Lineo F. Mxakaza, Victor Mashindi, Cebisa E. Linganiso, Nosipho Moloto, Zikhona N. Tetana
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Platinum dichalcogenides, PtX<sub>2</sub> (X=S, Se, Te), are an interesting member of transition metal dichalcogenides (TMDs) as these show an immense hybridization of the Pt d orbitals and chalcogen p orbitals because of closely correlated orbital energies. The trend in electronic properties of these materials changes drastically as the chalcogen is changed, with PtS<sub>2</sub> reported to exhibit semi-conductor properties, PtSe<sub>2</sub> is semi-metallic or semi-conductive, depending on the number of layers, while PtTe<sub>2</sub> is metallic. The effect of varying the chalcogen atom on the HER activity of Pt dichalcogenides will be studied. Pt dichalcogenides have previously been prepared by direct high-temperature chalcogen deposition of Pt substrate and evaluated as electrocatalysts for HER in H<sub>2</sub>SO<sub>4</sub>. The previously employed synthesis procedures for PtX<sub>2</sub> limit these compounds′ mass production and post-synthesis treatment. In this study, we demonstrated, for the first time the preparation of PtSe<sub>2</sub> and PtTe<sub>2</sub> by colloidal synthesis. Colloidal synthesis offers the possibility of large-scale synthesis of materials and affords the employment of the colloids at various concentrations in ink formulation. The electrochemical HER results acquired in 1 M KOH indicate that PtTe<sub>2</sub> has a superior HER catalytic activity to PtSe<sub>2</sub>. A potential of 108 mV for PtTe<sub>2</sub> and 161 mV for PtSe<sub>2</sub> is required to produce a current density of −10 mA cm<sup>−2</sup> from these catalysts. PtTe<sub>2</sub> has a low Tafel slope of 79 mVdec<sup>−1</sup>, indicating faster HER kinetics on PtTe<sub>2</sub>. 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Alkaline HER (<span></span><math></math>\\n) is harder to achieve relative to acidic HER (<span></span><math></math>\\n), this is attributed to the additional water dissociation step that occurs in basic HER to generate H<sup>+</sup> ions. In fact, for most catalysts, their HER activity decreases tremendously when the electrolyte is changed from acidic to basic conditions. Platinum dichalcogenides, PtX<sub>2</sub> (X=S, Se, Te), are an interesting member of transition metal dichalcogenides (TMDs) as these show an immense hybridization of the Pt d orbitals and chalcogen p orbitals because of closely correlated orbital energies. The trend in electronic properties of these materials changes drastically as the chalcogen is changed, with PtS<sub>2</sub> reported to exhibit semi-conductor properties, PtSe<sub>2</sub> is semi-metallic or semi-conductive, depending on the number of layers, while PtTe<sub>2</sub> is metallic. The effect of varying the chalcogen atom on the HER activity of Pt dichalcogenides will be studied. Pt dichalcogenides have previously been prepared by direct high-temperature chalcogen deposition of Pt substrate and evaluated as electrocatalysts for HER in H<sub>2</sub>SO<sub>4</sub>. The previously employed synthesis procedures for PtX<sub>2</sub> limit these compounds′ mass production and post-synthesis treatment. In this study, we demonstrated, for the first time the preparation of PtSe<sub>2</sub> and PtTe<sub>2</sub> by colloidal synthesis. Colloidal synthesis offers the possibility of large-scale synthesis of materials and affords the employment of the colloids at various concentrations in ink formulation. The electrochemical HER results acquired in 1 M KOH indicate that PtTe<sub>2</sub> has a superior HER catalytic activity to PtSe<sub>2</sub>. 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引用次数: 0
摘要
在碱性电解质中使用过渡金属二卤化物进行氢进化反应(HER)是一个尚未开发的研究领域。相对于酸性氢演化反应(H + + 2 e - → H 2 + O H - ${{2H}_{2}O+2{e\ }^{-}\to {H}_{2}+{OH}^{-}{\rm \ }}$),碱性氢演化反应(2 H 2 O + 2 e - → H 2 + O H - ${{2H}_{2}O+2{e\ }^{-}\to {H}_{2}+{OH}^{-}{\rm \ }}$)更难实现、这是因为在碱性 HER 中会发生额外的水解离步骤以生成 H+ 离子。事实上,对于大多数催化剂来说,当电解质从酸性条件转变为碱性条件时,它们的 HER 活性会大大降低。二掺铂化合物 PtX2(X=S、Se、Te)是过渡金属二掺铂化合物(TMDs)中一个有趣的成员,因为这些材料的轨道能量密切相关,铂的 d 轨道和掺铂化合物的 p 轨道发生了巨大的杂化。据报道,PtS2 具有半导电特性,PtSe2 具有半金属或半导电特性(取决于层数),而 PtTe2 则具有金属特性。我们将研究改变铬原子对二卤化铂的氢反应活性的影响。以前曾通过直接高温沉积铂基底制备过铂二碲化物,并将其作为 H2SO4 中的 HER 电催化剂进行了评估。之前采用的 PtX2 合成程序限制了这些化合物的大规模生产和合成后处理。在本研究中,我们首次展示了通过胶体合成制备 PtSe2 和 PtTe2 的方法。胶体合成法提供了大规模合成材料的可能性,并能在油墨配方中使用不同浓度的胶体。在 1 M KOH 中获得的电化学 HER 结果表明,PtTe2 的 HER 催化活性优于 PtSe2。要使这些催化剂产生 -10 mA cm-2 的电流密度,PtTe2 和 PtSe2 分别需要 108 mV 和 161 mV 的电位。PtTe2 的塔菲尔斜率较低,为 79 mVdec-1,这表明 PtTe2 的 HER 动力学更快。尽管如此,这些催化剂在碱性介质中的稳定性仍有待提高,以使其成为出色的 HER 电催化剂。
Evaluating the Hydrogen Evolution Reaction Activity of Colloidally Prepared PtSe2 and PtTe2 Catalysts in an Alkaline Medium
The hydrogen evolution reaction (HER) in alkaline electrolytes using transition metal dichalcogenides is a research area that is not tapped into. Alkaline HER (
) is harder to achieve relative to acidic HER (
), this is attributed to the additional water dissociation step that occurs in basic HER to generate H+ ions. In fact, for most catalysts, their HER activity decreases tremendously when the electrolyte is changed from acidic to basic conditions. Platinum dichalcogenides, PtX2 (X=S, Se, Te), are an interesting member of transition metal dichalcogenides (TMDs) as these show an immense hybridization of the Pt d orbitals and chalcogen p orbitals because of closely correlated orbital energies. The trend in electronic properties of these materials changes drastically as the chalcogen is changed, with PtS2 reported to exhibit semi-conductor properties, PtSe2 is semi-metallic or semi-conductive, depending on the number of layers, while PtTe2 is metallic. The effect of varying the chalcogen atom on the HER activity of Pt dichalcogenides will be studied. Pt dichalcogenides have previously been prepared by direct high-temperature chalcogen deposition of Pt substrate and evaluated as electrocatalysts for HER in H2SO4. The previously employed synthesis procedures for PtX2 limit these compounds′ mass production and post-synthesis treatment. In this study, we demonstrated, for the first time the preparation of PtSe2 and PtTe2 by colloidal synthesis. Colloidal synthesis offers the possibility of large-scale synthesis of materials and affords the employment of the colloids at various concentrations in ink formulation. The electrochemical HER results acquired in 1 M KOH indicate that PtTe2 has a superior HER catalytic activity to PtSe2. A potential of 108 mV for PtTe2 and 161 mV for PtSe2 is required to produce a current density of −10 mA cm−2 from these catalysts. PtTe2 has a low Tafel slope of 79 mVdec−1, indicating faster HER kinetics on PtTe2. Nonetheless, the stability of these catalysts in an alkaline medium needs to be improved to render them excellent HER electrocatalysts.
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