{"title":"用于碱性介质中高效电催化氢气进化反应的四烷基/烷基三苯基鏻六钨酸盐:基于硅的实验和同步方法","authors":"Debojyoti Kundu, Gajiram Murmu, Sanjukta Zamindar, Naresh Chandra Murmu, Priyabrata Banerjee, Sumit Saha","doi":"10.1021/acsaem.4c01315","DOIUrl":null,"url":null,"abstract":"The development of stable, cost-effective, noble metal-free, and highly efficient electrocatalysts embraces great potential for efficient hydrogen production through water electrolysis. Herein, tetraalkyl/alkyltriphenylphosphonium hexatungstate-based Lindqvist polyoxometalates named <b>HTC-1</b> and <b>HTC-2</b>, respectively, have been synthesized and characterized as promising electrocatalysts for effectual water-splitting reactions. The inclusion of tetrabutyl- and allyltriphenylphosphonium bromides as precursors into hexatungstate ions (W<sub>6</sub>O<sub>19</sub><sup>2–</sup>) exhibited a synergistic effect that promoted a notable improvement in the hydrogen evolution reaction (HER) performance. It also imposes extra surface-active sites and facilitates the electronic transition to boost HER activity in alkaline medium with a lower overpotential value of 136 and 185 mV at benchmark current density and a Tafel slope of 88 and 121 mV dec<sup>–1</sup>, respectively. Density functional theory (DFT) calculations also corroborated the experimental finding that <b>HTC-1</b> acts as a more efficient electrocatalyst due to the presence of a more electron-rich center than <b>HTC-2</b>. The experimental results are further unequivocally corroborated by the <i>in silico</i> approaches, which include density functional theory, reactive site analysis, electronic property analysis, and Gibbs free energy analysis. These results conclusively demonstrate that <b>HTC-1</b> exhibits a lower energy barrier in promoting the adsorption of HER intermediates, particularly, hydrogen adsorption. These observations represent an auspicious “proof of concept” for developing more efficient hexatungstate-based electrocatalysts in the future.","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 1","pages":""},"PeriodicalIF":5.4000,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Tetraalkyl/Alkyltriphenylphosphonium Hexatungstates for Efficient Electrocatalytic Hydrogen Evolution Reaction in Alkaline Media: An Experimental and In Silico-Based Synchronization Approach\",\"authors\":\"Debojyoti Kundu, Gajiram Murmu, Sanjukta Zamindar, Naresh Chandra Murmu, Priyabrata Banerjee, Sumit Saha\",\"doi\":\"10.1021/acsaem.4c01315\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The development of stable, cost-effective, noble metal-free, and highly efficient electrocatalysts embraces great potential for efficient hydrogen production through water electrolysis. Herein, tetraalkyl/alkyltriphenylphosphonium hexatungstate-based Lindqvist polyoxometalates named <b>HTC-1</b> and <b>HTC-2</b>, respectively, have been synthesized and characterized as promising electrocatalysts for effectual water-splitting reactions. The inclusion of tetrabutyl- and allyltriphenylphosphonium bromides as precursors into hexatungstate ions (W<sub>6</sub>O<sub>19</sub><sup>2–</sup>) exhibited a synergistic effect that promoted a notable improvement in the hydrogen evolution reaction (HER) performance. It also imposes extra surface-active sites and facilitates the electronic transition to boost HER activity in alkaline medium with a lower overpotential value of 136 and 185 mV at benchmark current density and a Tafel slope of 88 and 121 mV dec<sup>–1</sup>, respectively. Density functional theory (DFT) calculations also corroborated the experimental finding that <b>HTC-1</b> acts as a more efficient electrocatalyst due to the presence of a more electron-rich center than <b>HTC-2</b>. The experimental results are further unequivocally corroborated by the <i>in silico</i> approaches, which include density functional theory, reactive site analysis, electronic property analysis, and Gibbs free energy analysis. These results conclusively demonstrate that <b>HTC-1</b> exhibits a lower energy barrier in promoting the adsorption of HER intermediates, particularly, hydrogen adsorption. These observations represent an auspicious “proof of concept” for developing more efficient hexatungstate-based electrocatalysts in the future.\",\"PeriodicalId\":4,\"journal\":{\"name\":\"ACS Applied Energy Materials\",\"volume\":\"7 1\",\"pages\":\"\"},\"PeriodicalIF\":5.4000,\"publicationDate\":\"2024-09-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Energy Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1021/acsaem.4c01315\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acsaem.4c01315","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Tetraalkyl/Alkyltriphenylphosphonium Hexatungstates for Efficient Electrocatalytic Hydrogen Evolution Reaction in Alkaline Media: An Experimental and In Silico-Based Synchronization Approach
The development of stable, cost-effective, noble metal-free, and highly efficient electrocatalysts embraces great potential for efficient hydrogen production through water electrolysis. Herein, tetraalkyl/alkyltriphenylphosphonium hexatungstate-based Lindqvist polyoxometalates named HTC-1 and HTC-2, respectively, have been synthesized and characterized as promising electrocatalysts for effectual water-splitting reactions. The inclusion of tetrabutyl- and allyltriphenylphosphonium bromides as precursors into hexatungstate ions (W6O192–) exhibited a synergistic effect that promoted a notable improvement in the hydrogen evolution reaction (HER) performance. It also imposes extra surface-active sites and facilitates the electronic transition to boost HER activity in alkaline medium with a lower overpotential value of 136 and 185 mV at benchmark current density and a Tafel slope of 88 and 121 mV dec–1, respectively. Density functional theory (DFT) calculations also corroborated the experimental finding that HTC-1 acts as a more efficient electrocatalyst due to the presence of a more electron-rich center than HTC-2. The experimental results are further unequivocally corroborated by the in silico approaches, which include density functional theory, reactive site analysis, electronic property analysis, and Gibbs free energy analysis. These results conclusively demonstrate that HTC-1 exhibits a lower energy barrier in promoting the adsorption of HER intermediates, particularly, hydrogen adsorption. These observations represent an auspicious “proof of concept” for developing more efficient hexatungstate-based electrocatalysts in the future.
期刊介绍:
ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.