桨轮MOF中Cu2+中心缺陷的研究:缺陷结构、EPR光谱和H2O吸附。

IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Chang-Chun Ding, Yong-Qiang Li, Yu-Jie Sun, Wei Jin, Tong Liu, Jun-Shan Hu
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引用次数: 0

摘要

由于不同的Cu2+中心,∞3[Cu2ICu2II(H2O)2L2Cl2] MOF被广泛地应用于电子顺磁共振(EPR)光谱研究,特别是关于它对气体分子的吸附能力。本文基于Cu2+在∞3中的占据位点[Cu2ICu2II(H2O)2L2Cl2],建立了三个相应的片段[CuO5]-[CuO5]二聚体(C0)、缺陷[CuO5] (C1)和[CuN4] (C2),研究了两种不同的EPR信号(Sa和Sb)和Cu2+的局部环境。利用自旋-哈密顿参数的阶摄动公式,由于反铁磁耦合Cu2+对在低(7 K)温度下的EPR沉默和Cu1+的沉默信号,可以排除C0和C2。因此,在∞3[Cu2ICu2II(H2O)2L2Cl2]中,两个单核Cu2+离子缺陷种(C1a和C1b)可以解释信号Sa和Sb,表明Cu2+的两种不同的周围环境。结合密度泛函理论计算结果,发现缺陷铜桨轮单元对水的吸附效果优于原始铜桨轮单元,有利于电化学析氢反应(HER)和析氧反应(OER)的进行。由此可见,微扰法研究mof的EPR光谱和吸附行为的可靠性得到了有力的证明,可以减少目前第一性原理计算所耗费的时间。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Investigation of the Defect Cu2+ Centers in the Paddle Wheel MOF: Defective Structures, EPR Spectra, and H2O Adsorption.

Due to the different Cu2+ centers, the 3[Cu2ICu2II(H2O)2L2Cl2] MOF has been widely studied using electron paramagnetic resonance (EPR) spectra, particularly regarding its capacity for gas molecule adsorption. In the present work, based on the occupation sites of Cu2+ in 3[Cu2ICu2II(H2O)2L2Cl2], three corresponding fragments, dimer [CuO5]-[CuO5] (C0), defective [CuO5] (C1), and [CuN4] (C2), are established to investigate the two different EPR signals (Sa and Sb) and the local environment of Cu2+. By applying the order perturbation formulas of the spin-Hamiltonian parameters, C0 and C2 can be excluded because of the EPR silence of the antiferromagnetically coupled Cu2+ pair at low (7 K) temperatures and the silent signal of Cu1+. Thus, two mononuclear Cu2+ ion defect species (C1a and C1b) in 3[Cu2ICu2II(H2O)2L2Cl2] can account for signals Sa and Sb, indicating two distinct surrounding environments of Cu2+. When the results from the density functional theory calculations are combined, the defective copper paddle wheel units are superior to the pristine ones in the adsorption of H2O, which is beneficial to the electrochemical hydrogen evolution reaction (HER) and oxygen evolution reactions (OER). Therefore, the reliability of the perturbation method to investigate the EPR spectra and the adsorption behavior of MOFs is powerfully demonstrated, which can reduce the time consumed by current first-principles calculations.

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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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