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氮掺杂还原氧化石墨烯负载的 Ni-Pd 纳米二聚体催化还原 4-硝基苯酚。

Catalytic reduction of 4-nitrophenol over Ni-Pd nanodimers supported on nitrogen-doped reduced graphene oxide.

机构信息

College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People⿿s Republic of China; Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA.

College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People⿿s Republic of China.

出版信息

J Hazard Mater. 2016 Dec 15;320:96-104. doi: 10.1016/j.jhazmat.2016.08.019. Epub 2016 Aug 8.

Abstract

Catalytic reduction of toxic 4-nitrophenol to 4-aminophenol over magnetically recoverable nanocatalysts has attracted much attention. Herein, we report a Ni-Pd/NrGO catalyst through the growth of Ni-Pd nanodimers (NDs) on nitrogen-doped reduced graphene oxide (NrGO). The Ni-Pd NDs show a heterogeneous nanostructure with Ni and Pd subparts contacting with each other, remarkably different from the frequently-observed core/shell nanoparticles (NPs) or nanoalloy. The formation of Ni-Pd NDs follows an initial deposition of Pd NPs on the graphene and in-situ catalytic generation of Ni subparts over the newly-generated Pd NPs. The resulting Ni-Pd/NrGO exhibits a superior catalytic activity towards the reduction of 4-nitrophenol at room temperature with a high rate constant (3400sg) and a low activated energy (29.1kJmol) as compared to unsupported Ni-Pd NDs and supported monometallic catalysts. The conversion rate of 4-NP is calculated to be 99.5% and the percent yield (%) of 4-AP is as high as 99.1%. A synergistic catalysis mechanism is rationally proposed, which is ascribed to the electronic modification of Ni-Pd metals due to the strong metal/support interaction (SMSI) effect as well as the electron transfer between Ni and Pd. The hybrid catalyst shows soft ferromagnetic properties and can be magnetically separated and recycled without obvious loss of activity.

摘要

磁性可回收纳米催化剂上催化还原有毒的 4-硝基苯酚为 4-氨基酚引起了广泛关注。在此,我们通过在氮掺杂还原氧化石墨烯(NrGO)上生长 Ni-Pd 纳米二聚体(NDs),报道了一种 Ni-Pd/NrGO 催化剂。Ni-Pd NDs 具有 Ni 和 Pd 亚部分相互接触的异质纳米结构,与常见的核/壳纳米颗粒(NPs)或纳米合金明显不同。Ni-Pd NDs 的形成遵循 Pd NPs 在石墨烯上的初始沉积和新生成的 Pd NPs 上原位催化生成 Ni 亚部分的过程。与未负载的 Ni-Pd NDs 和负载的单金属催化剂相比,所得到的 Ni-Pd/NrGO 在室温下对 4-硝基苯酚的还原表现出优异的催化活性,具有高反应速率常数(3400s)和低活化能(29.1kJmol)。4-NP 的转化率计算为 99.5%,4-AP 的产率(%)高达 99.1%。合理提出了协同催化机制,归因于由于强金属/载体相互作用(SMSI)效应以及 Ni 和 Pd 之间的电子转移导致 Ni-Pd 金属的电子修饰。该杂化催化剂表现出软铁磁性,可以通过磁场分离和回收,而没有明显的活性损失。

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