Bimetallic palladium-cobalt nanomaterials as highly efficient catalysts for dehydrocoupling of dimethylamine borane

doi:10.1016/j.ijhydene.2019.01.215

International Journal of Hydrogen Energy

Volume 45, Issue 5, 29 January 2020, Pages 3569-3576

https://doi.org/10.1016/j.ijhydene.2019.01.215 Get rights and content

Highlights

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Monodisperse PdCo@GO was prepared by the ultrasonic reduction method.
•
Monodisperse PdCo NPs were decorated on graphene oxide as efficient and stable catalysts.
•
PdCo@GO NPs exhibited a high catalytic activity with a 226.80 h⁻¹ TOF value.
•
The detailed kinetic study of the dehydrocoupling reaction of DMAB catalyzed by PdCo@GO NPs was studied.

Abstract

In this work, we report the synthesis, characterization and application of graphene oxide stabilized PdCo nanoparticles (PdCo@GO) for the dehydrocoupling of dimethylamine borane (DMAB) as a model reaction. Bimetallic graphene oxide stabilized PdCo nanoparticles were readily synthesized using an ultrasonic reduction technique, in which both metals of Pd and Co were reduced with GO. The dispersion of PdCo nanoparticles on the surface of GO was enhanced with the help of the ultrasonic reduction method which result in the enhancing of dispersion of both metals without any agglomeration problem. The characterization studies revealed that graphene oxide stabilized PdCo nanoparticles have a uniform, homogeneous distribution on graphene oxide and an average particle size of 3.48 ± 0.22 nm. After fully characterization of graphene oxide stabilized PdCo nanoparticles, they have been tried in model reaction as a catalyst and exhibited a high catalytic performance compared the previous catalysts in literature with a TOF value of 226.80 h⁻¹. The investigation of kinetic parameters showed that graphene oxide stabilized PdCo nanoparticles have very high negative entropy (ΔS: −170.85 J mol⁻¹ K⁻¹) value and a low activation energy value (Ea: 17.53 ± 2 kJ mol⁻¹) for the model reaction.

Introduction

Hydrogen is considered to be clean energy source since it does not cause any damage to the environment. However, some problems with the storage of hydrogen affect negatively the hydrogen economy. There are many types of hydrogen sources such as sodium borohydride, ammonia boranes, dimethylamine boranes, methylamine boranes etc. [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14], [15]. Among these sources, ammonia boranes (ABs) have been used many times due to their some advantages such as high hydrogen content (19.5%), ease of use, stability, and non-flammability [16], [17], [18], [19], [20]. Another derivative of ABs is dimethylamine borane (DMAB) which has acceptable hydrogen content, crystalline structure and a constant form in the air. The dehydrogenation reaction of dimethylamine borane takes places easily under room conditions with the use of a suitable catalyst which is shown in Scheme 1. So far, different heterogeneous and homogeneous catalysts containing palladium, ruthenium, iridium, and rhodium, etc have been tested for the dehydrogenation reaction of dimethylamine borane as shown in Table 1. According to several studies in the literature [21], [22], [23], [24], [25], [26], [27], [28], Pd based nanomaterials have been used and they have increased the stability and the catalytic activity of chemical reactions. As shown in Table 1, in our laboratory, we have also tried many catalysts for this model reaction and obtained very good performance for dehydrocoupling of AB derivatives. Especially, Pd and Co based nanomaterials have paid attention in our last measurements due to their very high performance. Hence, in this study, we report the preparation and characterization of graphene oxide supported PdCo nanomaterials (PdCo@GO) exhibiting high catalytic performance for the model reaction.

The prepared nanomaterials were prepared by using the ultrasonic reduction technique and characterized by some of the advanced analytical techniques as given in supporting information. Additionally, some detailed kinetic studies of model reaction catalyzed by graphene oxide stabilized PdCo nanoparticles were investigated in detail.

Section snippets

The procedure of preparing of PdCo nanoparticles decorated on GO

The graphene oxide stabilized PdCo nanoparticles were prepared with the help of the ultrasonic reduction technique as shown in Fig. S1. Further, the preparation of graphene oxide and the characterization techniques of prepared materials and their detailed kinetic studies for model reaction were given in supporting information. As a summary for the preparation of nanomaterial, A solution containing 25 mg/mL GO, 0.25 mmol CoCl₂ and 0.25 mmol K₂PdCl₄ were mixed under ultrasonic conditions for a

Characterization of graphene oxide stabilized palladium cobalt nanoparticles

The characterizations of graphene oxide stabilized PdCo nanoparticles were performed with various analytical techniques. For instance, the morphology, compositions and the mean particle size of the prepared graphene oxide stabilized PdCo nanoparticles were investigated using Transmission electron microscopy analysis as shown in Fig. 1. The mean particle size of graphene oxide stabilized PdCo nanoparticles was found to be 3.48 ± 0.22 nm counting over 100 particles as shown in Fig. 1b. Further,

Conclusions

As a result, highly active, stable and durable graphene oxide stabilized PdCo nanoparticles were synthesized, characterized and performed for the dehydrocoupling of DMAB as a model reaction and the obtained results can be summarized as shown below:

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Graphene oxide stabilized PdCo nanoparticles were readily synthesized using an ultrasonic reduction technique, in which both Pd and Co were reduced by Graphene oxide.
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The dispersion of PdCo alloy nanoparticles on the surface of graphene oxide was

Acknowledgments

The authors would like to thank Kutahya Dumlupinar University (2014-05) for financial support.

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Bimetallic palladium-cobalt nanomaterials as highly efficient catalysts for dehydrocoupling of dimethylamine borane

Highlights

Abstract

Introduction

Section snippets

The procedure of preparing of PdCo nanoparticles decorated on GO

Characterization of graphene oxide stabilized palladium cobalt nanoparticles

Conclusions

Acknowledgments

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