Electrochemical science advances最新文献

{"title":"Electrochemical, EPR, and quantum chemical study of reductive cleavage of cone-Calix[4]arene nosylates – New electrosynthetic approach","authors":"Alan Liška,&nbsp;Markéta Řezanková,&nbsp;Jiří Klíma,&nbsp;Jiří Urban,&nbsp;Jan Budka,&nbsp;Jiří Ludvík","doi":"10.1002/elsa.202100221","DOIUrl":"10.1002/elsa.202100221","url":null,"abstract":"<p>The mechanism of electrochemical reduction of a series of six <i>cone</i>-calix[4]arene-bis-nosylates (4-nitrophenylsulfonate aryl esters) was investigated on mercury electrodes using DC-polarography and cyclic voltammetry (CV) combined with in situ electron paramagnetic resonance (EPR)-spectroelectrochemistry in aprotic dimethylformamide. Model compounds – expected fragments and products - were studied for comparison. The experimental results are supported by quantum chemical calculations. All calix[4]arene-bis-nosylates are reduced in a first reversible step to bis-(radical anion) by two simultaneous one-electron transfers. Each of the two electrons is unpaired and separately localized on two nosylate groups.</p><p>In the second reduction step next 2×2 electrons are transferred and both sulfonate ester groups are cleaved to two 4-nitro-benzenesulfinate ions and a calixarene bis-phenolate (95%). This electroreductive generation of arylsulfinate anions is a significant finding from the electrosynthetic point of view. Activated arylsulfinates, the synthesis of which is generally difficult, can be easily prepared by electrochemical reduction of the nosyl esters.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100221","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46681334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ammonia electrocatalytic synthesis from nitrate","authors":"Dimitra Anastasiadou,&nbsp;Yvette van Beek,&nbsp;Emiel J. M. Hensen,&nbsp;Marta Costa Figueiredo","doi":"10.1002/elsa.202100220","DOIUrl":"https://doi.org/10.1002/elsa.202100220","url":null,"abstract":"<p>The interest in electrochemical processes to produce ammonia has increased in recent years. The motivation for this increase is the attempt to reduce the carbon emissions associated with its production, since ammonia is responsible for 1.8% of the global CO₂ emissions. Moreover, green ammonia is also seen as a possible transportation fuel in various renewable energy transition scenarios. Several electrochemical processes are being investigated such as N₂, NO₃^–, or NO conversion. Since nitrates are an attractive source of nitrogen, due to their role as water contaminants and facility to break N-O bonds, this mini review is focused on the electrocatalytic synthesis of ammonia from NO₃⁻ reduction. Here, we summarized the important work on reaction mechanisms and electrocatalysts for this reaction.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100220","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"50127807","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ammonia electrocatalytic synthesis from nitrate","authors":"Dimitra Anastasiadou, Yvette Beek, E. Hensen, Marta Costa Figueiredo","doi":"10.1002/elsa.202100220","DOIUrl":"https://doi.org/10.1002/elsa.202100220","url":null,"abstract":"","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"51125071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Voltammetric study of new psychoactive substance 3-fluorophenmetrazine","authors":"Eliška Jiroušková,&nbsp;Radomír Čabala,&nbsp;Romana Sokolová","doi":"10.1002/elsa.202100223","DOIUrl":"10.1002/elsa.202100223","url":null,"abstract":"<p>Electrochemical oxidation of the new psychoactive substance 3-fluorophenmetrazine (FPM) was studied in phosphate buffers by cyclic voltammetry and differential pulse voltammetry (DPV) on a glassy carbon electrode. The redox potential of FPM in buffered solution strongly depends on pH. Cyclic voltammetry behavior shows the partial influence of adsorption on the electrode process not allowing detailed analysis of the individual steps of the reaction scheme, it means the involvement of electron transfer (E) and chemical reaction (C). Nevertheless, the irreversible shape of the cyclic voltammogram is explained by the participation of hydroxylation nucleophilic addition of water (hydroxylation) after two-electron/two-proton oxidation of molecule at the tetrahydro-1,4-oxazine ring. The suggested mechanism leading to hydroxylated derivative 2-(3-fluorophenyl)-3-methyl-5-hydroxymorfolin is supported by the calculated highest occupied molecular orbital spatial distribution and atomic charges calculations for electrochemically formed radical cation. Infrared spectroelectrochemistry performed during oxidation in acetonitrile/water also supported the formation of this product.</p><p>The analytical method of FPM determination on glassy carbon electrode was developed using DPV with an attained limit of detection = 4.7 μmol/L in phosphate buffer of pH 9. The linear range of the calibration curve is from 7.0 to 107.00 μmol/L, correlation coefficient (<i>r</i>) = 0.9988.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100223","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46074958","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Numerical analysis on influence of surface structures of cathode catalyst layers on performance of polymer electrolyte fuel cells","authors":"Kayoung Park,&nbsp;Yuting Wei,&nbsp;Magnus So,&nbsp;Tae Hyoung Noh,&nbsp;Naoki Kimura,&nbsp;Yoshifumi Tsuge,&nbsp;Gen Inoue","doi":"10.1002/elsa.202200003","DOIUrl":"https://doi.org/10.1002/elsa.202200003","url":null,"abstract":"<p>Because it is time-consuming to optimize the design of a cathode catalyst layer (CCL), a numerical simulation to predict the reaction and mass transport characteristics without trial and error is desirable. This study used numerical analysis to investigate how the mass transport occurring in CCLs with flat and three-dimensional (3D) structures influenced the performance. The simulations included the reconstruction of the CCLs and their electrochemical calculation using our multi-block model. The simulation results showed the reduction of the proton resistance in the ionomer was a factor in improving the performance in the 3D structure in comparison with the flat structure. An increasing aspect ratio of the 3D structure improved the cell performance and decreased the proton resistance in the ionomer. These results were due to the shortened conductive path of the protons from the polymer electrolyte membrane to the gas diffusion layer side surface in the 3D structure. Finally, the cell performance with an increase in the ionomer content was predicted. This numerical analysis made it possible to understand the reaction of the 3D structure and mass transport and predict ways to optimize the structural design to improve cell performance.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202200003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"50145118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical contributions: Gustav Theodor Fechner (1801–1887)","authors":"Evgeny Katz","doi":"10.1002/elsa.202260001","DOIUrl":"https://doi.org/10.1002/elsa.202260001","url":null,"abstract":"<p>Gustav Theodor Fechner (Figure 1) was a German physicist, psychologist, and philosopher. His scientific contributions were mostly in the area of experimental psychology. He was a founder of psychophysics and he is particularly credited for discovering the non-linear relationship between psychological sensation and the physical intensity of a stimulus. However, for the purpose of this historical note, his contribution to electrochemistry must be emphasized.</p><p>Fechner extensively performed electrochemical experiments, particularly testing Ohm's law for electrolyte solutions in galvanic cells. He was the first to introduce into electrochemical science the parameter of the charge transfer resistance at an electrode/electrolyte interface. This factor is highly important for electrochemical kinetics in modern electrochemistry. Fechner was the first who reported in 1828 the observation of electrochemical oscillations during the anodic dissolution of nickel in nitric acid (Figure 2A). From that time, numerous systems with non-stationary oscillating behavior have been discovered.</p><p>Fechner designed an electroscope (electrometer) with improved sensitivity. This instrument consisted of 800 to 1000 pairs of metal foils charging two metal condenser plates. A thin strip of gold foil was hung between these plates (Figure 2B). A deviation of the gold foil from its vertical position was used for sensing an electric charge on it with very high sensitivity.</p><p>Fechner was very influential by translating and completely rewriting volume 3 (<i>Lehrbuch des Galvanismus und der Elektrochemie</i>) of Jean Baptiste Biot's textbook on experimental physics in which he gives a full account of the state of knowledge in electrochemistry of his time, including his findings.</p><p>This article is part of a series featuring historic contributions in and around electrochemistry. At least one such article appears in every issue of <i>Electrochemical Science Advances</i>.</p><p>The author declares no conflict of interest.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"2 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202260001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"137562690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The gas diffusion electrode setup as a testing platform for evaluating fuel cell catalysts: A comparative RDE-GDE study","authors":"Sven Nösberger,&nbsp;Jia Du,&nbsp;Jonathan Quinson,&nbsp;Etienne Berner,&nbsp;Alessandro Zana,&nbsp;Gustav K.H. Wiberg,&nbsp;Matthias Arenz","doi":"10.1002/elsa.202100190","DOIUrl":"https://doi.org/10.1002/elsa.202100190","url":null,"abstract":"<p>Gas diffusion electrode (GDE) setups have been recently introduced as a new experimental approach to test the performance of fuel cell catalysts under high mass transport conditions, while maintaining the simplicity of rotating disk electrode (RDE) setups. In contrast to experimental RDE protocols, for investigations using GDE setups only few systematic studies have been performed. In literature, different GDE arrangements were demonstrated, for example, with and without an incorporated proton exchange membrane. Herein, we chose a membrane-GDE approach for a comparative RDE–GDE study, where we investigate several commercial standard Pt/C fuel cell catalysts with respect to the oxygen reduction reaction (ORR). Our results demonstrate both the challenges and the strengths of the new fuel cell catalyst testing platform. We highlight the analysis and the optimization of catalyst film parameters. That is, instead of focusing on the intrinsic catalyst ORR activities that are typically derived in RDE investigations, we focus on parameters, such as the catalyst ink recipe, which can be optimized for an individual catalyst in a much simpler manner as compared to the elaborative membrane electrode assembly (MEA) testing. In particular, it is demonstrated that ∼50% improvement in ORR performance can be reached for a particular Pt/C catalyst by changing the Nafion content in the catalyst layer. The study therefore stresses the feasibility of the GDE approach used as an intermediate “testing step” between RDE and MEA tests when developing new fuel cell catalysts.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100190","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"50135590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical redox properties of bridged and non-bridged annulenediones","authors":"Aviv Gazit,&nbsp;James Y. Becker","doi":"10.1002/elsa.202100168","DOIUrl":"10.1002/elsa.202100168","url":null,"abstract":"<p>The present article is fully confined to cyclic voltammetric measurements of a series of bridged and non-bridged annulenediones (quinones of large conjugated rings of aromatic character). The evaluation of their electrochemical redox properties shed light on remarkable and interesting conclusions such as aromaticity, electrostatic repulsion, disproportionation constants, and stability of their reduced charged intermediates. The results reveal that in the case of the non-bridged quinones <b>1</b>–<b>4</b>, as the number of fused rings increases the reduction becomes gradually more difficult because the aromatic stabilization of the ‘quinone’ on conversion to aromatic ‘hydroquinone’ system decreases. However, since all studied annulenediones <b>5</b>–<b>11</b> possess a ‘C₂’ bridge that keeps the macrocycles flat, causing better aromaticity, they are relatively easily reduced at both E₁ and E₂ potentials and therefore, they could be considered as quinones of aromatic systems. On the other hand, when the bridge is longer (as in <b>12</b> and <b>13</b>) the macrocycles tend to bend, causing a decrease in the degree of aromaticity and as a consequence, their reduction becomes more difficult.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100168","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49204012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Capture and analysis of double-stranded DNA with the α-hemolysin nanopore: Fundamentals and applications","authors":"Shekemi Denuga,&nbsp;Donal E. Whelan,&nbsp;Shane P. O'Neill,&nbsp;Robert P. Johnson","doi":"10.1002/elsa.202200001","DOIUrl":"10.1002/elsa.202200001","url":null,"abstract":"<p>The α-hemolysin nanopore has attracted much attention as a tool for the single-molecule analysis of DNA due to its potential as an ultra-sensitive, specific, and label-free sensing technique. The vast majority of DNA sensing research with the α-hemolysin nanopore has focused on interrogating single-stranded DNA. Nevertheless, the structure of the α-hemolysin pore, specifically the circa 32.6 cubic nanometer vestibule, is of sufficient size for a short section of double-stranded DNA (dsDNA) to reside before unzipping into its single-stranded constituents. In this review, we describe past and current literature relating to the rich information that can be obtained from the interrogation of dsDNA while residing within the α-hemolysin nanopore vestibule, and the subsequent voltage-driven unzipping of the residing DNA into its single-stranded constituents. Applications for dsDNA interrogation and unzipping that have been implemented include DNA sequencing, disease diagnosis, and the identification of epigenetic modifications.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"2 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202200001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45125698","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and electrochemical performance of in-situ and ex-situ carbon- coated Na2Ti3O7, as a promising anode for sodium-ion batteries","authors":"Anwesa Mukherjee,&nbsp;Debasish Das,&nbsp;Susanta Banerjee,&nbsp;Subhashish Basu Majumder","doi":"10.1002/elsa.202100118","DOIUrl":"10.1002/elsa.202100118","url":null,"abstract":"<p>Insertion-type layered Na₂Ti₃O₇ has attracted the attention of the researchers and is considered to be one of the promising low-voltage anode materiasl for sodium-ion batteries. In spite of its fascinating electrochemical properties, the low electronic conductivity and structural instability of Na₂Ti₃O₇ are major drawbacks that restrict its practical application. Surface modification with pyrolytic carbon is one of the effective ways to reduce irreversible capacity loss caused by electrolytic degradation. In this work, attempts have been made to investigate the effects of different carbon coating approaches on the electrochemical properties of sol-gel-synthesized Na₂Ti₃O₇ microrods. The as-synthesized Na₂Ti₃O₇ rods are coated with a uniform carbon layer both by in-situ and ex-situ methods using citric acid and polyvinyl alcohol as carbon source, respectively. Ex-situ carbon-coated Na₂Ti₃O₇ (Na₂Ti₃O₇@C), due to better coating uniformity and higher graphitized carbon percentage, shows enhanced cyclability and rate performance compared to bare material and in-situ carbon composite (Na₂Ti₃O₇/C). Following the ex-situ carbonization method using PVA as carbon source, it is found that increase of carbon content from 5wt% to 10wt% significantly improves its electrochemical properties. However, further increase in PVA amount has adverse effect on the cycling as well as rate performance of Na₂Ti₃O7@C. Surface modified Na₂Ti₃O₇@C with optimum carbon content (10wt% C) shows improved cycling capacity (capacity retention ∼74.75% after100 cycle) and rate performance (∼67 mAhg-1 at 1.5 Ag-1). Both excess and inadequate carbon content have detrimental effect on the electrochemical properties of Na2Ti3O7 anode.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100118","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45066586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}