(21f) Development of Metal-Rich Two-Dimensional Catalysts for Highly Efficient Hydrogen Evolution Reaction

Development of
Metal-rich Two-Dimensional Catalysts for Highly Efficient Hydrogen Evolution
Reaction

Alireza
Kondori ¹, Chris Coble ^1,2, and Mohammad Asadi ^{1, ⸸}

¹
Department of Chemical and Biological Engineering, Illinois Institute of
Technology, Chicago, IL 60616, United States

²
Materials Science Division, Argonne National Laboratory, Lemont, IL 60439,
United States

Abstract

Hydrogen
is thought to be a promising alternative to non-renewable energy sources due to
its high-energy density and zero environmental impact [1]. Platinum (Pt) is the
most well-known catalyst that can effectively perform the Hydrogen Evolution
Reaction (HER) at the lowest possible overpotential [2-5]. However, Pt-based
catalysts are expensive and platinum itself is rare in the Earth’s crust. These
limitations have prompted the search for new materials that can efficiently
promote the HER while also being both earth-abundant and inexpensive. Among the
reported materials, molybdenum disulfide (MoS₂) has been shown to
exhibit tremendous HER performance with activity and acid-stability close to
Pt-based materials [6-9]. Several computational and electrocatalytic studies
have confirmed that the high HER activity of MoS₂ is aroused by
metal terminated edge atoms, known as active sites, while the sulfur terminated
basal plane is nearly inactive for HER [6-8].

Here
we are presenting a study of chemically synthesized two-dimensional nanomaterials
that possess transition metals at both the basal plane and edge structures. We
have shown that not only the number of active sites but also the intrinsic
catalytic activity of edge atoms is increased when transition metals (i.e.,
molybdenum) bond with elements such as nitrogen, carbon and phosphorus in place
of sulfur. Once the nanostructured materials were synthesized, cyclic
voltammetry (CV) experiments were performed in 0.5 M H₂SO₄
electrolyte to test the catalytic activity of each material. More than two
times improvement in onset overpotentials were achieved when the molybdenum
binds with the phosphorus and the carbon. The Turnover Frequency (TOF) results,
actual edge atoms activity, also confirmed catalytic activity of edge atoms is
increased by two orders of magnitude compared with MoS₂ at 200 mV overpotential.
Several characterization methods such as X-Ray Diffraction (XRD), X-Ray
Photoelectron Spectroscopy (XPS), Raman spectroscopy and Scanning Transmission
Electron Microscopy (STEM) were used to identify the atomic structure of
synthesized nanomaterials. The inexpensive and highly active catalysts
developed in this study can open a new route toward efficient and
cost-effective generation of hydrogen, thus promoting it further as a promising
alternative to fossil fuels.

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