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一种基于聚合物-碳纳米管的杂化纳米催化剂的非原位合成与表征,该催化剂在室温条件下对硼氢化肼水解脱氢具有最高催化活性和稳定性之一。

Ex situ synthesis and characterization of a polymer-carbon nanotube-based hybrid nanocatalyst with one of the highest catalytic activities and stabilities for the hydrolytic dehydrogenation of hydrazine-borane at room temperature conditions.

作者信息

Demirkan Buse, Kuyuldar Esra, Karataş Yaşar, Gülcan Mehmet, Sen Fatih

机构信息

Sen Research Group, Biochemistry Department, Faculty of Arts and Science, Dumlupinar University, Evliya Celebi Campus, 43100 Kutahya, Turkey.

Chemistry Department, Faculty of Science, Van Yüzüncü Yıl University, Zeve Campus, 65080 Van, Turkey.

出版信息

J Colloid Interface Sci. 2019 Sep 15;552:432-438. doi: 10.1016/j.jcis.2019.05.075. Epub 2019 May 24.

DOI:10.1016/j.jcis.2019.05.075
PMID:31152963
Abstract

In this study, a facile ex situ synthesis of a polyaniline-multiwalled carbon nanotube-based Pt nanocatalyst (Pt@PANI-MWCNT) with an average particle size of 3.18 ± 0.12 nm was performed successfully. The obtained Pt@PANI-MWCNT nanocatalysts were isolated from the solution medium by centrifugation and then were characterized by spectroscopy and microscopy methods. The characterization studies showed that the prepared Pt nanoparticles were formed on PANI-MWCNT surface, and H evolution was obtained by the dehydrogenation of hydrazine-borane in water as a model reaction under room temperature conditions, with the help of the synthesized nanocatalyst. It was observed that the Pt@PANI-MWCNT nanocatalyst had a very high catalytic activity for the hydrolytic dehydrogenation of hydrazine-borane and generated 2.95 mol of H for 1 mol of hydrazine-borane. The initial turn-over frequency (TOF) value of the prepared nanocatalyst for the model reaction at room temperature conditions was found to be 168.5 min. The calculations for the kinetics of the hydrolytic dehydrogenation reaction showed that the hydrazine-borane catalytic reaction kinetics are first order, with respect to the catalyst concentration; several activation parameters, such as entropy (ΔS,  = -72.11 ± 3 J/mol K), enthalpy (ΔH,  = 43.5 ± 2 kJ/mol) and activation energy (E = 45.5 ± 2 kJ/mol), of the catalytic reaction with the Pt@PANI-MWCNT nanocatalyst were calculated using these kinetic data.

摘要

在本研究中,成功进行了一种基于聚苯胺-多壁碳纳米管的铂纳米催化剂(Pt@PANI-MWCNT)的简便非原位合成,其平均粒径为3.18±0.12纳米。通过离心从溶液介质中分离得到所制备的Pt@PANI-MWCNT纳米催化剂,然后采用光谱和显微镜方法对其进行表征。表征研究表明,所制备的铂纳米颗粒形成于PANI-MWCNT表面,在室温条件下,以水合肼硼烷脱氢作为模型反应,借助合成的纳米催化剂获得了氢气析出。观察到Pt@PANI-MWCNT纳米催化剂对水合肼硼烷的水解脱氢具有非常高的催化活性,1摩尔水合肼硼烷可产生2.95摩尔氢气。所制备的纳米催化剂在室温条件下对模型反应的初始周转频率(TOF)值为168.5分钟⁻¹。水解脱氢反应动力学计算表明,水合肼硼烷催化反应动力学对催化剂浓度为一级反应;利用这些动力学数据计算了Pt@PANI-MWCNT纳米催化剂催化反应的几个活化参数,如熵(ΔS = -72.11±3 J/mol K)、焓(ΔH = 43.5±2 kJ/mol)和活化能(E = = 45.5±2 kJ/mol)。

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