在碱性介质中通过镍掺杂方法增强鲜为人知的 α-MnO2 的 OER 动力学,Inorganic Chemistry

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在碱性介质中通过镍掺杂方法增强鲜为人知的 α-MnO2 的 OER 动力学
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-11-25 , DOI: 10.1021/acs.inorgchem.1c03236
Krishnendu Bera _{1,

2} , Arun Karmakar _{1,

2} , Kannimuthu Karthick _{1,

2} , Selvasundarasekar Sam Sankar _{1,

2} , Sangeetha Kumaravel _{1,

2} , Ragunath Madhu _{1,

2} , Subrata Kundu _{1,

2}

Affiliation

开发用于水分解的低成本过渡金属基催化剂对于以工业规模生产绿色氢至关重要。最近，已经合成了各种基于过渡金属的氧化物、氢氧化物、硫化物和其他硫属化物基材料，以开发适合用于析氧反应 (OER) 的负极材料。在各种过渡金属基催化剂中，它们的氧化物在 OER 中得到了很多考虑，特别是在较低的 pH 条件下，MnO ₂是其中一种被广泛使用的氧化物。MnO ₂结构无序的巨大变化和电极-电解质界面处的内阻限制了其大规模应用。通过考虑 MnO 的上述限制_{如图2所示}，在这项工作中，我们通过简单的湿化学合成路线设计了Ni掺杂的MnO ₂，已成功应用于0.1 M KOH溶液中的OER应用。将不同数量的 Ni 掺杂到 MnO ₂晶格中改善了 OER 性能，并且为了实现 10 mA/cm ^{2 的}电流密度，含有 0.02 M Ni ²⁺离子的 Ni 掺杂的 MnO ₂（称为 MnO ₂ -Ni _{0.002( M)} ) 仅需要 445 mV 的过电位，而裸 MnO ₂需要 610 mV 的过电位。有人提出将镍离子掺入 MnO ₂晶格导致电子从 Ni ³⁺离子转移到 Mn ⁴⁺，这反过来又促进了 Mn-O 八面体单元中的 Jahn-Teller 畸变。这种电子转移和Mn 位点结构无序的产生导致MnO ₂材料的OER 性能的改善。

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Enhancement of the OER Kinetics of the Less-Explored α-MnO2via Nickel Doping Approaches in Alkaline Medium

Development of a low-cost transition metal-based catalyst for water splitting is of prime importance for generating green hydrogen on an industrial scale. Recently, various transition metal-based oxides, hydroxides, sulfides, and other chalcogenide-based materials have been synthesized for developing a suitable anode material for the oxygen evolution reaction (OER). Among the various transition metal-based catalysts, their oxides have received much consideration for OER, especially in lower pH condition, and MnO₂ is one of the oxides that have widely been used for the same. The large variation in the structural disorder of MnO₂ and internal resistance at the electrode–electrolyte interfaces have limited its large-scale application. By considering the above limitations of MnO₂, here in this work, we have designed Ni-doped MnO₂via a simple wet-chemical synthetic route, which has been successfully applied for OER application in 0.1 M KOH solution. Doping of various quantities of Ni into the MnO₂ lattices improved the OER properties, and for achieving 10 mA/cm² current density, the Ni-doped MnO₂ containing 0.02 M of Ni²⁺ ions (coined as MnO₂-Ni_0.002(M)) demands only 445 mV overpotential, whereas the bare MnO₂ required 610 mV overpotential. It has been proposed that the incorporation of nickel ions into the MnO₂ lattices leads to an electron transfer from the Ni³⁺ ions to Mn⁴⁺, which in turn facilitates the Jahn–Teller distortion in the Mn–O octahedral unit. This electron transfer and the creation of a structural disorder in the Mn sites result in the improvization of the OER properties of the MnO₂ materials.

更新日期：2021-12-20

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