RESUMEN
Metal-organic frameworks (MOFs) with carboxylate ligands as co-catalysts are very efficient for the oxygen evolution reaction (OER). However, the role of local adsorbed carboxylate ligands around the in-situ-transformed metal (oxy)hydroxides during OER is often overlooked. We reveal the extraordinary role and mechanism of surface-adsorbed carboxylate ligands on bi/trimetallic layered double hydroxides (LDHs)/MOFs for OER electrocatalytic activity enhancement. The results of X-ray photoelectron spectroscopy (XPS), synchrotron X-ray absorption spectroscopy, and density functional theory (DFT) calculations show that the carboxylic groups around metal (oxy)hydroxides can efficiently induce interfacial electron redistribution, facilitate an abundant high-valence state of nickel species with a partially distorted octahedral structure, and optimize the d-band center together with the beneficial Gibbs free energy of the intermediate. Furthermore, the results of inâ situ Raman and FTIR spectra reveal that the surface-adsorbed carboxylate ligands as Lewis base can promote sluggish OER kinetics by accelerating proton transfer and facilitating adsorption, activation, and dissociation of hydroxyl ions (OH- ).
RESUMEN
The multi metal organic frameworks (BTC-CoNiFeZn) were used as the precursors of in situ structure reconstruction in alkaline solution, and we synthesized hierarchical porous Ni,Fe-codoped Co-hydroxide nanowire array (Ni0.8Fe0.2/Co-H NAs/NF) catalyst for the oxygen evolution reaction (OER). Benefiting from the rational micro-structure, rich ion-accessible nanopores, and abundant defect sites, the target catalysts possess enhanced intrinsic activity. The obtained Ni0.8Fe0.2/Co-H NAs/NF catalysts show superior OER catalytic activity with a low overpotential of 231 mV at 10 mA cm-2, a small Tafel slope of 32.9 mV dec-1, and high cycle stability for 135 h with performance degradation of only about 4.4%.
RESUMEN
A stable pillared-layer metal-organic framework (MOF) was obtained through post-synthesis modification from an unstable fence-like MOF for the first time. By virtue of high exposure of active sites on the layers, the evolved MOF with Fe doping exhibits an ultralow overpotential of 238 mV at 10 mA cm-2 during the oxygen evolution reaction (OER). Moreover, it shows a superior electrocatalytic stability with almost no attenuation for more than 168 h.
RESUMEN
Low-cost transition-metal dichalcogenides (MS2) have attracted great interest as alternative catalysts for hydrogen evolution. However, a significant challenge is the formation of sulfur-hydrogen bonds on MS2 (S-Hads), which will severely suppress hydrogen evolution reaction (HER). Here we report Cu nanodots (NDs)-decorated Ni3S2 nanotubes (NTs) supported on carbon fibers (CFs) (Cu NDs/Ni3S2 NTs-CFs) as efficient electrocatalysts for HER in alkaline media. The electronic interactions between Cu and Ni3S2 result in Cu NDs that are positively charged and can promote water adsorption and activation. Meanwhile, Ni3S2 NTs are negatively charged and can weaken S-Hads bonds formed on catalyst surfaces. Therefore, the Cu/Ni3S2 hybrids can optimize H adsorption and desorption on electrocatalysts and can promote both Volmer and Heyrovsky steps of HER. The strong interactions between Cu and Ni3S2 cause the Cu NDs/Ni3S2 NTs-CFs electrocatalysts to exhibit the outstanding HER catalytic performance with low onset potential, high catalytic activity, and excellent stability.
