Preparation and application of g-C_3N_4-ZnS-DNA nanocomposite with enhanced electrocatalytic activity

We successfully designed and prepared a g-C3N4-ZnS-DNA nanocomposite by a simple method and systematically investigated its morphology,microstructure,and electrocatalytic properties.The as-prepared g-C3N4-ZnS-DNA nanocomposite possessed the electrocatalytic activity of g-C3N4-ZnS and the conductivity of DNA.The presence of DNA was found to enhance the electrocatalytic response of the nanocomposite towards environmental hormones,e.g.pentachlorophenol and nonylphenol,owing to the interaction between g-C3N4-ZnS and DNA,indicating that a stable nanocomposite was formed.The three components showed synergistic effects during electrocatalysis.Electrochemical impedance spectra indicated that the g-C3N4-ZnS-DNA nanocomposite dramatically facilitated the electron transfer of a modified electrode.The co-doping of g-C3N4 film with ZnS and DNA doubled the electrochemical response of the modified electrode in comparison with that of unmodified g-C3N4 film.The detection limits（3 S/N） of pentachlorophenol and nonylphenol were3.3×10^-9 mol L^-1.Meanwhile,we propose a possible Z-scheme mechanism for electron transfer in the g-C3N4-ZnS-DNA nanocomposite and the possible pentachlorophenol and nonylphenol electrocatalytic oxidation mechanism.The g-C3N4-ZnS-DNA nanocomposite-modified electrode was demonstrated to be effective for electrochemical sensing of trace environmental hormones in water samples.

Electrochemically reduced graphene oxide with enhanced electrocatalytic activity toward tetracycline detection

An electrochemically reduced graphene oxide sample, ERGO_0.8v, was prepared by electrochemical reduction of graphene oxide （GO） at -0.8 V, which shows unique electrocatalytic activity toward tetracycline （TTC） detection compared to the ERGO-12v （GO applied to a negative potential of-1.2 V）, GO, chemically reduced GO （CRGO）-modified glassy carbon electrode （GC） and bare GC electrodes. The redox peaks of TTC on an ERGO-0.8v-modifled glass carbon electrode （GC/ERGO-0.8v） were within 0-0.5 V in a pH 3.0 buffer solution with the oxidation peak current correlating well with TTC concentration over a wide range from 0.1 to 160 mg/L Physical characterizations with Fourier transform infrared （FT-IR）, Raman, and X-ray photoelectron spectroscopies （XPS） demonstrated that the oxygen-containing functional groups on GO diminished after the electrochemical reduction at -0.8 V, yet still existed in large amounts, and the defect density changed as new sp2 domains were formed. These changes demonstrated that this adjustment in the number of oxygen-containing groups might be the main factor affecting the electrocatalytic behavior of ERGO. Additionally, the defect density and sp2 domains also exert a profound influence on this behavior. A possible mechanism for the TTC redox reaction at the GC/ERGO-0.8v electrode is also presented. This work suggests that the electrochemical reduction is an effective method to establish new catalytic activities of GO by setting appropriate parameters.

Synergistic Effects in CNTs-PdAu/Pt Trimetallic Nanoparticles with High Electrocatalytic Activity and Stability

We present a straightforward physical approach for synthesizing multiwalled carbon nanotubes(CNTs)-Pd Au/Pt trimetallic nanoparticles(NPs), which allows predesign and control of the metal compositional ratio by simply adjusting the sputtering targets and conditions. The small-sized CNTs-Pd Au/Pt NPs(~3 nm, Pd/Au/Pt ratio of 3:1:2) act as nanocatalysts for the methanol oxidationreaction(MOR), showing excellent performance with electrocatalytic peak current of 4.4 A mg^(-1) Pt and high stability over 7000 s. The electrocatalytic activity and stability of the Pd Au/Pt trimetallic NPs are much superior to those of the corresponding Pd/Pt and Au/Pt bimetallic NPs,as well as a commercial Pt/C catalyst. Systematic investigation of the microscopic, crystalline, and electronic structure of the Pd Au/Pt NPs reveals alloying and charge redistribution in the Pd Au/Pt NPs, which are responsible for the promotion of the electrocatalytic performance.

Enhanced electrocatalytic activity for H_2O_2 production by the oxygen reduction reaction: Rational control of the structure and composition of multi-walled carbon nanotubes

Hydrogen peroxide(H2O2)is a very useful chemical reagent,but the current industrial methods for its production suffer from serious energy consumption problems.Using high-activity and high-selectivity catalysts to electrocatalyze the oxygen reduction reaction(ORR)through a two-electron(2e^-)pathway is a very promising route to produce H2O2.In this work,we obtained partially oxidized multi-walled carbon nanotubes(MWCNTs)with controlled structure and composition by oxidation with concentrated sulfate and potassium permanganate at 40℃ for 1 h(O-CNTs-40-1).The outer layers of O-CNTs-40-1 are damaged with defects and oxygen-containing functional groups,while the inner layers are maintained intact.The optimized structure and composition of the partially oxidized MWCNTs ensure that O-CNTs-40-1 possesses both a sufficient number of catalytic sites and good conductivity.The results of rotating ring disk electrode measurements reveal that,among all oxidized MWCNTs,O-CNTs-40-1 shows the greatest improvement in hydrogen peroxide selectivity(from ~ 30% to ~ 50%)and electron transfer number(from ~ 3.4 to ~ 3.0)compared to those of the raw MWCNTs.The results of electrochemical impedance spectroscopy measurements indicate that both the charge-transfer and intrinsic resistances of O-CNTs-40-1 are lower than those of the raw MWCNTs and of the other oxidized MWCNTs.Finally,direct tests of the H2O2 production confirm the greatly improved catalytic activity of O-CNTs-40-1 relative to that of the raw MWCNTs.

Preparation and Electrocatalytic Activity of Polyaniline-poly (Propylene Oxide) Modified by Pt Nanoparticles

The preparation and electrocatalytic activity of polyaniline-poly （ propylene oxide ） （ PAN-PPO ） modified by Pt particles （ Pt/ PAN-PPO ） were investigated. Pt/ PAN-PPO was characterized by scanning electron microscopy （SEM） and energy dispersive spectroscopy （ EDS ）. Pt particles on PAN-PPO were in the nanometer range, and dispersed in a three-dimensional distribution on the surface of PAN-PPO film. Compared with polyaniline and glassy carbon modified with Pt particles under the same conditions, Pt/PAN-PPO exhibited a high electrocatalytic activity for lysine oxidation.

Platinum Nanoparticles Supported on Graphite Nanofibers Prepared by Microwave Irradiation and Its Electrocatalytic Activity

Platinum nanoparticles supported on graphite nanofibers (GNFs) were prepared bymicrowave assistant heating polyol process. TEM images showed that microwave prepared Ptnanoparticles supported on GNFs were small and uniform, and the average diameter was about 3.4nm. Cyclic voltammetric test showed that Pt/GNFs exhibited very high electrocatalytic activity formethanol oxidation.

Enhanced electrocatalytic activity of carbon cloth by synergetic effect of plasma and acid treatment

Commercial carbon cloth(CC)is an ideal electrocatalysis material to produce oxygen evolution reaction(OER)due to its high conductive and 3D flexible structure,but the lacked active sites limit its application.For improving its OER performance,the present study proposed an effective method combining plasma and acid treatment to introduce oxygen-containing functional groups and produce more active sites on its surface.Compared to the pristine CC,the plasma and acid treated carbon cloth(PN-CC)delivers a reduced overpotential by 34.6%to achieve current density of 10 mA cm^(−2).The Tafel slope declines from 97.5 mV dec^(–1)(pristine CC)to 55.9 mV dec–1(PN-CC),showing an increased OER kinetic.Additionally,PN-CC electrocatalyst shows outstanding stability after 5000 cycles or 25000 s.The combination of plasma and acid treatment shows a significant potential in surface modification for electrocatalysts.

Electro-oxidation treatment of Sn/PANI electrode and electrocatalytic activity of Pt/Sn hydroxide/PANI composite electrodes

After being electro-oxidized by cyclic voltammetry(CV) method in 0.5 mol/L H2SO4 solution or in 0.2 mol/L H2O2+0.5 mol/L H2SO4 solution, the Sn/polyaniline (PANI) electrodes were modified with Pt microparticles by pulse galvanostatic method, thus Pt/Sn hydroxide/PANI electrodes were prepared. The electrocatalytic activities of the Pt/Sn/PANI electrode and Pt/Sn hydroxide/PANI electrode for formaldehyde electro-oxidation were investigated by CV method. The effects of deposition charges (Qdep) of PANI, Sn and Pt, scan rate and formaldehyde concentration on the electrocatalytic activity of Pt/Sn hydroxide/PANI electrode were also studied. The results show that the electrocatalytic activities of the Pt/Sn hydroxide/PANI electrodes are much higher than those of the Pt/Sn/PANI electrode.

Electrocatalytic Activity of Ni/C Electrodes Prepared by Metal Vapor Synthesis For Hydrogen Evolution in Alkaline Solution

The metal vapor synthesis (MVS) methed was used to prepare activatedcarbon supported nickel electrode. The electrocatalytic activity of the electrode forhydrogen evolution reaction(HGR) in alkaline solution was studied. Cathodicpolarization curves showed the electrocatalytic activity of Ni/C electrode prepared byMVS method was higher than that of the one prepared by conventional method.

Electrocatalytic Activity of Tungsten Carbide and Natural Zeolite Composite in Aqueous Solution

Tungsten carbide and zeolite nanocomposite was prepared by combining a mechanochemical approach with a reduction and carbonization approach,using natural zeolite and ammonia metatungstate as precursors.The sample was characterized by X-ray diffraction and scanning electron microscope.The results showed that the crystal phase of the sample is composed of zeolite,monotungsten carbide and bitungsten carbide.The mass percentage and the crystallite diameter of tungsten carbide change along with the reacted time.Its electrocatalytic activity was measured with a microelectrode system with three electrodes.The results show that its electrocatalytic property is related to its crystal phase and the mass percentage of tungsten carbide,and its electrocatalytic activity is connected with the property of electrolyte,in which it is measured.Synergistic effect between tungsten carbide and zeolite is found during electrocatalysis.

THE ELECTROCATALYTIC ACTIVITY OF NiCo2O4 FOR THE OXYGEN EVOLUTION REACTION

A spinel oxide NiCo204 prepared by thermal decomposition is of very high activity for the oxygen evolution reaction(OER)in alkaline solution.The oxygen evolution overpotential on NiCo204 is 0.252-0.262V in 10 M NaOH solution at 343K and current density 100 mAcm^(-2).

Iron Species-Impregnated Granular Activated Carbon as Modified Particle Electrodes Applied in Benzothiazole Adsorption and Electrocatalytic Degradation

The object of this study is to prepare iron species-impregnated granular activated carbon as particle electrodes in order to improve their adsorption and electrocatalytic degradation capacity in Benzothiazole removal.The incorporation of Fe-containing catalysts was performed by Fe(NO_3)_3 impregnation.The obtained samples were characterized by BET,Fourier transform infrared spectroscopy,SEM-EDS,powder X-ray diffraction,X-ray photoelectron spectra and TG.Compared with pure activated carbon,this modified particle electrodes show higher static adsorption capacities and TOC removal,which have respectively increased by25.9% and 54.4%.Both physisorption and chemisorption exist in the process of benzothiazole adsorption,where the latter plays a major role.In this way,the Fe-containing catalysts on modified particle electrodes are demonstrated to make a greater contribution to the improvement of electrocatalytic degradation by decreasing the activated energy by 32%.

Enhanced performance in the direct electrocatalytic synthesis of ammonia from N2 and H2O by an in-situ electrochemical activation of CNT-supported iron oxide nanoparticles

The direct electrocatalytic synthesis of ammonia from N2 and H2O by using renewable energy sources and ambient pressure/temperature operations is a breakthrough technology,which can reduce by over 90%the greenhouse gas emissions of this chemical and energy storage process.We report here an in-situ electrochemical activation method to prepare Fe2O3-CNT(iron oxide on carbon nanotubes)electrocatalysts for the direct ammonia synthesis from N2 and H2O.The in-situ electrochemical activation leads to a large increase of the ammonia formation rate and Faradaic efficiency which reach the surprising high values of 41.6μg mgcat^−1 h^−1 and 17%,respectively,for an in-situ activation of 3 h,among the highest values reported so far for non-precious metal catalysts that use a continuous-flow polymer-electrolytemembrane cell and gas-phase operations for the ammonia synthesis hemicell.The electrocatalyst was stable at least 12 h at the working conditions.Tests by switching N2 to Ar evidence that ammonia was formed from the gas-phase nitrogen.The analysis of the changes of reactivity and of the electrocatalyst characteristics as a function of the time of activation indicates a linear relationship between the ammonia formation rate and a specific XPS(X-ray-photoelectron spectroscopy)oxygen signal related to O2−in iron-oxide species.This results together with characterization data by TEM and XRD suggest that the iron species active in the direct and selective synthesis of ammonia is a maghemite-type iron oxide,and this transformation from the initial hematite is responsible for the in-situ enhancement of 3-4 times of the TOF(turnover frequency)and NH3 Faradaic efficiency.This transformation is likely related to the stabilization of the maghemite species at CNT defect sites,although for longer times of preactivation a sintering occurs with a loss of performances.

INVESTIGATION OF SURFACE MORPHOLOGY, STRUCTURE AND ELECTROCATALYTIC PROPERTIES FOR O_2 EVOLUTION OF TITANIUM BASED IrO_2+Ta_2O_5 COATINGS

Titanium based IrO2 +Ta2O5 oxide anodes with different compositions and pyrolysis temperatures were prepared by termodecompoisition method. By using X-ray diffraction (XRD), the structure and texture coefficient of the coatings, TC(hkl), of IrO2 rutile crystal have been tested. It showed that, the crystallization processes of IrO2 and Ta2O5 in xIrO2 +(100-x) Ta2 O5 (x is in mol%) films affected and confined each other.In the mixed system, IrO2 rutile phase existed as a solid solution with Ta, and attained the maximum solubility when x=70mol%, i.e. for the coating of 70% IrO2 +Ta2O5.For the coatings of low iridium content or at low preparing tem pemture, (110) and (101) pwtered orientations were dominant. However, preferred growth of IrO2 weakened with increasing either iridium content or temperature. Three typical surface morphologies were observed by using scanning electron tnicroscopy(SEM). The crystallite size of the mixed oxide coatings were finest for the the film of 70%IrO2 +30%Ta2O5,and decreased with the pyrolysis tempemture. As the results of the finest crystallite segregating on sudece and the maxitnum solid solubility of Ir and Ta component in deposits, the coatings with the composition of 70%IrO2 +Ta2O5 prepared at 450℃ presented the mdrimutn electrocatalgtic activitg for O2 evolution in 0. 5M H2SO4 solution.UP to 550℃, Ti base suffered to oxidation resulting in decreasing anode conductivity,therefore, coatings performed a low activity.

Substitute of Expensive Pt with Improved Electrocatalytic Performance and Higher Resistance to CO Poisoning for Methanol Oxidation: the Case of Synergistic Pt-Co_3O_4 Nanocomposite

In this paper, Pt-Co_3O_4 nanocomposite was synthesized by a sol gel process combined with electrodeposition method. Its electrocatalytic activity towards methanol oxidation was investigated at room temperature using cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS) and current density time curve. It is found that the resultant Pt-Co_3O_4 catalysts with minute amount of Pt exhibite attractive electrocatalytic activity for methanol oxidation reaction(MOR) but with a high resistance CO poisoning due to the synergistic effects from Pt and Co_3O_4. Together with the low manufacturing cost of Co_3O_4, the reported nanostructured Pt-Co_3O_4 catalyst is expected to be a promising electrode material for direct methanol fuel cells(DMFC).

Preparation and electrocatalytic properties of Ti/IrO_2-Ta_2O_5 anodes for oxygen evolution

The preparation and electrocatalytic activity for oxygen evolution of the thermally prepared Ti anodes coated with IrO2-Ta2O5 were studied. The structure and morphologies of the oxide films with different contents of IrO2 were determined by XRD and SEM respectively. Their electrochemical properties were studied by Linear Sweep Voltammetry, Tafel Plot and Cyclic Voltammetry. The results show that iridium and tantalum can form solid solution and the mutual solubility is affected by the ratio of Ir to Ta in coating solution. With increasing IrO2 content in the coatings, the amount of fine crystallites of IrO2 is increased and the electrocatalytic capability of oxygen evolution is strengthened. The coating adhesion and rigidity decrease, which affects electrochemical activity of the anode when the content of IrO2 is too high. The electrochemically active surface area is determined not only by the content of IrO2but also the structure and morphology of the anode coatings. It is probably due to the existence of proper quantities of inert Ta2O5 which results in a typical morphology of cracks and solid solution structure.

Amorphous MoS_(3) enriched with sulfur vacancies for efficient electrocatalytic nitrogen reduction

Developing low-priced,yet effective and robust catalysts for the nitrogen reduction reaction(NRR) is of vital importance for scalable and renewable electrochemical NH3 synthesis.Herein,we provide the first demonstration of MoS_3 as an efficient and durable NRR catalyst in neutral media.The prepared amorphous MoS_3 naturally possessed enriched S vacancies and delivered an NH3 yield of 51.7 μg h^(-1) mg^(-1)and a Faradaic efficiency of 12.8% at-0.3 V(RHE) in 0.5 M LiClO_4,considerably exceeding those of MoS_2 and most reported NRR catalysts.Density functional theory calculations unraveled that S vacancies involved in MoS_3 played a crucial role in activating the NRR via a consecutive mechanism with a low energetics barrier and simultaneously suppressing the hydrogen evolution reaction.

Synthesis of monodisperse palladium nanocubes and their catalytic activity for methanol electrooxidation

The single crystalline palladium nanocubes with an average size of 7 nm were prepared in the presence of poly （vinyl pyrrolidone） （PVP） and KBr using the polyol method. The as-prepared Pd nanocubes were highly uniform in both size and shape. The ordered packing structures including monolayer and multilayer can be fabricated via the rate-controlled evaporation of solution solvent. The electrochemical catalytic activity of these Pd nanocubes towards methanol oxidation was found to be higher than that of spherical Pd nanoparticles of similar size.

Effect of Rotation Rate on the Formation of Platinum-modified Polyaniline Film and Electrocatalytic Oxidation of Methanol

The oxidation of methanol was investigated on platinum-modified polyaniline electrode. Changes in the electrode rotation rates (Ω) during platinum electrodeposition remarkably affect the formation and distribution of platinum in the polymer matrix and consequently lead to different currents of methanol oxidation. The results show that platinum loading is proportional to rotation ratesΩ1/2.

Electrosynthesis, Characterization and Electrocatalytic Behaviour of Organic-Metal Thin-Films Based on 2,2’-Bithiophene-5-carboxylic Acid and Metal Ions

2,2’-Bithiophene-5-carboxylic acid (BTA) thin-films on platinum (Pt) electrodes were electrochemically prepared in acetonitrile solution containing 0.1 M tetrabutylammonium perchlorate (TBAP) and 0.05 M BTA. These films were complexes with several metal ions such as Cu2+, Ag+ and Co2+. Their structural characteristics were compared with those of powder complexes chemically prepared from BTA and the corresponding metal ion. IR and XPS techniques reveal that the film complexes with metal ions have the same structures as the corresponding powder complexes. The electrocatalytic activity of BTA film-metal ions has been investigated toward ascorbic acid (AA) oxidation and compared to that obtained on a free BTA film. BTA film-metal ions exhibit good catalytic proprieties and better detection of AA than a free BTA film. This new propriety allows these films to be used as electrochemical sensors. This electronic document is a “live” template. The various components of your paper [title, text, heads, etc.] are already defined on the style sheet, as illustrated by the portions given in this document.