Synergistic Niobium Doped Two-Dimensional Zirconium Diselenide: An Efficient Electrocatalyst for O2 Reduction Reaction

IF 3.7 Q2 CHEMISTRY, PHYSICAL
Ashok Singh,  and , Srimanta Pakhira*, 
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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).

Abstract Image

Abstract Image

掺杂铌的二维二硒化锆协同催化剂:一种高效的氧气还原反应电催化剂
开发高活性、低价格的阴极催化剂来促进电化学反应迟缓的氧气还原反应(ORR)对于实现燃料电池的商业化应用非常重要。在此,我们采用弥散校正密度泛函理论(DFT-D)方法研究了二维单层掺铌二硒化锆(2D Nb-ZrSe2)对 ORR 的电催化活性。通过这项研究,我们计算了二维 Nb-ZrSe2 和 ORR 中间体的结构特性、电子特性和能量学,从而分析了二维 Nb-ZrSe2 的电催化性能。电子特性计算表明,二维单层 ZrSe2 具有 1.48 eV 的较大带隙,不利于 ORR 机制。掺入铌后,电子带隙消失,二维铌-ZrSe2 成为导体。我们研究了氧化还原反应还原氧分子(O2)的解离和结合途径。我们的研究结果表明,在二维 Nb-ZrSe2 表面还原 O2 的更有利途径是 4e- 关联途径。通过计算吉布斯自由能(ΔG)的变化,我们探索了详细的 ORR 机制(包括缔合和解离)。所有 ORR 反应中间步骤在热力学上都是稳定的,在能量上也是有利的。缔合路径的自由能曲线显示了自由能与反应步骤之间的下坡行为,表明所有 ORR 中间结构对 4e- 缔合路径都具有催化活性,并且具有较高的 4e- 还原路径选择性。因此,二维 Nb-ZrSe2 是一种很有前景的 ORR 催化剂,与昂贵的铂(Pt)相比,它可以作为一种替代 ORR 催化剂。
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来源期刊
CiteScore
3.70
自引率
0.00%
发文量
0
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
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