Electrochemical science advances最新文献

{"title":"Electrochemical Contributions: Svante August Arrhenius (1859–1927)","authors":"Evgeny Katz","doi":"10.1002/elsa.202400020","DOIUrl":"10.1002/elsa.202400020","url":null,"abstract":"<p>Svante August Arrhenius (Figure 1) was a Swedish scientist, educated as a physicist, but mostly contributed to chemistry. He established a new scientific filed of <i>physical chemistry</i>. Although he was not the only founder of this novel area combining physics and chemistry, his work was critically important for formulation and methodology of physical chemistry (Figure 2).</p><p>The most important scientific contribution made by Arrhenius was invention of the electrolytic dissociation theory. This theory explained ionic conductivity in salt/acid/base-solutions and provided background for research of electrochemical processes, including electroanalytical chemistry, electrolysis and battery chemistry. The first formulation of this theory, presently known as the Arrhenius dissociation theory, was made in his PhD thesis submitted in 1884: “<i>Recherches sur la conductibilite galvanique des electrolytes</i>” (Investigations on the galvanic conductivity of electrolytes). The theoretical assumption made by him was well supported with extensive experimental work made by Arrhenius, still being a student. The electrical conductivity in aqueous solutions of salts, acids and bases was explained by splitting the dissolved molecules or crystals in ions (positively charged cations and negatively charged anions). Particularly for acids and bases, he suggested their definitions based on generation of H<sup>+</sup> and OH<sup>−</sup> ions in the case of acids and bases, respectively. This definition of the acids and bases still keeps his name: Arrhenius acids and Arrhenius bases.</p><p>The Arrhenius theory had some connections to the early work made by Michael Faraday (English scientist, 1791–1867). Faraday, while studying electrolysis process, also proposed generation of cations and anions supporting conductivity in solutions. However, Faraday believed that their formation proceeds at electrode surfaces only upon pathing electric current through solutions. This explanation is incorrect according to the modern science. The Arrhenius theory proposed the cation and anion formation just upon dissolution of salts, acids, or bases, regardless the electric current applied. The dissociation of molecules into cations and anions (<b>x2</b>), according to the Arrhenius theory, proceeds due to weakening polaric chemical bonds in solutions based on solvents with the high dielectric constants (high polarity of the solvent molecules, water in the original Arrhenius work). This explanation appears to be correct.</p><p>It is interesting to note that the theory of the electrolytic dissociation was so much novel that it was poorly accepted by the scientific community, particularly, his PhD thesis received a low score. Notably, later his theory was awarded with the Nobel Prize. Arrhenius received the Nobel Prize for Chemistry in 1903, becoming the first Nobel laureate in Sweden. Shortly after that, in 1905, Arrhenius became the director of the Nobel Institute, where he remaine","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"4 4","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202400020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141648865","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: Tatyana Aleksandrovna Kryukova (1906–1987)","authors":"Evgeny Katz","doi":"10.1002/elsa.202400001","DOIUrl":"10.1002/elsa.202400001","url":null,"abstract":"<p>Tatyana Alexandrovna Kryukova (Figure 1), a Russian scientist and electrochemist, made important contributions to electroanalytical chemistry (Figure 2), particularly working in close collaboration with Professor Aleksandr Naumovich Frumkin, who was the greatest Russian scientist in the area of electrochemistry. Kryukova is particularly remembered for developing the theory of polarographic maxima, which were observed as a sharp increase in the current produced upon polarographic measurements under some conditions (Figure 3). These current peaks originated from tangential movements (rotation) of a mercury droplet electrode, then stimulating diffusion in the depletion layer and current increase. Kryukova experimentally observed and theoretically explained the formation and then inhibition of these peaks upon adsorption of organic substances (mostly surfactants) on a mercury droplet electrode. It should be noted that for the first time, the effect of surfactants on polarographic measurements was reported in the 1920s in the laboratory of Professor Jaroslav Heyrovský (polarography inventor and Nobel Prize laureate in 1959), and the study of this effect was published in 1931. However, the study of the surfactant effect performed by Heyrovský was only fragmental. Then, the credit for a detailed explanation of the reasons for the polarographic maxima origin and a systematic study of this effect belongs to Kryukova.</p><p>In 1949, Kryukova discovered another very unusual phenomenon, later named as “Kryukova effect” (Figure 4). This effect was observed as a sudden decrease in the current at very negative potentials upon polarographic reduction of anionic species, for example, persulfate or dichromate anions, particularly when a very diluted supporting electrolyte was present in the analyte solution. This current minimum disappeared when the electrolyte concentration was increased. Later, in 1952, Frumkin and G. M. Florianovich (a graduate student at that time) theoretically explained the effect observed by Kryukova as the repulsion of redox anions from the negatively charged electrode surface, as predicted by the Frumkin theory of 1933. This is exactly why the effect was only observed for anionic redox species particularly with very negative potentials, providing a negative charge at the working electrode. As expected, the high concentration of the supporting electrolyte was screening the electrostatic interaction between the negative Hg droplet electrode and the negative redox-anions, then eliminating the current decrease.</p><p>It should be noted that the electrochemical study of persulfate ions when the “Kryukova effect” was observed, had not only gained theoretical interest demonstrating a fundamental electrostatic effect at polarized electrodes, but it was also practically important as a part of the Russian uranium project because they were used as a reagent in the separation of uranium isotopes.</p><p>Kryukova published many important research pa","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202400001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139532283","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: Ludwig Mond (1839−1909)","authors":"Evgeny Katz","doi":"10.1002/elsa.202400002","DOIUrl":"10.1002/elsa.202400002","url":null,"abstract":"<p>The general concept of fuel cells starts from the experiments of British physicist William Grove who published the first results on fuel cells in 1839. He used hydrogen and oxygen as a fuel and oxidizer, respectively, reacting on platinum catalytic electrodes and generating electric power. However, his research was considered only as scientific proof of the process reversed to the water electrolysis with no practical importance. Indeed, the cell invented by Grove produced a very small current and voltage over a short time. Obviously, after the concept demonstration, some engineering had to be done for improving the cell efficiency to make it feasible for practical use.</p><p>During the late 1880s, two British chemists, Ludwig Mond and his assistant Carl Langer (Figure 1), developed a fuel cell with a longer service life with improved geometry of the catalytic electrodes and flow channels (Figure 2). They used the known scientific concept from Grove's cell, but with the improved engineering. Their fuel cell generated 6 amps per square foot current density and 730 mV voltage. The cell operated with coal-derived gas as a fuel and air (actually oxygen in the air) as an oxidizer. The cell was filled with diluted sulfuric acid and included thin perforated platinum electrodes separated with a porous nonconducting membrane. The first engineered fuel cell was demonstrated and patented in 1889. Note that Ludwig Mond and Carl Langer were the first to introduce the term “fuel cell” which is commonly used now.</p><p>The author declares that he has no conflict of interest.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"4 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202400002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139532914","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: John Alfred Valentine Butler (1899–1977)","authors":"Evgeny Katz","doi":"10.1002/elsa.202400003","DOIUrl":"10.1002/elsa.202400003","url":null,"abstract":"<p>John Alfred Valentine Butler was the first to connect the kinetic electrochemistry built up in the second half of the twentieth century with the thermodynamic electrochemistry that dominated the first half. John Alfred Valentine Butler had, to his credit, not only the first exponential relation between current and potential (1924) but also (along with R.W. Gurney) the introduction of energy-level thinking into electrochemistry (1951).</p><p>However, Butler was not alone in this study and therefore it is necessary to give credit also to Max Volmer, a great German surface chemist, and his student (at that time) Erdey-Gruz. Butler's very early contribution in 1924 and the Erdey-Gruz and Volmer contribution in 1930 form the basis of phenomenological kinetic electrochemistry. The resulting famous Butler-Volmer equation is very important in electrochemistry.</p><p>The author declares no conflict of interest.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"4 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202400003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139625114","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":"Sustainable supercapacitor with a natural rubber‐based electrolyte and natural graphite‐based electrodes","authors":"K. Perera, K. Vidanapathirana, Lewis J. Adams, N. Balakrishnan","doi":"10.1002/elsa.202300025","DOIUrl":"https://doi.org/10.1002/elsa.202300025","url":null,"abstract":"Supercapacitors are at the forefront of energy storage devices due to their ability to fulfill quick power requirements. However, safety and cost are important parameters for their real‐world applications. Green materials‐based electrodes and electrolytes can make them safer and cost‐effective. Herein, a supercapacitor based on a methyl‐grafted natural rubber/salt‐based electrolyte and natural graphite (NG)‐based electrodes are fabricated and characterized. Zinc trifluoromethanesulfonate [Zn(CF3SO3)2] is used as the salt for the electrolyte. A mixture of NG, activated charcoal, and polyvinylidenefluoride is used for electrodes. Our supercapacitor shows a single electrode specific capacitance, Csc of 4.2 Fg−1 from impedance measurement. Moreover, the capacitive and resistive features are dominant at low and high frequencies, respectively. The cyclic voltammetry test shows the dependence of Csc on the scan rate with a high value at slow scan rates. Performance of the supercapacitor during 5000 charge and discharge cycles at a constant current of 90 μA shows a rapid decrease of single electrode specific discharge capacitance at the beginning, but it starts to stabilize after about 2500 cycles. These findings are relevant to further developments of green materials‐based supercapacitors, offering opportunities to expand the functionalities of supercapacitors in green technologies.","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"91 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139154833","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":"Electrical energy input efficiency limitations in CO₂‐to‐CO electrolysis and attempts for improvement","authors":"Thomas Reichbauer, Bernhard Schmid, Kim‐Marie Vetter, David Reinisch, Nemanja Martić, Christian Reller, Alexander Grasruck, Romano Dorta, Günter Schmid","doi":"10.1002/elsa.202300024","DOIUrl":"https://doi.org/10.1002/elsa.202300024","url":null,"abstract":"Abstract Electrochemical CO 2 reduction is a potentially up‐coming technology to convert anthropogenic emitted CO 2 into chemical feedstock. Due to alkaline operating conditions of CO 2 ‐electrolyis in gas diffusion electrodes, exothermal hydroxide ion neutralization with the excess of supplied CO 2 leads to unavoidable electricity‐to‐heat conversion at the cathode, therefore limiting electrical energy input efficiency. The decomposition reaction of carbonates by protons from water oxidation completes the inherent CO 2 transport at the anode. In this work, different production routes to CO are thermodynamically examined and experimentally validated. Using formic acid as an intermediate towards CO the electrical energy input efficiency can rise to 71% on a thermodynamical basis. Additionally, the possibility of altering the mechanism of CO 2 reduction under acidic conditions is investigated, which would lead to even larger electrical energy input efficiencies. The concept was investigated by pH series measurements (pH = 0–6) at 50 mA/cm 2 where Pb derived from Pb 3 O 4 was used as a CO 2 reduction catalyst. The reduction to formic acid under acidic bulk electrolyte pH is stable at FE HCOOH = 70% down to pH ≈ 1, while HER is becoming dominant below. Even under such acidic bulk electrolyte conditions no change in reduction mechanism could be forced, which is reflected in invariant cell voltages in the model experiment.","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"136 30","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136351807","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":"Through the interface: New insights of the hydrogen evolution and oxidation reactions in aqueous solutions","authors":"Ershuai Liu,&nbsp;Li Jiao,&nbsp;Qingying Jia,&nbsp;Sanjeev Mukerjee","doi":"10.1002/elsa.202300016","DOIUrl":"10.1002/elsa.202300016","url":null,"abstract":"<p>Hydrogen evolution and oxidation reactions (HER/HOR) are the most fundamental reactions in electrocatalysis. Despite the practical significance, the mechanisms of HER/HOR in aqueous solutions are still elusive. Various theories have been proposed to rationalize the pH effect, cation effect, and structure effect of HER/HOR but none of them can explain all observations. In this review, we discuss four schools of thought for the HER/HOR, focusing on the strengths and shortcomings of each hypothesis and highlighting the magnitude of electrochemical interface structure in hydrogen electrocatalysis.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"4 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202300016","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136102851","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":"Investigation of physicochemical drivers directing ionic liquid assembly on polymeric nanoparticles","authors":"Sara X. Edgecomb, Christine M. Hamadani, Angela Roberts, George Taylor, Anya Merrell, Ember Suh, Mahesh Loku Yaddehige, Indika Chandrasiri, Davita L. Watkins, Eden E. L. Tanner","doi":"10.1002/elsa.202300013","DOIUrl":"https://doi.org/10.1002/elsa.202300013","url":null,"abstract":"Abstract Ionic liquids (ILs) have emerged as promising biomaterials for enhancing drug delivery by functionalizing polymeric nanoparticles (NPs). Despite the biocompatibility and biofunctionalization they confer upon the NPs, little is understood regarding the degree in which non‐covalent interactions, particularly hydrogen bonding and electrostatic interactions, govern IL‐NP supramolecular assembly. Herein, we use salt (0‐1 M sodium sulfate) and acid (0.25 M hydrochloric acid at pH 4.8) titrations to disrupt IL‐functionalized nanoassembly for four different polymeric platforms during synthesis. Through quantitative 1 H‐nuclear magnetic resonance spectroscopy and dynamic light scattering, we demonstrate that the driving force of choline trans‐2‐hexenoate (CA2HA 1:1) IL assembly varies with either hydrogen bonding or electrostatics dominating, depending on the structure of the polymeric platform. In particular, the covalently bound or branched 50:50 block co‐polymer systems (diblock PEG‐PLGA [DPP] and polycaprolactone [PCl]‐poly[amidoamine] amine‐based linear‐dendritic block co‐polymer) are predominantly affected by hydrogen bonding disruption. In contrast, a purely linear block co‐polymer system (carboxylic acid terminated poly[lactic‐co‐glycolic acid]) necessitates both electrostatics and hydrogen bonding to assemble with IL and a two‐component electrostatically bound system (electrostatic PEG‐PLGA [EPP]) favors hydrogen‐bonding with electrostatics serving as a secondary role.","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"48 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135596822","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":"Correlation of the electronic structure and Li‐ion mobility with modulus and hardness in LiNi_0.6Co_0.2Mn_0.2O₂ cathodes by combined near edge X‐ray absorption finestructure spectroscopy, atomic force microscopy, and nanoindentation","authors":"Florian Hausen, Niklas Scheer, Bixian Ying, Karin Kleiner","doi":"10.1002/elsa.202300017","DOIUrl":"https://doi.org/10.1002/elsa.202300017","url":null,"abstract":"Abstract The electrochemical performance of cathode materials in Li‐ion batteries is reflected in macroscopic observables such as the capacity, the voltage, and the state of charge (SOC). However, the physical origin of performance parameters are atomistic processes that scale up to a macroscopic picture. Thus, revealing the function and failure of electrochemical devices requires a multiscale (and ‐time) approach using spectroscopic and microscopic techniques. In this work, we combine near‐edge X‐ray absorption fine structure spectroscopy (NEXAFS) to determine the chemical binding state of transition metals in LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622), electrochemical strain microscopy to understand the Li‐ion mobility in such materials, and nanoindentation to relate the mechanical properties exhibited by the material to the chemical state and ion mobility. Strikingly, a clear correlation between the chemical binding, the mechanical properties, and the Li‐ion mobility is found. Thereby, the significant relation of chemo‐mechanical properties of NCM622 on a local and global scale is clearly demonstrated.","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"27 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136315345","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":"Probing passivity of corroding metals using scanning electrochemical probe microscopy","authors":"Sebastian Amland Skaanvik,&nbsp;Samantha Michelle Gateman","doi":"10.1002/elsa.202300014","DOIUrl":"10.1002/elsa.202300014","url":null,"abstract":"<p>Passive films are essential for the longevity of metals and alloys in corrosive environments. A great deal of research has been devoted to understanding and characterizing passive films, including their chemical composition, uniformity, thickness, porosity, and conductivity. Many characterization techniques are conducted under vacuum, which do not portray the true in-service environments passive films will endure. Scanning electrochemical probe microscopy (SEPM) techniques have emerged as necessary tools to complement research on characterizing passive films to enable the in situ extraction of passive film parameters and monitoring of local breakdown events of compromised films. Herein, we review the current research efforts using scanning electrochemical microscopy, scanning electrochemical cell microscopy (or droplet cell measurements), and local electrochemical impedance spectroscopy techniques to advance the knowledge of local properties of passivated metals. The future use of SEPM for quantitative extraction of local film characteristics within in-service environments (i.e., with varying pH, solution composition, and applied potential) is promising, which can be correlated to nanostructural and microstructural features of the passive film and underlying metal using complementary microscopy and spectroscopy methods. The outlook on this topic is highlighted, including exciting avenues and challenges of these methods in characterizing advanced alloy systems and protective surface films.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"4 5","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202300014","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46622445","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}