RESUMO
The defects formed by N doping always coexist with pyrrole nitrogen (Po) and pyridine nitrogen (Pd), and the synergistic mechanisms of H2O2 production and PMS activation between the different Po: Pd are unknown. This paper synthesized MOF-derived carbon materials with different nitrogen-type ratios as cathode materials in an electro-Fenton system using precursors with different nitrogen-containing functional groups. Several catalysts with different Po: Pd ratios (0:4, 1:3, 2:2, 3:1, 4:0) were prepared, and the best catalyst for LEV degradation was FC-CN (Po: Pd=3:1). X-ray Photoelectron Spectroscopy (XPS) and density-functional theory (DFT) calculations show that the introduction of nitrogen creates an interfacial micro-electric field (IMEF) in the carbon layer and the metal, accelerates the electron transfer from the carbon layer to the Co atoms, and promotes cycling between the Fe3+/Co2+ redox pairs, with the electron transfer reaching a maximum at Po: Pd = 3:1. FC-CN (Po: Pd=3:1) achieved more than 95 % LEV degradation in 90 min at pH = 3-9, with a lower energy consumption of 0.11 kWh m-3 order-1. and the energy consumption of the catalyst for LEV degradation is lower than that of those catalysts reported. In addition, the degradation pathway of LEV was proposed based on UPLC-MS and Fukui function. This study offers some valuable information for the application of MOF derivatives.
RESUMO
The oxygen evolution reaction (OER) is an important semi-reaction in the electrocatalytic water splitting for hydrogen energy production, and the development of efficient and low-cost electrocatalysts to solve the problem of slow 4-electron transport kinetics in the OER process is key. In this work, a pre-electrocatalyst with the heterogeneous interfacial structure, Prussian blue-modified nickel sulfide with sulfur vacancies (PB/NS-Sv), was designed and then converted to iron-nickel bilayer hydroxyl oxides in oxygen-rich vacancies (FeOOH/NiOOH-Ov@NS) through electrochemical oxidative reconstruction to obtain a truly stable and efficient active material. The study utilized in situ Raman to observe the transition from PB/NS-Sv to FeOOH/NiOOH-Ov@NS during the reaction. The electronic density of states in FeOOH/NiOOH-Ov@NS is regulated by the bilayer hydroxyl metal oxide synergistic effect and the abundant oxygen defect of Mental-OOH-Ov, which significantly improves OER catalytic performance. FeOOH/NiOOH-Ov@NS requires a low overpotential of only 257 mV in 1 mol/L KOH at 100 mA cm-2 current density, has a small Tafel slope of 35.2 mV dec-1 and has excellent stability for 150 h at 100 mA cm-2 current density, making it a promising candidate for industrial applications.
RESUMO
Metal-organic frameworks (MOFs) are considered as one of the most promising catalysts for oxygen evolution reaction (OER). However, only a few have introduced redox-active ligands into MOFs and explored their role in the OER process. In this work, we synthesized FeNi DHBQ/NF using the redox-active ligand 2,5-dihydroxy-1,4-benzoquinone (DHBQ), which exhibited excellent redox activity and required only 207 and 242 mV overpotentials to achieve current densities of 10 and 100 mA cm-2. Our research confirms that (i) the doping of Fe leads to the formation of Ni â O â Fe electron transfer channels in the MOFs and stronger electron transfer, attributed to the stronger d-π conjugation between the metal center and the ligand and reduced the d-orbital crystal field splitting energy of Fe3+; (ii) the rate determination step (RDS) in the OER process of the catalyst is the formation of O*, while Fe and redox-active ligands effectively regulate the adsorption energy of oxygen-containing intermediates, reducing the energy barrier of the RDS; (iii) the redox-active ligands can act as "electron reservoirs" in the electrochemical process, making Ni more readily oxidized to Ni3+ or even Ni4+ at low potentials, which is beneficial to the subsequent OER process.
