Ag/ZnO Catalysts with Different ZnO Nanostructures for Non‐enzymatic Detection of Urea

Silver coated ZnO nanorods and nanoflakes with different crystallographic orientations were synthesized by a combination of sputter deposition and solution growth process. Catalytic properties of morphology‐dependent Ag/ZnO nanostructures were then investigated for urea sensors without enzyme. Ag/ZnO nanorods on carbon electrodes exhibit a higher catalytic activity and an improved efficiency than Ag/ZnO nanoflakes on carbon electrodes. Ag/ZnO nanorod catalysts with more electrochemically surface area (169 cm² mg^?1) on carbon electrode facilitate urea electrooxidation due to easier electron transfer, which further promotes the urea electrolysis. The Ag/ZnO nanorod catalysts also show a significant reduction in the onset voltage (0.410 V vs. Ag/AgCl) and an increase in the current density (12.0 mA cm^?2 mg^?1) at 0.55 V vs Ag/AgCl. The results on urea electrooxidation show that Ag/ZnO nanostructures can be a potential catalyst for non‐enzymatic biosensors and fuel cells.     

Heterostructured CoO/3D-TiO<Subscript>2</Subscript> nanorod arrays for photoelectrochemical water splitting hydrogen production

Homogeneous p-type cobalt (II) oxide (CoO) nanoparticles were successfully deposited on n-type three-dimensional branched TiO₂ nanorod arrays (3D-TiO₂) through photochemical deposition and thermal decomposition to form a novel CoO/3D-TiO₂ p-n heterojunction nanocomposite. Due to the narrow band gap of CoO nanoparticles (~2.4 eV), the as-synthesized CoO/3D-TiO₂ exhibited an excellent visible light absorption. The amounts of deposited CoO nanoparticles obviously influence the hydrogen production rate in the photoelectrochemical (PEC) water splitting. The as-synthesized CoO/3D-TiO₂-5 obtains the highest PEC hydrogen production rate of 0.54 mL h^?1 cm^?2 after five-time CoO deposition cycles (at a potential of 0.0 V vs Ag/AgCl). The photocurrent density of CoO/3D-TiO₂-5 is 1.68 mA cm^?1, which is ca. 2.5 times greater than that of pure 3D-TiO₂. The results showed that the formation of internal electrical-field between the CoO/3D-TiO₂ heterojunction, which has a direction from n-type TiO₂ to p-type CoO, facilitated the charge separation and transfer and resulted in a high efficiency and stable PEC activity.     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A novel architecture of CdS/ZnO nanorods with plasmonic silver (Ag) nanoparticles deposited at the interface of ZnO nanorods and CdS nanocrystallites, was designed as a photoanode for solar hydrogen generation, with photocurrent density achieving 4.7 mA/cm² at 1.6 V (vs. RHE), which is 8 and 1.7 times as high as those of pure ZnO and CdS/ZnO nanorod films, respectively. Additionally, with optical absorption onset extended to ～660 nm, CdS/Ag/ZnO nanorod film exhibits significantly increased incident photo-to-current efficiency (IPCE) in the whole optical absorption region, reaching 23.1% and 9.8% at 400 nm and 500 nm, respectively. The PEC enhancement can be attributed to the one-dimensional ZnO nanorod structure maintained for superior charge transfer, and the extended visible-light absorption of CdS nanocrystallites. Moreover, the incorporated plasmonic Ag nanoparticles could further promote the interfacial charge carrier transfer process and enhance the optical absorption ability, due to its excellent plasmon resonance effect.     

Anodized Iron Oxide Nanostructures on Different Carbon Steels for Photoelectrochemical Water Splitting

In this study, two different nanostructural iron oxide films were prepared on two kinds of carbon steels (CS) with different contents of impurities via anodization in a mixture of aqueous ammonium fluoride solution and ethylene glycol, respectively, and apply to photoelectrochemical (PEC) water splitting. After annealing, iron oxide nanotubes (NTs) was coated on surface of lower purity CS and iron oxide nanoporous (NPs) was coated on surface of higher purity CS via scanning electron microscope. X‐ray diffraction pattern shows both of samples contain a major phase of α‐Fe₂O₃ and a slight phase of Fe₃O₄. Compared with NPs, NTs behaves better absorbance ability in visible spectra range via UV‐visible absorbance spectra. From PEC response, the iron oxide NTs showed higher water splitting performance (0.10 mA/cm² at 0.4 V vs. Ag/AgCl) than NPs (0.04 mA/cm² at 0.4 V vs. Ag/AgCl) due to better absorbance, higher car‐ rier concentration and low charge transfer resistance.     

UV-Visible and IR Spectroelectrochemical Properties of V2O5 Crystalline Films Charged/Discharged in Extended Potential Range

Electrochemical properties of amorphous and crystalline V₂O₅ films, dip-coated from V-oxoisopropoxide sols and thermally treated at various temperatures (100, 150, 200 and 300°C), have been studied in extended potential range, i.e. from 1.4 to –1.6 V vs. Ag/AgCl in 1M LiClO₄/propylen carbonate (PC) electrolyte. The formation of various lithiated (-, -, - and -Li _x V₂O₅) phases was correlated with the values of insertion coefficient x obtained from cyclic voltammograms (CV) of crystalline V₂O₅ films (300°C). Reversible charging was observed when films were cycled up to –1.0 V vs. Ag/AgCl, while the extension of the potential to –1.3 V vs. Ag/AgCl change the CV of films irreversibly. Charging of crystalline V₂O₅ films was followed by the help of in-situ UV-visible spectroscopy, that revealed the intensity variations of the polaron absorption above 600 nm and the presence of the absorbing V³⁺ species between 550 and 650 nm. Ex-situ IR spectra of the crystalline films charged/discharged at –1.6V/1.4V vs. Ag/AgCl confirmed the amorphisation of the films' structure.     

Cathodic stripping voltammetry of technetium in the tetraphenylarsonium chloride/chloroform extract at a hanging mercury drop electrode

Technetium(VII) was separated from interfering substances by extraction with 0.01M tetraphenylarsonium chloride in chloroform. To avoid back-extraction, enrichment at the hanging mercury drop electrode (HMDE) has been carried out directly in the organic phase after addition of 0.01M NaOH as an electrolyte and ethanol as a homogenized agent. By application of a deposition voltage of –1.6 V, as well as DPCSV, a distinct current signal at –0.26 V (vs. Ag/AgCl) was obtained. The detection limit was found to be 3·10^–8 M Tc.     

Cu2O-Ag Tandem Catalysts for Selective Electrochemical Reduction of CO2 to C2 Products

The electrochemical carbon dioxide reduction reaction (CO₂RR) to C₂ chemicals has received great attention. Here, we report the cuprous oxide (Cu₂O) nanocubes cooperated with silver (Ag) nanoparticles via the replacement reaction for a synergetic CO₂RR. The Cu₂O-Ag tandem catalyst exhibits an impressive Faradaic efficiency (FE) of 72.85% for C₂ products with a partial current density of 243.32 mA·cm⁻². The electrochemical experiments and density functional theory (DFT) calculations reveal that the introduction of Ag improves the intermediate CO concentration on the catalyst surface and meanwhile reduces the C-C coupling reaction barrier energy, which is favorable for the synthesis of C₂ products.     

Carbon fiber microelectrodes modified with carbon nanotubes as a new support for immobilization of glucose oxidase

Carboxylated carbon nanotubes were coated onto carbon microfiber electrodes to create a micron-scale bioelectrode. This material has a high surface area and can serve as a support for immobilization of enzymes such as glucose oxidase. A typical carbon nanotube loading of 13???g?cm^?1 yields a coating thickness of 17???m and a 2000-fold increase in surface capacitance. The modified electrode was further coated with a biocatalytic hydrogel composed of a conductive redox polymer, glucose oxidase, and a crosslinker to create a glucose bioelectrode. The current density on oxidation of glucose is 16.6?mA?cm^?2 at 0.5?V (vs. Ag/AgCl) in oxygen-free glucose solution. We consider this approach to be useful for designing and characterizing surface treatments for carbon mats and papers by mimicking their local microenvironment.

Sm0.5Sr0.5Co1−xNixO3−δ—A Novel Bifunctional Electrocatalyst for Oxygen Reduction/Evolution Reactions

The development of non-precious metal catalysts with excellent bifunctional activities is significant for air–metal batteries. ABO₃-type perovskite oxides can improve their catalytic activity and electronic conductivity by doping transition metal elements at B sites. Here, we develop a novel Sm_0.5Sr_0.5Co_1−xNi_xO_3−δ (SSCN) nanofiber-structured electrocatalyst. In 0.1 M KOH electrolyte solution, Sm_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ (SSCN82) with the optimal Co: Ni molar ratio exhibits good electrocatalytic activity for OER/ORR, affording a low onset potential of 1.39 V, a slight Tafel slope of 123.8 mV dec⁻¹, and a current density of 6.01 mA cm⁻² at 1.8 V, and the ORR reaction process was four-electron reaction pathway. Combining the morphological characteristic of SSCN nanofibers with the synergistic effect of cobalt and nickel with a suitable molar ratio is beneficial to improving the catalytic activity of SSCN perovskite oxides. SSCN82 exhibits good bi-functional catalytic performance and electrochemical double-layer capacitance.     

Bioactive Electroconductive Hydrogels: The Effects of Electropolymerization Charge Density on the Storage Stability of an Enzyme-Based Biosensor

Electrode-supported hydrogels were conferred with the biospecificity of enzymes during the process of electropolymerization to give rise to a class of bioactive, stimuli-responsive co-joined interpenetrating networks of inherently conductive polymers and highly hydrated hydrogels. Glucose responsive biotransducers were prepared by potentiostatic electropolymerization [750 mV vs. Ag/AgCl (3 M KCl)] of pyrrole at Poly(hydoxyethyl methacrylate)-based hydrogel-coated Pt micro-electrodes (Φ = 100 μm) from aqueous solutions of pyrrole and glucose oxidase (GOx; 0.4 M pyrrole, 1.0 mg/ml GOx) to 1.0 and 10.0 mC/cm². Polypyrrole was them over-oxidized by cyclic voltammetry (0–1.2 V vs. Ag/AgCl, 40 cycles in PBKCl, pH = 7.0). Biotransducers were stored at 4 °C in PBKCl for up to 18 days. Amperometric dose–response at 0.4 V vs. Ag/AgCl followed by Lineweaver–Burk analysis produced enzyme kinetic parameters as a function of electropolymerization charge density and storage time. Apparent Michaelis constant (K _Mapp) increased from 18.6–152.0 mM (1.0 mC/cm²) and from 2.7–6.1 mM (10.0 mC/cm²). Biotransducer sensitivity increased to 21.2 nA/mM after 18 days and to 12.8 pA/mM after 10 days for the 1.0 and 10.0 mC/cm² membranes, respectively. Maximum current, I _max, also increased over time to 2.7 nA (1.0 mC/cm²) and to 170 pA (10.0 mC/cm²). Electropolymerization of polypyrrole is shown to be an effective means for imparting bioactivity to a hydrogel-coated microelectrode. GOx was shown to be stabilized and to increase activity over time within the electroconductive hydrogel.     

Enhanced photoelectrochemical performance of Bi2S3/Ag2S/ZnO novel ternary heterostructure nanorods

The current work investigates the morphology, crystallinity and photoelectrochemical (PEC) performance of bismuth sulfide/silver sulfide/zinc oxide nanorods (Bi₂S₃/Ag₂S/ZnO NRAs) photoelectrodes as prepared at different annealing temperature. ZnO NRAs was initially grown hydrothermally, deposited in sequence with Ag₂S and Bi₂S₃ via successive ionic layer adsorption and reaction (SILAR) method before undergoing the annealing treatment. The optimised photoelectrode (Bi₂S₃/Ag₂S/ZnO NRAs-400 °C) possesses an optical bandgap of 1.60 eV extending the absorption edge of ZnO to visible light spectrum. The current-voltage characterization of Bi₂S₃/Ag₂S/ZnO NRAs photoelectrodes revealed that the photocurrent density and photoconversion efficiency were strongly dependent on the annealing temperature. The PEC study shows that the photoelectrode annealed at 400 °C achieved impressive photocurrent density of 12.95 mA/cm² at +0.5 V (vs Ag/AgCl/saturated KCl) under 100 mW/cm² illumination with superior photoconversion efficiency of 12.63%. This improvement is due to the cascade-designed band structure alignment of Bi₂S₃/Ag₂S/ZnO/ITO and to the brilliant role of Ag₂S as an intermediate layer that reduced random chance of electron-hole (e⁻_-h⁺) pairs recombination and improved the electrons collection efficiency. This work is highly anticipated to give contribution on further utilisation of Bi₂S₃/Ag₂S/ZnO NRAs as a promising semiconductor material in PEC related applications.     

CuInSe2 thin-film deposition on flexible plastic substrate: electrolyte recirculation rate and deposition potential effects

Copper indium diselenide (CuInSe₂; CIS) layer was electrolytically plated from an aqueous medium at room temperature onto electroless nickel deposited on flexible plastic (Kapton). The CIS depositions were carried out under constant deposition potentials (−0.5 to −1.1 V vs. Ag/AgCl) and at various electrolyte flow rates (0.3 to 1.5 ml/s) under constant applied current. The resulting thin films were characterized using atomic force microscopy, energy-dispersive X-ray spectroscopy, environmental scanning electron microscopy, and X-ray diffraction. The surface morphology and the atomic composition of the deposited CIS film were found to be influenced by the deposition potential under potential control and the electrolyte recirculation rate under current control. Low electrolyte flow rates under constant current control and high cathodic deposition potential under voltage control favor the deposition of indium. CIS films of uniform deposit, smoother surfaces, and with better adhesion properties are favored by moderate electrolyte recirculation rate. At a current density of 0.6 mA/cm², the electrolyte recirculation rate required to achieve ideal CIS atomic composition was found to be 1.0 ml/s in such a setting. The crystallinity of the film improved after annealing for 2 h at 390 °C under argon atmosphere.     

Air diffusion biocathode with CueO as electrocatalyst adsorbed on carbon particle-modified electrodes

The current density of biofuel cells which use dissolved O₂ as electron acceptor is limited by O₂ supply to the electrode surface due to the low solubility and small diffusion coefficient of O₂ in the electrolyte solution. In order to increase the current density, we constructed an air diffusion biocathode which uses O₂ directly from the air. As cathodic biocatalyst, we utilized CueO from Escherichia coli, which belongs to the family of multi-copper oxidases. O₂ reduction was catalyzed by CueO adsorbed on Ketjen black-modified carbon paper electrodes. The hydrophobic electrode surface was obtained by optimizing the weight ratio of polytetrafluoroethylene binder to Ketjen black. The current density of O₂ reduction reached values as high as 20 mA cm^− 2 at 0 V vs. Ag|AgCl, KCl(sat.) in a citrate buffer (1.0 M, pH 5.0, 25 °C).     

A Water-Soluble Sodium Pectate Complex with Copper as an Electrochemical Catalyst for Carbon Dioxide Reduction

A selective noble-metal-free molecular catalyst has emerged as a fruitful approach in the quest for designing efficient and stable catalytic materials for CO₂ reduction. In this work, we report that a sodium pectate complex of copper (PG-NaCu) proved to be highly active in the electrocatalytic conversion of CO₂ to CH₄ in water. Stability and selectivity of conversion of CO₂ to CH₄ as a product at a glassy carbon electrode were discovered. The copper complex PG-NaCu was synthesized and characterized by physicochemical methods. The electrochemical CO₂ reduction reaction (CO₂RR) proceeds at −1.5 V vs. Ag/AgCl at ~10 mA/cm² current densities in the presence of the catalyst. The current density decreases by less than 20% within 12 h of electrolysis (the main decrease occurs in the first 3 h of electrolysis in the presence of CO₂). This copper pectate complex (PG-NaCu) combines the advantages of heterogeneous and homogeneous catalysts, the stability of heterogeneous solid materials and the performance (high activity and selectivity) of molecular catalysts.     

Direct Z-scheme CdS-CdS Nanorod Arrays Photoanode: Synthesis,Characterization and Photoelectrochemical Performance

Direct Z-scheme CdO-CdS 1-dimensional nanorod arrays were constructed through a facile and simple hydrothermal process. The structure, morphology, photoelectrochemical properties and H\begin{document}$_2$\end{document} evolution activity of this catalyst were investigated systematically. The morphology of the obtained nanorod is a regular hexagonal prism with 100-200 nm in diameter. The calcination temperature and time were optimized carefully to achieve the highest photoelectrochemical performance. The as-fabricated hybrid system achieved a photocurrent density up to 6.5 mA/cm\begin{document}$^{2}$\end{document} and H\begin{document}$_{2}$\end{document} evolution rate of 240 μmol\begin{document}$\cdot$\end{document}cm\begin{document}$^{-2}$\end{document}\begin{document}$\cdot$\end{document}h\begin{document}$^{-1}$\end{document} at 0 V vs. Ag/AgCl, which is about 2-fold higher than that of the bare CdS nanorod arrays. The PEC performance exceeds those previously reported similar systems. A direct Z-scheme photocatalytic mechanism was proposed based on the structure and photoelectrochemical performance characterization results, which can well explain the high separation efficiency of photoinduced carriers and the excellent redox ability.     

Surviving High‐Temperature Calcination: ZrO2‐Induced Hematite Nanotubes for Photoelectrochemical Water Oxidation

Nanotubular Fe₂O₃ is a promising photoanode material, and producing morphologies that withstand high‐temperature calcination (HTC) is urgently needed to enhance the photoelectrochemical (PEC) performance. This work describes the design and fabrication of Fe₂O₃ nanotube arrays that survive HTC for the first time. By introducing a ZrO₂ shell on hydrothermal FeOOH nanorods by atomic layer deposition, subsequent high‐temperature solid‐state reaction converts FeOOH‐ZrO₂ nanorods to ZrO₂‐induced Fe₂O₃ nanotubes (Zr‐Fe₂O₃ NTs). The structural evolution of the hematite nanotubes is systematically explored. As a result of the nanostructuring and shortened charge collection distance, the nanotube photoanode shows a greatly improved PEC water oxidation activity, exhibiting a photocurrent density of 1.5 mA cm⁻² at 1.23 V (vs. reversible hydrogen electrode, RHE), which is the highest among hematite nanotube photoanodes without co‐catalysts. Furthermore, a Co‐Pi decorated Zr‐Fe₂O₃ NT photoanode reveals an enhanced onset potential of 0.65 V (vs. RHE) and a photocurrent of 1.87 mA cm⁻² (at 1.23 V vs. RHE).     

Fabrication of Vertical-Standing Co-MOF Nanoarrays with 2D Parallelogram-like Morphology for Aqueous Asymmetric Electrochemical Capacitors

Metal organic frameworks (MOFs) have been considered as one of the most promising electrode materials for electrochemical capacitors due to their large specific surface area and abundant pore structure. Herein, we report a Co-MOF electrode with a vertical-standing 2D parallelogram-like nanoarray structure on a Ni foam substrate via a one-step solvothermal method. The as-prepared Co-MOF on a Ni foam electrode delivered a high area-specific capacitance of 582.0 mC cm⁻² at a current density of 2 mA cm⁻² and a good performance rate of 350.0 mC cm⁻² at 50 mA cm⁻². Moreover, an asymmetric electrochemical capacitor (AEC) device (Co-MOF on Ni foam//AC) was assembled by using the as-prepared Co-MOF on a Ni foam as the cathode and a active carbon-coated Ni foam as the anode to achieve a maximum energy density of 0.082 mW cm⁻² at a power density of 0.8 mW cm⁻², which still maintained 0.065 mW cm⁻² at a high power density of 11.94 mW cm⁻². Meanwhile, our assembled device exhibited an excellent cycling stability with a capacitance retention of nearly 100% after 1000 cycles. Therefore, this work provides a simple method to prepare MOF-based material for the application of energy storage and conversion.     

Direct electrochemistry of cytochrome P450 27B1 in surfactant films

We report the first direct electrochemistry of cytochrome P450 27B1 (CYP27B1) immobilized on an edge-plane pyrolytic graphite (EPG) electrode coated with a film of didodecyldimethylammonium bromide (DDAB). Cyclic voltammetry (CV) in a deoxygenated solution revealed excellent electrochemical reversibility with an average midpoint potential of −180 ± 5 mV vs. Ag/AgCl and an apparent surface coverage of (7.0 ± 2.5) × 10¹³ molecules per cm². The rate of heterogeneous electron transfer between CYP27B1 and the EPG electrode was determined to be 3.5 ± 0.6 s⁻¹. Upon addition of oxygen, a significant increase in cathodic current occurred, likely due to electrocatalytic reduction of dioxygen to peroxide and/or water by CYP27B1. Characterization of the electrochemical properties of CYP27B1 is an important first step toward developing a bioelectrochemical method for measuring vitamin D in serum.     

电解液成分、厚度及表面改性对旋涂法制备的BiVO4膜层光电化学性能的影响

采用旋涂法在FTO（SnO₂∶F）导电玻璃衬底上沉积得到BiVO₄多孔薄膜用以光解水,改变前驱体的浓度和旋涂次数以调控薄膜的厚度。研究了电解液成分、膜层厚度及表面改性等因素对刚经历过退火处理的BiVO₄薄膜光电化学（PEC）性能的影响。结果表明：通过在电解液中添加适量的空穴吞噬剂Na₂SO₃,或对表面进行Co-Pi改性均能有效改善BiVO₄薄膜的PEC活性。这些措施均能有效抑制固液界面处的载流子复合反应。经Co-Pi改性的BiVO₄薄膜在0.6 V（vs SCE）偏压下,0.1 mol·L^-1 Na₂SO₄+0.1 mol·L^-1 Na₂SO₃的电解液中展现出最高的光电流密度（4.3 mA·cm^-2）。此外,选用一个代表性BiVO₄薄膜作为光阳极制备了一个PEC生物传感器,在检测谷胱甘肽（GSH）上表现出比较高的灵敏度。本研究证实了BiVO₄薄膜的PEC性能严重依赖着光俘获效率和载流子输运过程。     

Organic interlayers for oxygen reducing electrodes based on bilirubin oxidase and MWCNT modified gold

Electrochemical properties of bilirubin oxidase (BOD) and multi-walled carbon nanotubes (MWCNT) modified gold electrodes were characterised by linear sweep voltammetry. For enhancement of the direct electron transfer of BOD an interlayer of different aromatic compounds was introduced between the adsorbed or covalently bound enzyme and the MWCNTs. By usage of pyrroloquinoline quinone (PQQ) an increased catalytic oxygen current was observed. The reduction process starts at a potential of +500 mV vs. Ag/AgCl, 1 M KCl. The peak current density in unstirred solution could be determined with about 500 μA/cm². A reduction of the diffusion layer thickness by stirring enhances the current density up to 1600 μA/cm² (at +250 mV).