Robust Porous TiN Layer for Improved Oxygen Evolution Reaction Performance.

The poor reversibility and slow reaction kinetics of catalytic materials seriously hinder the industrialization process of proton exchange membrane (PEM) water electrolysis. It is necessary to develop high-performance and low-cost electrocatalysts to reduce the loss of reaction kinetics. In this study, a novel catalyst support featured with porous surface structure and good electronic conductivity was successfully prepared by surface modification via a thermal nitriding method under ammonia atmosphere. The morphology and composition characterization-confirmed that a TiN layer with granular porous structure and internal pore-like defects was established on the Ti sheet. Meanwhile, the conductivity measurements showed that the in-plane electronic conductivity of the as-developed material increased significantly to 120.8 S cm−1. After IrOx was loaded on the prepared TiN-Ti support, better dispersion of the active phase IrOx, lower ohmic resistance, and faster charge transfer resistance were verified, and accordingly, more accessible catalytic active sites on the catalytic interface were developed as revealed by the electrochemical characterizations. Compared with the IrOx/Ti, the as-obtained IrOx/TiN-Ti catalyst demonstrated remarkable electrocatalytic activity (η10 mA cm−2 = 302 mV) and superior stability (overpotential degradation rate: 0.067 mV h−1) probably due to the enhanced mass adsorption and transport, good dispersion of the supported active phase IrOx, increased electronic conductivity and improved corrosion resistance provided by the TiN-Ti support.

Stainless Steel-Supported Amorphous Nickel Phosphide/Nickel as an Electrocatalyst for Hydrogen Evolution Reaction.

Recently, nickel phosphides (Ni-P) in an amorphous state have emerged as potential catalysts with high intrinsic activity and excellent electrochemical stability for hydrogen evolution reactions (HER). However, it still lacks a good strategy to prepare amorphous Ni-P with rich surface defects or structural boundaries, and it is also hard to construct a porous Ni-P layer with favorable electron transport and gas-liquid transport. Herein, an integrated porous electrode consisting of amorphous Ni-P and a Ni interlayer was successfully constructed on a 316L stainless steel felt (denoted as Ni-P/Ni-316L). The results demonstrated that the pH of the plating solution significantly affected the grain size, pore size and distribution, and roughness of the cell-like particle surface of the amorphous Ni-P layer. The Ni-P/Ni-316L prepared at pH = 3 presented the richest surface defects or structural boundaries as well as porous structure. As expected, the as-developed Ni-P/Ni-316L demonstrated the best kinetics, with η10 of 73 mV and a Tafel slope of ca. 52 mV dec-1 for the HER among all the electrocatalysts prepared at various pH values. Furthermore, the Ni-P/Ni-316L exhibited comparable electrocatalytic HER performance and better durability than the commercial Pt (20 wt%)/C in a real water electrolysis cell, indicating that the non-precious metal-based Ni-P/Ni-316L is promising for large-scale processing and practical use.

Au-TiO2/Ti Hybrid Coating as a Liquid and Gas Diffusion Layer with Improved Performance and Stability in Proton Exchange Membrane Water Electrolyzer.

The liquid and gas diffusion layer is a key component of proton exchange membrane water electrolyzer (PEMWE), and its interfacial contact resistance (ICR) and corrosion resistance have a great impact on the performance and durability of PEMWE. In this work, a novel hybrid coating with Au contacts discontinuously embedded in a titanium oxidized layer was constructed on a Ti felt via facile electrochemical metallizing and followed by a pre-oxidization process. The physicochemical characterizations, such as scanning electron microscopy, energy dispersive spectrometer, and X-ray diffraction results confirmed that the distribution and morphology of the Au contacts could be regulated with the electrical pulse time, and a hybrid coating (Au-TiO2/Ti) was eventually achieved after the long-term stability test under anode environment. At the compaction force of 140 N cm-2, the ICR was reduced from 19.7 mΩ cm2 of the P-Ti to 4.2 mΩ cm2 of the Au-TiO2/Ti. The corrosion current density at 1.8 V (RHE) is 0.689 µA cm-2. Both the ICR and corrosion resistance results showed that the prepared protective coating could provide comparable ICR and corrosion resistance to a dense Au coating.

Synthesis, Physical Properties and Electrocatalytic Performance of Nickel Phosphides for Hydrogen Evolution Reaction of Water Electrolysis.

Nickel phosphides have been investigated as an alternative to noble metals and have emerged as potential catalysts that can efficiently catalyze the hydrogen evolution reaction (HER). However, the impacts of facet morphology and crystal structure of the nickel phosphides on their catalytic reactivity have not been systematically investigated. Herein, nickel phosphides with different crystalline states were prepared through a facile calcination treatment. It was found that the calcination treatment had important effects on the phase compositions, morphologies, and crystallinity of nickel phosphides, which are closely related to their HER activity. Generally, the crystallized Ni-P catalysts exhibited faster kinetics than the amorphous Ni-P. In particular, the Ni-P 300 showed remarkable HER performance with η10 of ca. 65 mV, along with a very low Tafel slope of ca. 44 mV dec-1 due to the increased catalytically active sites. Furthermore, the Ni-P 300 exhibited negligible decay during the 140 h galvanostatic electrolysis, showing better catalytic stability than the commercial Pt/C catalyst. Compared with the amorphous Ni-P, the boosted HER activity of the Ni-P 300 could benefit from the mixed nanocrystalline Ni2P and Ni3P, which could contribute to the Hads adsorption/desorption abilities and helped provide more activity sites, promoting the HER performance.

Preparation and Performance Study of the Anodic Catalyst Layer via Doctor Blade Coating for PEM Water Electrolysis.

The membrane electrode assembly (MEA) is the core component of proton exchange membrane (PEM) water electrolysis cell, which provides a place for water decomposition to generate hydrogen and oxygen. The microstructure, thickness, IrO2 loading as well as the uniformity and quality of the anodic catalyst layer (ACL) have great influence on the performance of PEM water electrolysis cell. Aiming at providing an effective and low-cost fabrication method for MEA, the purpose of this work is to optimize the catalyst ink formulation and achieve the ink properties required to form an adherent and continuous layer with doctor blade coating method. The ink formulation (e.g., isopropanol/H2O of solvents and solids content) were adjusted, and the doctor blade thickness was optimized. The porous structure and the thickness of the doctor blade coating ACL were further confirmed with the in-plane and the cross-sectional SEM analyses. Finally, the effect of the ink formulation and the doctor blade thickness of the ACL on the cell performance were characterized in a PEM electrolyzer under ambient pressure at 80 °C. Overall, the optimized doctor blade coating ACL showed comparable performance to that prepared with the spraying method. It is proved that the doctor blade coating is capable of high-uniformity coating.