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MoS2 and WS2 Nanosheets Decorated on Metal–Organic Framework-Derived Cobalt/Carbon Nanostructures as Electrocatalysts for Hydrogen Evolution
ACS Applied Nano Materials ( IF 5.3 ) Pub Date : 2022-07-20 , DOI: 10.1021/acsanm.2c02028
Shadab Saifi 1 , Gargi Dey 1 , Jeyakumar Karthikeyan 1 , A. S. K. Sinha 2 , Arshad Aijaz 1
Affiliation  

The replacement of platinum with nonprecious metal electrocatalysts for hydrogen evolution reaction (HER) remains an important challenge. We report facile synthesis of precious-metal-free HER electrocatalysts that are made up of metal–organic framework-derived cobalt/carbon nanostructures and semicrystalline ultrathin MoS2 or WS2 nanosheets. The as-synthesized catalysts MoS2/Co@NC and WS2/Co@NC delivered an electrochemical HER current density of 25 mA cm–2 at overpotentials of 0.23 and 0.28 V, respectively. Both the catalysts were found to be highly stable in 0.5 M H2SO4 with small Tafel slope values. The high-performance HER activity can be related to (i) covalent cobalt doping into MoS2 and WS2 layers confirmed by X-ray photoelectron spectroscopy, (ii) the presence of cobalt nanoparticles in close vicinity of MoS2 and WS2 layers, (iii) the presence of bridging disulfide S22– into MoS2 and WS2 layers, and (iv) synergistic cooperation among multicomponents present in the catalyst structure. Density functional theory calculations suggested that Co doping at Mo sites in MoS2 has a favorable Gibb’s free energy (ΔG) value for HER. Interestingly, the interface between the Co nanocluster and MoS2 is found to be a favorable HER active site with localization of electrons. To the best of our knowledge, the simultaneous effect of single metal substitution and metal clusters in/on MoS2 and WS2 layers has not been studied for HER. Moreover, we have also demonstrated a durable acid–base water electrolyzer using MoS2/Co@NC and WS2/Co@NC as cathodes, generating 10 mA cm–2 current density at a cell voltage of ∼0.89 V.

中文翻译:

MoS2 和 WS2 纳米片装饰在金属-有机框架衍生的钴/碳纳米结构上作为析氢的电催化剂

用非贵金属电催化剂代替铂用于析氢反应(HER)仍然是一个重要的挑战。我们报告了由金属-有机框架衍生的钴/碳纳米结构和半结晶超薄 MoS 2或 WS 2纳米片组成的无贵金属 HER 电催化剂的简便合成。合成后的催化剂 MoS 2 /Co@NC 和 WS 2 /Co@NC分别在 0.23 和 0.28 V 的过电位下提供了 25 mA cm -2的电化学 HER 电流密度。发现这两种催化剂在 0.5 MH 2 SO 4中高度稳定具有较小的 Tafel 斜率值。高性能 HER 活性可能与 (i) X 射线光电子能谱证实的共价钴掺杂到 MoS 2和 WS 2层中,(ii) 在 MoS 2和 WS 2层附近存在钴纳米颗粒, (iii) 桥接二硫化物 S 2 2-进入 MoS 2和 WS 2层的存在,以及 (iv) 催化剂结构中存在的多组分之间的协同作用。密度泛函理论计算表明,在 MoS 2中 Mo 位点的 Co 掺杂具有良好的 Gibb 自由能(Δ G) 对 HER 的价值。有趣的是,发现Co纳米团簇和MoS 2之间的界面是具有电子定位的有利HER活性位点。据我们所知,单金属取代和金属簇在 MoS 2和 WS 2层中/上的同时影响尚未针对 HER 进行过研究。此外,我们还展示了一种耐用的酸碱水电解槽,使用 MoS 2 /Co@NC 和 WS 2 /Co@NC 作为阴极,在约 0.89 V 的电池电压下产生 10 mA cm -2的电流密度。
更新日期:2022-07-20
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