Tuning Mo Incorporation in Ni-Fe-Mo Solid Solutions: Towards an Improved Hydrogen Adsorption Energy
Authors: Rafei Mouna , Wu Xiuyu , Piñeiro Alexis , Miranda La Hera Vladimir , Wågberg Thomas , Gracia-Espino Eduardo 
Published: February 2024

The production of hydrogen by water electrolysis has emerged as a promising pathway to achieve a 100% renewable and sustainable hydrogen economy. Up to now, alkaline water electrolysis has been highlighted as a truly alternative strategy for hydrogen production due to the usage of non-expensive electrocatalysts. Ni-based electrocatalysts already have a long century history because of high conductivity, stability, and earth abundancy. However, their strong hydrogen interaction energy slows the Hydrogen Evolution Reaction (HER) activity. Tuning the morphology of the catalyst by increasing the active surface area (e.g., production of nanosheets, nanowires, nanoparticles, etc.) and enhancing the intrinsic activity (e.g., doping, alloying, etc.) can improve the catalytic activity. Binary and ternary alloys based on nickel are a common route to boost their intrinsic activity and tune the morphology. Ternary alloys like CuAlNi, NiMoFe and NiMoW have been previously proposed, although the role of each element is still not fully investigated. Among the alloys, Ni-Fe mixtures have shown better catalytic activity towards HER, and the Mo incorporation has resulted in a reduced onset potential due to favorable hydrogen-metal interaction and development of active sites. The strategy for NiFeMo synthesis is mainly by hydrothermal method or electrodeposition which are limited by low material loading and production volume. Therefore, searching for a technique which is capable of producing trimetallic alloys with a scalable amount is of high interest for the development of hydrogen production. Here, we studied the preparation of FeNi3Mox via a fast and straightforward solution precursor plasma spraying (SPPS) method. The liquid precursors containing metal salts of Ni, Fe, and Mo are used to produce trimetallic solid solutions. The non-stoichiometric nanostructured electrocatalysts are deposited onto stainless-steel mesh (SS-mesh), Ni foam, and carbon paper for the HER in alkaline. We found that tuning Mo content (~9 At%) in the solution precursor conducts to an improved overpotential of 112 mV (iR-corrected) at -10 mA cm-2 and a Tafel slope of 109 mV dec-1 in agreement with a Volmer-Heyrovsky HER route. Energy dispersive X-ray spectroscopy (XPS) has confirmed the reduction in the superficial Ni and Fe oxides with Mo insertion which is directly affecting the electron transport. In addition, to investigate the effect of Mo in more detail, we evaluated the work function using ultraviolet photoelectron spectroscopy (UPS) which shows that Mo incorporation changes linearly the electrocatalyst’s work function and it is highly correlated to the hydrogen binding energy. Consequently, the change in the work function, resulting in a weaker hydrogen adsorption energy which leads to an improved hydrogen production. Theoretical catalytic activity maps from Density Functional Theory (DFT) studies have revealed the enhanced HER activity is the responsibility of the active sites near the superficial Mo atoms.

Figure 1