Multimetal Incorporation into 2D Conductive Metal-Organic Framework Nanowires Enabling Excellent Electrocatalytic Oxidation of Benzylamine to Benzonitrile.
Multimetal Incorporation into 2D Conductive Metal-Organic Framework Nanowires Enabling Excellent Electrocatalytic Oxidation of Benzylamine to Benzonitrile.
复制标题
将多金属掺入二维导电金属有机框架纳米线中，可实现苄胺优异的电催化氧化为苯甲腈。
DOI：
10.1021/acsami.0c05094
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发表时间：
2020
影响因子：
9.5
通讯作者：
Zhai Quanguo
中科院分区：
文献类型：
--
作者：
Wang Ying;Xue Yingying;Yan Liting;Li Haipeng;Li Yongpeng;Yuan Enhui;Li Meng;Li Shuni;Zhai Quanguo
苯腈作为一种重要的有机中间体，广泛应用于有机合成化学和医药、染料工业。然而，探索一种更高效、可控的合成技术和相应的绿色催化剂来合成BN仍然是一个很大的挑战。本文以多金属二维导电金属有机骨架（2D cMOF）为阳极电催化剂，开发了一种绿色、便捷、高效的氮化硼电化学合成策略。由于其固有的二维导电结构和优化后的多金属耦合催化效应，所制得的多金属二维cMOFs具有优异的苯胺（BA）电氧化性能。特别是，三金属二维cMOF （NiCoFe-CAT）需要1.29 V vs可逆氢电极（RHE）的超低电位才能达到10 mA·cm - 2的电流密度，这表明反应速度最快，热力学条件最有利。在1.45 V电氧化条件下，苯腈的产率（0.058 mmol·mg-1·h-1）和催化效率（~ 87%）均很高。反应机理研究表明，MII/MIII的各种氧化还原介质（Ni, Co, Fe）可视为促进BA转化的多金属活性物质。此外，其优异的循环耐久性进一步促进了其潜在的实际应用。这些电催化性能被认为是优秀的，几乎超过了所有其他报道的镍基无机物或mof基电催化剂对苄胺的电催化氧化。
As an important organic intermediate, benzonitrile (BN) is widely involved in organic synthetic chemistry and pharmaceutical and dyestuff industries. However, the exploration of a more efficient and controllable synthesis technique and the corresponding greener catalysts for the synthesis of BN still poses a great challenge. Herein, with multimetallic two-dimensional conductive metal–organic frameworks (2D cMOF) as anodic electrocatalysts, we develop a green, convenient, and highly efficient electrochemical synthesis strategy for BN. Thanks to the intrinsic 2D electrically conductive structure and the optimized the multimetallic coupling catalytic effect, the resulting multimetallic 2D cMOFs exhibit excellent benzylamine (BA) electrooxidation performance. Especially, the trimetallic 2D cMOF (NiCoFe-CAT) requires an ultralow potential of 1.29 V vs reversible hydrogen electrode (RHE) to achieve a 10 mA·cm–2current density, which indicates the fastest reaction and the most favorable thermodynamic condition. A very high yield (0.058 mmol·mg–1·h–1) and faradic efficiency (∼87%) of benzonitrile are both achieved during the BA electrooxidation reaction at 1.45 V. The reaction mechanism investigations indicated that the various redox mediators of MII/MIII(Ni, Co, Fe) may be regarded as multimetal active species to promote BA conversion. Also, the excellent cycling durability of multimetallic 2D cMOFs further promotes their potential practical applications. These electrocatalytic performances are considered excellent and nearly surpass all other reported Ni-based inorganics or MOF-based electrocatalysts for the electrocatalytic oxidation of benzylamine.