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一种制备MgAl层状双氢氧化物-铜金属有机骨架结构的新方法:在甲醛电催化氧化中的应用。

A new method for the preparation of MgAl layered double hydroxide-copper metal-organic frameworks structures: application to electrocatalytic oxidation of formaldehyde.

作者信息

Habibi Biuck, Pashazadeh Ali, Pashazadeh Sara, Saghatforoush Lotf Ali

机构信息

Electroanalytical Chemistry Laboratory, Department of Chemistry, Faculty of Sciences, Azarbaijan Shahid Madani University, Tabriz, 53714-161, Iran.

Department of Chemistry, Payame Noor University, Tehran, 19395-4697, Islamic Republic of Iran.

出版信息

Sci Rep. 2024 Mar 3;14(1):5222. doi: 10.1038/s41598-024-55770-7.

Abstract

In this research, we present a novel design protocol for the in-situ synthesis of MgAl layered double hydroxide-copper metal-organic frameworks (LDH-MOFs) nanocomposite based on the electrocoagulation process and chemical method. The overall goal in this project is the primary synthesis of para-phthalic acid (PTA) intercalated MgAl-LDH with Cu (II) ions to produce the paddle-wheel like Cu-(PTA) MOFs nanocrystals on/in the MgAl-LDH structure. The physicochemical properties of final product; Cu-(PTA) MOFs/MgAl-LDH, were characterized by the surface analysis and chemical identification methods (SEM, EDX, TEM, XRD, BET, FTIR, CHN, DLS, etc.). The Cu-(PTA) MOFs/MgAl-LDH nanocomposite was used to modification of the carbon paste electrode (CPE); Cu-(PTA) MOFs/MgAl-LDH/CPE. The electrochemical performance of Cu-(PTA) MOFs/MgAl-LDH/CPE was demonstrated through the utilization of electrochemical methods. The results show a stable redox behavior of the Cu (III)/Cu (II) at the surface of Cu-(PTA) MOFs/MgAl-LDH/CPE in alkaline medium (aqueous 0.1 M NaOH electrolyte). Then, the Cu-(PTA) MOFs/MgAl-LDH/CPE was used as a new electrocatalyst toward the oxidation of formaldehyde (FA). Electrochemical data show that the Cu-(PTA) MOFs/MgAl-LDH/CPE exhibits superior electrocatalytic performance on the oxidation of FA. Also the diffusion coefficient, exchange current density (J°) and mean value of catalytic rate constant (K) were found to be 1.18 × 10 cm s, 23 mA cm and 0.4537 × 10 cm mol s, respectively. In general, it can be said the Cu-(PTA) MOFs/MgAl-LDHs is promising candidate for applications in direct formaldehyde fuel cells.

摘要

在本研究中,我们基于电凝聚过程和化学方法,提出了一种用于原位合成镁铝层状双氢氧化物 - 铜金属有机框架(LDH - MOFs)纳米复合材料的新颖设计方案。该项目的总体目标是将对苯二甲酸(PTA)插层的MgAl - LDH与铜(II)离子进行初步合成,以在MgAl - LDH结构上/内部生成桨轮状的Cu - (PTA) MOFs纳米晶体。最终产物Cu - (PTA) MOFs/MgAl - LDH的物理化学性质通过表面分析和化学鉴定方法(扫描电子显微镜、能量散射X射线光谱、透射电子显微镜、X射线衍射、比表面积分析仪、傅里叶变换红外光谱、元素分析仪、动态光散射等)进行表征。Cu - (PTA) MOFs/MgAl - LDH纳米复合材料用于修饰碳糊电极(CPE),即Cu - (PTA) MOFs/MgAl - LDH/CPE。通过电化学方法证明了Cu - (PTA) MOFs/MgAl - LDH/CPE的电化学性能。结果表明,在碱性介质(0.1 M NaOH水溶液电解质)中,Cu - (PTA) MOFs/MgAl - LDH/CPE表面的Cu(III)/Cu(II)具有稳定的氧化还原行为。然后,将Cu - (PTA) MOFs/MgAl - LDH/CPE用作甲醛(FA)氧化的新型电催化剂。电化学数据表明,Cu - (PTA) MOFs/MgAl - LDH/CPE对FA的氧化表现出优异的电催化性能。此外,扩散系数、交换电流密度(J°)和催化速率常数(K)的平均值分别为1.18×10⁻⁵ cm² s⁻¹、23 μA cm⁻²和0.4537×10⁻⁵ cm² mol⁻¹ s⁻¹。总体而言,可以说Cu - (PTA) MOFs/MgAl - LDHs是直接甲醛燃料电池应用中有前景的候选材料。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b242/10909854/0f8a816cbd15/41598_2024_55770_Fig1_HTML.jpg

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