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This study presents a novel synthesis of self-standing MoP and Mo2N heterostructured electrocatalysts with enhanced stability and catalytic performance. Facilitated by the controlled phase and interfacial microstructure, the seamless structures of these catalysts minimize internal resistivity and prevent local corrosion, contributing to increased stability. The chemical synthesis proceeds with an etching step to activate the surface, followed by phosphor-nitriding in a chemical vapor deposition chamber to produce MoP-Mo2N@Mo heterostructured electrocatalysts. X-ray diffraction analyses confirmed the presence of MoP, Mo2N, and Mo phases in the electrocatalyst. Morphology studies using scanning electron microscopy characterize the hierarchical growth of structures, indicating successful formation of the heterostructure. X-ray photoelectron spectroscopy (XPS) analyses of the as-synthesized and postcatalytic activity samples reveal the chemical shift in terms of the binding energy (BE) of the Mo 3d XPS peak, especially after catalytic activity. The XPS BE shifts are attributed to changes in the oxidation state, electron transfer, and surface reconstruction during catalysis. Electrochemical evaluation of the catalysts indicates the superior performance of the MoP-Mo2N@Mo heterostructured catalyst in hydrogen evolution reactions (HER), with lower overpotentials and enhanced Tafel slopes. The stability tests reveal changes in double layer capacitance over time, suggesting surface reconstruction and an increased active surface area during catalysis. Operando electrochemical impedance spectroscopy (EIS) further elucidates the dynamic changes in resistance and charge transfer during HER. Overall, a comprehensive understanding of the synthesis, characterization, and electrochemical behavior of the developed MoP-Mo2N@Mo heterostructured electrocatalyst, as presented in this work, highlights its potential utilization in sustainable energy applications.
RESUMO
The projection of developing sustainable and cost-efficient electrocatalysts for hydrogen production is booming. However, the full potential of electrocatalysts fabricated from earth-abundant metals has yet to be exploited to replace Pt-group metals due to inadequate efficiency and insufficient design strategies to meet the ever-increasing demands for renewable energies. To improve the electrocatalytic performance, the primary challenge is to optimize the structure and electronic properties by enhancing the intrinsic catalytic activity and expanding the active catalytic surface area. Herein, we report synthesizing a 3D nanoarchitecture of aligned Ni5P4-Ni2P/NiS (plate/nanosheets) using a phospho-sulfidation process. The durability and unique design of prickly pear cactus in desert environments by adsorbing moisture through its extensive surface and ability to bear fruits at the edges of leaves inspire this study to adopt a similar 3D architecture and utilize it to design an efficient heterostructure catalyst for HER activity. The catalyst comprises two compartments of the vertically aligned Ni5P4-Ni2P plates and the NiS nanosheets, resembling the role of leaves and fruits in the prickly pear cactus. The Ni5P4-Ni2P plates deliver charges to the interface areas, and the NiS nanosheets significantly influence Had and transfer electrons for the HER activity. Indeed, the synergistic presence of heterointerfaces and the epitaxial NiS nanosheets can substantially improve the catalytic activity compared to nickel phosphide catalysts. Notably, the onset overpotential of the best-modified ternary catalysts exhibits (35 mV) half the potential required for nickel phosphide catalysts. This promising catalyst demonstrates 70 and 115 mV overpotentials to attain current densities of 10 and 100 mA cm-2, respectively. The obtained Tafel slope is 50 mV dec-1, and the measured double-layer capacitance from cyclic voltammetry (CV) for the best ternary electrocatalyst is 13.12 mF cm-2, 3 times more than the nickel phosphide electrocatalyst. Further, electrochemical impedance spectroscopy (EIS) at the cathodic potentials reveals that the lowest charge transfer resistance is linked to the best ternary electrocatalyst, ranging from 430 to 1.75 Ω cm-2. This improvement can be attributed to the acceleration of the electron exchangeability at the interfaces. Our findings demonstrate that the epitaxial NiS nanosheets expand the active catalytic surface area and simultaneously elevate the intrinsic catalytic activity by introducing heterointerfaces, which leads to accommodating more Had at the interfaces.
RESUMO
BACKGROUND: The poor biological performance of zirconium implants in the human body resulting from their bio-inertness and vulnerability to corrosion and bacterial activity reflects the need for further studies on substitution or performing the surface modification. The suggestion of employing zirconia (ZrO2) bioceramic coatings for surface modification seems beneficial. OBJECTIVES: This systematic review aims to identify and summarize existing documents reporting the biological responses for ZrO2 coatings produced by the PEO process on zirconium implants. METHODS: PubMed, Scopus, and Web of Science international databases were searched for the original and English-language studies published between 2000 and 2021. All publications reported at least one study about in-vitro (cellular and immersion studies), in-vivo (animal studies), and antibacterial topics for ZrO2-PEO coated zirconium implants. RESULTS: Throughout the initial search, 496 publications were found, and 296 papers remained following the elimination of duplicates. Finally, after multiple screening and eligibility assessments, 25 publications were qualified and included in the review. Among them, 25 in-vitro (cellular and immersion in SBF and Hanks' solutions studies), one in-vivo (animal studies), and eight antibacterial studies were found. CONCLUSION: The ZrO2 coated samples demonstrate no cytotoxicity, high cell viability rate, and excellent biocompatibility. However, changing the solution composition and electrical parameters during the PEO procedures result in significant changes to in-vitro responses. As an instance, the ZrO2 coating surface demonstrates greater biocompatibility after irradiated by UV, which makes the surface more suitable for cell growth. Due to weak apatite-forming ability, the zirconium sample shows low bioactivity in SBF. However, most cases (13 out of 16) show that the specific morphology and chemical composition of the ZrO2 coating promote apatite-forming ability with good bioactivity in SBF. Nevertheless, few papers (three out of 16) showed that the ZrO2 coatings immersed in SBF had no apatite precipitates and so no bioactivity. These cases limit the bioactivity enhancement to treatment by UV-light irradiation, hydrothermal and chemical treatment, thermal evaporation, and cathodic polarization post-treatment on ZrO2 coatings. Both zirconium and ZrO2 coated samples do not show apatite-forming ability in Hanks' solution. The ZrO2 coated implant with the bone together indicates a greater shear strength and rapid new bone formation ability during 12 weeks because of containing Ca-P compounds and porous structure. The UV post-treated ZrO2 coating induces faster new bone formation and firmer connection of bond with bone than those of untreated ZrO2 coatings. A stronger antibacterial activity of ZrO2 coatings is confirmed in half of the selected papers (four out of eight studies) compared to the bare zirconium samples. The antibacterial protection of ZrO2 coatings can be influenced by the PEO procedure variables, i.e., solution composition, electrical parameters, and treatment time. In three cases, the antibacterial activity of ZrO2 coatings is enhanced by deposition of Zn, Ag, or Cu antibacterial layers through thermal evaporation post-treatment.