Catalytic Detection of Iodide at Cationic Kaolinite Modified Gold Electrode in Presence of Thiosulfate

A gold electrode modified by a thin film of cationic kaolinite was used for the electrochemical detection of iodide in aqueous solution in the presence of thiosulfate. At gold electrode, iodide showed two electrochemical systems in the potential range explored (0.10 V to 0.85 V). The pH‐independent system was assigned to the redox couple I₂/I^? and the pH‐dependent one assigned to the redox couple HIO/ . For increased amount of thiosulfate the oxidation peak intensity of the first system increases sharply followed by the gradual decrease of the reduction peak, due to the chemical reaction between thiosulfate and oxidized iodide. The calibration curve in the presence of excess thiosulfate resulted in an increase of the sensitivity by a factor of 7. To improve this sensitivity, the bare gold electrode was coated by a thin film of an anionic exchanger kaolinite, obtained by grafting the ionic liquid (1‐(2‐hydroxyethyl)‐4‐(tert‐butyl) pyridinium chloride). Accumulation‐detection method yielded a spectacular increase of the oxidation peak current of iodide in the presence of thiosulfate ions. At optimized experimental conditions, a sensitivity of 2.45 μA.μM^?1 and a detection limit of 65 nM were obtained. The method was successfully applied for total iodine determination in povidone?iodine formulation.     

Development of a new parameter optimization scheme for a reactive force field based on a machine learning approach

Reactive molecular dynamics (MD) simulation is performed using a reactive force field (ReaxFF). To this end, we developed a new method to optimize the ReaxFF parameters based on a machine learning approach. This approach combines the k-nearest neighbor and random forest regressor algorithm to efficiently locate several possible ReaxFF parameter sets. As a pilot test of the developed approach, the optimized ReaxFF parameter set was applied to perform chemical vapor deposition (CVD) of an α-Al₂O₃ crystal. The crystal structure of α-Al₂O₃ was reasonably reproduced even at a relatively high temperature (2000 K). The reactive MD simulation suggests that the (110) surface grows faster than the (0001) surface, indicating that the developed parameter optimization technique could be used for understanding the chemical reaction in the CVD process. © 2019 Wiley Periodicals, Inc.     

On the interfacial energy of extended-chain crystals from polyethylene melt by revised Flory equations of fusion

To analyze extended-chain crystalline systems composed of linear polyethylene, Flory's conventional theory of fusion is reconsidered by introducing a new concept of crystallinity. When this new treatment is applied to a melting case of a low molecular weight polyethylene fraction (M_n = 5600) isothermally bulk crystallized, a certain result that very large lamellar thickness was caused by a very small increase in crystallization temperature can satisfactorily be explained by a significant change in interfacial free energy of the crystallite end. Further, it shows 14–17 kJ/mol as a nonequilibrium value range of interfacial free energy for highly crystalline polyethylene fractions of low molecular weight M_n ≦ 5600 by using the previous data presented by other workers. A similar result is also obtained on the M_n = 5600 fraction by analyzing from a standpoint of equilibrium crystallinity. In either case, the estimated range of interfacial free energy is consistent with the conventional range. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1293–1303, 1998     

Detection of bendamustine anti-cancer drug via AlN and Si-doped C nanocone and nanosheet sensors by DFT

Bendamustine or Treanda? is used as an anti-cancer drug, especially in treatment of hematologic malignancies. In view of the immense importance of drug/sensor issues, here we report adsorption behavior of this drug in presence of six nanosensors including aluminum nitride (AlN), carbon, and Si-doped carbon nanocones and nanosheets, at B3LYP/6-31G* level of theory. Electrical conductivity of these nanoadsorbents is probed against that of bendamustine for assessing their abilities of drug sensing with possible implications in drug delivery. The adsorption energy (E_ad), doping energy (E_dop), HOMO energy (E_H), LUMO energy (E_L), HOMO-LUMO band gap (E_g), change of band gaps in percent (%?E_g), change of natural bond orbital (NBO) charges (?Q), conduction electron population (N), and density of state (DOS) plots are calculated. More E_ad, ?Q, and N values imply more interaction between bendamustine and nanosensor which lead to a strong recognition of the drug. The interaction of AlN nanosheet and bendamustine shows the highest E_ad, %?E_g, and ?Q (??28.8 kcal/mol, ??33.6%, and 0.4 e, respectively) which make AlN nanosheet as the most promising among our scrutinized nanosensors. A negative E_dop indicates an exothermic doping process, where Si atom improves the electronic sensitivity of C nanocone and nanosheet. All calculated E_ad and %?E_g turn out as negative values which reveal that electrical conductivity of our scrutinized nanostructures are increased upon adsorbing process which makes them efficient sensors for bendamustine.

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Influence of Plasma Treatment on the Electroless Deposition of Copper on Carbon Fibers

Air and nitrogen glow discharge were used to replace chromic acid pretreatment to deposit copper film on carbon fiber surfaces from an CuSO₄‐HCHO electroless system. A greater copper uptake and a more uniformly coated copper film were obtained for plasma‐treated carbon fibers. The adhesion between the copper film and the carbon fibers was also improved. An orthogonal table L₉(3⁴) was used to study the effects of discharge pressure, discharge power, time and gas type on the copper uptake. Scanning electron microscopy (SEM), reflection absorption infrared spectroscopy (RAIR) and X‐ray photoelectron spectroscopy (XPS) at different depths were applied to characterize the physical and chemical changes of the surface of the carbon fibers. The results showed that after plasma treatment, the carbon fiber surface became rough and several types of polar oxygen groups, such as carboxylic acid COOH, esters COOC, quinones Ph?O, etc., were introduced into the carbon fiber surface. A mechanism of plasma treatment effects on copper electroless deposition on the carbon fiber surface is also suggested.     

Oxidative addition of 1,4‐dichloro‐2‐butyne to an organoplatinum complex: A new precursor for synthesis of ultrasmall Pt nanoparticles thin film at liquid/liquid interface as the electrocatalyst in methanol oxidation reaction

In this study, the usage of ClCH₂CCCH₂Cl alkyne as a reagent for the oxidative addition reaction with organoplatinum?(II) complex [PtMe₂(bipy)] ( 1 ), in which bipy = 2,2′‐bipyridine to give a mixture including of trans‐[PtClMe₂(CH₂CCCH₂Cl)(bipy)] ( 2a ) and a cis‐[PtClMe₂(CH₂CCCH₂Cl)(bipy)] ( 2b ) complexes is reported. Kinetic study was investigated by monitoring the disappearance of the metal‐to‐ligand charge transfer (MLCT) band in the UV–Vis spectra. ¹H NMR experimental results confirmed that trans isomer ( 2a ) is more stable than its corresponding cis isomer. A liquid–liquid planar interface has been employed as a template for self‐assembly of platinum nanoparticles. The as prepared complex was applied for the synthesis of platinum thin film that characterized by transmission electron microscopy (TEM), X‐ray diffraction (XRD), energy dispersive analysis of X‐rays (EDAX), field emission‐scanning electron micrographs (FE‐SEM) and elemental mapping. The electrocatalytical activity of Pt thin film was investigated in methanol oxidation reaction.     

Selective,sensitive, and fast determination of S-layer proteins by a molecularly imprinted photonic polymer coated film and a fiber-optic spectrometer

A newly developed molecularly imprinted photonic polymer (MIPP) film, which was prepared by colloidal crystal templating and surface molecular imprinting, was used for selective capture of S-layer protein (SLP) from a complex Lactobacillus acidophilus sample. The colloidal crystal templates were formed by a dipping process followed by chemical binding of the imprinted template SLP molecules. A sandwich structure consisting of two glass slides was formed after the SLP–silica layer had been covered with a poly(methyl methacrylate) glass slide. After polymerization of the SLP–silica layer with the preprepared polymerization solution, hydrofluoric acid and acetic phosphate buffer solutions removed the silica particles and SLP molecules, respectively. The MIPP film obtained exhibited a three-dimensional, highly ordered and interconnected macroporous structure (pore size greater than 200 nm), which is specifically accessible to SLP molecules. The adsorbed SLP molecules were simply and straightforwardly detected by a fiber-optic spectrometer. The redshift of the Bragg diffraction peak of the MIPP film was linearly related to the number of SLP molecules that had been harvested in the film. The detection limit of the SLP–MMIP–fiber-optic spectrometer method for SLP was 1 ng mL^-1. The MIPP sensor was successfully applied to detect SLP molecules in a crudely extracted Lactobacillus acidophilus sample. Our results prove the applicability of the SLP–MIPP film for fast and real-time measurement of SLP.

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CeO2/CdS heterojunction decorated cotton fabric as a recyclable photocatalyst for efficient light driven degradation of methylene blue

In this work, visible light response CeO₂/CdS decorated cotton fabrics as durable and facile recyclable composite photocatalysts were fabricated for photo-degradation of methylene blue (MB). First of all, amino-functionalized CeO₂/CdS heterojunctions were synthesized through a fast, efficient and low-cost co-precipitation method. Subsequently, the as-prepared CeO₂/CdS heterojunctions were immobilized on aldehyde-functionalized cotton fabric surfaces as composite photocatalysts via "amine-aldehyde" chemical reaction. The surface microstructure and chemical composition of the CeO₂/CdS decorated cotton fabric (CeO₂/CdS-CF) were characterized by SEM, FTIR and XPS, respectively. The results showed that CeO₂/CdS heterojunctions were successfully anchored and uniformly distributed on the surface of cotton fabric. Since the CeO₂/CdS heterostructure with efficient photo-generated charge transfer and separation, the as-prepared CeO₂/CdS-CF exhibited excellent photocatalytic activity, degrading MB under simulated sunlight irradiation with a degradation efficiency of 93.8% within 90 min. In addition, the degradation efficiency remained above 90.3% even after five successive degradation cycles, indicating the outstanding stability and recyclability of the obtained CeO₂/CdS-CF. This work opened up a facile preparation way for the fabrication of durable and recyclable composite photocatalysts, and has a promising application in treating dye contaminated wastewater.

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Effect of oxygen-containing functional groups on the wettability of coal through DFT and MD simulation

To investigate the wettability of different oxygen-containing functional group (OFG) surfaces, graphite substrates were used as a model for coal adsorbents. The substrates were modified with COOH, OH, CO, and OCH₃. The adsorption-diffusion behavior of H₂O molecules/water droplets on different OFG surfaces was investigated using molecular dynamics (MD) simulations with frontier orbital energy difference as a metric for different surface wettability degrees in quantum chemical analysis. The results indicated that the frontier orbital energy difference of the H₂O molecule was 3.480, 3.491, 3.631, and 3.680 eV for PhCOOH, PhOH, PhCO, and PhOCH₃, respectively. In addition, the equilibrium contact angle, interaction energy, and number of hydrogen bonds after the adsorption equilibrium of water droplets for COOH, OH, CO, and OCH₃ surfaces were 22.34°, ?5.03 kcal/mol, and 652; –23.72°, ?4.19 kcal/mol, and 450; 68.01°, ?0.79 kcal/ mol, and 61; 90.51°, ?0.50 kcal/mol, and 28, respectively. The smaller the energy difference between the frontier orbitals of the H₂O molecule and the OFG, the smaller the equilibrium contact angle between the water droplet and the OFG surface, the more hydrogen bonds were formed, and the larger the absolute value of the interaction energy, the better the wettability of the surface of the OFG. The order of wettability of the different OFG surfaces was COOH > OH > CO > OCH₃, which is consistent with the radial distribution function and the analysis results for the extended area, etc. The results of density functional theory (DFT) calculations and MD simulations exhibited identical patterns, indicating the reasonableness of the simulations. This study may serve as a reference for the suppression of hydrophilicity in low-order coal and the enhancement of the flotation effect.     

Electrochemistry of metal adlayers on metal chalcogenides

Electrodeposition of metal adlayers on semiconductor metal chalcogenides (CdSe, CdS, PbTe, PbSe, PbS, Bi₂Te₃) is reviewed. Cathodic underpotential deposition of metal adlayer on metal chalcogenide is the electrochemically irreversible surface limited reaction. The irreversibility of the upd increases in the row from tellurides to selenides and further to sulfides. The underpotential shift on chalcogenide nanoparticles increases with particle size. Metal upd on chalcogenides is applied as a means of measurement of electroactive surface area of chalcogenide electrodes. The method is especially advantageous for multicomponent systems with other component not supporting upd, such as CdSe-TiO₂, CdSe-ZnO. Differences of voltammetric profiles of Pb upd on Bi₂Te₃ and Te are applied for detection of Bi₂Te₃ surface contamination by elemental tellurium. The further tasks in the electrochemistry of metal adlayers are their incorporation as interlayers in layered chalcogenides and electrodeposition of superlattices.

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Electrolysis energy efficiency of highly concentrated FeCl2 solutions for power-to-solid energy storage technology

An electrochemical cycle for the grid energy storage in the redox potential of Fe involves the electrolysis of a highly concentrated aqueous FeCl₂ solution yielding solid iron deposits. For the high overall energy efficiency of the cycle, it is crucial to maximize the energy efficiency of the electrolysis process. Here we present a study of the influence of electrolysis parameters on the energy efficiency of such electrolysis, performed in an industrial-type electrolyzer. We studied the conductivity of the FeCl₂ solution as a function of concentration and temperature and correlated it with the electrolysis energy efficiency. The deviation from the correlation indicated an important contribution from the conductivity of the ion-exchange membrane. Another important studied parameter was the applied current density. We quantitatively showed how the contribution of the resistance polarization increases with the current density, causing a decrease in overall energy efficiency. The highest energy efficiency of 89 ± 3% was achieved using 2.5 mol L⁻¹ FeCl₂ solution at 70 °C and a current density of 0.1 kA m⁻². In terms of the energy input per Fe mass, this means 1.88 Wh g⁻¹. The limiting energy input per mass of the Fe deposit was found to be 1.76 Wh g⁻¹_.

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Singlet-Triplet Excited-State Inversion in Heptazine and Related Molecules: Assessment of TD-DFT and ab initio Methods

We have investigated the origin of the S₁-T₁ energy levels inversion for heptazine, and other N-doped π-conjugated hydrocarbons, leading thus to an unusually negative singlet-triplet energy gap ( ). Since this inversion might rely on substantial doubly-excited configurations to the S₁ and/or T₁ wavefunctions, we have systematically applied multi-configurational SA-CASSCF and SC-NEVPT2 methods, SCS-corrected CC2 and ADC(2) approaches, and linear-response TD-DFT, to analyze if the latter method could also face this challenging issue. We have also extended the study to B-doped π-conjugated systems, to see the effect of chemical composition on the results. For all the systems studied, an intricate interplay between the singlet-triplet exchange interaction, the influence of doubly-excited configurations, and the impact of dynamic correlation effects, serves to explain the values found for most of the compounds, which is not predicted by TD-DFT.     

Design and physicochemical characterization of magnetic nano-dendritic catalysts: a novel approach for vitamin K3 selective production

High pollution, low-productivity, formation of by-products, and costly recovery of the vitamin are the challenges in common vitamin K₃ synthesis methods on the industrial scale. These have encouraged us to design and characterize novel magnetic dendrimer nanoparticles based on silica-coated iron oxide (SCIO-(l5/l8)-G_2.0) for nano-encapsulation of Pd, Mn, and Co to highly efficiently selectively synthesize vitamin K₃. The CHN, BET, ICP, AAS, TEM, FESEM, TGA, DLS, EDS and XPS techniques were employed to intensively identify the obtained dendritic catalysts. Furthermore, the chemical stability of dendritic catalysts and influence of four various experimental factors were assessed by long-term study and response surface methodology analysis, respectively. The characterization results confirmed that all dendritic catalysts have a quasi-spherical morphology with mean size 20–30 nm, which could provide abundant active sites, high specific surface area and also increase the contact efficiency between the active sites and reactants. These results illustrated that the catalytic efficiency (TOF) depend strongly on the chemical structures as well as Lewis sites and natures (SCIO-l8-G_2.0-Pd(II)?>?SCIO-l8-G_2.0-Co(II)?>?SCIO-l8-G_2.0-Mn(II)?>?SCIO-l5-G_2.0-Pd(II)).

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β-cyclodextrin modified xanthan gum as an eco-friendly corrosion inhibitor for L80 steel in 1 M HCl

The development of eco-friendly corrosion inhibitors is a subject of several investigations, especially natural polymers. Aimed at suppressing the corrosion of L80 steel in 1 mol/L hydrochloric acid (HCl), a novel natural polymer inhibitor was developed based on xanthan gum (XG) and β-Cyclodextrin (β-CD) in this work. The corrosion inhibition effect of β-cyclodextrin modified xanthan gum (β-CD-XG) on L80 steel was evaluated by electrochemical methods, and surface analysis technology. Adsorption isotherm studies, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) were used to explore the corrosion inhibition mechanism of β-CD-XG on L80 steel. The results suggested that β-CD-XG was classified as a mixed-type inhibitor, and mainly suppressed the anode metal dissolution by a tight adsorption film. The formation of the film was attributed to the chemisorption of –OH, –COO-, –CH₂–O–, and –CH₂–O–CH₂– groups on the surface of L80 steel, which conformed to the Langmuir adsorption model. The experimental results illustrated that the maximum corrosion inhibition efficiency of 94.74% was acquired at 200 mg/L β-CD-XG at 293 K.

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Catalytic resonance theory: parallel reaction pathway control

Catalytic enhancement of chemical reactions via heterogeneous materials occurs through stabilization of transition states at designed active sites, but dramatically greater rate acceleration on that same active site can be achieved when the surface intermediates oscillate in binding energy. The applied oscillation amplitude and frequency can accelerate reactions orders of magnitude above the catalytic rates of static systems, provided the active site dynamics are tuned to the natural frequencies of the surface chemistry. In this work, differences in the characteristics of parallel reactions are exploited via selective application of active site dynamics (0 < ΔU < 1.0 eV amplitude, 10⁻⁶ < f < 10⁴ Hz frequency) to control the extent of competing reactions occurring on the shared catalytic surface. Simulation of multiple parallel reaction systems with broad range of variation in chemical parameters revealed that parallel chemistries are highly tunable in selectivity between either pure product, even when specific products are not selectively produced under static conditions. Two mechanisms leading to dynamic selectivity control were identified: (i) surface thermodynamic control of one product species under strong binding conditions, or (ii) catalytic resonance of the kinetics of one reaction over the other. These dynamic parallel pathway control strategies applied to a host of simulated chemical conditions indicate significant potential for improving the catalytic performance of many important industrial chemical reactions beyond their existing static performance.

Branched catalytic reaction networks with oscillating chemical pathways perfectly select for reaction products at varying frequency.     

Plasma-assisted oxidation of Cu(100) and Cu(111)

Oxidized copper surfaces have attracted significant attention in recent years due to their unique catalytic properties, including their enhanced hydrocarbon selectivity during the electrochemical reduction of CO₂. Although oxygen plasma has been used to create highly active copper oxide electrodes for CO₂RR, how such treatment alters the copper surface is still poorly understood. Here, we study the oxidation of Cu(100) and Cu(111) surfaces by sequential exposure to a low-pressure oxygen plasma at room temperature. We used scanning tunnelling microscopy (STM), low energy electron microscopy (LEEM), X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and low energy electron diffraction (LEED) for the comprehensive characterization of the resulting oxide films. O₂-plasma exposure initially induces the growth of 3-dimensional oxide islands surrounded by an O-covered Cu surface. With ongoing plasma exposure, the islands coalesce and form a closed oxide film. Utilizing spectroscopy, we traced the evolution of metallic Cu, Cu₂O and CuO species upon oxygen plasma exposure and found a dependence of the surface structure and chemical state on the substrate''s orientation. On Cu(100) the oxide islands grow with a lower rate than on the (111) surface. Furthermore, while on Cu(100) only Cu₂O is formed during the initial growth phase, both Cu₂O and CuO species are simultaneously generated on Cu(111). Finally, prolonged oxygen plasma exposure results in a sandwiched film structure with CuO at the surface and Cu₂O at the interface to the metallic support. A stable CuO(111) surface orientation is identified in both cases, aligned to the Cu(111) support, but with two coexisting rotational domains on Cu(100). These findings illustrate the possibility of tailoring the oxidation state, structure and morphology of metallic surfaces for a wide range of applications through oxygen plasma treatments.

A low-pressure oxygen plasma oxidized Cu(100) and Cu(111) surfaces at room temperature. The time-dependent evolution of surface structure and chemical composition is reported in detail for a range of exposure times up to 30 min.     

An investigation on the structure,spectroscopy, and thermodynamic aspects of clusters: A combined Parallel tempering and DFT based study

The problem of identifying low-energy structures of (n = 1-6) was investigated, and the evaluation of important properties like heat capacity, solvation energy, and vertical detachment energy for each of the clusters was carried out. The problem was handled at two different theoretical levels. First, an adequately chosen empirical potential energy surface was used to account for the major interactions between the constituents of the cluster studied. Once the surface was chosen, the Parallel tempering algorithm was employed to search out the low-energy critical points on this surface, which gave geometries at this level. To refine the structures further, these pre-optimized structures were used as inputs for quantum chemical evaluation to complete the final refinement. To check whether the structures found were reasonable, sensitive properties like heat capacity, solvation energy, and vertical detachment energy were calculated. Then, an effort was made to understand and explain the variations in these properties with change in the cluster size. To understand the process of cluster formation further, thermodynamic aspects like △H (298.15 K), △G (298.15 K), and heat capacity (C_v) changes were also evaluated. Infrared spectroscopic features were also studied to see whether the introduction of the ion caused reasonable shifts compared to a pure water cluster.     

Zein film as a novel natural biopolymer membrane in electrochemical detections

Permselective modifier films are very important in preparing highly sensitive electrochemical sensors. In this work, for the first time, the behavior of gold and glassy carbon electrodes coated with biocompatible zein film as a permselective membrane for the electrochemical detection of various compounds has been investigated. For this purpose, several electroactive cationic (methylene blue, brilliant green, and thionine) and anionic (potassium ferricyanide, alizarin red S, and riboflavin-5’-phosphate) compounds have been used as model. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) showed that zein membranes prepared from casting solution containing 1% zein in ethanol/water have porous structures with high nanometric roughness. The capacitance values of electrical double layers of electrodes modified with zein film were very high for hydrophilic ions in comparison with hydrophobic ions. Point of zero charge pH (pH_pzc) of zein membrane was 4.8. The results of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) as well as pH_pzc study indicated that zein permselective membrane acts as ion exchanger film for selected cationic compounds with fast electrochemical kinetics responses in aqueous solution (pH=7). This behavior was confirmed by circulating solutions containing model compounds from homemade continuous cell equipped with polyamide membranes modified with zein film.

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Ruthenium-based Conjugated Polymer and Metal-organic Framework Nanocomposites for Glucose Sensing

Many studies have focused on effective ways to exploit enzyme immobilization on an electrode surface to help improve the performance of enzymatic electrochemical biosensors. Herein, a novel glucose sensor was fabricated by immobilizing glucose oxidase (GOx) onruthenium-based conjugated polymer (CP) and metal-organic framework (MOF) nanocomposites. This has not only reduced the applied potential to 0.2 V (vs. Ag/AgCl), but also improved the effective surface area for enzyme immobilization.PPG@Ru@UiO-66-NH₂ was tailored by controlled chemical synthesis from a pre-synthesized water-soluble conjugated polymer (poly(N-phenylglycine)) and metal-organic framework (UiO-66-NH₂). The resulting nanocomposites were characterized using Fourier transform infrared spectroscopy, X-ray fluorescence, scanning electron microscopy, and cyclic voltammetry. The PPG@Ru@UiO-66-NH₂/GOx coated electrodedisplayed a linear measurementrange for glucose from 1 mM to 10 mM, with a sensitivity of 45.92 μA ⋅ mM⁻¹cm⁻¹ and limit of detection of5 μM( ). Furthermore, the practical application of the fabricatedglucosesensor was tested in simulative blood samples with satisfactoryaccuracy. This approach alsoopens a new door for applications regarding both enzymatic electrochemical biosensors and enzymatic biofuel cells (EBFCs).     

Highly Selective Electrochemical Reduction of CO2 to Alcohols on an FeP Nanoarray

Electrochemical reduction of CO₂ into various chemicals and fuels provides an attractive pathway for environmental and energy sustainability. It is now shown that a FeP nanoarray on Ti mesh (FeP NA/TM) acts as an efficient 3D catalyst electrode for the CO₂ reduction reaction to convert CO₂ into alcohols with high selectivity. In 0.5 m KHCO₃, such FeP NA/TM is capable of achieving a high Faradaic efficiency (FE ) up to 80.2 %, with a total FE of 94.3 % at ?0.20 V vs. reversible hydrogen electrode. Density functional theory calculations reveal that the FeP(211) surface significantly promotes the adsorption and reduction of CO₂ toward CH₃OH owing to the synergistic effect of two adjacent Fe atoms, and the potential‐determining step is the hydrogenation process of *CO.