{"title":"用于氧还原反应的锰钨矿{111}面米粒状纳米粒子中的金属对金属电子转移","authors":"","doi":"10.1016/j.electacta.2024.145125","DOIUrl":null,"url":null,"abstract":"<div><div>Commercial interest in Pt and Pt-based catalysts is hindered by their high cost. Herein, we have synthesized {111} faceted rice-grain like nanoparticles of <em>p</em>-MnWO<sub>4</sub> with wolframite structure by a polyol method, and applied as catalysts for the ORR in alkaline electrolyte. It enabled a transfer of electron from t<sub>2g</sub> orbital of Mn 3d to the empty antibonding orbital of W 5d, producing plentiful Mn<sup>3+</sup> states towards ORR. Moreover, it showed superior ORR activity to CoWO<sub>4</sub> and FeWO<sub>4</sub> prepared similarly, and to a <em>h</em>-MnWO<sub>4</sub> prepared by a hydrothermal procedure. <em>p</em>-MnWO<sub>4</sub> exhibited lowest negative onset potential (0.92 V vs RHE) and smallest Tafel slope (50 mV dec<sup>‑1</sup>). Moreover, it achieved highest redox reaction mediated current density (-4.2 mA cm<sup>-2</sup>), attributable to Mn<sup>3+</sup> to Mn<sup>2+</sup> reduction and promising stability (96.6 %) over 6 h Excellent performance of <em>p</em>-MnWO<sub>4</sub> is associated with optimal O<sub>2</sub> adsorption energies caused by metal to metal charge transfer and {111} faceted rice-grain like <em>p</em>-MnWO<sub>4</sub> nanoparticles.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":null,"pages":null},"PeriodicalIF":5.5000,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Metal to metal electron transfer in {111} faceted rice-grain like nanoparticles of Mn-wolframite for oxygen reduction reaction\",\"authors\":\"\",\"doi\":\"10.1016/j.electacta.2024.145125\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Commercial interest in Pt and Pt-based catalysts is hindered by their high cost. Herein, we have synthesized {111} faceted rice-grain like nanoparticles of <em>p</em>-MnWO<sub>4</sub> with wolframite structure by a polyol method, and applied as catalysts for the ORR in alkaline electrolyte. It enabled a transfer of electron from t<sub>2g</sub> orbital of Mn 3d to the empty antibonding orbital of W 5d, producing plentiful Mn<sup>3+</sup> states towards ORR. Moreover, it showed superior ORR activity to CoWO<sub>4</sub> and FeWO<sub>4</sub> prepared similarly, and to a <em>h</em>-MnWO<sub>4</sub> prepared by a hydrothermal procedure. <em>p</em>-MnWO<sub>4</sub> exhibited lowest negative onset potential (0.92 V vs RHE) and smallest Tafel slope (50 mV dec<sup>‑1</sup>). Moreover, it achieved highest redox reaction mediated current density (-4.2 mA cm<sup>-2</sup>), attributable to Mn<sup>3+</sup> to Mn<sup>2+</sup> reduction and promising stability (96.6 %) over 6 h Excellent performance of <em>p</em>-MnWO<sub>4</sub> is associated with optimal O<sub>2</sub> adsorption energies caused by metal to metal charge transfer and {111} faceted rice-grain like <em>p</em>-MnWO<sub>4</sub> nanoparticles.</div></div>\",\"PeriodicalId\":305,\"journal\":{\"name\":\"Electrochimica Acta\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.5000,\"publicationDate\":\"2024-09-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Electrochimica Acta\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0013468624013628\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ELECTROCHEMISTRY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Electrochimica Acta","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0013468624013628","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ELECTROCHEMISTRY","Score":null,"Total":0}
引用次数: 0
摘要
铂和铂基催化剂的高成本阻碍了其商业应用。在此,我们采用多元醇法合成了具有黑钨矿结构的{111}面米粒状 p-MnWO4 纳米颗粒,并将其用作碱性电解液中 ORR 的催化剂。它使电子从 Mn 3d 的 t2g 轨道转移到 W 5d 的空反键轨道,从而产生大量的 Mn3+ 态,实现 ORR。p-MnWO4 的负起始电位(0.92 V vs RHE)最低,塔菲尔斜率(50 mV dec-1)最小。此外,p-MnWO4 的氧化还原反应介导电流密度(-4.2 mA cm-2)最高,这归功于 Mn3+ 对 Mn2+ 的还原作用以及 6 小时的稳定性(96.6 %)。 p-MnWO4 的优异性能与金属对金属电荷转移产生的最佳氧气吸附能以及类似 p-MnWO4 纳米颗粒的{111}面米粒有关。
Metal to metal electron transfer in {111} faceted rice-grain like nanoparticles of Mn-wolframite for oxygen reduction reaction
Commercial interest in Pt and Pt-based catalysts is hindered by their high cost. Herein, we have synthesized {111} faceted rice-grain like nanoparticles of p-MnWO4 with wolframite structure by a polyol method, and applied as catalysts for the ORR in alkaline electrolyte. It enabled a transfer of electron from t2g orbital of Mn 3d to the empty antibonding orbital of W 5d, producing plentiful Mn3+ states towards ORR. Moreover, it showed superior ORR activity to CoWO4 and FeWO4 prepared similarly, and to a h-MnWO4 prepared by a hydrothermal procedure. p-MnWO4 exhibited lowest negative onset potential (0.92 V vs RHE) and smallest Tafel slope (50 mV dec‑1). Moreover, it achieved highest redox reaction mediated current density (-4.2 mA cm-2), attributable to Mn3+ to Mn2+ reduction and promising stability (96.6 %) over 6 h Excellent performance of p-MnWO4 is associated with optimal O2 adsorption energies caused by metal to metal charge transfer and {111} faceted rice-grain like p-MnWO4 nanoparticles.
期刊介绍:
Electrochimica Acta is an international journal. It is intended for the publication of both original work and reviews in the field of electrochemistry. Electrochemistry should be interpreted to mean any of the research fields covered by the Divisions of the International Society of Electrochemistry listed below, as well as emerging scientific domains covered by ISE New Topics Committee.