Nickel and Cobalt Phosphides Fabricated through a Codeposition-Annealing Technique As Low-Cost Electrocatalytic Layers for Efficient Hydrogen Evolution Reaction
Authors: Bernasconi Roberto , Khalil Md Ibrahim , Cakmakci Dogukan Selahattin , Bektas Yagmur , Iaquinta Clara , Lenardi Cristina , Nobili Luca , Magagnin Luca 
Published: December 2020

In the perspective of sustainable development, future economy will be increasingly dominated by carbon-free and renewable energy sources. In this context, hydrogen will play a fundamental role in the energy transition from fossil to green sources. Hydrogen can be easily produced employing water electrolysis, stored in large amounts and subsequently re-electrified in fuel cells. It offers the possibility to smooth the intermittency typical of many renewable energy sources and it constitutes an ideal complement for batteries in the transport sector. Efficient water electrolysis, however, makes use of noble metal electrocatalysts to lower the overpotential required for the Hydrogen Evolution Reaction (HER) to take place. Due to the limited availability and consequent high cost of noble metals, research is currently focusing on the development of low-cost alternative catalytic materials. One of the most studied electrocatalytic compounds are transition metal phosphides [1]. These materials present remarkable advantages over commonly used Pt based catalysts: lower cost, high abundancy and ease of manufacturing. In many cases, phosphides offer performances comparable to the noble metal electrocatalysts.
In the present work, transition metal phosphides were fabricated through a simple and costless codeposition-annealing process. Amorphous Ni-P and Co-P alloys were codeposited with red phosphorus particles and subsequently annealed. The annealing step was applied to promote the formation of intermetallics and the interdiffusion between pure phosphorus particles and the metallic matrix. As a result, different phase pure metal phosphides were obtained. The most important advantage of this methodology is the possibility to overcome the compositional limit typical of electrodeposited phosphorus-based alloys [2]. Elemental phosphorus codeposition allows to reach P concentrations higher than 50 % at., whereas simple Ni-P solid solution electrodeposition is compositionally limited to 25 % at. Enhancing P content is fundamental to obtain phosphorus rich compounds like Ni2P and Co2P, which are characterized by high catalytic activities for HER [3]. Another interesting benefit of the technique presented is the confinement of elemental P inside the coating during the annealing step. This peculiarity strongly optimizes material usage and it limits the presence of gaseous phosphorus, which is typical of many phosphorization processes used in literature to obtain metal phosphides [4] and it can result into the formation of the unstable white P allotrope.
Specifically, Ni-P and Co-P were codeposited with red P particles and process conditions were optimized to maximize elemental P particles concentration. Annealing temperature and duration were varied to investigate their influence on final electrocatalytic perfrormances. Characterization techniques like XRD, SEM, EDS, cross-sectional analysis and XPS were used to determine phase composition of the materials obtained and to characterize their morphology. The electrocatalytic HER activity and stability of the different transition metal phosphides were tested in 0.5 M H2SO4. In all the cases, remarkable results were obtained, which matched up well with present existing literature where similar electrocatalysts have been fabricated through different methods [5]. The lowest overpotential was obtained in the case of Co-P/P codeposition and subsequent annealing at 290 °C: 62 mV vs. RHE at a current density of 10 mA/cm2 in 0.5 M H2SO4 solution.
[1] P. Xiao et al., Adv. Energy Mater. 5, 1500985 (2015)
[2] R. L. Zeller and U. Landau, J. Electrochem. Soc. 139(12), 3464 (1992)
[3] A. R. J. Kucernak et al., J. Mater. Chem. A 2, 17435 (2014)
[4] X. Wang et al., Angew. Chem. 54(28), 8188 (2015)
[5] Z. Pu et al., Chem.Mater. 26(15), 4326 (2014)