Enhancement of hydrogen evolution reaction kinetics in alkaline media by fast galvanic displacement of nickel with rhodium – from smooth surfaces to electrodeposited nickel foams

Energy-efficient hydrogen production is one of the key factors for advancing the hydrogen-based economy. Alkaline water electrolysis is the main route for the production of high-purity hydrogen, but further improvements of hydrogen evolution reaction (HER) catalysts are still needed. Industrial alkaline electrolysis relies on Ni-based catalysts, and here we describe a drastic improvement of HER activity of Ni in alkaline media using several model catalysts for HER obtained upon nickel surface modification in aqueous solution of rhodium salts, when a spontaneous deposition of rhodium takes place based on the chemical displacement reaction 3Ni + 2Rh3+ = 3Ni2+ + 2Rh. In the case of smooth Ni-poly electrodes, HER activity surpasses the activity of Pt-poly already after 30 s of exchange with Rh. SEM analysis showed that Rh is uniformly distributed, while surface roughness changes within 10%, agreeing with electrochemical measurements. Furthermore, XPS analysis has shown effective incorporation of Rh in the surface, while DFT calculations suggest that hydrogen binding is significantly weakened on the Rh-modified Ni surfaces. Such tuning of the hydrogen binding energy is seen as the main factor governing HER activity improvements. The same galvanic displacement protocols were employed for nickel foam electrodes and electrodeposited Ni on Ti mesh. In both cases, somewhat longer Rh exchange times are needed to obtain superior activities than for the smooth Ni surface, but up to 10 min. HER overpotential corresponding to −10 mA cm−2 for nickel foam and electrodeposited Ni electrodes, after modification with Rh, amounted to only −0.07 and −0.09 V, respectively. Thus, it is suggested that a fast spontaneous displacement of Ni with Rh could effectively boost HER in alkaline media with minor cost penalties compared to energy saving in the electrolysis process.

Investigation into Mechanical Properties and Sliding Wear Behavior of Friction Stir Processed Surface Composite Material

One of the different and pioneering solid-state techniques, friction stir processing (FSP), is employed for the production of surface composites. In this research, the matrix selected was copper-nickel (CuNi) with hard boron carbide particle as reinforcement. The objective of the current research work is to produce reinforced 90/10 copper-nickel surface composites reinforced with B4C fabricated via FSP. The influence of tool rotational speed on macrostructure, microstructure, grain size analysis, microhardness, and wear studies of friction stir processed (FSPed) CuNi/B4C surface composites was assessed. For high rotational speed (1400 rpm) of stir tool, the modified surface area found is a maximum of 44.4 mm2 with uniform dispersion of hard particle reinforcement. The presence of hard particle in the surface area is revealed through the electron imaging and the spectroscopic results. Spectra mapping shows the uniform distribution of hard particle over the FSPed area, and the evidence is obtained with XRD analysis. From the experimentation, it is interesting to report that the reinforcements have decreased the surface hardness for an increased rotational speed of stir tool. The hardness recorded for minimum rotational speed is 223 HV which has gradually decreased to 178 HV for 1300 rpm. It has directly influenced the wear rate of modified FSPed, as hardness is directly proportional to wear behavior. The worn surface and fractured morphology of the CuNi/B4C surface composites were also studied using Field Emission Scanning Electron Microscope (FESEM).

Kinetic Assessment of the Dry Reforming of Methane over a Solid Solution Ni–La Oxide Catalyst

The dry reforming of methane is a promising technology for the abatement of CH₄ and CO₂. Solid solution Ni–La oxide catalysts are characterized by their long–term stability (100h) when tested at full conversion. The kinetics of dry reforming over this type of catalysts has been studied using both power law and Langmuir–Hinshelwood based approaches. However, these studies typically deal with fitting the net CH₄ rate hence disregarding competing and parallel surface processes and the different possible configurations of the active surface. In this work, we synthesized a solid solution Ni–La oxide catalyst and tested six Langmuir–Hinshelwood mechanisms considering both single and dual active sites for assessing the kinetics of dry reforming and the competing reverse water gas shift reaction and investigated the performance of the derived kinetic models. In doing this, it was found that: (1) all the net rates were better fitted by a single–site model that considered that the first C–H bond cleavage in methane occurred over a <a>metal−oxygen </a>pair site; (2) this model predicted the existence of a nearly saturated nickel surface with chemisorbed oxygen adatoms derived from the dissociation of CO₂; (3) the dissociation of CO₂ can either be an inhibitory or an irrelevant step, and it can also modify the apparent activation energy for CH₄ activation. These findings contribute to a better understanding of the dry reforming reaction's kinetics and provide a robust kinetic model for the design and scale–up of the process.

Kinetic Assessment of the Dry Reforming of Methane over a Solid Solution Ni–La Oxide Catalyst

The dry reforming of methane is a promising technology for the abatement of CH₄ and CO₂. Solid solution Ni–La oxide catalysts are characterized by their long–term stability (100h) when tested at full conversion. The kinetics of dry reforming over this type of catalysts has been studied using both power law and Langmuir–Hinshelwood based approaches. However, these studies typically deal with fitting the net CH₄ rate hence disregarding competing and parallel surface processes and the different possible configurations of the active surface. In this work, we synthesized a solid solution Ni–La oxide catalyst and tested six Langmuir–Hinshelwood mechanisms considering both single and dual active sites for assessing the kinetics of dry reforming and the competing reverse water gas shift reaction and investigated the performance of the derived kinetic models. In doing this, it was found that: (1) all the net rates were better fitted by a single–site model that considered that the first C–H bond cleavage in methane occurred over a <a>metal−oxygen </a>pair site; (2) this model predicted the existence of a nearly saturated nickel surface with chemisorbed oxygen adatoms derived from the dissociation of CO₂; (3) the dissociation of CO₂ can either be an inhibitory or an irrelevant step, and it can also modify the apparent activation energy for CH₄ activation. These findings contribute to a better understanding of the dry reforming reaction's kinetics and provide a robust kinetic model for the design and scale–up of the process.