Electrochemical partial reduction of Ni(OH)_(2) to Ni(OH)_(2)/Ni via coupled oxidation of an interfacing NiAl intermetallic compound for robust hydrogen evolution

Ni-based porous electrocatalysts have been widely used in the hydrogen evolution reaction(HER)in alkaline water electrolysis,and the catalysts are produced by selective leaching of Al from Ni-Al alloys.It is well known that chemical leaching of Ni-Al intermetallic compound(IMC)generates a high surface area in Ni(OH)_(2).However,the Ni(OH)_(2) produced by leaching the Ni-Al intermetallic compound retards the hydrogen evolution reaction,which is attributed to its weak hydrogen adsorption energy.In this study,we controlled the chemical state of Ni using plasma vapor deposition(PVD)followed by heat treatment,selective Al leaching,and electrochemical reduction.X-ray diffraction(XRD),scanning microscopy(SEM),transmission electron microscopy(TEM),and energy-dispersive X-ray spectroscopy(EDS)were used to confirm the phase evolution of the electrocatalysts during fabrication.We reveal that the heat-treated Ni-Al alloy with a thick Ni2Al3surface layer underwent selective Al leaching and produced biphasic interfaces comprising Ni(OH)_(2) and NiAl IMCs at the edges of the grains in the outermost surface layer.Coupled oxidation of the interfacing NiAl IMCs facilitated the partial reduction of Ni(OH)_(2) to Ni(OH)_(2)/Ni in the grains during electrochemical reduction,as confirmed by X-ray photoelectron spectroscopy(XPS).An electrocatalyst containing partially reduced Ni(OH)_(2)/Ni exhibited an overpotential of 54 mV at 10 mA/cm^(2) in a half-cell measurement,and a cell voltage of 1.675 V at 0.4 A/cm2for single-cell operation.A combined experimental and theoretical study(density functional theory calculations)revealed that the superior HER activity was attributed to the presence of partially reduced metallic Ni with various defects and residual Al,which facilitated water adsorption,dissociation,and finally hydrogen evolution.

Selective conversion of N_(2) to NH_(3) on highly dispersed RuO_(2) using amphiphilic ionic liquid-anchored fibrous carbon structure

Ammonia (NH_(3)) plays a key role in the agricultural fertilizer and commodity chemical industries and is useful for exploring hydrogen storage carriers.The electrochemical nitrogen reduction reaction (NRR) is receiving attention as an environmentally sustainable NH_(3) synthesis replacement for the traditional Haber–Bosch process owing to its near ambient reaction conditions (<100℃ and 1 atm).However,its NH_(3) yield and faradaic efficiency are extremely low because of the sluggish kinetics of N≡N bond dissociation and the hindrance from competitive hydrogen evolution.To overcome these challenges,we herein introduce a dual-functionalized ionic liquid (1-(4-hydroxybutyl)-3-methylimidazolium hydroxide[HOBIM]OH) for a highly dispersed ruthenium oxide electrocatalyst to achieve a biased NRR.The observed uniform distribution of RuO_(2) on the carbon fiber and increase in the surface area for N_(2) adsorption by limiting proton access can be attributed to the presence of imidazolium ions.Moreover,extensive N_(2) adsorption contributes to enhanced NRR selectivity with an NH_(3) yield of 3.0×10^(-10)mol cm^(-2)s^(-1)(91.8μg h^(-1)mg^(-1)) and a faradaic efficiency of 2.2%at-0.20 V_(RHE).We expect our observations to provide new insights into the design of effective electrode structures for electrochemical NH;synthesis.

Prognostics and health management of alkaline water electrolyzer: Techno-economic analysis considering replacement moment

Recently,considerable attention has been paid to the installation of renewable energy capacity to mitigate global CO_(2) emissions.H_(2) produced using water electrolysis and renewable energy is regarded as a clean energy carrier,generating electricity without CO_(2) emissions,called‘Green H 2’.In this paper,a prognostics and health man-agement model for an alkaline water electrolyzer was proposed to predict the load voltage on the electrolyzer to obtain the state of health information.The prognostics and health management model was developed by training historical operating data via machine learning models,support vector machine and gaussian process regression,showing the root mean square error of 1.28×10^(−3) and 8.03×10^(−6).In addition,a techno-economic analysis was performed for a green H_(2) production system,composed of 1 MW of photovoltaic plant and 1 MW of alkaline water electrolyzer,to provide economic insights and feasibility of the system.A levelized cost of H_(2) of$6.89 kgH_(2)−1 was calculated and the potential to reach the levelized cost of H_(2) from steam methane reforming with carbon capture and storage was shown by considering the learning rate of the photovoltaic module and elec-trolyzer.Finally,the replacement of the alkaline water electrolyzer at around 10 years was preferred to increase the net present value from the green H_(2) production system when capital expenditure and replacement cost are low enough.