Nickel foam-supported Fe,Ni-Polyporphyrin microparticles: Efficient bifunctional catalysts for overall water splitting in alkaline media

Developing highly active, stable and sustainable electrocatalysts for overall water splitting is of great importance to generate renewable H₂ for fuel cells. Herein, we report the synthesis of electrocatalytically active, nickel foam-supported, spherical core-shell Fe-poly(tetraphenylporphyrin)/Ni-poly(tetraphenylporphyrin) microparticles (FeTPP@NiTPP/NF). We also show that FeTPP@NiTPP/NF exhibits efficient bifunctional electrocatalytic properties toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Electrochemical tests in KOH solution (1 M) reveal that FeTPP@NiTPP/NF electrocatalyzes the OER with 100 mA cm⁻² at an overpotential of 302 mV and the HER with 10 mA cm⁻² at an overpotential of 170 mV. Notably also, its catalytic performance for OER is better than that of RuO₂, the benchmark OER catalyst. Although its catalytic activity for HER is slightly lower than that of Pt/C (the benchmark HER electrocatalyst), it shows greater stability than the latter during the reaction. The material also exhibits electrocatalytic activity for overall water splitting reaction at a current density of 10 mA cm⁻² with a cell voltage of 1.58 V, along with a good recovery property. Additionally, the work demonstrates a new synthetic strategy to an efficient, noble metal-free-coordinated covalent organic framework (COF)-based, bifunctional electrocatalyst for water splitting.     

Electrophoretic deposition of ZnCo2O4 spinel and its electrocatalytic properties for oxygen evolution reaction

In this paper, ZnCo₂O₄ was deposited on nickel substrate by electrophoretic deposition (EPD) method as electrocatalyst for the oxygen evolution reaction. The effect of electrophoresis variables including the deposition time, the applied voltages was discussed. XRD, SEM, and electrochemical measurement techniques were used to characterize the deposit and ZnCo₂O₄/Ni electrode. Compared with the ZnCo₂O₄ electrode prepared by nitrate decomposition method, the electrophoretic ZnCo₂O₄ electrodes exhibit better electrocatalytic properties and higher mechanical stability. And the electrode prepared at 10 V for 5 min has the best electrocatalytic properties with the overpotential of only 0.203 V at current density of 100 mA cm⁻².     

Nonwoven Ni–NiO/carbon fibers for electrochemical water oxidation

The development of technologically efficient anodes for water oxidation is crucial to improve hydrogen production via water splitting. Electrodes based on metallic active sites dispersed in carbon matrices have been shown to be an attractive way to attain this goal. However, challenges remain to prevent catalyst agglomeration that otherwise can result in a decrease of performance over time.In this work, we report an alternative and efficient method to produce nickel-nickel oxide nanoparticles-embedded in carbon nanofibers (Ni–NiO/C), by the solution blow spinning (SBS) process. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses show the carbon nanofibrillar matrix as a robust support, with well-dispersed nickel nanoparticles on the surface. The responses of the linear scanning voltammetry, cyclic voltammetry and electrochemical impedance spectroscopy demonstrate how a small fraction of nickel on the fiber surface (≈1.2–5.3%) is enough to promote substantial improvement in performance (η = 278 and 309 mV vs RHE for 10 mA cm^?2) and a significant turnover frequency (TOF) values of 1.38 (η = 278) and 1.30 s^?1 (η = 309). These promising results are correlated with a large amount of Ni³⁺ present on the fiber surfaces, as identified by X-ray Photoelectron Spectroscopy (XPS). This work provides a low-cost and rapid preparation technique that can be extended for the manufacture of a wide variety of electrodes based on metals supported on carbon nanofibers.     

Additively manufactured 316L stainless steel: An efficient electrocatalyst

In the quest of finding an economical, yet efficient material, the idea of fabricating 316L stainless steel using additive manufacturing technology was explored to produce material with refined sub-granular structure. The surface of the stainless steel was further chemically treated with an etching solution to expose the grain boundaries. The grain boundary enriched surface resulted in more active sites for the oxygen evolution reaction (OER) in additively manufactured treated (AM-T) 316L stainless steel. AM-T sample manifests enhanced catalytic activity for OER with an overpotential of 310 mV to draw a 10 mA/cm² current density, along with a lower Tafel slope of 42 mV/dec compared to AM and wrought samples. These features were validated from the increased double-layer capacitance of AM-T and approximately 1.5 times larger electrochemically effective surface area of AM-T due to etching treatment compared to the wrought sample. Furthermore, AM-T also possesses stable activity retention for 100 h at a current density of 10 mA/cm².     

Highly active and durable FexCuyNi1-x-y/FeOOH/NiOOH/CuO complex oxides for oxygen evolution reaction in alkaline media

Oxygen evolution reaction (OER) catalyzed by Ru/Ir-free electrocatalysts is pivotal for preparing oxygen in efficient way, yet our understanding of the relationship between microphysical properties and OER performance is still insufficient. Here we report on 41 kinds of Fe_xCu_yNi_1-x-y/FeOOH/NiOOH/CuO complexes (FCN-x) to investigate the Cu and Fe induced electronic perturbation and what it brings to OER performance. As result, the activity mapping of FCN-x shows an optimal composition of 1:2:7 (FCN-7) showing a comparable overpotential potential of 170.3 mV, Tafel slop of 75.9 mV dec^?1 and durability of 24 h (～29% activity loss) to that of mainstream Ru/Ir-free catalysts. Such enhancement could be attributed to the role of alloying contribution of Fe/Cu, electronic perturbation and surface modification of surface oxides. Additionally, the incompletely oxidized Fe_xCu_yNi_1-x-y not only provide a platform for electron conduction, but also work as a sacrificial material to forming fresh oxides to maintain the content of surface oxides, which is a key driver of the excellent durability of FCN-7. This synthetic strategy may give an effective way to design and screen Ru/Ir-free OER catalysts.     

Development of an experimentally validated semi-empirical fully-coupled performance model of a PEM electrolysis cell with a 3-D structured porous transport layer

A semi-empirical non-isothermal model incorporating coupled momentum, heat and mass transport phenomena for predicting the performance of a proton exchange membrane (PEM) water electrolysis cell operating without flow channels is presented. Model input parameters such as electro-kinetics properties and mean pore size of the porous transport layer (PTL) were determined by rotating disc electrode and capillary flow porometry, respectively. This is the first report of a semi-empirical fully coupled model which allows one to quantify and investigate the effect of the gas phase and bubble coverage on PEM cell performance up to very high current densities of about 5 A/cm². The mass transport effects are discussed in terms of the operating conditions, design parameters and the microstructure of the PTL. The results show that, the operating temperature and pressure, and the inlet water flowrate and thickness of the PTL are the critical parameters for mitigating mass transport limitation at high current densities. The model presented here can serve as a tool for further development and scale-up effort in the area of PEM water electrolysis, and provide insight during the design stage.     

CoSe2@NF双功能电催化剂用于高效碱性全解水

开发用于水分解的高效稳定、低成本非贵金属电催化剂，特别是在同一电解质中对阴极的析氢反应(HER)和阳极的析氧反应(OER)都具有高效作用的电催化剂是一项挑战。以六水合硝酸钴、尿素、氟化铵和硒粉为原料，采用水热和高温固相法在镍网上原位构筑了CoSe2@NF，采用XRD、XPS、SEM和TEM对CoSe2@NF进行物相分析和形貌表征，并在碱性电解液中对CoSe2@NF的电催化析氧和析氢性能进行了测试。结果表明，表面粗糙的串珠状纳米线结构极大地增加了CoSe2有效活性位点的数量。该催化电极在OER和HER中均表现出高而稳定的催化活性。将CoSe2@NF作为全解水槽的阴阳极，在1.6 V槽电压下即可产生10 mA/cm2的电流，并可在1.7 V的电压下稳定运行100 h。这项研究为全解水提供了一种经济有效的解决方案.     

IrO2-SiO2 binary oxide films: Preparation, physiochemical characterization and their electrochemical properties

Mixed IrO₂-SiO₂ oxide films were prepared on titanium substrate by the thermo-decomposition of hexachloroiridate (H₂IrCl₆) and tetraethoxysilane (TEOS) mixed precursors in organic solvents. The solution chemistry and thermal decomposition kinetics of the mixed precursors were investigated by ultra violet/visible (UV/vis) spectroscopy and thermogravimetry (TGA) and differential thermal analysis (DTA), respectively. The physiochemical characterization of the resulting materials was conducted by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. It is shown from the UV/vis spectra that the electronic absorption intensity of IrCl₆²⁻ complexes in the precursors decreases in the presence of TEOS, indicating the interaction between these two components. Thermal analysis shows the decomposition reaction of H₂IrCl₆ is inhibited by TEOS in the low temperature range, but the further oxidation reaction at high temperatures of formed intermediates is independent of the presence of silane component. Physical measurements show a restriction effect of silica on the crystallization and crystal growth processes of IrO₂, leading to the formation of finer oxide particles and the porous morphology of the binary oxide films. The porous composite films exhibit high apparent electrocatalytic activity toward the oxygen evolution reaction. In addition, the long-term stability of Ti-supported IrO₂ electrodes is found to apparently improve with appropriate amount of SiO₂ incorporation, as tested under galvanostatic electrolysis.     

Design of laser-induced graphene electrodes for water splitting

Efficient energy storage from intermittent renewables can rely on the conversion of temporary energy excess by alkaline electrolysis, yielding oxygen and green hydrogen, which can be stored and used on demand. Electrodes made of laser-induced graphene (LIG) materials offer many advantages over the traditional graphene processing routes, due to inherent simplicity and low cost-benefit. Despite poorly studied, LIG electrodes are promising for water splitting when properly doped/modified with metals. However, proper design and processing optimization should be considered. The present study is devoted to the laser processing effects on the LIG electrode performance towards water splitting in alkaline media. Promising guidelines were obtained for hydrogen production, showing high electrochemical activity, while the microstructural degradation can be minimised by selecting suitable laser processing conditions, such as 3.6 W of laser power, 100 mm/s of laser scan rate, 36 mJ/mm of energy density and 2 laser scans.