PtNiAu trimetallic nanoalloys enabled by a digestive-assisted process as highly efficient catalyst for hydrogen generation

doi:10.1016/j.nanoen.2016.03.017

Nano Energy

Volume 23, May 2016, Pages 145-152

https://doi.org/10.1016/j.nanoen.2016.03.017 Get rights and content

Highlights

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A digestive-assisted strategy was developed to enable immiscible Au, Pt and Ni to alloy into trimetallic nanocrystals.
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The composition of the product could be readily adjusted in a quite wide range.
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The as-prepared PtNiAu showed remarkable catalytic activity and excellent long-term stability for the hydrolysis of AB.
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The prominent activity is attributed to the modulated electronic interaction and enhanced charge transfer ability.

Abstract

The synergistic effect has endowed Au-contain nanohybrids outstanding catalytic performance. However, it is difficult to introduce Au into Pt-M (M=Fe, Co, Ni etc) alloys owing to the redox potential difference and the complicated thermodynamic miscibility. In this paper, a digestive-reduction combined strategy is developed to enable the successful preparation of network-like PtNiAu trimetallic nanoalloys with a single phase structure. The as-prepared products show excellent catalytic activity and long-term stability towards the hydrolysis of ammonia borane (AB). The TOF value of the Pt₅₈Ni₃₃Au₉ alloy is as high as 496. To the best of our knowledge, it is among the most active noble metal-based catalysts ever reported in this field, even close to that of MOF-supported catalyst. The prominent catalytic activity of the PtNiAu is attributed to the delicately modulated electronic interaction and accelerated charge transfer. Furthermore, the composition of the product can be readily adjusted in a quite wide range by simply regulating the feed ratio, and on a large scale, they exhibit remarkable AB hydrolytic activity. The presented strategy not only offers a new idea for the designed synthesis of multimetallic nanoalloys, but also promotes the practical development of AB as a hydrogen storage medium.

Graphical abstract

A digestive-assisted strategy is developed to synthesis network-like PtNiAu trimetallic nanoalloys, which exhibits superior catalytic activity and excellent long-term stability for H₂ generation from hydrolysis of AB in a quite broad composition regime.

Introduction

Hydrogen (H₂) has been considered as a promising candidate to sustainable and clean energy supply because of its emission-free, high energy efficiency and renewability. Secure storage and effective release of hydrogen are two most crucial technological barriers for the implementation of hydrogen energy [1], [2], [3]. The distinct advantages such as high hydrogen capacity (19.6 wt%), low molecular weight (30.9 g mol⁻¹), good stability and non-toxicity make ammonia borane (NH₃BH₃, AB) one of the best alternative to on-board hydrogen application [4], [5], [6]. The catalytic hydrolysis, with as much as 3 equiv of H₂ generation at room temperature, provides an efficient approach [7], [8], [9], [10]. Nobel metals (such as Pt, Ru, Rh etc.) demonstrate highly activities towards the hydrolytic dehydrogenation of AB [11]. To reduce the usage of reserve limited costly noble metal and further improve the catalytic performance, bimetallic nanocatalysts by alloying noble metal with transition metals (TM) such as Fe, Co and Ni were explored [12], [13], [14], [15]. However, the catalytic efficiency still reveals huge space to promote the practical applicability of AB as promising hydrogen storage material.

Since Haruta et al. discovered the superior catalysis activities of Au-TM oxides composites [16], [17], the synergistic effect of Au has generated enormous scientific interests. It was found that the introduction of Au could not only provide surface protection, but more importantly improve the catalytic activity by subtly adjusting the electronic state and accelerating the electron transfer [18], [19], [20]. Therefore, it is reasonable to expect a superior catalytic performance for Au-Pt-TM trimetallic nanocomposites. Among various possible configurations (such as hetero-aggregate, core-shell and homogeneous structures), alloys are considered to provide fully electronic modification and more active sites due to the maximized atomic interaction [21], [22]. However, it is difficult for Au to alloy with either magnetic metals (like Fe, Co, Ni) [23], [24], [25] for the large atomic size mismatch or noble metals (like Pt, Ru, Rh) [26], [27], [28] for the thermodynamic incompatibility. On the other hand, since the simultaneous nucleation is one of the prerequisites for the successful alloying, the different reduction kinetics pose another serious restriction in synthesizing Au-Pt-TM multimetallic alloys [29], [30]. The synthesis challenge greatly arrests the investigation to further improve the catalytic performance and thus the in-depth understanding of the underlying catalytic hydrogen generation mechanism.

In this paper, we demonstrated the successful introduction of Au into a trimetallic nanoalloy system via a sequential digestive-reduction strategy with PtNiAu as a model system. The as-prepared PtNiAu trimetallic nanoalloys exhibited remarkable catalytic activity and long-term stability towards the hydrolysis of ammonia borane in a quite wide composition range. To the best of our knowledge, it is among the most efficient support-free catalyst ever reported for the hydrolysis of AB.

Section snippets

Chemical reagents and materials

Nickel(II) acetylacetonate (99%), oleylamine (80%–90%), oleic acid (90%), diphenyl ether (99%), 1,2-dodecandiol (90%) were all purchased from Alfa Aesar. Hydrogen tetrachloroaurate(III) trihydrate (HAuCl₄·3H₂O), dihydrogen hexachloroplatinate hexahydrate (H₂PtCl₆·6H₂O) was bought from Shenyang Jinke Chemical Reagent Company. Alcohol was purchased from Beijing Chemical Reagent Company. All chemicals were used as received without further purification.

Synthesis of Au@Ni nanoparticles

Au@Ni nanoparticles (NPs) were synthesized use

Results and discussion

In the very beginning of our study, we tried to get PtNiAu trimetallic nanoalloys via a commonly adopted co-reduction method using a strong reducing agent, NaBH₄, to overcome the redox potential difference. However, further characterizations indicated that Au segregation is unavoidable (Fig. S1) and their catalytic performance is not satisfying (Fig. S2).

Digestive-ripening process has been proved as an effective strategy to narrow the size distribution of noble metal (including Au, Pd, Ag etc.)

Conclusion

In summary, we have developed a digestive-assisted sequential alloying strategy to synthesize network-like PtNiAu trimetallic nanoalloys. This digestive-alloying process skillfully overcame the restriction of phase separation caused by redox potential difference or thermodynamic immiscibility, providing a new idea for the preparation of other multimetallic nanoalloys. The as-prepared PtNiAu trimetallic nanoalloy manifested both superior catalytic activity and excellent long-term stability for H₂

Acknowledgments

The project is supported by the National Natural Science Foundation of China (21173015, 21471013), Beijing Natural Science Foundation, China (2162021), Fundamental Research Funds for the Central Universities (YWF-15-HHXY-14) and Innovation Foundation of BUAA for PhD Graduates.

Jian-Xin Kang was born in Shandong of China in 1989. He received his BS degree in School of Chemistry and Environment, Beihang University in 2010. After that, he joined Lin Guo’s group as a Ph.D. candidate in 2010. His research interests focus on controlled synthesis of nanomaterials and their applications.

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Ting-Wen Chen was born in Anhwei of China in 1991. He received his BS degree in School of Chemistry and Environment, Beihang University in 2014. Now, he is a Ph.D. student under the supervision of Prof. Lin Guo and Dong-Feng Zhang. His research interests focus on the design of multi-metallic materials and their applications as catalysis.

Dong-Feng Zhang received her Ph.D. degree in Inorganic Materials from Peking University under the supervision of Prof. Chun-Hua Yan in 2004. Currently, she is an associate professor at School of Chemistry and Environment in Beihang University. Her research interests focus on the preparation, assembly technique of multimetallic, oxide/chalcogenide, composite nanomaterials and their applications in energy and microelectronics-related applications.

Lin Guo was born in 1964. He received the Ph.D. degree in Beijing University of Institute of Technology, Beijing, China, in 1997. Currently, He is a professor in School of Chemistry and Environment, Beihang University. His research interests focus on the development of new methods for the synthesis of nano-structured materials and the characterization of their unique properties with high potential for future applications. Prof. Dr. Guo is a member of Chinese Chemical Society, as well as the vice-dean of the School of Chemistry and Environment, Beihang University.

¹: These authors contributed equally to this work.

View full text

PtNiAu trimetallic nanoalloys enabled by a digestive-assisted process as highly efficient catalyst for hydrogen generation

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemical reagents and materials

Synthesis of Au@Ni nanoparticles

Results and discussion

Conclusion

Acknowledgments

Nano Energy

Nano Energy

Nano Energy

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