Highly efficient anode catalyst with a Ni@Pd Pt core–shell nanostructure for methanol electrooxidation in alkaline media

To enhance the electrocatalytic activity of anode catalysts used in alkaline-media direct methanol fuel cells(DMFCs), a Ni@Pd Pt electrocatalyst was successfully prepared using a three-phase-transfer method. The Ni@Pd Pt electrocatalyst was characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM), and high-resolution TEM(HRTEM) techniques. The experimental results indicate that the average particle size of the core–shell-structured Ni@Pd Pt electrocatalyst is approximately 5.6 nm. The Ni@Pd Pt electrocatalyst exhibits a catalytic activity 3.36 times greater than that of Pd Pt alloys for methanol oxidation in alkaline media. The developed Ni@Pd Pt electrocatalyst offers a promising alternative as a highly electrocatalytically active anode catalyst for alkaline DMFCs.     

Electrochemical characterization of the Pt /PEDOT electrode in DMFC

Poly-(3, 4-ethylenedioxythiophene) (PEDOT) was applied in making electrodes and gas diffusion layer for direct methanol fuel cells (DMFC). Electrochemical characterizations of Pt/PEDOT electrodes, made by two different methods, were investigated by cyclic voltammetry, methanol oxidation tests and DMFC performance. The platinum particle structure in PEDOT/PSS (poly?styrene sulfonic acid) films was investigated by SEM and TEM. Our research work showed that PEDOT influenced the catalytic activity behavior in three different ways when it was applied to the anode, cathode and the gas diffusion layer. The DMFC performance agreed with the cyclic voltammetry and methanol oxidation test results.     

Synthesis and characterization of Pt-MoOx-TiO2 electrodes for direct ethanol fuel cells

To enhance the CO-tolerance performance of anode catalysts for direct ethanol fuel cells,carbon nanotubes were modified by titanium dioxide (donated as CNTs@TiO2) and subsequently served as the support for the preparation of Pt/CNTs@TiO2 and Pt-Mo/CNTs@TiO2 electrocatalysts via a UV-photoreduction method.The physicochemical characterizations of the catalysts were carried out by using X-ray diffraction (XRD),transmission electron microscopy (TEM),X-ray photoelectron spectroscopy (XPS),and infrared spectroscopy of adsorbed probe ammonia molecules.The electrocatalytic properties of the catalysts for methanol oxidation were investigated by the cyclic voltammetry technique.The results show that Pt-Mo/CNTs@TiO2 electrode exhibits the highest performance in all the electrodes.It is explained that,the structure,the oxidation states,and the acid-base properties of the catalysts are influenced due to the strong interaction between Ti and Mo species by adding TiO2 and MoOx to the Pt-based catalysts.     

Synthesis,characterization and electrocatalytic studies of palladium–manganese oxyhydroxide nanocomposite towards direct ethylene glycol fuel cell

The palladium nanoparticle grafted manganese oxyhydroxide nanorod （MON） electrocatalyst has been synthesized and tested for the electrooxidation of ethylene glycol （EG） in an alkaline medium. The MON was prepared using the hydrothermal method and the Pd nano- particles were coated on the MON using an in situ reduction method. The nanocatalyst thus prepared was characterized by powder X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy and electrochemical methods. The microscopic studies confirm the formation of MON and reveal that the Pd nanoparticles were grafted uniformly on the MON. In the voltammetric studies, the Pd/MON catalyst exhibited a six-fold improved peak current for ethylene glycol electrooxidation compared with the C/Pd. The EG electrooxidation reaction performances of the Pd/MON nanocatalyst in the alkaline solutions containing different quantities of EG were tested through cyclic voltammetry. The catalytic removal of the poisonous intermediates formed during electrooxidation of EG was explained. The present study shows that MON can act as an active support for the Pd nanocatalyst.     

Silicon-based micro direct methanol fuel cell with an N-inputs-N-outputs anode flow pattern

A micro direct methanol fuel cell(μDMFC) is suitable for use in notebook computers,mobile phones,and other digital products.To resolve the poor mass-transport efficiency problem in the anode flow channel,this paper presents an N-inputs-N-outputs parallel flow pattern with rectangular convexes to reinforce methanol mass transport and reduce concentration polarization.The simulation results show that the N-inputs-N-outputs parallel flow channels with the rectangle convexes improve the performance.μDMFCs,which have four anode flow patterns,are fabricated using MEMS(microelectromechanical systems) technology.The experimental results show that the μDMFC with the rectangle convexes has a performance better than previously reported systems,and has a peak power density of 19.96 mW/cm2.The simulation and experimental results are in good agreement.     

Effect of TiO_2 nanoparticles on hydrogen evolution reaction activity of Ni coatings

The electrocatalytic activity of electrodeposited Ni and Ni–TiO_2 coatings with regard to the alkaline hydrogen evolution reaction(HER) was investigated. The Ni coatings were electrodeposited from an acid chloride bath at different current densities, and their HER activities were examined in a 1.0-mol·L~(-1) KOH medium. The variations in the HER activity of the Ni coatings with changes in surface morphology and composition were examined via the electrochemical dissolution and incorporation of nanoparticles. Electrochemical analysis methods were used to monitor the HER activity of the test electrodes; this activity was confirmed via the quantification of gases that evolved during the analysis. The obtained results demonstrated that the Ni–TiO_2 nanocomposite test electrode exhibited maximum activity toward the alkaline HER. The surface appearance, composition, and the phase structure of all developed coatings were analyzed using scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), and X-ray diffraction(XRD), respectively. The improvement in the electrocatalytic activity of Ni–TiO_2 nanocomposite coating toward HER was attributed to the variation in surface morphology and increased number of active sites.     

Effect of TiO<Subscript>2</Subscript> nanoparticles on hydrogen evolution reaction activity of Ni coatings

The electrocatalytic activity of electrodeposited Ni and Ni-TiO₂ coatings with regard to the alkaline hydrogen evolution reaction (HER) was investigated. The Ni coatings were electrodeposited from an acid chloride bath at different current densities, and their HER activities were examined in a 1.0-mol·L-1 KOH medium. The variations in the HER activity of the Ni coatings with changes in surface morphology and composition were examined via the electrochemical dissolution and incorporation of nanoparticles. Electrochemical analysis methods were used to monitor the HER activity of the test electrodes; this activity was confirmed via the quantification of gases that evolved during the analysis. The obtained results demonstrated that the Ni-TiO₂ nanocomposite test electrode exhibited maximum activity toward the alkaline HER. The surface appearance, composition, and the phase structure of all developed coatings were analyzed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD), respectively. The improvement in the electrocatalytic activity of Ni-TiO₂ nanocomposite coating toward HER was attributed to the variation in surface morphology and increased number of active sites.     

Effects of drug-polymer dispersions on solubility and <Emphasis Type="Italic">in vitro</Emphasis> diffusion of artemisinin across a polydimethylsiloxane membrane

Artemisinin(ART) is a sesquiterpene lactone with an endo-peroxide bridge that is thought to be responsible for its antimalarial activity.It has low oral bioavailability because of aqueous insolubility,which leads to local toxicity at the site of aggregation.The present work focused on increasing its solubility and evaluating its permeation across a model membrane to mimic transdermal delivery that bypasses the hepatic metabolism.For this purpose,physical mixtures(PM),solid dispersions(SD) and lyophilized dispersions(LD) with different drug-polymer ratios(1:0.5,1:1,1:2,1:4 and 1:9) were prepared using the hydrophilic polymer polyvinylpyrrolidone(PVP).Drug-polymer dispersions were characterized using X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FTIR).Solubility was measured in three solvents:de-ionized water,phosphate buffered saline(PBS) and methanol.The toluene-water partition coefficient was evaluated and compared with the literature and calculated logP values.In vitro diffusion of ART was studied across a polydimethylsiloxane membrane from a saturated solution of drug-polymer dispersions.XRD patterns showed a gradual decrease in crystallinity of ART with increasing polymer concentration,while FTIR confirmed no interactions between ART and PVP.Solubility was increased up to 4-,5-and 8-fold for LD in water,PBS and methanol,respectively.The logP for toluene-water was 2.65 ± 0.3,which is in good agreement with literature and calculated logP values.Permeation was enhanced,which is attributed to the decrease in crystallinity and increase in wettability of the drug.The ART flux was significantly higher than that of pure ART(0.12 ± 0.01) with increasing PVP concentration for SD and LD formulations.In conclusion,drug-polymer dispersions with PVP improve the pharmaceutical properties of ART in the order LD>SD>PM.     

Photocatalytic degradation of methylene blue by nanostructured Fe/FeS powder under visible light

The photocatalytic performance of mechano-thermally synthesized Fe/FeS nanostructures formed from micron-sized starting materials was compared with that of a thermally synthesized nanostructure with nano-sized precursors in this paper. The properties of as-synthesized materials were studied by X-ray diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), diffuse reflectance spectroscopy (DRS), and ultraviolet-visible (UV-Vis) spectroscopy. The effects of irradiation time, methylene blue (MB) concentration, catalyst dosage, and pH value upon the degradation of MB were studied. Magnetic properties of the samples showed that both as-synthesized Fe/FeS photocatalysts are magnetically recoverable, eliminating the need for conventional filtration steps. Degradation of 5 ppm of the MB solution by mechano-thermally synthesized Fe/FeS with a photocatalyst dosage of 1 kg/m3 at pH 11 can reach 96% after 12 ks irradiation under visible light. The photocatalytic efficiency is higher in alkaline solution. The kinetics of photocatalytic degradation in both samples is controlled by a first-order reaction. However, the rate-constant value in the thermally synthesized Fe/FeS photocatalyst sample is only 1.5 times greater than that of the mechano-thermally synthesized one.     

Mesoporous iron oxide-silica supported gold catalysts for low-temperature CO oxidation

Mesoporous iron oxide-silica composite with a high silica content was synthesized by hydrothermal method, and another composite material with a high iron content was obtained by etching part of silica in alkaline solution. Gold catalysts were loaded onto both composites by a deposition-precipitation method, and used for CO oxidation. The samples were characterized by Brumauer- Emmet-Teller （BET）, X-ray diffraction （XRD）, X-ray photoelectron spectra （XPS）, transmission electron micro- scope （TEM） and scanning electron microscope （SEM） techniques. Both composites had high specific surface areas and were amorphous. The Au nanoparticles dispersed on the surface of the composites existed in metallic state. Composite with high silica content was not suitable for Au loading, and its supported gold catalyst showed poor per- formance in catalytic reaction. In contrast, composite with high iron content allowed efficient Au loading, and CO could be oxidized completely at low temperature on its supported gold catalyst. The effects of deposition-precipi- tation pH values on Au loading and activity of the catalyst were investigated, and the results indicated that Au loading was the highest and the catalyst was the most active for CO oxidation when the synthesis pH was adjusted to 8.     

Expression of recombinant human lysozyme in the milk of transgenic mice

Human lysozyme is a 130-aa (amino acid) alkaline polypeptide, and has both anti-bacterial and anti-viral properties which make it an important component of human natural immunity system. As a first step toward the ultimate goal of improving the anti-bacterial properties of bovine and ovine milk, a transgenic mouse that contains the genomic DNA sequence of the human lysozme gene has been generated for the first time. From 83 mice generated by microinjection, a total of 6 positive transgenic mice were identified by PCR and Southern blot. F1 mice positive for transgene in lines were also detected by PCR. This shows that transgene could be transmitted from founder transgenic mice to their offspring. Recombinant human lysozyme (rHlys) was found in the whey of 3 female positive transgenic mice by Western blot. The highest concentration of rHlys for transgenic mice was 0.2mg/mL. The antibacterial activity of the whey for transgenic mice was highly enhanced up to 0.4 times as much as that of human, while that of non-transgenic mouse was very low. Although the lysozyme activity of transgenic mice is still lower than that of human, the rHlys exhibits the same specific activity as that of human lysozyme. It provides a strong basis for further studies into the possible application of rHlys express in mammary gland.     

Effect of solvent on Se-modified ruthenium/carbon catalyst for oxygen reduction

Se-modified ruthenium supporting on carbon(Sex–Ru/C) electrocatalyst was prepared by solvothermal one-step synthesis method. The reaction mechanism was revealed after discussing impact of different solvents(i-propanol and EG) in solvotermal reaction. The result showed that the grain size of Se-modified ruthenium electrocatalyst was as small as 1 to 3 nm and highly dispersed on carbon surface. X-ray photoelectron spectroscopy(XPS) presented that selenium mainly existed in the catalyst in the form of elemental selenium and selenium oxides when the solvent was EG and i-propanol, respectively. The oxygen reduction reaction(ORR) performance was improved by appearance of selenium oxides.     

Effects of environmental factors on corrosion behaviors of metal-fiber porous components in a simulated direct methanol fuel cell environment

To enable the use of metallic components in direct methanol fuel cells (DMFCs), issues related to corrosion resistance must be considered because of an acid environment induced by the solid electrolyte. In this study, we report the electrochemical behaviors of metal-fiber-based porous sintered components in a simulated corrosive environment of DMFCs. Three materials were evaluated: pure copper, AISI304, and AISI316L. The environmental factors and related mechanisms affecting the corrosion behaviors were analyzed. The results demonstrated that AISI316L exhibits the best performance. A higher SO₄2- concentration increases the risk of material corrosion, whereas an increase in methanol concentration inhibits corrosion. The morphological features of the corroded samples were also characterized in this study.     

Energy consumption of electrooxidation systems with boron-doped diamond electrodes in the pulse current mode

A pulse current technique was conducted in a boron-doped diamond (BDD) anode system for electrochemical wastewater treatment. Due to the strong generation and weak absorption of hydroxyl radicals on the diamond surface, the BDD electrode possesses a powerful capability of electrochemical oxidation of organic compounds, especially in the pulse current mode. The influences of pulse current parameters such as current density, pulse duty cycle, and frequency were investigated in terms of chemical oxygen demand (COD) removal, average current efficiency, and specific energy consumption. The results demonstrated that the relatively high COD removal and low specific energy consumption were obtained simultaneously only if the current density or pulse duty cycle was adjusted to a reasonable value. Increasing the frequency slightly enhanced the COD removal and average current efficiency. A pulse-BDD anode system showed a stronger energy saving ability than a constant-BDD anode system when the electrochemical oxidation of phenol of the two systems was compared. The results prove that the pulse current technique is more cost-effective and more suitable for a BDD anode system for real wastewater treatment. A kinetic analysis was presented to explain the above results.     

Low temperature synthesis of NiO/Co3O4 composite nanosheets as high performance Li-ion battery anode materials

NiO/Co3O4 composite nanosheets have been synthesized via a facile method at low temperature for the first time.The as prepared materials were characterized by X-ray powder diffraction(XRD) and transmission electron microscopy(TEM),and the performance of Li-ion batteries(LIBs) as anode materials were also studied.By controlling the atom ratio of Ni:Co,not only the size of the nanosheets can be controlled,the electrode’s conductivity and stability could also be greatly improved.The composite material showed a stable capacity retention during cycling(87% of the second capacity was retained after 15 cycles) even at a relatively large current rate(400 mA/g).The NiO/Co3O4 nanosheet might be promising candidate anode materials in high performance Li-ion batteries.     

Photocatalytic activity of ferric oxide/titanium dioxide nanocomposite films on stainless steel fabricated by anodization and ion implantation

A simple surface treatment was used to develop photocatalytic activity for stainless steel. AISI 304 stainless steel specimens after anodization were implanted by Ti ions at an extracting voltage of 50 kV with an implantation dose of 3 × 1015 atoms·cm?2 and then annealed in air at 450℃ for 2 h. The morphology was observed by scanning electron microscopy. The microstructure was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The photocatalytic degradation of methylene blue solution was carried out under ultraviolet light. The corrosion resistance of the stainless steel was evaluated in NaCl solution (3.5 wt%) by electrochemical polarization curves. It is found that the Ti ions depth profile resembles a Gaussian distribution in the implanted layer. The nanostructured Fe₂O₃/TiO₂ composite film exhibits a remarkable enhancement in photocatalytic activity referenced to the mechanically polished specimen and anodized specimen. Meanwhile, the annealed Ti-implanted specimen remains good corrosion resistance.     

PtCo alloy nanoparticles supported on graphene nanosheets with high performance for methanol oxidation

PtCo alloy nanoparticles are deposited onto graphene sheets through a facile and reproducible hydrothermal method.During the hydrothermal reaction,the reduction of graphene oxide and PtCo alloy nanoparticles loading can be achieved.X-ray diffraction (XRD) analyses reveal a good crystallinity of the supported Pt nanoparticles in the composites and the formation of PtCo alloy.X-ray photoelectron spectra (XPS) results depict that Pt mainly exists in the metallic form,while much of the cobalt is oxidized.Transmission electron microscope (TEM) observations show that the PtCo alloy nanoparticles are uniformly dispersed on graphene nanosheets compared with multiwalled carbon nanotubes (MWNTs).This PtCo-graphene composite exhibits excellent electrocatalytic activity and high poison tolerance toward poisoning species for methanol oxidation reaction,far outperforming the Pt-graphene or PtCo-MWNTs composites with the same feeding ratio of Pt/carbon.     

Pretreatment and thiosulfate leaching of refractory gold-bearing arsenosulfide concentrates

A hydrometallurgical process for refractory gold-bearing arsenosulfide concentrates at ambient temperature and pressure was presented, including fine grinding with intensified alkali-leaching (FGLAL), enhanced agitation alkali-leaching (EAAL), thiosulfate leaching and displacement. Experimental results on a refractory gold concentrate showed that the total consumption of NaOH in alkaline leaching is only 41% of those theoretically calculated under the conditions of full oxidization for the same amount of arsenides and sulfides transformed into arsenates and sulfates, and 72.3% of gold is synchro-dissoluted by thiosulfate self-generated during alkaline leaching. After alkaline leaching, thiosulfate leaching was carried out for 24 h. The dissolution of gold is increased to 91.9% from 4.6% by cyanide without the pretreatment. The displacement of gold by zinc powder in the solution gets to 99.2%. Due to an amount of thiosulfate self-generated during alkaline leaching, the reagent addition in thiosulfate leaching afterwards is lower than the normal.     

Alkaline pressure oxidative leaching of bismuth-rich and arsenic-rich lead anode slime

A new alkaline pressure oxidative leaching process(with NaNO3 as the oxidant and NaOH as the alkaline reagent)is proposed herein to remove arsenic,antimony,and lead from bismuth-rich and arsenic-rich lead anode slime for bismuth,gold,and silver enrichment.The effects of the temperature,liquid-to-solid ratio,leaching time,and reagent concentration on the leaching ratios of arsenic,antimony,and lead were investigated to identify the optimum leaching conditions.The experimental results under optimized conditions indicate that the average leaching ratios of arsenic,antimony and lead are 95.36%,79.98%,63.08%,respectively.X-ray diffraction analysis indicated that the leaching residue is composed of Bi,Bi2O3,Pb2Sb2O7,and trace amounts of NaSb(OH)6.Arsenic,antimony,and lead are thus separated from lead anode slime as Na3AsO4·10H2O and Pb2Sb2O7.Scanning electron microscopy and energy-dispersive spectrometry imaging revealed that the samples undergo appreciable changes in their surface morphology during leaching and that the majority of arsenic,lead,and antimony is removed.X-ray photoelectron spectroscopy was used to demonstrate the variation in the valence states of the arsenic,lead,and antimony.The Pb(IV)and Sb(V)content was found to increase substantially with the addition of NaNO3.