首页 > 最新文献

Electrochemical science advances最新文献

英文 中文
Electrochemical contributions: Marcel Pourbaix (1904–1998) 电化学贡献:Marcel Pourbaix (1904-1998)
Q2 ELECTROCHEMISTRY Pub Date : 2023-01-06 DOI: 10.1002/elsa.202200015
Evgeny Katz

Marcel Pourbaix (Figure 1) was a Belgian chemist (born in Russia) who greatly contributed to studies on corrosion. His biggest achievement is the derivation of potential-pH diagrams, better known as “Pourbaix Diagrams” (Figure 2a). Pourbaix Diagrams are thermodynamic charts constructed using the Nernst equation. They visualize the relationship between possible redox states of a system, bounded by lines representing the reactions between them under thermodynamic equilibrium. The Pourbaix diagrams can be read much like phase diagrams. In 1963, Pourbaix produced “Atlas of Electrochemical Equilibria in Aqueous Solutions” (Figure 2b), which contains potential-pH diagrams for all elements known at the time. Pourbaix and his collaborators began preparing the work in the early 1950s and continued the diagram updates over many years.

The author declares no conflict of interest.

Marcel Pourbaix(图1)是一位出生于俄罗斯的比利时化学家,他对腐蚀的研究做出了巨大贡献。他最大的成就是推导出电位- ph图,更广为人知的是“Pourbaix图”(图2a)。Pourbaix图是用能斯特方程构造的热力学图。他们可视化了系统中可能的氧化还原状态之间的关系,并用代表它们之间在热力学平衡下的反应的线为界。Pourbaix图可以像相图一样阅读。1963年,Pourbaix制作了“水溶液中电化学平衡图谱”(图2b),其中包含了当时已知的所有元素的电位ph图。Pourbaix和他的合作者在20世纪50年代初开始准备这项工作,并在多年的时间里继续更新图表。作者声明不存在利益冲突。
{"title":"Electrochemical contributions: Marcel Pourbaix (1904–1998)","authors":"Evgeny Katz","doi":"10.1002/elsa.202200015","DOIUrl":"10.1002/elsa.202200015","url":null,"abstract":"<p>Marcel Pourbaix (Figure 1) was a Belgian chemist (born in Russia) who greatly contributed to studies on corrosion. His biggest achievement is the derivation of potential-pH diagrams, better known as “Pourbaix Diagrams” (Figure 2a). Pourbaix Diagrams are thermodynamic charts constructed using the Nernst equation. They visualize the relationship between possible redox states of a system, bounded by lines representing the reactions between them under thermodynamic equilibrium. The Pourbaix diagrams can be read much like phase diagrams. In 1963, Pourbaix produced “Atlas of Electrochemical Equilibria in Aqueous Solutions” (Figure 2b), which contains potential-pH diagrams for all elements known at the time. Pourbaix and his collaborators began preparing the work in the early 1950s and continued the diagram updates over many years.</p><p>The author declares no conflict of interest.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202200015","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47528882","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}
引用次数: 0
What is limiting the potential window in aqueous sodium-ion batteries? Online study of the hydrogen-, oxygen- and CO2-evolution reactions at NaTi2(PO4)3 and Na0.44MnO2 electrodes 是什么限制了钠离子水电池的电位窗口?NaTi2(PO4)3 和 Na0.44MnO2 电极上的氢、氧和二氧化碳溶解反应在线研究
Q2 ELECTROCHEMISTRY Pub Date : 2022-12-20 DOI: 10.1002/elsa.202200012
Daniel Winkler, Teja Stüwe, Daniel Werner, Christoph Griesser, Christoph Thurner, David Stock, Julia Kunze-Liebhäuser, Engelbert Portenkirchner

NaTi2(PO4)3 (NTP) and Na0.44MnO2 (NMO), and their derivatives, have emerged as the most promising materials for aqueous Na-ion batteries. For both, NTP and NMO, avoiding the evolution of hydrogen and oxygen is found to be mandatory in order to mitigate material dissolution. Intriguingly, however, no direct determination of the hydrogen and oxygen evolution reactions (HER and OER) has yet been carried out. Using differential electrochemical mass spectrometry (DEMS) we directly identify the onset potentials for the HER and OER. Surprisingly, the potential window is found to be significantly smaller than suggested by commonly employed cyclic voltammetry measurements. CO2 evolution, upon decomposition of carbon black, is observed at an onset potential of 1.61 VRHE, which is 0.25 V more cathodic than the OER for the NMO electrode. Our results show that the state-of-the-art carbon additive plays a crucial role in the stability of the positive NMO electrode in the ion battery.

NaTi2(PO4)3(NTP)和 Na0.44MnO2(NMO)及其衍生物已成为最有前途的水性钠离子电池材料。对于 NTP 和 NMO 来说,避免氢和氧的演化是减轻材料溶解的必要条件。然而,耐人寻味的是,目前还没有直接测定氢和氧的进化反应(HER 和 OER)。利用差分电化学质谱法(DEMS),我们直接确定了氢进化反应和氧进化反应的起始电位。令人惊讶的是,我们发现该电位窗口明显小于常用的循环伏安法测量结果。在碳黑分解时,二氧化碳在 1.61 VRHE 的起始电位上发生进化,这比 NMO 电极的 OER 的阴极电位高出 0.25 V。我们的研究结果表明,最先进的碳添加剂对离子电池中 NMO 正极的稳定性起着至关重要的作用。
{"title":"What is limiting the potential window in aqueous sodium-ion batteries? Online study of the hydrogen-, oxygen- and CO2-evolution reactions at NaTi2(PO4)3 and Na0.44MnO2 electrodes","authors":"Daniel Winkler,&nbsp;Teja Stüwe,&nbsp;Daniel Werner,&nbsp;Christoph Griesser,&nbsp;Christoph Thurner,&nbsp;David Stock,&nbsp;Julia Kunze-Liebhäuser,&nbsp;Engelbert Portenkirchner","doi":"10.1002/elsa.202200012","DOIUrl":"10.1002/elsa.202200012","url":null,"abstract":"<p>NaTi<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NTP) and Na<sub>0.44</sub>MnO<sub>2</sub> (NMO), and their derivatives, have emerged as the most promising materials for aqueous Na-ion batteries. For both, NTP and NMO, avoiding the evolution of hydrogen and oxygen is found to be mandatory in order to mitigate material dissolution. Intriguingly, however, no direct determination of the hydrogen and oxygen evolution reactions (HER and OER) has yet been carried out. Using differential electrochemical mass spectrometry (DEMS) we directly identify the onset potentials for the HER and OER. Surprisingly, the potential window is found to be significantly smaller than suggested by commonly employed cyclic voltammetry measurements. CO<sub>2</sub> evolution, upon decomposition of carbon black, is observed at an onset potential of 1.61 V<sub>RHE</sub>, which is 0.25 V more cathodic than the OER for the NMO electrode. Our results show that the state-of-the-art carbon additive plays a crucial role in the stability of the positive NMO electrode in the ion battery.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202200012","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"51125079","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}
引用次数: 2
Perspective on the electrochemical recovery of phosphate from wastewater streams 废水中磷酸盐的电化学回收研究进展
Q2 ELECTROCHEMISTRY Pub Date : 2022-12-09 DOI: 10.1002/elsa.202200010
Nicholas A. Snyder, Carlos G. Morales-Guio

The presently increasing global population demands increased food production. Consequently, phosphate – an indispensable fertilizer component – will be needed in ever greater amounts. Current levels of mining of phosphate's most important constituent element, phosphorus (P), are unsustainable, and P rock is predicted to soon be completely depleted. Because P is a non-renewable resource, techniques to recover and reuse waste phosphate are necessary. Large amounts of unused phosphate exist in both municipal and agricultural wastewater streams, as well as in sewage sludge. Approaches to recovering phosphate from these sources fall into three main categories: biological, chemical, and electrochemical. Biological phosphate recovery has seen some plant-scale use, but significant drawbacks including the complication of operation have prevented it from becoming widespread. The most common method of phosphate recovery, chemical phosphate recovery, has been applied at scale with success due to the stability and reliability of the process. However, disadvantages such as the exorbitant amounts of alkali dosing required to maintain the high pH necessary for phosphate precipitation leave room for improvement. In recent years, electrochemical phosphate recovery has gained traction because of its potential to overcome the weaknesses of traditional chemical approaches by utilizing water electrolysis to induce a high pH without the need for an added base. But before plant-scale electrochemical methods can be considered economically viable, the steep energy requirements of water electrolysis must be mitigated through the development of improved electrocatalysts or circumvented through the discovery and application of new electrochemical processes to generate hydroxyl ions needed to induce a high pH. In this review, the three broad categories of phosphate recovery techniques are discussed and an outlook on the future of electrocatalysis for phosphate recovery is presented. Particularly, the requirements for improved and Earth-abundant electrocatalysts are considered alongside a critical discussion of the possibility of a decentralized network of onsite wastewater treatment facilities powered by renewable electricity.

目前,全球人口不断增长,需要增加粮食产量。因此,磷酸盐--一种不可或缺的肥料成分--的需求量将越来越大。磷酸盐最重要的组成元素磷(P)目前的开采水平是不可持续的,预计磷矿石很快就会完全枯竭。由于磷是不可再生资源,因此必须采用技术来回收和再利用废弃磷酸盐。大量未使用的磷酸盐存在于城市和农业废水流以及污水污泥中。从这些来源中回收磷酸盐的方法主要分为三类:生物法、化学法和电化学法。生物磷酸盐回收在一些工厂得到了大规模应用,但由于操作复杂等重大缺陷,这种方法未能得到普及。最常见的磷酸盐回收方法是化学磷酸盐回收,由于该工艺稳定可靠,已成功地大规模应用。然而,其缺点是,为了保持磷酸盐沉淀所需的高 pH 值,需要投加大量的碱,因此仍有改进的余地。近年来,电化学磷酸盐回收法克服了传统化学方法的缺点,利用水电解产生高 pH 值,无需添加碱,因此受到越来越多的关注。但是,在工厂规模的电化学方法被认为具有经济可行性之前,必须通过开发改进的电催化剂来降低水电解所需的高能量,或者通过发现和应用新的电化学过程来产生诱导高 pH 值所需的羟基离子,从而避免水电解所需的高能量。本综述讨论了三大类磷酸盐回收技术,并对磷酸盐回收电催化技术的未来进行了展望。特别是考虑了对改进型和地球丰富电催化剂的要求,同时对利用可再生电力驱动的分散式现场废水处理设施网络的可能性进行了批判性讨论。
{"title":"Perspective on the electrochemical recovery of phosphate from wastewater streams","authors":"Nicholas A. Snyder,&nbsp;Carlos G. Morales-Guio","doi":"10.1002/elsa.202200010","DOIUrl":"10.1002/elsa.202200010","url":null,"abstract":"<p>The presently increasing global population demands increased food production. Consequently, phosphate – an indispensable fertilizer component – will be needed in ever greater amounts. Current levels of mining of phosphate's most important constituent element, phosphorus (P), are unsustainable, and P rock is predicted to soon be completely depleted. Because P is a non-renewable resource, techniques to recover and reuse waste phosphate are necessary. Large amounts of unused phosphate exist in both municipal and agricultural wastewater streams, as well as in sewage sludge. Approaches to recovering phosphate from these sources fall into three main categories: biological, chemical, and electrochemical. Biological phosphate recovery has seen some plant-scale use, but significant drawbacks including the complication of operation have prevented it from becoming widespread. The most common method of phosphate recovery, chemical phosphate recovery, has been applied at scale with success due to the stability and reliability of the process. However, disadvantages such as the exorbitant amounts of alkali dosing required to maintain the high pH necessary for phosphate precipitation leave room for improvement. In recent years, electrochemical phosphate recovery has gained traction because of its potential to overcome the weaknesses of traditional chemical approaches by utilizing water electrolysis to induce a high pH without the need for an added base. But before plant-scale electrochemical methods can be considered economically viable, the steep energy requirements of water electrolysis must be mitigated through the development of improved electrocatalysts or circumvented through the discovery and application of new electrochemical processes to generate hydroxyl ions needed to induce a high pH. In this review, the three broad categories of phosphate recovery techniques are discussed and an outlook on the future of electrocatalysis for phosphate recovery is presented. Particularly, the requirements for improved and Earth-abundant electrocatalysts are considered alongside a critical discussion of the possibility of a decentralized network of onsite wastewater treatment facilities powered by renewable electricity.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202200010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42489018","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}
引用次数: 0
Role of oxide support in electrocatalytic nitrate reduction on Cu 氧化物载体在铜电催化硝酸盐还原中的作用
Q2 ELECTROCHEMISTRY Pub Date : 2022-11-29 DOI: 10.1002/elsa.202100201
O. Quinn Carvalho, Sophia R. S. Jones, Ashley E. Berninghaus, Richard F. Hilliard, Tyler S. Radniecki, Kelsey A. Stoerzinger

The electrochemical nitrate reduction reaction (NO3RR) has the potential for distributed water treatment and renewable chemical synthesis. Cu is an active monometallic electrocatalyst for the NO3RR in acidic and alkaline electrolytes, where activity is limited by the reduction of adsorbed nitrate to nitrite. Oxygen-vacancy forming metal-oxide supports provide sites for N-O bond activation in thermal reduction, impacting product distribution as well. Here we compare the electrochemical NO3RR activity of Cu deposited on two metal-oxide supports (cerium dioxide [Cu/CeO2-δ] and fluorine-doped tin dioxide [Cu/FTO]) to a Cu foil benchmark. Considering activity in phosphate-buffered neutral media, nitrate and adsorbed hydrogen compete for surface sites under NO3RR conditions. The less-cathodic overpotential on Cu/CeO2-δ compared to Cu/FTO is attributed to stronger nitrate adsorption, similar to thermal nitrate reduction. Utilization of CeO2-δ as an electrocatalyst support slightly shifting product distribution toward more oxidized products, either by enhancing nitrate affinity or by a more dynamic process involving the formation and healing of oxygen vacancies (𝑣O••). These results suggest supporting catalysts on metal oxides may enhance activity by promoting the adsorption of anionic reactants on cathodic electrocatalysts.

电化学硝酸盐还原反应(NO3RR)具有分布式水处理和可再生化学合成的潜力。铜是在酸性和碱性电解质中进行 NO3RR 反应的活性单金属电催化剂,其活性受到吸附的硝酸盐还原为亚硝酸盐的限制。氧空位形成的金属氧化物支撑为热还原过程中的 N-O 键活化提供了场所,同时也影响了产物的分布。在此,我们将沉积在两种金属氧化物支撑物(二氧化铈 [Cu/CeO2-δ] 和掺氟二氧化锡 [Cu/FTO])上的铜的电化学 NO3RR 活性与铜箔基准进行了比较。考虑到在磷酸盐缓冲中性介质中的活性,在 NO3RR 条件下,硝酸盐和吸附氢会竞争表面位点。与 Cu/FTO 相比,Cu/CeO2-δ 的阴极过电位较低,这是因为硝酸盐吸附力较强,类似于硝酸盐热还原。利用 CeO2-δ 作为电催化剂,可以通过提高硝酸盐的亲和力,或通过涉及氧空位(𝑣O--)的形成和愈合的更动态过程,使产物分布略微转向更多的氧化产物。这些结果表明,在金属氧化物上支撑催化剂可以通过促进阴极电催化剂对阴离子反应物的吸附来提高活性。
{"title":"Role of oxide support in electrocatalytic nitrate reduction on Cu","authors":"O. Quinn Carvalho,&nbsp;Sophia R. S. Jones,&nbsp;Ashley E. Berninghaus,&nbsp;Richard F. Hilliard,&nbsp;Tyler S. Radniecki,&nbsp;Kelsey A. Stoerzinger","doi":"10.1002/elsa.202100201","DOIUrl":"10.1002/elsa.202100201","url":null,"abstract":"<p>The electrochemical nitrate reduction reaction (NO<sub>3</sub>RR) has the potential for distributed water treatment and renewable chemical synthesis. Cu is an active monometallic electrocatalyst for the NO<sub>3</sub>RR in acidic and alkaline electrolytes, where activity is limited by the reduction of adsorbed nitrate to nitrite. Oxygen-vacancy forming metal-oxide supports provide sites for N-O bond activation in thermal reduction, impacting product distribution as well. Here we compare the electrochemical NO<sub>3</sub>RR activity of Cu deposited on two metal-oxide supports (cerium dioxide [Cu/CeO<sub>2-δ</sub>] and fluorine-doped tin dioxide [Cu/FTO]) to a Cu foil benchmark. Considering activity in phosphate-buffered neutral media, nitrate and adsorbed hydrogen compete for surface sites under NO<sub>3</sub>RR conditions. The less-cathodic overpotential on Cu/CeO<sub>2-δ</sub> compared to Cu/FTO is attributed to stronger nitrate adsorption, similar to thermal nitrate reduction. Utilization of CeO<sub>2-δ</sub> as an electrocatalyst support slightly shifting product distribution toward more oxidized products, either by enhancing nitrate affinity or by a more dynamic process involving the formation and healing of oxygen vacancies (𝑣<sub>O</sub><sup>••</sup>). These results suggest supporting catalysts on metal oxides may enhance activity by promoting the adsorption of anionic reactants on cathodic electrocatalysts.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46044562","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}
引用次数: 0
Calculation of the Tafel slope and reaction order of the oxygen evolution reaction between pH 12 and pH 14 for the adsorbate mechanism 针对吸附剂机理计算 pH 值 12 和 pH 值 14 之间氧进化反应的塔菲尔斜率和反应阶次
Q2 ELECTROCHEMISTRY Pub Date : 2022-11-25 DOI: 10.1002/elsa.202100213
Denis Antipin, Marcel Risch

Despite numerous experimental and theoretical studies devoted to the oxygen evolution reaction (OER), the mechanism of the OER on transition metal oxides remains controversial. This is in part owing to the ambiguity of electrochemical parameters of the mechanism such as the Tafel slope and reaction orders. We took the most commonly assumed adsorbate mechanism and calculated the Tafel slopes and reaction orders with respect to pH based on microkinetic analysis using the steady-state approximation. The analysis was performed for an ideal electrocatalyst without scaling of the intermediates as well as for one on the top of a volcano relation and one on each leg of the volcano relation which exhibits scaling of the intermediates. For these four cases, the number of possible Tafel slopes strongly depends on surface coverage. Furthermore, the Tafel slope becomes pH-dependent when the coverage of intermediates changes with pH. These insights complicate the identification of a rate-limiting step by a single Tafel slope at a single pH. Yet, simulations of reaction orders complementary to Tafel slopes can solve some ambiguities to distinguish between possible rate-limiting steps. The most insightful information can be obtained from the low overpotential region of the Tafel plot. The simulations in this work provide clear guidelines to experimentalists for the identification of the limiting steps in the adsorbate mechanism using the observed values of the Tafel slope and reaction order in pH-dependent studies.

尽管针对氧进化反应(OER)进行了大量实验和理论研究,但过渡金属氧化物上的 OER 机理仍存在争议。部分原因是该机理的电化学参数(如塔菲尔斜率和反应阶数)不明确。我们采用了最常见的吸附机理假设,并基于稳态近似的微动力学分析,计算了塔菲尔斜率和反应阶数与 pH 值的关系。分析针对的是没有中间产物缩放的理想电催化剂,以及位于火山关系顶端的理想电催化剂和位于火山关系每条腿上的理想电催化剂,后者表现出中间产物的缩放。在这四种情况下,可能的塔菲尔斜率数量在很大程度上取决于表面覆盖率。此外,当中间产物的覆盖率随 pH 值变化时,塔菲尔斜率也会随 pH 值变化而变化。这些见解使在单一 pH 值下通过单一塔菲尔斜率确定限速步骤的工作变得复杂。然而,与塔菲尔斜率互补的反应顺序模拟可以解决一些模糊问题,从而区分可能的限速步骤。从塔菲尔图的低过电位区域可以获得最有洞察力的信息。这项工作中的模拟为实验人员提供了明确的指导,使他们能够利用在 pH 依赖性研究中观察到的塔菲尔斜率值和反应阶次来确定吸附机理中的限制步骤。
{"title":"Calculation of the Tafel slope and reaction order of the oxygen evolution reaction between pH 12 and pH 14 for the adsorbate mechanism","authors":"Denis Antipin,&nbsp;Marcel Risch","doi":"10.1002/elsa.202100213","DOIUrl":"https://doi.org/10.1002/elsa.202100213","url":null,"abstract":"<p>Despite numerous experimental and theoretical studies devoted to the oxygen evolution reaction (OER), the mechanism of the OER on transition metal oxides remains controversial. This is in part owing to the ambiguity of electrochemical parameters of the mechanism such as the Tafel slope and reaction orders. We took the most commonly assumed adsorbate mechanism and calculated the Tafel slopes and reaction orders with respect to pH based on microkinetic analysis using the steady-state approximation. The analysis was performed for an ideal electrocatalyst without scaling of the intermediates as well as for one on the top of a volcano relation and one on each leg of the volcano relation which exhibits scaling of the intermediates. For these four cases, the number of possible Tafel slopes strongly depends on surface coverage. Furthermore, the Tafel slope becomes pH-dependent when the coverage of intermediates changes with pH. These insights complicate the identification of a rate-limiting step by a single Tafel slope at a single pH. Yet, simulations of reaction orders complementary to Tafel slopes can solve some ambiguities to distinguish between possible rate-limiting steps. The most insightful information can be obtained from the low overpotential region of the Tafel plot. The simulations in this work provide clear guidelines to experimentalists for the identification of the limiting steps in the adsorbate mechanism using the observed values of the Tafel slope and reaction order in pH-dependent studies.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100213","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138558228","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}
引用次数: 0
Editorial: 100 years of polarography 社论:极谱100年
Q2 ELECTROCHEMISTRY Pub Date : 2022-11-20 DOI: 10.1002/elsa.202260007
Jiří Ludvík
<p>The young journal <i>Electrochemical Science Advances</i> copublished by Wiley-VCH and Chemistry Europe has had a great start. Its constitution reflects the increasing interest in electrochemical research and development. Its content is therefore devoted not only to fundamental research in electrochemistry but (importantly) to consequential applications like generation and storage of electricity, photovoltaics, corrosion, electrochemical sensors, analysers, electrochromism, (photo)electrocatalysis, electrosynthesis, photo- and spectroelectrochemistry, molecular electronics, and alternative electrodes etc.</p><p>The beginning of electrochemistry is dated about three centuries back, and its development is connected with the names like Luigi Galvani (1737–1798), Alessandro Volta (1745–1827), Humphry Davy (1778-1829), John F. Daniell (1790–1845), Michael Faraday (1791–1867), and many others. In the 19th century, electrochemistry was rather a part of physics connected with the general studies of electricity—at first its generation (Volta, Daniell), then its combination with biology (Galvani), later electrolyses and metal electrodeposition (Faraday), surface effects, and conductivity of electrolytes etc.</p><p>The current collection of this new journal is symbolically devoted to the <i>100th anniversary of polarography</i> invented at the Charles University, Prague, by <i>Jaroslav Heyrovský</i> (Nobel Prize 1959). In February 1922, the first polarographic curve was recorded, where for the first time, the electrochemical current was plotted against potential (i-E curve) offering simultaneously qualitative as well as quantitative analytical data. Therefore, the year 1922 is considered as the true <i>start of modern electrochemistry</i> as a part of chemical sciences. The instrument itself—<i>polarograph</i>—was at that time the first fully automatic analytical device where after filling the cell, connecting electrodes, setting the conditions (scan rate, initial and final potential, sensitivity, drop size etc.) and switching ON the instrument, the whole experiment including photographic recording was running automatically.</p><p>After the initial applications in electroanalysis, the development continued toward organic electrosynthesis, redox characterization of new molecules, and investigation of the relationship between their structure and chemical properties. Because electrochemistry, as an alternative to the classic thermal redox chemistry, uses “pure” electrons generated or accepted by an electrode for reduction and oxidation reactions, respectively, it represents an approach and tool suitable for all branches of chemistry.</p><p>Although currently electrochemistry goes through enormous and fascinating development both in fundamental research and in applied sciences, still, the original polarography that means voltammetry utilizing mercury drop as the working electrode (today mostly computer-controlled) has and will have its permanent position amo
由Wiley-VCH和Chemistry Europe共同出版的年轻杂志《电化学科学进展》(Electrochemical Science Advances)已经有了一个良好的开端。它的构成反映了人们对电化学研究和发展日益增长的兴趣。因此,它的内容不仅致力于电化学的基础研究,而且(重要的是)涉及诸如电力的产生和储存、光伏、腐蚀、电化学传感器、分析仪、电致变色、(光)电催化、电合成、光和光谱电化学、分子电子学和替代电极等相关应用。电化学的开始可以追溯到大约三个世纪以前。它的发展与路易吉·伽伐尼(1737-1798)、亚历山德罗·沃尔特(1745-1827)、汉弗莱·戴维(1778-1829)、约翰·f·丹尼尔(1790-1845)、迈克尔·法拉第(1791-1867)等许多人的名字有关。在19世纪,电化学是与一般的电学研究相联系的物理学的一部分——首先是它的产生(伏特,丹尼尔),然后是它与生物学的结合(伽伐尼),后来是电解和金属电沉积(法拉第),表面效应,电解质的导电性等。这本新杂志的当前收藏是象征性地献给在布拉格查尔斯大学发明的极谱法100周年。雅罗斯拉夫Heyrovský(1959年诺贝尔奖)。1922年2月,第一次记录了极谱曲线,其中电化学电流与电位(i-E曲线)相对应,同时提供了定性和定量分析数据。因此,1922年被认为是现代电化学作为化学科学的一部分的真正开始。仪器本身——极谱仪——在当时是第一台全自动分析设备,在填充电池、连接电极、设置条件(扫描速率、初、终电位、灵敏度、液滴大小等)并打开仪器后,包括照相记录在内的整个实验就自动运行了。在最初的电分析应用之后,继续向有机电合成、新分子的氧化还原表征以及其结构和化学性质之间关系的研究发展。电化学作为经典热氧化还原化学的替代方法,分别使用电极产生或接受的“纯”电子进行还原和氧化反应,因此它代表了一种适用于所有化学分支的方法和工具。尽管目前电化学在基础研究和应用科学方面都经历了巨大而迷人的发展,但原始的极谱法,即利用汞滴作为工作电极的伏安法(今天主要是计算机控制的)已经并将在电化学研究的标准技术中占有永久的地位。这期包含实际研究结果的杂志应该说明从极谱根培养的电化学生长树的丰富作物。作者声明不存在利益冲突。
{"title":"Editorial: 100 years of polarography","authors":"Jiří Ludvík","doi":"10.1002/elsa.202260007","DOIUrl":"10.1002/elsa.202260007","url":null,"abstract":"&lt;p&gt;The young journal &lt;i&gt;Electrochemical Science Advances&lt;/i&gt; copublished by Wiley-VCH and Chemistry Europe has had a great start. Its constitution reflects the increasing interest in electrochemical research and development. Its content is therefore devoted not only to fundamental research in electrochemistry but (importantly) to consequential applications like generation and storage of electricity, photovoltaics, corrosion, electrochemical sensors, analysers, electrochromism, (photo)electrocatalysis, electrosynthesis, photo- and spectroelectrochemistry, molecular electronics, and alternative electrodes etc.&lt;/p&gt;&lt;p&gt;The beginning of electrochemistry is dated about three centuries back, and its development is connected with the names like Luigi Galvani (1737–1798), Alessandro Volta (1745–1827), Humphry Davy (1778-1829), John F. Daniell (1790–1845), Michael Faraday (1791–1867), and many others. In the 19th century, electrochemistry was rather a part of physics connected with the general studies of electricity—at first its generation (Volta, Daniell), then its combination with biology (Galvani), later electrolyses and metal electrodeposition (Faraday), surface effects, and conductivity of electrolytes etc.&lt;/p&gt;&lt;p&gt;The current collection of this new journal is symbolically devoted to the &lt;i&gt;100th anniversary of polarography&lt;/i&gt; invented at the Charles University, Prague, by &lt;i&gt;Jaroslav Heyrovský&lt;/i&gt; (Nobel Prize 1959). In February 1922, the first polarographic curve was recorded, where for the first time, the electrochemical current was plotted against potential (i-E curve) offering simultaneously qualitative as well as quantitative analytical data. Therefore, the year 1922 is considered as the true &lt;i&gt;start of modern electrochemistry&lt;/i&gt; as a part of chemical sciences. The instrument itself—&lt;i&gt;polarograph&lt;/i&gt;—was at that time the first fully automatic analytical device where after filling the cell, connecting electrodes, setting the conditions (scan rate, initial and final potential, sensitivity, drop size etc.) and switching ON the instrument, the whole experiment including photographic recording was running automatically.&lt;/p&gt;&lt;p&gt;After the initial applications in electroanalysis, the development continued toward organic electrosynthesis, redox characterization of new molecules, and investigation of the relationship between their structure and chemical properties. Because electrochemistry, as an alternative to the classic thermal redox chemistry, uses “pure” electrons generated or accepted by an electrode for reduction and oxidation reactions, respectively, it represents an approach and tool suitable for all branches of chemistry.&lt;/p&gt;&lt;p&gt;Although currently electrochemistry goes through enormous and fascinating development both in fundamental research and in applied sciences, still, the original polarography that means voltammetry utilizing mercury drop as the working electrode (today mostly computer-controlled) has and will have its permanent position amo","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"2 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202260007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49253495","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}
引用次数: 0
Electrochemical and spectral studies of rhodanine in view of heavy metals determination 罗丹宁在重金属测定中的电化学和光谱研究
Q2 ELECTROCHEMISTRY Pub Date : 2022-10-28 DOI: 10.1002/elsa.202100218
Ovidiu Teodor Matica, Alina Giorgiana Brotea, Eleonora-Mihaela Ungureanu, Luisa Roxana Mandoc, Liviu Birzan

The electrochemical study of 2-Sulfanylidene-1,3-thiazolidin-4-one (rhodanine, R) was performed on a glassy carbon working electrode by using three methods: differential pulse voltammetry (DPV), cyclic voltammetry (CV), and linear sweep voltammetry (LSV) at rotating disk electrode voltammetry (RDE). The CV, DPV, and LSV at RDE curves for R were recorded at different concentrations in 0.1 M TBAP/CH3CN. Polymeric films were formed by successive cycling at different potentials and by controlled potential electrolysis. The film formation was proved by recording the CV curves of the chemically modified electrodes (CMEs) in transfer solutions containing ferrocene in 0.1 M TBAP/CH3CN. The obtained CMEs were used for the detection of heavy metal ions. Synthetic samples of heavy metal ions (Cd (II), Pb (II), Cu (II), Hg (II)) of concentrations between 10−7 and 10−5 M were analyzed using CMEs prepared in different conditions. The most intense signal was obtained for Pb(II) ion (estimated detection limit = 10−7 M), which shows that these CMEs can be used for Pb(II) ion detection. The ability of R to form complexes with Pb(II) ion was also tested by UV-Vis spectrometry. The obtained results showed the formation of Pb(II)R2 as the most stable complex.

采用微分脉冲伏安法(DPV)、循环伏安法(CV)和旋转盘电极伏安法(RDE)线性扫描伏安法(LSV)三种方法,在玻璃碳工作电极上对 2-硫代-1,3-噻唑烷-4-酮(罗丹宁,Rhodanine,R)进行了电化学研究。在 0.1 M TBAP/CH3CN 中记录了不同浓度 R 的 CV、DPV 和 LSV 曲线。通过在不同电位下连续循环和控制电位电解,形成了聚合物薄膜。通过记录化学修饰电极(CME)在 0.1 M TBAP/CH3CN 中含有二茂铁的转移溶液中的 CV 曲线,证明了薄膜的形成。获得的 CME 用于检测重金属离子。使用在不同条件下制备的 CME 分析了浓度在 10-7 和 10-5 M 之间的重金属离子(镉 (II)、铅 (II)、铜 (II)、汞 (II))合成样品。Pb(II) 离子获得了最强烈的信号(估计检测限 = 10-7M),这表明这些 CMEs 可用于 Pb(II) 离子的检测。紫外可见光谱法还测试了 R 与铅(II)离子形成络合物的能力。结果表明,形成的 Pb(II)R2 是最稳定的络合物。
{"title":"Electrochemical and spectral studies of rhodanine in view of heavy metals determination","authors":"Ovidiu Teodor Matica,&nbsp;Alina Giorgiana Brotea,&nbsp;Eleonora-Mihaela Ungureanu,&nbsp;Luisa Roxana Mandoc,&nbsp;Liviu Birzan","doi":"10.1002/elsa.202100218","DOIUrl":"10.1002/elsa.202100218","url":null,"abstract":"<p>The electrochemical study of 2-Sulfanylidene-1,3-thiazolidin-4-one (rhodanine, <b>R</b>) was performed on a glassy carbon working electrode by using three methods: differential pulse voltammetry (DPV), cyclic voltammetry (CV), and linear sweep voltammetry (LSV) at rotating disk electrode voltammetry (RDE). The CV, DPV, and LSV at RDE curves for <b>R</b> were recorded at different concentrations in 0.1 M TBAP/CH<sub>3</sub>CN. Polymeric films were formed by successive cycling at different potentials and by controlled potential electrolysis. The film formation was proved by recording the CV curves of the chemically modified electrodes (CMEs) in transfer solutions containing ferrocene in 0.1 M TBAP/CH<sub>3</sub>CN. The obtained CMEs were used for the detection of heavy metal ions. Synthetic samples of heavy metal ions (Cd (II), Pb (II), Cu (II), Hg (II)) of concentrations between 10<sup>−7</sup> and 10<sup>−5</sup> M were analyzed using CMEs prepared in different conditions. The most intense signal was obtained for Pb(II) ion (estimated detection limit = 10<sup>−7</sup> M), which shows that these CMEs can be used for Pb(II) ion detection. The ability of <b>R</b> to form complexes with Pb(II) ion was also tested by UV-Vis spectrometry. The obtained results showed the formation of Pb(II)<b>R</b><sub>2</sub> as the most stable complex.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100218","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43645539","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}
引用次数: 3
Surface microstructures and oxygen evolution properties of cobalt oxide deposited on Ir(111) and Pt(111) single crystal substrates Ir(111)和Pt(111
Q2 ELECTROCHEMISTRY Pub Date : 2022-09-11 DOI: 10.1002/elsa.202200007
Naoto Todoroki, Hiroto Tsurumaki, Arata Shinomiya, Toshimasa Wadayama

We investigated the oxygen evolution reaction (OER) activity changes of cobalt oxide (CoOx) thin films on Ir(111) and Pt(111) substrates by repeated OER measurements in 0.1 M KOH. Atomic force microscopy and X-ray photoelectron spectroscopy analysis of the as-prepared CoOx/Ir(111) and CoOx/Pt(111) showed similar surface morphologies of the CoOx thin films and almost the same OER overpotentials, which were estimated to be around 430 mV. However, after three OER measurements, the overpotential of CoOx/Ir(111) decreased by 70 mV, whereas that of CoOx/Pt(111) increased slightly. Structural analysis showed that CoOx/Ir(111) revealed the island-like nanostructures of CoOx dispersed on Ir(111) surface, accompanied by the generation of CoOOH. In contrast, for CoOx/Pt(111), the Pt(111) substrate remains covered by the CoOx thin film. The results suggest that the interaface at CoOx (CoOOH) nano-islands and Ir(111) substrate are responsible for reducing the OER overpotential.

我们通过在 0.1 M KOH 中反复测量氧化钴(CoOx)薄膜在 Ir(111) 和 Pt(111) 基底上的氧演化反应(OER)活性变化进行了研究。对制备的 CoOx/Ir(111) 和 CoOx/Pt(111) 进行的原子力显微镜和 X 射线光电子能谱分析表明,CoOx 薄膜的表面形态相似,OER 过电位几乎相同,估计在 430 mV 左右。然而,经过三次 OER 测量后,CoOx/Ir(111) 的过电位下降了 70 mV,而 CoOx/Pt(111) 的过电位则略有上升。结构分析表明,CoOx/Ir(111)显示了分散在 Ir(111) 表面的岛状 CoOx 纳米结构,并伴随着 CoOOH 的生成。相反,对于 CoOx/Pt(111),铂(111)基底仍然被 CoOx 薄膜覆盖。结果表明,CoOx(CoOOH)纳米带和 Ir(111)基底之间的界面是降低 OER 过电位的原因。
{"title":"Surface microstructures and oxygen evolution properties of cobalt oxide deposited on Ir(111) and Pt(111) single crystal substrates","authors":"Naoto Todoroki,&nbsp;Hiroto Tsurumaki,&nbsp;Arata Shinomiya,&nbsp;Toshimasa Wadayama","doi":"10.1002/elsa.202200007","DOIUrl":"10.1002/elsa.202200007","url":null,"abstract":"<p>We investigated the oxygen evolution reaction (OER) activity changes of cobalt oxide (CoO<i><sub>x</sub></i>) thin films on Ir(111) and Pt(111) substrates by repeated OER measurements in 0.1 M KOH. Atomic force microscopy and X-ray photoelectron spectroscopy analysis of the as-prepared CoO<i><sub>x</sub></i>/Ir(111) and CoO<i><sub>x</sub></i>/Pt(111) showed similar surface morphologies of the CoO<i><sub>x</sub></i> thin films and almost the same OER overpotentials, which were estimated to be around 430 mV. However, after three OER measurements, the overpotential of CoO<i><sub>x</sub></i>/Ir(111) decreased by 70 mV, whereas that of CoO<i><sub>x</sub></i>/Pt(111) increased slightly. Structural analysis showed that CoO<i><sub>x</sub></i>/Ir(111) revealed the island-like nanostructures of CoO<i><sub>x</sub></i> dispersed on Ir(111) surface, accompanied by the generation of CoOOH. In contrast, for CoO<i><sub>x</sub></i>/Pt(111), the Pt(111) substrate remains covered by the CoO<i><sub>x</sub></i> thin film. The results suggest that the interaface at CoO<i><sub>x</sub></i> (CoOOH) nano-islands and Ir(111) substrate are responsible for reducing the OER overpotential.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202200007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43907437","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}
引用次数: 1
Unprecedented formation of reactive BrO– ions and their role as mediators for organic compounds degradation: The fate of bromide ions released during the anodic oxidation of Bromophenol blue dye 活性溴离子的空前形成及其作为有机化合物降解介质的作用:溴酚蓝染料阳极氧化过程中释放的溴离子的命运
Q2 ELECTROCHEMISTRY Pub Date : 2022-09-04 DOI: 10.1002/elsa.202100225
Camila Carvalho de Almeida, Soliu O. Ganiyu, Carlos A. Martínez-Huitle, Elisama Vieira dos Santos, Katlin Ivon Barrios Eguiluz, Giancarlo Richard Salazar-Banda

Based on the existing literature, active chlorine-mediated electrochemical oxidation has been extensively studied when Cl is added or Cl is already present in the water matrices, as well as when Cl is released from the target organic pollutants during their degradation. However, no attempts have been published concerning the fate and role of bromide (Br) ions released during the anodic oxidation (AO) of organobromine compounds. Therefore, the AO of bromophenol blue dye (BPB) was investigated in a parallel plate flow reactor using a boron-doped diamond (BDD) anode. The effect of the applied current on the color removal efficiency and mineralization of BPB solution was examined and compared with AO of phenol red (PR) which has a similar molecular structure to BPB (but without Br) in order to understand the role of Br heteroatoms on the mineralization of BPB. Faster and higher mineralization and discoloration were achieved when treated with BPB solution compared to PR under similar experimental conditions. This behavior was associated with the electrogeneration of BrO, from the heteroatom Br which is released as the bromide ion (Br), during the degradation of BPB. The active bromine species are formed via direct and indirect oxidation approaches which were proposed based on ion chromatography and linear scanning voltammetry analysis.

根据现有文献,当水中添加 Cl- 或已经存在 Cl- 时,以及当目标有机污染物在降解过程中释放出 Cl- 时,以氯为介质的活性电化学氧化作用已得到广泛研究。不过,目前还没有关于有机溴化合物阳极氧化(AO)过程中释放的溴离子(Br-)的归宿和作用的尝试。因此,我们在平行板流反应器中使用掺硼金刚石(BDD)阳极研究了溴酚蓝染料(BPB)的阳极氧化。研究了外加电流对 BPB 溶液脱色效率和矿化度的影响,并将其与分子结构与 BPB 相似(但不含 Br)的酚红(PR)的 AO 进行了比较,以了解 Br 杂原子对 BPB 矿化度的作用。在相似的实验条件下,与 PR 相比,用 BPB 溶液处理 BPB 时,矿化速度更快,褪色程度更高。这种行为与 BPB 降解过程中从杂原子 Br(以溴离子(Br-)的形式释放)电生成的 BrO- 有关。根据离子色谱法和线性扫描伏安分析法提出的直接和间接氧化方法形成了活性溴物种。
{"title":"Unprecedented formation of reactive BrO– ions and their role as mediators for organic compounds degradation: The fate of bromide ions released during the anodic oxidation of Bromophenol blue dye","authors":"Camila Carvalho de Almeida,&nbsp;Soliu O. Ganiyu,&nbsp;Carlos A. Martínez-Huitle,&nbsp;Elisama Vieira dos Santos,&nbsp;Katlin Ivon Barrios Eguiluz,&nbsp;Giancarlo Richard Salazar-Banda","doi":"10.1002/elsa.202100225","DOIUrl":"10.1002/elsa.202100225","url":null,"abstract":"<p>Based on the existing literature, active chlorine-mediated electrochemical oxidation has been extensively studied when Cl<sup>‒</sup> is added or Cl<sup>‒</sup> is already present in the water matrices, as well as when Cl<sup>‒</sup> is released from the target organic pollutants during their degradation. However, no attempts have been published concerning the fate and role of bromide (Br<sup>‒</sup>) ions released during the anodic oxidation (AO) of organobromine compounds. Therefore, the AO of bromophenol blue dye (BPB) was investigated in a parallel plate flow reactor using a boron-doped diamond (BDD) anode. The effect of the applied current on the color removal efficiency and mineralization of BPB solution was examined and compared with AO of phenol red (PR) which has a similar molecular structure to BPB (but without Br) in order to understand the role of Br heteroatoms on the mineralization of BPB. Faster and higher mineralization and discoloration were achieved when treated with BPB solution compared to PR under similar experimental conditions. This behavior was associated with the electrogeneration of BrO<sup>‒</sup>, from the heteroatom Br which is released as the bromide ion (Br<sup>‒</sup>), during the degradation of BPB. The active bromine species are formed via direct and indirect oxidation approaches which were proposed based on ion chromatography and linear scanning voltammetry analysis.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100225","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47135054","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}
引用次数: 1
Designing multinary noble metal-free catalyst for hydrogen evolution reaction 设计多种无贵金属析氢催化剂
Q2 ELECTROCHEMISTRY Pub Date : 2022-08-25 DOI: 10.1002/elsa.202100224
Wissam A. Saidi, Tarak Nandi, Timothy Yang

The hydrogen evolution reaction (HER), the key reaction for electrocatalytic production of hydrogen, is of fundamental importance due to its simplicity yet is very important for renewable energy. Notwithstanding, Pt is still the main catalyst for this reaction, which is not practical for the industrial deployment of this technology owing to the high cost and scarcity of Pt. The successful synthesis of high entropy alloy (HEA) nanoparticles opens a new frontier for the development of new catalysts. Herein we investigate the design of a multinary noble metal-free HER catalyst based on earth-abundant elements Co, Mo, Fe, Ni, and Cu. Using a machine learning (ML) approach in conjunction with first-principles methods, we build a model that can rapidly compute the hydrogen adsorption energy on the alloyed surfaces with high fidelity. Within the large composition space of the CoMoFeNiCu HEA, a large number of alloy combinations are shown to optimally bind hydrogen with a high probability. Further, most of these alloy compositions are found stable against dissociation into intermetallics, and hence synthesizable as a solid solution, by virtue of a large mixing entropy compared to mixing enthalpy and a small lattice mismatch between the elements. This finding is partly consistent with recent experimental results that synthesized five different CoMoFeNiCu HEA compositions. Our study underscores the significant impact that computational modeling and ML can have on developing new cost-effective electrocatalysts in the nearly-infinite materials design space of HEAs, and calls for experimental validation.

氢进化反应(HER)是电催化制氢的关键反应,因其简单性而具有根本性的重要意义,但对可再生能源却非常重要。尽管如此,铂仍是该反应的主要催化剂,但由于铂的高成本和稀缺性,该技术的工业应用并不现实。高熵合金(HEA)纳米粒子的成功合成为新型催化剂的开发开辟了新的领域。在此,我们研究了基于地球富集元素 Co、Mo、Fe、Ni 和 Cu 的不含二元贵金属的 HER 催化剂的设计。利用机器学习(ML)方法和第一原理方法,我们建立了一个模型,该模型可以快速、高保真地计算合金表面的氢吸附能。在 CoMoFeNiCu HEA 的巨大成分空间内,大量合金组合被证明能以很高的概率优化氢结合。此外,由于混合熵与混合焓相比较大,且元素间的晶格失配较小,因此发现这些合金组合中的大多数在解离成金属间化合物时是稳定的,因而可合成为固溶体。这一发现与最近合成五种不同的 CoMoFeNiCu HEA 成分的实验结果部分吻合。我们的研究强调了计算建模和 ML 对在几乎无限的 HEA 材料设计空间中开发新的经济高效的电催化剂的重要影响,并呼吁进行实验验证。
{"title":"Designing multinary noble metal-free catalyst for hydrogen evolution reaction","authors":"Wissam A. Saidi,&nbsp;Tarak Nandi,&nbsp;Timothy Yang","doi":"10.1002/elsa.202100224","DOIUrl":"10.1002/elsa.202100224","url":null,"abstract":"<p>The hydrogen evolution reaction (HER), the key reaction for electrocatalytic production of hydrogen, is of fundamental importance due to its simplicity yet is very important for renewable energy. Notwithstanding, Pt is still the main catalyst for this reaction, which is not practical for the industrial deployment of this technology owing to the high cost and scarcity of Pt. The successful synthesis of high entropy alloy (HEA) nanoparticles opens a new frontier for the development of new catalysts. Herein we investigate the design of a multinary noble metal-free HER catalyst based on earth-abundant elements Co, Mo, Fe, Ni, and Cu. Using a machine learning (ML) approach in conjunction with first-principles methods, we build a model that can rapidly compute the hydrogen adsorption energy on the alloyed surfaces with high fidelity. Within the large composition space of the CoMoFeNiCu HEA, a large number of alloy combinations are shown to optimally bind hydrogen with a high probability. Further, most of these alloy compositions are found stable against dissociation into intermetallics, and hence synthesizable as a solid solution, by virtue of a large mixing entropy compared to mixing enthalpy and a small lattice mismatch between the elements. This finding is partly consistent with recent experimental results that synthesized five different CoMoFeNiCu HEA compositions. Our study underscores the significant impact that computational modeling and ML can have on developing new cost-effective electrocatalysts in the nearly-infinite materials design space of HEAs, and calls for experimental validation.</p>","PeriodicalId":93746,"journal":{"name":"Electrochemical science advances","volume":"3 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/elsa.202100224","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43228854","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}
引用次数: 6
期刊
Electrochemical science advances
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1