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二维金属有机框架衍生的金属碳杂化催化剂用于尿素电氧化和 4-硝基苯酚还原。

2D Trimetal-organic framework derived metal carbon hybrid catalyst for urea electro-oxidation and 4-nitrophenol reduction.

机构信息

Department of BioNano Technology, Gachon University, GyeongGi -Do, 13120, Republic of Korea; CSIR - Central Electrochemical Research Institute, Karaikudi, 630003, Tamil Nadu, India.

Department of Chemical Engineering, Sunchon National University, #255 Jungang-ro, Suncheon-si, Jeollanam-do, 57922, Republic of Korea.

出版信息

Chemosphere. 2021 Mar;267:129243. doi: 10.1016/j.chemosphere.2020.129243. Epub 2020 Dec 7.

Abstract

Because of the abundance of transition metals, their enhanced electrochemical/chemical efficiency on par with the benchmark catalysts, long-term stability, etc., the expansion of transition metal/metal oxide-based electrocatalysts for oxygen evolution, urea oxidation reactions and 4-nitrophenol reduction becomes indispensable. In particular, the abundant availability along with improved electrochemical performance is crucial for fuel cell applications when it comes to large scale commercialization. In this work, we report the synthesis of a trimetallic metal-organic framework based on Ni, Co and Zn using BTC as a linker and the preparation of its metal oxide - carbon composites at different temperatures, 600, 700 and 800 °C (TM-MOF-600, TM-MOF-700, and TM-MOF-800) by carbonization under an inert atmosphere. The PXRD pattern of TM-MOF complemented well with the simulated XRD patterns of Co-Ni-BTC MOF as well as Zn-BTC MOF, whereas the PXRD pattern of the carbonized samples indicated the presence of three types of metal oxides i.e., CoO, NiO, and ZnO. TEM indicated spherical morphology of TM-MOF, upon calcination, an irregular agglomeration occurred and the average particle size was found to be 60-110 nm. The as-prepared TM-MOF and its carbon composites were tested for their electrocatalytic as well as catalytic activities towards oxygen evolution, urea oxidation and 4-nitrophenol reduction reactions. Electrochemical results indicate the better performance of TM-MOF-800 in both OER and UOR reactions with an onset potential of 1.66 V (OER) and 1.37 V (UOR) at a current density of 10 mA cm. The long-term stability of these catalysts under alkaline conditions indicates excellent stability. Besides, the urea electrolyzed products were analyzed by gas chromatography to get clear insights on the formed products. Catalytic reduction of 4-nitrophenol in the presence of excess NaBH showed excellent conversion to 4-amino phenol in short duration.

摘要

由于过渡金属的丰富性,它们在电化学/化学效率方面与基准催化剂相当,具有长期稳定性等,因此,扩展基于过渡金属/金属氧化物的电催化剂对于氧气析出、尿素氧化反应和 4-硝基苯酚还原反应变得不可或缺。特别是,对于大规模商业化的燃料电池应用来说,丰富的可用性以及改进的电化学性能至关重要。在这项工作中,我们报告了一种基于 Ni、Co 和 Zn 的三金属金属有机骨架的合成,该骨架使用 BTC 作为连接体,并在惰性气氛下碳化制备其金属氧化物-碳复合材料,温度分别为 600、700 和 800°C(TM-MOF-600、TM-MOF-700 和 TM-MOF-800)。TM-MOF 的 PXRD 图谱与 Co-Ni-BTC MOF 和 Zn-BTC MOF 的模拟 XRD 图谱非常吻合,而碳化样品的 PXRD 图谱表明存在三种类型的金属氧化物,即 CoO、NiO 和 ZnO。TEM 表明 TM-MOF 的形态为球形,煅烧后发生不规则团聚,平均粒径为 60-110nm。制备的 TM-MOF 及其碳复合材料用于测试其对氧气析出、尿素氧化和 4-硝基苯酚还原反应的电催化和催化活性。电化学结果表明,在 OER 和 UOR 反应中,TM-MOF-800 的性能更好,在电流密度为 10 mA cm 时,OER 的起始电位为 1.66 V,UOR 的起始电位为 1.37 V。这些催化剂在碱性条件下的长期稳定性表明其具有优异的稳定性。此外,通过气相色谱分析对尿素电解产物进行了分析,以更清楚地了解形成的产物。在过量 NaBH 存在下,4-硝基苯酚的催化还原在短时间内显示出优异的转化率为 4-氨基酚。

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