Templated synthesis, characterization, and sensing application of macroscopic platinum nanowire network electrodes

Novel platinum nanowire network electrodes have been fabricated through electrodeposition using mesoporous silica thin films as templates. These electrodes were characterized by X-ray diffraction, transmission electron microscope, and scanning electron microscope. The electrochemical properties of the electrodes, such as electrochemical active area and methanol oxidation, have also been studied. Compared with conventional polycrystalline Pt electrodes, these novel nanowire network electrodes possess high electrochemical active areas and demonstrate higher current densities and a lower onset potential for methanol electro-oxidation. Enzymatic Pt nanowire-network-based sensors show higher sensitivity for glucose detection than that using conventional polycrystalline Pt electrode. Such macroscopic nanowire network electrodes provide ideal platforms for sensing and other device applications.     

Comparison of Micro- and Nano-Pore Platinum Working Electrodes for CMOS Integrated Nondisposable Biosensor Applications

In this paper, micro-pore and nano-pore platinum (Pt) electrodes are fabricated, characterized, and compared in order to check the effects of the pore sizes of the working electrode in the electrochemical analysis. These electrodes are also fabricated on silicon substrate for developing nondisposable and continuous monitoring biosensors fully integrated with a CMOS read out circuit. The micro-pore Pt electrode was fabricated by using micromachining technique. The nano-pore Pt electrode was fabricated by using a nonionic surfactant C ₁₆EO₈ (octaethylene glycol monohexadecyl ether) and an electrodeposition technique. The micro-pore array Pt electrode has approximately 10 mum in pore diameter and 80 mum in height, while the nano-pore array Pt electrode has approximately 2.5 nm in diameter. The measured current responses of the fabricated nano-pore, micro-pore, and plane Pt electrodes are approximately 4600 nA/mm² , 92.4 nA/mm², and 9.9 nA/mm² in 0.1 M phosphate buffered saline solution mixed with 10 mM glucose solution, respectively     

Fabrication of graphene–platinum nanocomposite for the direct electrochemistry and electrocatalysis of myoglobin

In this paper a platinum (Pt) nanoparticle decorated graphene (GR) nanosheet was synthesized and used for the investigation on direct electrochemistry of myoglobin (Mb). By integrating GR–Pt nanocomposite with Mb on the surface of carbon ionic liquid electrode (CILE), a new electrochemical biosensor was fabricated. UV-Vis absorption and FT-IR spectra indicated that Mb remained its native structure in the nanocomposite film. Electrochemical behaviors of Nafion/Mb–GR–Pt/CILE were investigated with a pair of well-defined redox peak appeared, which indicated that direct electron transfer of Mb was realized on the underlying electrode with the usage of the GR–Pt nanocomposite. The fabricated electrode showed good electrocatalytic activity to the reduction of trichloroacetic acid in the linear range from 0.9 to 9.0 mmol/L with the detection limit as 0.32 mmol/L (3σ), which showed potential application for fabricating novel electrochemical biosensors and bioelectronic devices.     

Electrochemical degradation of chlorobenzene on boron-doped diamond and platinum electrodes

In this paper the electrochemical degradation of chlorobenzene (CB) was investigated on boron-doped diamond (BDD) and platinum (Pt) anodes, and the degradation kinetics on these two electrodes was compared. Compared with the total mineralization with a total organic carbon (TOC) removal of 85.2% in 6 h on Pt electrode, the TOC removal reached 94.3% on BDD electrode under the same operate condition. Accordingly, the mineralization current efficiency (MCE) during the mineralization on BDD electrode was higher than that on the Pt electrode. Besides TOC, the conversion of CB, the productions and decay of intermediates were also monitored. Kinetic study indicated that the decay of CB on BDD and Pt electrodes were both pseudo-first-order reactions, and the reaction rate constant (k_s) on BDD electrode was higher than that on Pt electrode. The different reaction mechanisms on the two electrodes were investigated by the variation of intermediates concentrations. Two different reaction pathways for the degradation of CB on BDD electrode and Pt electrode involving all these intermediates were proposed.     

Nano iron oxide (Fe2O3)/carbon black electrodes as electrode material for electrochemical capacitors: Effect of the nanoparticles dispersion quality

In the present study, nano Fe₂O₃/carbon black electrodes are proposed for electrochemical capacitors and the effect of nanoparticles dispersion quality on the surface morphology, nature and electrochemical properties of the electrodes are investigated. Mechanical pressing is accompanied by different mixing (mechanical and sonication) processes to prepare the electrode. Electrochemical properties of the produced nanocomposites are studied using cyclic voltammetry and electrochemical impedance spectroscopy tests in 2 M KCl electrolyte. Scanning electron microscopy is used to characterize the microstructure and the nature of the nanoparticles on the nanocomposites produced. Results obtained show that the sonicated and unsonicated 10:80:10 (CB:Fe₂O₃:PTFE) electrodes have specific capacitance of 22.02 and 22.35 F g⁻¹ respectively, at scan rate of 10 mV s⁻¹. Sonication process breaks the agglomerated particles and disperses them on the electrode surface, uniformly. This increases the specific surface area and the electrical resistance of the electrodes. The sonicated electrodes show a higher charge separation capability at electrolyte/electrode interfaces, lower ratio of outer to total charge (q_O*/q_T*) of 0.13 and lower current response at end potentials. Energy density was increased after the sonication process from 0.686 to 1.498 (Wh kg⁻¹). Charge/discharge cycling results confirmed that the uniform dispersion of active material on the electrode surface postpones the electrolyte decomposition and improves the electrical conductivity during cycling.     

Low-cost quasi-solid-state dye-sensitized solar cells based on a metal-free organic dye and a carbon aerogel counter electrode

Low-cost quasi-solid-state dye-sensitized solar cells (DSSCs) are designed and fabricated by using a metal-free organic dye and a mesoporous carbon aerogel instead of expensive ruthenium-based sensitizers and Pt electrode. The electrospun TiO₂ nanorods are added into a polyvinylidene fluoride (PVDF) solution to form a 3D network nanocomposite gel electrolyte. The presence of TiO₂ nanorods in the gel electrolyte obviously increases the ionic conductivity and decreases charge-transfer resistance of the DSSC. The effects of the gel electrolyte and the carbon aerogel counter electrode on electrochemical and photovoltaic properties have been investigated in detail. Particularly, an optimized DSSC with a nanocomposite gel electrolyte and a carbon aerogel counter electrode affords a power conversion efficiency (PCE) of 6.20% at a light intensity of 100 mW cm⁻².     

Biosensor enhanced by glucose oxidase biomimetic membrane containing the platinum and silica nanoparticles

In this paper, glucose biosensor is fabricated with immobilization of glucose oxidase (GOx) in platinum and silica sol. The glucose biosensor combined with Pt and SiO₂ nanoparticles could make full use of the properties of nanoparticles. A set of experimental results indicates that the current response for the enzyme electrode containing platinum and silica nanoparticles increases from 0.32 µA cm^− 2 to 33 µA cm^− 2 in the solution of 10 mM β-D-glucose. The linear range is 3 × 10^− 5 to 3.8 × 10^− 3 M with a detection limit of 2 × 10^− 5 M at 3σ. The effects of the various volume ratios of Pt and SiO₂ sols with respect to the current response and the stability of the enzyme electrodes are studied.     

Electrochemical strategy with zeolitic imidazolate framework‐8 and ordered mesoporous carbon for detection of xanthine

An accurate, safe, environmentally friendly, fast and sensitive electrochemical biosensors were developed to detect xanthine in serum. The metal‐organic framework ZIF‐8 was synthesised and elemental gold was supported on the surface of ZIF‐8 by reduction method to synthesise Ag‐ZIF‐8. The mesoporous carbon material and the synthesised Ag‐ZIF‐8 were, respectively, applied to a glassy carbon electrode to construct biosensors. The constructed biosensor has a good linear relation in the range of 1–280 μmol l⁻¹ of xanthine and the detection limit is 0.167 μmol l⁻¹. The relative standard deviation value in serum samples was <5%, and the recoveries were 96–106%, indicating the good selectivity, stability and reproducibility of this electrochemical biosensor.Inspec keywords: zeolites, electrochemical sensors, voltammetry (chemical analysis), mesoporous materials, biosensors, gold, reduction (chemical), nanosensors, nanofabrication, organic compounds, electrochemical electrodes, carbon, nanoparticlesOther keywords: xanthine, detection limit, serum samples, zeolitic imidazolate framework‐8, sensitive electrochemical biosensors, metal‐organic framework ZIF‐8, elemental gold, reduction method, mesoporous carbon material, glassy carbon electrode, linear relation, ordered mesoporous carbon, Ag, C     

Preparation and characterization of poly(3,4-ethylenedioxythiophene)–poly(styrene sulfonate) composite thin films highly loaded with platinum nanoparticles

In this work, we propose a simple and efficient, low-temperature (∼120 °C) process to prepare transparent thin films of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS) loaded with high concentration (up to 22.5 wt%) of platinum (Pt) nanoparticles. Firstly, an improved polyol method was modified to synthesize nano-sized (∼5 nm) and mono-dispersed Pt particles. These nanoparticles were incorporated into the matrix of PEDOT:PSS thin films via a spin coating/drying procedure. The electrochemical activities of the PEDOT:PSS thin film modified electrodes with respect to the I⁻/I₃⁻ redox reactions were investigated. It was found that the modified electrode of PEDOT:PSS thin film containing 22.5 wt% Pt exhibited the electrochemical activity comparable to the conventional Pt thin film electrode, suggesting that this electrode has good potential to serve as a counter electrode in dye-sensitized solar cells.     

Layer-by-layer assemblies of chitosan/multi-wall carbon nanotubes and glucose oxidase for amperometric glucose biosensor applications

A novel amperometric glucose biosensor based on multilayer films containing chitosan, multi-wall carbon nanotubes (MWCNTs) and glucose oxidase (GOD) was developed. MWCNTs were solubilized in chitosan (Chit-MWCNTs) used to interact with GOD. Poly (allylamine) (PAA) and polyvinylsulfuric acid potassium salt (PVS) were alternately deposited on the cleaned Pt electrode surface ((PVS/PAA)₃/Pt). The (PVS/PAA)₃/Pt electrode was alternately immersed in Chit-MWCNTs and GOD to assemble different layers of multilayer films. PBS washing was applied at the end of each assembly deposition for dissociating the weak adsorption. Micrographs of MWCNTs were obtained by scanning electron microscope, and properties of the resulting biosensors were measured by electrochemical measurements. Among the resulting biosensors, the biosensor based on eight layers of multilayer films was best. The resulting biosensor was able to efficiently monitor glucose, with the response time within 8 s, a detection limit of 21 μM estimated at a signal-to-noise ratio of 3, a linear range of 1–10 mM, the sensitivity of 0.45 μA/mM, and well stability. The study can provide a feasible simple approach on developing a new immobilization matrix for biosensors and surface functionalization.     

Preparation of Pt/multiwalled carbon nanotubes modified Au electrodes via Pt–Cu co-electrodeposition/Cu stripping protocol for high-performance electrocatalytic oxidation of methanol

Pt nanoparticles well dispersed on multiwalled carbon nanotubes (MWCNTs) were prepared for high-performance electrocatalytic oxidation of methanol in both acidic and alkaline media via the co-electrodeposition/stripping (CS) protocol, namely, co-electrodeposition of Pt and Cu followed by electrochemical stripping of Cu, as examined by cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The Pt catalyst prepared by the CS protocol on MWCNTs (Pt_cs/MWCNTs/Au) exhibited a specific electrocatalytic activity of 519 and 2210 A g⁻¹ toward cyclic voltammetric electrooxidation (50 mV s⁻¹) of methanol in 0.5 M CH₃OH + 0.5 M H₂SO₄ and 0.5 M CH₃OH + 1.0 M NaOH media, respectively, which are larger than those prepared by conventional electrodeposition from chloroplatinic acid on Au and MWCNTs/Au, as well as that by a CS protocol on Au. The Pt_cs/MWCNTs/Au electrode also possessed the highest stability, which maintained 91% and 90% of its initial catalytic activity after 120-cycle CV in 0.5 M CH₃OH + 0.5 M H₂SO₄ and 0.5 M CH₃OH + 1.0 M NaOH, respectively. The electrode kinetics of methanol oxidation is also briefly discussed. The nanosubstrate-based CS protocol is simple, convenient and efficient, which is expected to find wide applications in film electrochemistry and electrocatalysis.     

Supercapacitor Electrodes Based on Hierarchical Mesoporous MnOx/Nitrided TiO2 Nanorod Arrays on Carbon Fiber Paper

Metal nitride nanoarrays are attractive to electrochemical energy storage and in this work, hierarchical mesoporous manganese oxide (MnO_x) nanoflakes and nitrided TiO₂ nanorod arrays (NTNA) are prepared on carbon fiber paper (CFP) by hydrothermal synthesis and electrodeposition. The MnO_x/NTNA/CFP electrode delivers outstanding electrochemical performance such as high areal capacitance of 327 mF cm⁻² at a current density of 0.25 mA cm⁻² and good cycling stability with 96% retention after 5000 cycles. Compared to the MnO_x/TiO₂/CFP and MnO_x/CFP electrodes, the MnO_x/NTNA/CFP electrode possesses better electrochemical properties such as higher areal capacitance, better electrochemical activity, and cycling life. The enhanced performance can be attributed to the nitrided TiO₂ nanorod arrays with higher conductivity offering low electrochemical impedance and fast ion/electron transfer. The MnO_x/NTNA/CFP electrode is a promising candidate in high‐performance supercapacitor applications.     

Highly Stable Vanadium Redox‐Flow Battery Assisted by Redox‐Mediated Catalysis

With good operation flexibility and scalability, vanadium redox‐flow batteries (VRBs) stand out from various electrochemical energy storage (EES) technologies. However, traditional electrodes in VRBs, such as carbon and graphite felt with low electrochemical activities, impede the interfacial charge transfer processes and generate considerable overpotential loss, which significantly decrease the energy and voltage efficiencies of VRBs. Herein, by using a facile electrodeposition technique, Prussian blue/carbon felt (PB/CF) composite electrodes with high electrochemical activity for VRBs are successfully fabricated. The PB/CF electrode exhibits excellent electrochemical activity toward VO²⁺/VO₂⁺ redox couple in VRB with an average cell voltage efficiency (VE) of 90% and an energy efficiency (EE) of 88% at 100 mA cm^?2. In addition, due to the uniformly distributed PB particles that are strongly bound to the surface of carbon fibers in CF, VRBs with the PB/CF electrodes show much better long‐term stabilities compared with the pristine CF‐based battery due to the redox‐mediated catalysis. A VRB stack consisting of three single cells (16 cm²) is also constructed to assess the reliability of the redox‐mediated PB/CF electrodes for large‐scale application. The facile technique for the high‐performance electrode with redox‐mediated reaction is expected to shed new light on commercial electrode design for VRBs.     

Poly(N-vinyl carbazole) and carbon nanotubes based composites and their application to rechargeable lithium batteries

In order to prepare poly(N-vinyl carbazole) (PVK) and carbon nanotube (CNs) based composites, electrochemical polymerization of N-vinyl carbazole (NVK) was studied by cyclic voltammetry (CV) in LiClO₄/acetonitrile solutions. Cyclic voltammograms recorded on a blank Pt electrode and those obtained when single or multi-walled carbon nanotubes (SWNTs or MWNTs) films were previously deposited onto the Pt electrode show a down-shift of the VK reduction peak potential in the latter case. The influence of monomer concentration and supporting electrolyte on the polymerization conditions and electrochemical properties of these composite materials were also investigated. Morphologic aspects as well as the photoluminescence properties of the PVK/CNs composite were also investigated. A covalent functionalization of carbon nanotubes with PVK is suggested on the basis of infrared (IR) spectroscopic studies. Using the PVK/CN composite as a positive electrode and an electrolytic solution containing LiPF₆, a higher specific discharge capacity of the rechargeable lithium cells, ∼45 and 115 mA h g⁻¹, are reported for PVK functionalized SWNTs and MWNTs, respectively.     

Pt/AlPO4 nanocomposite thin-film electrodes for ethanol electrooxidation

The enhanced catalytic properties toward ethanol electrooxidation on Pt/AlPO₄ nanocomposite thin-film electrodes were investigated. The Pt/AlPO₄ nanocomposites with various Al/Pt ratios (0.27, 0.57, and 0.96) were fabricated by a co-sputtering method. All of the Pt/AlPO₄ nanocomposites showed a negative shift in the onset potential and a higher current density than those of pure Pt electrode for the electrooxidation of ethanol. Among the various Pt/AlPO₄ nanocomposite thin-film electrodes, the electrode with an atomic ratio of Al to Pt of 0.57 showed the highest electrocatalytic activity for ethanol electrooxidation. The activation enthalpy for the optimum Pt/AlPO₄ nanocomposite was approximately 0.05 eV lower than that of pure Pt. It is believed that the enhancement in catalytic activity is due to the electron-rich Pt resulting from the Fermi-energy difference between Pt and AlPO₄.     

Ultrahigh Mass Activity Pt Entities Consisting of Pt Single atoms,Clusters, and Nanoparticles for Improved Hydrogen Evolution Reaction

Platinum is one of the best-performing catalysts for the hydrogen evolution reaction (HER). However, high cost and scarcity severely hinder the large-scale application of Pt electrocatalysts. Constructing highly dispersed ultrasmall Platinum entities is thereby a very effective strategy to increase Pt utilization and mass activities, and reduce costs. Herein, highly dispersed Pt entities composed of a mixture of Pt single atoms, clusters, and nanoparticles are synthesized on mesoporous N-doped carbon nanospheres. The presence of Pt single atoms, clusters, and nanoparticles is demonstrated by combining among others aberration-corrected annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, and electrochemical CO stripping. The best catalyst exhibits excellent geometric and Pt HER mass activity, respectively ≈4 and 26 times higher than that of a commercial Pt/C reference and a Pt catalyst supported on nonporous N-doped carbon nanofibers with similar Pt loadings. Noteworthily, after optimization of the geometrical Pt electrode loading, the best catalyst exhibits ultrahigh Pt and catalyst mass activities (56 ± 3 A mg⁻¹_Pt and 11.7 ± 0.6 A mg⁻¹_Cat at −50 mV vs. reversible hydrogen electrode), which are respectively ≈1.5 and 58 times higher than the highest Pt and catalyst mass activities for Pt single-atom and cluster-based catalysts reported so far.     

Preparation and characterization of biocompatible carbon electrodes

Electron transfer in microbial fuel cell and biosensors could be facilitated through high conductive materials with enhanced active surface area and appropriate redox potential suited to microbial metabolism. In the first strategy based on bulk doping, graphite/epoxy composite electrode (GECE) bulk was modified with six types of metal ion which were prepared through a wet impregnation procedure. In the second strategy, immobilization of redox dye on carbon cloth and graphite sheet was carried out using N,N′-dicyclohexylcarbodiimide for surface modification. Crystallinity, morphology, surface chemistry and electrochemical properties of all modified electrodes were investigated. Influence of redox behavior of electrodes suited to microbial metabolism and conducive to biofilm formation have been examined. It was observed that the Fe³⁺ doped GECE surfaces exhibited significantly high biofilm formation of 1.10(±0.18) × 10⁷ CFU/cm² as compared to other dopants. The microbial growth on the carbon cloth electrode and carbon fiber reinforced plate were found to be less (2.6(±0.97) × 10⁴, 4.8(±1.8) × 10³ CFU/cm² respectively) compared to GECEs.     

Effects of swift copper (Cu2+) ion irradiation on structural,optical and electrochemical properties of Co3O4-CuO-MnO2/GO nanocomposites powder

The properties of conjugated and irradiated Co₃O₄-CuO-MnO₂/GO nanostructured nanocomposites powder for possible applications in various sphere of life were studied in this research work. The hydrothermal technique was employed to the synthesis of high quality nanocomposite powder and dr. blades technique was employed to construct thin films known as electrodes. The properties of Co₃O₄-CuO-MnO₂/GO nanostructured composite powder (electrodes) were evaluated using SEM, EDS, XRD, FTIR and DRS. The electrochemical properties were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a 1.0 M solution of Na₂SO₄ electrolytic solution with a triple electrodes arrangement. The electrode irradiated with 2.25 × 10¹⁵ ions/cm² offered the highest specific capacitance of 1590 F/g at a scan rate of 10 mV/s. The results of electrochemical studies indicate that the combination of three transition metal oxides with GO irradiated by moderate ions is a noble contender for electrode applications.     

Electrocatalytic activity of surface atoms of platinum supported on silicon

The influence of a carrier matrix on the electrocatalytic activity of platinum nanoparticles with respect to the reaction of methanol oxidation in an acid medium has been studied using a cyclic voltammetry technique. Platinum nanoparticles were formed on the surface of carbon black (commercial E-TEK type catalyst), p-type silicon single-crystals wafers with different resistivities, and mesoporous silicon. It is established that the activity of surface Pt atoms is higher for platinum nanoparticles supported on silicon than on carbon black. An increase in the resistivity of silicon favors growth in the catalytic activity of platinum. The most pronounced carrier effect is produced by the mesoporous silicon matrix.     

Determination of alcohols using a Ni-Pt alloy amperometric sensor

An amperometric sensor for monitoring ethanol concentration using a Ni-Pt alloy electrode has been developed. The films of Ni-Pt alloy were electrodeposited under various potentials on an Au/Al₂O₃ substrate. To examine the effects of Ni-Pt alloy films on the sensing performance, the electrodes with various Ni:Pt atomic proportions of 100:0, 25:75, 70:30, 82:18 and 0:100 were prepared and tested. X-ray diffraction and scanning electron microscope analyses indicate that Ni atoms of Ni-Pt alloy electrodes are inserted in the Pt lattice and a pyramid-like structure is formed with an increase of Pt content in the film. All the prepared electrodes have a linear relationship between response current and ethanol concentration for the detection range of 50 to 300 ppm ethanol in alkaline solutions. With an increase of Pt content in the film, the response time of the Ni-Pt alloy electrodes was reduced whereas the sensitivity was decreased. The sensor with 70 at.% Pt in the film was most stable with the duration over a 63-day-period. The sensitivity of the Ni-Pt alloy electrodes for detecting glucose, various alcohols and acids have also been studied.