% TiO2 loading at 1 kHz, as compared to 5.01 for the neat P(VDF-HFP). The enhanced dielectric constant was attributed to the interface polarization originated from the large interface area between the TiO2 nanowire and polymer matrix. The discharged energy density of the composite significantly increased to 1.35 J/cm3 with 7.5 vol% TiO2 nanowire clusters, which was two times higher than that of the neat P(VDF-HFP) at the same condition. The findings of this work can shed a light on improving the energy density of energy storage device via morphology modification.

Long term performance of porous platinum coated neural electrodes.

Over the last several years, there has been a growing interest in neural implants for the study and diagnostics of neurological disorders as well as for the symptomatic treatment of central nervous system related diseases. One of the major challenges is the trade-off between small electrode sizes for high selectivity between single neurons and large electrode-tissue interface areas for excellent stimulation and recording properties. This paper presents an approach of increasing the real surface area of the electrodes by creating a surface microstructure. Two major novelties let this work stand out from existing approaches which mainly make use of porous coatings such as platinum black or iridium oxide, or Poly(3,4-ethylenedioxythiophene) (PEDOT). Roughening is carried out by a dry etching process on the silicon electrode core before being coated by a sputtered platinum layer, eliminating complicated deposition processes as for the materials described above. The technology is compatible with any commonly used coating material. In addition, the surface roughening is compatible with high aspect ratio penetrating electrode arrays such as the well-established Utah electrode array, whose unique geometry presents a challenge in the surface modification of active electrode sites. The dry etching process is well characterized and yields a high controllability of pore size and depth. This paper confirms the superior electrochemical properties including impedance, charge injection capacity, and charge storage capacity of surface engineered electrode arrays compared to conventional arrays over a period of 12weeks. Furthermore, mechanical stability of the modified electrodes was tested by implantation in the brain of a recently deceased rat. In conclusion, the larger interface surface of the electrodes does not only decrease the impedance which should lead to enhanced Signal to noise ratio (SNR) for recording purposes, but also yields higher charge injection capacities, which improve the stimulation characteristics of the implants.

X-ray structure of a protease-resistant mutant form of human galectin-9 having two carbohydrate recognition domains with a metal-binding site

Galectin-9 (G9) is a tandem-repeat type β-galactoside-specific animal lectin having N-terminal and C-terminal carbohydrate recognition domains (N-CRD and C-CRD, respectively) joined by a linker peptide that is involved in the immune system. G9 is divalent in glycan binding, and structural information about the spatial arrangement of the two CRDs is very important for elucidating its biological functions. As G9 is protease sensitive due to the long linker, the protease-resistant mutant form of G9 (G9Null) was developed by modification of the linker peptide, while retaining its biological functions. The X-ray structure of a mutant form of G9Null with the replacement of Arg221 by Ser (G9Null_R221S) having two CRDs was determined. The structure of G9Null_R221S was compact to associate the two CRDs in the back-to-back orientation with a large interface area, including hydrogen bonds and hydrophobic interactions. A metal ion was newly found in the galectin structure, possibly contributing to the stable structure of protein. The presented X-ray structure was thought to be one of the stable structures of G9, which likely occurs in solution. This was supported by structural comparisons with other tandem-repeated galectins and the analyses of protein thermostability by CD spectra measurements.

Rational construction of 3D NiCo2O4@CoMoO4 core/shell nanoarrays as a positive electrode for asymmetric supercapacitor

Optimized nanostructures design for composite continuously improved the electrochemical performances of supercapacitors in the past few years. Herein, we have successfully fabricated NiCo2O4 Nanosheets@CoMoO4nanoflakes Core/shell Arrays on Ni foam by two steps of hydrothermal processing. The proposed nanoarchitectural design of active materials provides large interfacial area, abundant active sites for the electrolytic ions with the electrode materials and fast electron transport, which significantly improve the capacitive performance of individual electrodes and hence of the fabricated asymmetric supercapacitor. This electrode exhibits high specific capacitance of 1543.14 F g−1 (corresponding to area specific capacitance of 5.4 F cm−2) at a current density of 5 mA cm−2, good rate capability, and superior cycling stability with ∼95% capacitance retention after 1000 cycles. Asymmetric supercapacitor (NiCo2O4@CoMoO4//AC/graphene) with a maximum voltage of 1.6 V has demonstrated a high energy density of 42.75Wh·kg−1, a high power density of 11427 W·kg−1 at 29.52 Wh·kg−1, and out standing cyclic stability with the capacitance retention of 104% after 10000 cycles.

Stabilization and functionalization of aqueous foams by Quillaja saponin-coated nanodroplets

We report evidence for stabilization and functionalization of aqueous foams stabilized by Quillaja saponin (QS)-coated nanodroplets. In contrast to foams stabilized by QS, stabilized the foams of QS-coated nanodroplets showed superior foamability, stability and multi-functional characteristics. Specifically, the half-life time of the foam stabilized by nanodroplets was approximately 4 times that of saponin. The microstructure observation indicates the nanodroplets from assembly of saponin around oil droplet were strong attachment at the gas-liquid interface and stabling a large gas-liquid interfacial area in a hierarchical structure. The surface dynamic adsorption and large deformation rheology were performed, revealed that QS nanodroplets were almost irreversibly adsorbed at air-liquid interface and exhibited less surface desorption and high elastic-viscous response to a large mechanical deformation. These nanodroplets stabilized foams presented a large capacity for loading hydrophobic flavors and nutrients (e.g., β-carotene and curcumin), which could be used to create a new class of foam food products with sustained release of flavors and/or health benefit functionality.

Fabrication of WO3@g-C3N4 with core@shell nanostructure for enhanced photocatalytic degradation activity under visible light

WO3@g-C3N4 composite photocatalysts with core@shell nanostructure were fabricated via a self-assembly method. A large heterojunction interfacial area of WO3@g-C3N4 can be provided in the nanoscale heterostructure. Furthermore, the electron mobility of the composite photocatalysts was improved with the introduction of WO3. These are favorable for increasing the separation efficiency of photoinduced electron-hole pairs and improving the photocatalytic efficiency of WO3@g-C3N4, which was confirmed by the measurements of photocurrent and electrochemical impedance spectroscopy. The results of the photocatalytic degradation of Rh B showed dramatic photocatalytic performance of this composite photocatalyst. The kinetic constant of Rh B degradation on the WO3@g-C3N4 was 0.95h−1, which was 7.7-fold and 3.5-fold higher than those on pure WO3 and g-C3N4 nanosheets, respectively. In addition, the stability of the composite photocatalyst was also satisfactory according to the result of the three-cycle experiment.

Sequential Dip-spin Coating Method: Fully Infiltration of MAPbI3-xClx into Mesoporous TiO2 for Stable Hybrid Perovskite Solar Cells

Organic-inorganic hybrid perovskite solar cells (PSCs) have reached a power conversion efficiency of 22.1% in a short period (∼7 years), which has been obtainable in silicon-based solar cells for decades. The high power conversion efficiency and simple fabrication process render perovskite solar cells as potential future power generators, after overcoming the lack of long-term stability, for which the deposition of void-free and pore-filled perovskite films on mesoporous TiO2 layers is the key pursuit. In this research, we developed a sequential dip-spin coating method in which the perovskite solution can easily infiltrate the pores within the TiO2 nanoparticulate layer, and the resultant film has large crystalline grains without voids between them. As a result, a higher short circuit current is achieved owing to the large interfacial area of TiO2/perovskite, along with enhanced power conversion efficiency, compared to the conventional spin coating method. The as-made pore-filled and void-free perovskite film avoids intrinsic moisture and air and can effectively protect the diffusion of degradation factors into the perovskite film, which is advantageous for the long-term stability of PSCs.

Facile Synthesis of Three-Dimensional Sandwiched MnO2@GCs@MnO2 Hybrid Nanostructured Electrode for Electrochemical Capacitors.

Designable control over the morphology and structure of active materials is highly desirable for achieving high-performance devices. Here, we develop a facile microwave-assisted synthesis to decorate MnO2 nanocrystals on three-dimensional (3D) graphite-like capsules (GCs) to obtain sandwich nanostructures (3D MnO2@GCs@MnO2) as electrode materials for electrochemical capacitors (ECs). A templated growth of the 3D GCs was carried out via catalytic chemical vapor deposition and MnO2 was decorated on the exterior and interior surfaces of the GC walls through microwave irradiation to build an engineered architecture with robust structural and morphological stability. The unique sandwiched architecture has a large interfacial surface area, and allows for rapid electrolyte diffusion through its hollow/open framework and fast electronic motion via the carbon backbone. Furthermore, the tough and rigid nature of GCs provides the necessary structural stability, and the strong synergy between MnO2 and GCs leads to high electrochemical activity in both neutral (265.1 F/g at 0.5 A/g) and alkaline (390 F/g at 0.5 A/g) electrolytes. The developed hybrid exhibits stable capacitance up to 6000 cycles in 1 M Na2SO4. The hybrid is a potential candidate for future ECs and the present study opens up an effective avenue to design hybrid materials for various applications.

Experimental investigation of horizontal air–water bubbly-to-plug and bubbly-to-slug transition flows in a 3.81 cm ID pipe

The present study seeks to investigate horizontal bubbly-to-plug and bubbly-to-slug transition flows. The two-phase flow structures and transition mechanisms in these transition flows are studied based on experimental database established using the local four-sensor conductivity probe in a 3.81cm inner diameter pipe. While slug flow needs to be distinguished from plug flow due to the presence of large number of small bubbles (and thus, large interfacial area concentration), both differences and similarities are observed in the evolution of interfacial structures in bubbly-to-plug and bubbly-to-slug transitions. The bubbly-to-plug transition is studied by decreasing the liquid flow rate at a fixed gas flow rate. It is found that as the liquid flow rate is lowered, bubbles pack near the top wall of the pipe due to the diminished role of turbulent mixing. As the flow rate is lowered further, bubbles begin to coalesce and form the large bubbles characteristic of plug flow. Bubble size increases while bubble velocity decreases as liquid flow rate decreases, and the profile of the bubble velocity changes its shape due to the changing interfacial structure. The bubbly-to-slug transition is investigated by increasing the gas flow rate at a fixed liquid flow rate. In this transition, gas phase becomes more uniformly distributed throughout the cross-section due to the formation of large bubbles and the increasing bubble-induced turbulence. The size of small bubbles decreases while bubble velocity increases as gas flow rate increases. The distributions of bubble size and bubble velocity become more symmetric in this transition. While differences are observed in these two transitions, similarities are also noticed. As bubbly-to-plug or bubbly-to-slug transition occurs, the formation of large elongated bubbles is observed not in the uppermost region of bubble layer, but in a lower region. At the beginning of transitions, relative differences in phase velocities near the top of the pipe cross-section to those near the pipe center become larger for both gas and liquid phases, because more densely packed bubbles introduce more resistance to both phases.

Smart Capsules for Lead Removal from Industrial Wastewater.

Ground and especially drinking water could be contaminated by heavy metal ions such as lead and chromium, or the metalloid arsenic, discarded from industrial wastewater. These heavy metal ions are regarded as highly toxic pollutants which could cause a wide range of health problems in case of a long-term accumulation in the body. Thus, there have been many efforts to reduce the concentration of lead ions in effluent wastewater. They have included the establishment of stringent permissible discharge levels and management policies, the application of various pollution-control technologies, and the development of adsorbent materials for lead reduction. According to Science [1] encapsulation, developed approximately 65 years ago, has been defined as a major interdisciplinary research technology. Encapsulation has been used to deliver almost everything from advanced drugs to unique consumer sensory experiences. In this chapter we review the art of encapsulation technology as a potential breakthrough solution for a recyclable removal system for lead ions. Moreover, in order to provide the readers with a comprehensive and in-depth understanding of recent developments and innovative applications in this field, we highlight some remarkable advantages of encapsulation for heavy metal remove, such as simplicity of preparation, applicability for a wide range of selective extractants, large special interfacial area, ability for concentration of metal ions from dilute solutions, and less leakage of harmful components to the environment.

Highly Active Three-Dimensional NiFe/Cu2 O Nanowires/Cu Foam Electrode for Water Oxidation.

Water splitting is of paramount importance for exploiting renewable energy-conversion and -storage systems, but is greatly hindered by the kinetically sluggish oxygen evolution reaction (OER). In this work, a three-dimensional, highly efficient, and durable NiFe/Cu2 O nanowires/Cu foam anode (NiFe/Cu2 O NWs/CF) for water oxidation in 1.0 m KOH was developed. The obtained electrode exhibited a current density of 10 mA cm-2 at a uniquely low overpotential of η=215 mV. The average specific current density (js ) was estimated, on the basis of the electrocatalytically active surface area, to be 0.163 mA cm-2 at η=310 mV. The electrode also displayed a low Tafel slope of 42 mV decade-1 . Moreover, the NiFe/Cu2 O NWs/CF electrode could maintain a steady current density of 100 mA cm-2 for 50 h at an overpotential of η=260 mV. The outstanding electrochemical performance of the electrode for the OER was attributed to the high conductivity of the Cu foam and the specific structure of the electrode with a large interfacial area.

Construction of tubular polypyrrole-wrapped biomass-derived carbon nanospheres as cathode materials for lithium–sulfur batteries

A promising hybrid material composed of tubular polypyrrole (T-PPy)-wrapped monodisperse biomass-derived carbon nanospheres (BCSs) was first synthesized successfully via a simple hydrothermal approach by using watermelon juice as the carbon source, and further used as an anchoring object for sulfur (S) of lithium–sulfur (Li–S) batteries. The use of BCSs with hydrophilic nature as a framework could provide large interface areas between the active materials and electrolyte, and improve the dispersion of T-PPy, which could help in the active material utilization. As a result, BCS@T-PPy/S as a cathode material exhibited a high capacity of 1143.6 mA h g−1 and delivered a stable capacity up to 685.8 mA h g−1 after 500 cycles at 0.5 C, demonstrating its promising application for rechargeable Li–S batteries.