Gokul Raj, Ravi Nandan, Soumen Midya, Kanhai Kumar, Abhishek Kumar Singh and Karuna Kar Nanda
{"title":"Comprehensive insights into hydrolysis-mediated hydrogen production using high-entropy quintuple alloy-grafted carbon black†","authors":"Gokul Raj, Ravi Nandan, Soumen Midya, Kanhai Kumar, Abhishek Kumar Singh and Karuna Kar Nanda","doi":"10.1039/D4TA06193D","DOIUrl":null,"url":null,"abstract":"<p >Hydrogen is a promising fuel with adequate energy density and zero carbon emissions upon combustion. Its fast and convenient production from hydrogen-rich materials like sodium borohydride (NaBH<small><sub>4</sub></small>) is of high practical importance. Herein, we report a novel quintuple high-entropy alloy of CrMnFeCoNi loaded on conductive carbon (HEACB) as an effective heterogeneous catalyst for the hydrolysis of NaBH<small><sub>4</sub></small> to produce hydrogen at room temperature. The optimized HEACB shows excellent performance with a turn over freequency (TOF) of about 188 mL g<small><sub>Mn</sub></small><small><sup>−1</sup></small> s<small><sup>−1</sup></small> and a minimum activation energy (<em>E</em><small><sub>a</sub></small>) of about 15 kJ mol<small><sup>−1</sup></small>, while the <em>E</em><small><sub>a</sub></small> of bare HEA is 43 kJ mol<small><sup>−1</sup></small>. Mott–Schottky analysis reveals n-type semiconductor behavior of the HEACB heterostructure at the electrolyte interface during the reaction with an optimal flat band potential. Electrochemical analysis is employed to understand the kinetic aspects of the observed catalytic behavior during hydrolysis. The onset potential, overpotential, Tafel slope, and charge transfer resistance extracted from linear sweep voltammetry and electrochemical impedance studies reveal that the HEA alloy stabilization greatly affects the overall catalytic efficiency towards NaBH<small><sub>4</sub></small> hydrolysis. Chemical and electrochemical investigations exhibit a pronounced correlation. Density Functional Theory (DFT) is applied to understand the interaction of the reaction intermediates and to provide insights into the hydrolysis process of borohydride on the HEA system.</p>","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":" 8","pages":" 5765-5776"},"PeriodicalIF":9.5000,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Chemistry A","FirstCategoryId":"88","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/ta/d4ta06193d","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Hydrogen is a promising fuel with adequate energy density and zero carbon emissions upon combustion. Its fast and convenient production from hydrogen-rich materials like sodium borohydride (NaBH4) is of high practical importance. Herein, we report a novel quintuple high-entropy alloy of CrMnFeCoNi loaded on conductive carbon (HEACB) as an effective heterogeneous catalyst for the hydrolysis of NaBH4 to produce hydrogen at room temperature. The optimized HEACB shows excellent performance with a turn over freequency (TOF) of about 188 mL gMn−1 s−1 and a minimum activation energy (Ea) of about 15 kJ mol−1, while the Ea of bare HEA is 43 kJ mol−1. Mott–Schottky analysis reveals n-type semiconductor behavior of the HEACB heterostructure at the electrolyte interface during the reaction with an optimal flat band potential. Electrochemical analysis is employed to understand the kinetic aspects of the observed catalytic behavior during hydrolysis. The onset potential, overpotential, Tafel slope, and charge transfer resistance extracted from linear sweep voltammetry and electrochemical impedance studies reveal that the HEA alloy stabilization greatly affects the overall catalytic efficiency towards NaBH4 hydrolysis. Chemical and electrochemical investigations exhibit a pronounced correlation. Density Functional Theory (DFT) is applied to understand the interaction of the reaction intermediates and to provide insights into the hydrolysis process of borohydride on the HEA system.
期刊介绍:
The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.