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组装在还原氧化石墨烯上的单分散铂纳米颗粒:用于甲醇氧化和二甲胺硼烷(DMAB)脱氢偶联的高效可重复使用催化剂。

Monodisperse Pt Nanoparticles Assembled on Reduced Graphene Oxide: Highly Efficient and Reusable Catalyst for Methanol Oxidation and Dehydrocoupling of Dimethylamine-Borane (DMAB).

作者信息

Yildiz Yunus, Erken Esma, Pamuk Handan, Sert Hakan, Sen Fatih

出版信息

J Nanosci Nanotechnol. 2016 Jun;16(6):5951-8. doi: 10.1166/jnn.2016.11710.

DOI:10.1166/jnn.2016.11710
PMID:27427656
Abstract

Herein, monodisperse platinum (0) nanocatalyst assembled on reduced graphene oxide (Pt(0)@RGO) was easily and reproducibly prepared by the double solvent reduction method at room temperature. Pt(0)@RGO was characterized by X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS) and transmission electron microscopy (TEM) measurements that verify the formation of monodisperse Pt (0) nanoparticles on RGO. The catalytic and electrocatalytic performances of Pt(0) @ RGO in terms of activity, isolability and reusability were investigated for both methanol oxidation and the dehydrocoupling of dimethylamine-borane (DMAB) in which Pt(0)@RGO was found to be highly active and reusable heterogeneous catalyst even at room temperature. The prepared nanoparticles can also electrocatalyze methanol oxidation with very high electrochemical activities (5.64 A/cm2 at 0.58 V for methanol). The activation energy (Ea), activation enthalpy (ΔH#), and activation entropy (ΔS#) for DMAB dehydrogenation were calculated to be 59.33 kJ mol(-1), 56.79 kJ mol(-1) and -151.68 J mol(-1) K(-1), respectively. The exceptional stability of new Pt(0) @ RGO nanoparticles towards agglomeration, leaching and CO poisoning allow these particles to be recycled and reused in the catalysis of DMAB dehydrogenation and methanol oxidation. After four subsequent reaction and recovery cycles, Pt(0) @ RGO retained ≥ 75% activity towards the complete dehydrogenation of DMAB.

摘要

在此,通过双溶剂还原法在室温下轻松且可重复地制备了组装在还原氧化石墨烯上的单分散铂(0)纳米催化剂(Pt(0)@RGO)。通过X射线衍射(XRD)、X射线光电子显微镜(XPS)和透射电子显微镜(TEM)测量对Pt(0)@RGO进行了表征,这些测量验证了在RGO上形成了单分散的Pt(0)纳米颗粒。研究了Pt(0)@RGO在甲醇氧化以及二甲胺硼烷(DMAB)脱氢偶联方面的催化和电催化性能,发现即使在室温下,Pt(0)@RGO也是高活性且可重复使用的多相催化剂。所制备的纳米颗粒还能以非常高的电化学活性电催化甲醇氧化(在0.58 V下甲醇的电流密度为5.64 A/cm²)。计算得出DMAB脱氢的活化能(Ea)、活化焓(ΔH#)和活化熵(ΔS#)分别为59.33 kJ mol⁻¹、56.79 kJ mol⁻¹和 -151.68 J mol⁻¹ K⁻¹。新型Pt(0)@RGO纳米颗粒在团聚、浸出和CO中毒方面具有出色的稳定性,使得这些颗粒能够在DMAB脱氢和甲醇氧化催化中循环再利用。经过四个连续的反应和回收循环后,Pt(0)@RGO对DMAB完全脱氢的活性保留≥75%。

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