Inspired by our recent finding that
Fe4.5Ni4.5S8 rock is a highly active
electrocatalyst for HER, we
set out to explore the influence of the Fe:Ni ratio on the performance
of the catalyst. We herein describe the synthesis of (Fe
x
Ni1–x
)9S8 (x = 0–1) along with a detailed
elemental composition analysis. Furthermore, using linear sweep voltammetry,
we show that the increase in the iron or nickel content, respectively,
lowers the activity of the electrocatalyst toward HER. Electrochemical
surface area analysis (ECSA) clearly indicates the highest amount
of active sites for a Fe:Ni ratio of 1:1 on the electrode surface
pointing at an altered surface composition of iron and nickel for
the other materials. Specific metal–metal interactions seem
to be of key importance for the high electrocatalytic HER activity,
which is supported by DFT calculations of several surface structures
using the surface energy as a descriptor of catalytic activity. In
addition, we show that a temperature increase leads to a significant
decrease of the overpotential and gain in HER activity. Thus, we showcase
the necessity to investigate the material structure, composition and
reaction conditions when evaluating electrocatalysts.
ConclusionsDetailed information regarding the structure of the sulfide particles in carbon-supported Mo and Co-Mo sulfide catalysts have been obtained.1. The catalysts probably consist of very small MoS, particles which contain on average 5-6 Mo ions (Mo/C) and 7-8 Mo ions (49) Bouwens, S. M. A. M.; Koningsberger, D. C.; de Beer, V. H. J.; Prins, R. CataI. Lett. 1988, I , 55. (50) Stern, E. A. In X-Ray Absorption, Principles. Applications, Techniques of EXAFS, SEXAFS, and X A N E S Koningsberger, D. C . , and Prins.
In order to design more powerful electrocatalysts, developing our understanding of the role of the surface structure and composition of widely abundant bulk materials is crucial. This is particularly true in the search for alternative hydrogen evolution reaction (HER) catalysts to replace platinum. We report scanning electrochemical cell microscopy (SECCM) measurements of the (111)-crystal planes of Fe Ni S , a highly active HER catalyst. In combination with structural characterization methods, we show that this technique can reveal differences in activity arising from even the slightest compositional changes. By probing electrochemical properties at the nanoscale, in conjunction with complementary structural information, novel design principles are revealed for application to rational material synthesis.
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