{"title":"Synergistic Niobium Doped Two-Dimensional Zirconium Diselenide: An Efficient Electrocatalyst for O2 Reduction Reaction","authors":"Ashok Singh, and , Srimanta Pakhira*, ","doi":"10.1021/acsphyschemau.3c00035","DOIUrl":null,"url":null,"abstract":"<p >The development of high-activity and low-price cathodic catalysts to facilitate the electrochemically sluggish O<sub>2</sub> reduction reaction (ORR) is very important to achieve the commercial application of fuel cells. Here, we have investigated the electrocatalytic activity of the two-dimensional single-layer Nb-doped zirconium diselenide (2D Nb-ZrSe<sub>2</sub>) toward ORR by employing the dispersion corrected density functional theory (DFT-D) method. Through our study, we computed structural properties, electronic properties, and energetics of the 2D Nb-ZrSe<sub>2</sub> and ORR intermediates to analyze the electrocatalytic performance of 2D Nb-ZrSe<sub>2</sub>. The electronic property calculations depict that the 2D monolayer ZrSe<sub>2</sub> has a large band gap of 1.48 eV, which is not favorable for the ORR mechanism. After the doping of Nb, the electronic band gap vanishes, and 2D Nb-ZrSe<sub>2</sub> acts as a conductor. We studied both the dissociative and the associative pathways through which the ORR can proceed to reduce the oxygen molecule (O<sub>2</sub>). Our results show that the more favorable path for O<sub>2</sub> reduction on the surface of the 2D Nb-ZrSe<sub>2</sub> is the 4e<sup>–</sup> associative path. The detailed ORR mechanisms (both associated and dissociative) have been explored by computing the changes in Gibbs free energy (Δ<i>G</i>). All of the ORR reaction intermediate steps are thermodynamically stable and energetically favorable. The free energy profile for the associative path shows the downhill behavior of the free energy vs the reaction steps, suggesting that all ORR intermediate structures are catalytically active for the 4e<sup>–</sup> associative path and a high 4e<sup>–</sup> reduction pathway selectivity. Therefore, 2D Nb-ZrSe<sub>2</sub> is a promising catalyst for the ORR, which can be used as an alternative ORR catalyst compared to expensive platinum (Pt).</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7000,"publicationDate":"2023-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00035","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Physical Chemistry Au","FirstCategoryId":"1085","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsphyschemau.3c00035","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The development of high-activity and low-price cathodic catalysts to facilitate the electrochemically sluggish O2 reduction reaction (ORR) is very important to achieve the commercial application of fuel cells. Here, we have investigated the electrocatalytic activity of the two-dimensional single-layer Nb-doped zirconium diselenide (2D Nb-ZrSe2) toward ORR by employing the dispersion corrected density functional theory (DFT-D) method. Through our study, we computed structural properties, electronic properties, and energetics of the 2D Nb-ZrSe2 and ORR intermediates to analyze the electrocatalytic performance of 2D Nb-ZrSe2. The electronic property calculations depict that the 2D monolayer ZrSe2 has a large band gap of 1.48 eV, which is not favorable for the ORR mechanism. After the doping of Nb, the electronic band gap vanishes, and 2D Nb-ZrSe2 acts as a conductor. We studied both the dissociative and the associative pathways through which the ORR can proceed to reduce the oxygen molecule (O2). Our results show that the more favorable path for O2 reduction on the surface of the 2D Nb-ZrSe2 is the 4e– associative path. The detailed ORR mechanisms (both associated and dissociative) have been explored by computing the changes in Gibbs free energy (ΔG). All of the ORR reaction intermediate steps are thermodynamically stable and energetically favorable. The free energy profile for the associative path shows the downhill behavior of the free energy vs the reaction steps, suggesting that all ORR intermediate structures are catalytically active for the 4e– associative path and a high 4e– reduction pathway selectivity. Therefore, 2D Nb-ZrSe2 is a promising catalyst for the ORR, which can be used as an alternative ORR catalyst compared to expensive platinum (Pt).
期刊介绍:
ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis