Two biologically inspired tetranuclear nickel(II) catalysts: effect of the geometry of Ni 4 core on electrocatalytic water oxidation,JBIC Journal of Biological Inorganic Chemistry

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Two biologically inspired tetranuclear nickel(II) catalysts: effect of the geometry of Ni 4 core on electrocatalytic water oxidation
JBIC Journal of Biological Inorganic Chemistry ( IF 2.7 ) Pub Date : 2021-02-05 , DOI: 10.1007/s00775-020-01846-4
Jinmiao Wang ₁ , Xiangmin Meng ₂ , Wangjing Xie ₁ , Xia Zhang ₁ , Yuhua Fan ₁ , Mei Wang ₁

Affiliation

Abstract

Two biologically inspired tetranuclear nickel complexes [Ni₄(L–H)₄(CH₃COO)₃]·Cl (1) and [Ni₄(L–H)₄(CH₃COO)₄]·2CH₃OH (2) (L = di(pyridin-2-yl)methanediol) have been synthesized and investigated by a combination of X-ray crystallography, PXRD, electrochemistry, in-situ UV–Vis spectroelectrochemistry and DLS. Both of the two complexes feature a core composed of four Ni(II) ions with the same peripheral ligation provided by the anionic di(pyridin-2-yl)methanediol and MeCOO⁻ ligands. Whereas, complex 1 possesses one distorted cubane-like [Ni₄(µ₃-O)₄] core, while 2 has one extended butterfly-like [Ni₄(µ₃-O)₂] core. The homogeneous electrocatalytic reactivity of the two water-soluble complexes for water oxidation have been thoroughly studied, which demonstrates that both of them can efficiently electrocatalyze water oxidation with high stability under alkaline conditions, at relatively low over-potentials (η) of 420–790 mV for 1 and 390–780 mV for 2, both in the pH range of 7.67–12.32, with the high TOF of about 139 s⁻¹ (1) and 69 s⁻¹ (2) at pH = 12.32, respectively. By a series of comparative experiments for complexes 1 and 2, we proposed that their crystal geometries play an important role in their electrocatalytic reactivity for water oxidation. We verified that biomimetic cubane geometry could promote OER catalysis with two very similar compounds for the first time.

Graphic abstract

Compared with 2, the biomimetic cubane topology of 1 could promote OER catalysis by facilitating efficient charge delocalization and electron-transfer.

中文翻译：

两种生物启发的四核镍(II)催化剂：Ni 4 核几何结构对电催化水氧化的影响

抽象的

两种生物启发的四核镍配合物 [Ni ₄ (L–H) ₄ (CH ₃ COO) ₃ ]·Cl ( 1 ) 和 [Ni ₄ (L–H) ₄ (CH ₃ COO) ₄ ]·2CH ₃ OH ( 2 ）（L = 二（吡啶-2-基）甲烷二醇）已通过 X 射线晶体学、PXRD、电化学、原位紫外-可见光谱电化学和 DLS 的组合进行合成和研究。这两种配合物均具有由四个 Ni(II) 离子组成的核心，并具有由阴离子二（吡啶-2-基）甲烷二醇和 MeCOO ^-配体提供的相同外围连接。而配合物1具有一个扭曲的立方烷状[Ni ₄ (μ ₃ -O) ₄ ]核心，而2则具有一个扩展的蝴蝶状[Ni ₄ (μ ₃ -O) ₂ ]核心。对两种水溶性配合物对水氧化的均相电催化反应活性进行了深入研究，表明它们都可以在碱性条件下以420-790相对较低的过电势（η）高效、高稳定性地电催化水氧化。 1的 mV 和2的 390–780 mV，均在 7.67–12.32 的 pH 范围内，在 pH = 12.32 时，TOF 分别约为 139 s ^-1 ( 1 ) 和 69 s ^-1 ( 2 ) 。通过对配合物1和2的一系列比较实验，我们提出它们的晶体几何形状在水氧化的电催化反应活性中发挥着重要作用。我们首次验证了仿生立方烷几何形状可以促进两种非常相似的化合物的 OER 催化。