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Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction

Nature Chemistry volume 2, pages 484–489 (2010)Cite this article

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Abstract

The facile decomposition of ammonia to produce hydrogen is critical to its use as a hydrogen storage medium in a hydrogen economy, and although ruthenium shows good activity for catalysing this process, its expense and scarcity are prohibitive to large-scale commercialization. The need to develop alternative catalysts has been addressed here, using microkinetic modelling combined with density functional studies to identify suitable monolayer bimetallic (surface or subsurface) catalysts based on nitrogen binding energies. The Ni–Pt–Pt(111) surface, with one monolayer of Ni atoms residing on a Pt(111) substrate, was predicted to be a catalytically active surface. This was verified using temperature-programmed desorption and high-resolution electron energy loss spectroscopy experiments. The results reported here provide a framework for complex catalyst discovery. They also demonstrate the critical importance of combining theoretical and experimental approaches for identifying desirable monolayer bimetallic systems when the surface properties are not a linear function of the parent metals.

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Figure 1: Ammonia decomposition volcano curve.
Figure 2: Normalized sensitivity coefficients of the kinetically significant elementary reaction steps for each monometallic metal.
Figure 3: Ammonia decomposition on different Ni–Pt surfaces.
Figure 4: TPD spectra of nitrogen desorption from a Ni–Pt–Pt surface after dosing 3 L ammonia at the specified temperature.

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Acknowledgements

This research was supported by the Office of Basic Energy Sciences, Department of Energy grants DE-FG02-06ER15795 and DE-FG02-00ER15104. The DFT calculations were performed using the TeraGrid resources provided by the University of Illinois National Center for Supercomputing Applications (NCSA)41.

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Authors and Affiliations

  1. Department of Chemical Engineering, Center for Catalytic Science and Technology, University of Delaware, Newark, 19716, Delaware, USA

    Danielle A. Hansgen, Dionisios G. Vlachos & Jingguang G. Chen

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  1. Danielle A. Hansgen
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  2. Dionisios G. Vlachos
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  3. Jingguang G. Chen
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Contributions

D.A.H. and D.G.V. designed and developed the microkinetic models. D.A.H. and J.G.C. designed and developed the UHV experiments. D.A.H. performed and analysed all modelling and experimental work. All authors contributed to writing the paper.

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Correspondence to Dionisios G. Vlachos or Jingguang G. Chen.

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The authors declare no competing financial interests.

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Hansgen, D., Vlachos, D. & Chen, J. Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction. Nature Chem 2, 484–489 (2010). https://doi.org/10.1038/nchem.626

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