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.

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.

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.

Stability and bifurcation analysis of a tumor-immune system with two delays and diffusion.

A tumor-immune system with diffusion and delays is proposed in this paper. First, we investigate the impact of delay on the stability of nonnegative equilibrium for the model with a single delay, and the system undergoes Hopf bifurcation when delay passes through some critical values. We obtain the normal form of Hopf bifurcation by applying the multiple time scales method for determining the stability and direction of bifurcating periodic solutions. Then, we study the tumor-immune model with two delays, and show the conditions under which the nontrivial equilibria are locally asymptotically stable. Thus, we can restrain the diffusion of tumor cells by controlling the time delay associated with the time of tumor cell proliferation and the time of immune cells recognizing tumor cells. Finally, numerical simulations are presented to illustrate our analytic results.

Toxic effects of arsenic trioxide on spermatogonia are associated with oxidative stress, mitochondrial dysfunction, autophagy and metabolomic alterations.

Arsenic is a toxic metalloid that can cause male reproductive malfunctions and is widely distributed in the environment. The aim of this study was to investigate the cytotoxicity of arsenic trioxide (ATO) induced GC-1 spermatogonial (spg) cells. Our results found that ATO increased the levels of catalase (CAT) and malonaldehyde (MDA) and reactive oxygen species (ROS), while decreasing glutathione (GSH) and the total antioxidant capacity (T-AOC). Therefore, ATO triggered oxidative stress in GC-1 spg cells. In addition, ATO also caused severe mitochondrial dysfunction that included an increase in residual oxygen consumption (ROX), and decreased the routine respiration, maximal and ATP-linked respiration (ATP-L-R), as well as spare respiratory capacity (SRC), and respiratory control rate (RCR); ATO also damaged the mitochondrial structure, including mitochondrial cristae disordered and dissolved, mitochondrial vacuolar degeneration. Moreover, degradation of p62, LC3 conversion, increasing the number of acidic vesicle organelles (AVOs) and autophagosomes and autolysosomes are demonstrated that the cytotoxicity of ATO may be associated with autophagy. Meanwhile, the metabolomics analysis results showed that 20 metabolites (10 increased and 10 decreased) were significantly altered with the ATO exposure, suggesting that maybe there are the perturbations in amino acid metabolism, lipid metabolism, glycan biosynthesis and metabolism, metabolism of cofactors and vitamins. We concluded that ATO was toxic to GC-1 spg cells via inducing oxidative stress, mitochondrial dysfunction and autophagy as well as the disruption of normal metabolism. This study will aid our understanding of the mechanisms behind ATO-induced spermatogenic toxicity.

Simultaneous Coating and Doping of a Nickel-Rich Cathode by an Oxygen Ion Conductor for Enhanced Stability and Power of Lithium-Ion Batteries.

With the rapid development of plug-in hybrid electric vehicles and electric vehicles, high-energy layered lithium nickel-rich oxides have received much attention, but there are still many challenges due to the inherent properties of materials. The poor cycling performance and initial capacity loss of the nickel-rich layered oxide are associated with the structural stability of the material and Li+/Ni2+ cation disorder. Moreover, the synergistic effect of the vacancy of Li and Ni in the delithiation process aggravates the instability of oxygen, eventually resulting in the release of oxygen. It can cause damage to the stability of the structure and even cause safety issues. In this work, we report that Ce0.8Dy0.2O1.9 solid electrolyte inhibits the release of oxygen and improves the structural stability and safety of the Ni-rich cathode material, which is rich in oxygen vacancies. Besides, Ni2+ could be oxidized to Ni3+ along with the strong oxidation of Ce4+ doping into the bulk structure, which suppresses the Li+/Ni2+ cation disorder and improves the initial Coulomb efficiency of the material. This study successfully designed a novel cathode material structure to provide a basis for the future development of layered lithium nickel-rich oxides, which can be used to improve the initial Coulomb efficiency and cycle life.