Further Insight into the Conversion of a Ni-Fe Metal-Organic Framework during Water-Oxidation Reaction.

Metal-organic frameworks (MOFs) are extensively investigated as catalysts in the oxygen-evolution reaction (OER). A Ni-Fe MOF with 2,5-dihydroxy terephthalate as a linker has been claimed to be among the most efficient catalysts for the oxygen-evolution reaction (OER) under alkaline conditions. Herein, the MOF stability under the OER was reinvestigated by electrochemical methods, X-ray diffraction, X-ray absorption spectroscopy, energy-dispersive spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy, nuclear magnetic resonance, operando visible spectroscopy, electrospray ionization mass spectroscopy, and Raman spectroscopy. The peaks corresponding to the carboxylate group are observed at 1420 and 1520 cm-1 using Raman spectroscopy. The peaks disappear after the reaction, suggesting the removal of the carboxylate group. A drop in carbon content but growth in oxygen content after the OER was detected by energy-dispersive spectra. This shows that after the OER, the surface of MOF is oxidized. SEM images also show deep restructures in the surface morphology of this Ni-Fe MOF after the OER. Nuclear magnetic resonance and electrospray ionization mass spectrometry show the decomposition of the linker in alkaline conditions and even in the absence of potential. These experimental data indicate that during the OER, the synthesized MOF transforms to a Fe-Ni-layered double hydroxide, and the formed metal oxide is a candidate for the OER catalysis. Generalization is not true; however, taken together, these findings suggest that the stability of Ni-Fe MOFs under harsh oxidation conditions should be reconsidered.

Surprisingly Low Reactivity of Layered Manganese Oxide toward Water Oxidation in Fe/Ni-Free Electrolyte under Alkaline Conditions.

So far, many studies on the oxygen-evolution reaction (OER) by Mn oxides have been focused on activity; however, the identification of the best performing active site and corresponding catalytic cycles is also of critical importance. Herein, the real intrinsic activity of layered Mn oxide toward OER in Fe/Ni-free KOH is studied for the first time. At pH ≈ 14, the onset of OER for layered Mn oxide in the presence of Fe/Ni-free KOH happens at 1.72 V (vs reversible hydrogen electrode (RHE)). In the presence of Fe ions, a 190 mV decrease in the overpotential of OER was recorded for layered Mn oxide as well as a significant decrease (from 172.8 to 49 mV/decade) in the Tafel slope. Furthermore, we find that both Ni and Fe ions increase OER remarkably in the presence of layered Mn oxide, but that pure layered Mn oxide is not an efficient catalyst for OER without Ni and Fe under alkaline conditions. Thus, pure layered Mn oxide and electrolytes are critical factors in finding the real intrinsic activity of layered Mn oxide for OER. Our results call into question the high efficiency of layered Mn oxides toward OER under alkaline conditions and also elucidate the significant role of Ni and Fe impurities in the electrolyte in the presence of layered Mn oxide toward OER under alkaline conditions. Overall, a computational model supports the conclusions from the experimental structural and electrochemical characterizations. In particular, substitutional doping with Fe decreases the thermodynamic OER overpotential up to 310 mV. Besides, the thermodynamic OER onset potential calculated for the Fe-free structures is higher than 1.7 V (vs RHE) and, thus, not in the stability range of Mn oxides.

Dendrimer-Ni-Based Material: Toward an Efficient Ni-Fe Layered Double Hydroxide for Oxygen-Evolution Reaction.

Ni/Fe oxides are among the most widely used catalysts for water splitting. This paper outlines a new approach to synthesize Ni-Fe layered double hydroxides (Ni-Fe LDHs) for oxygen-evolution reaction (OER). Herein, we show that a dendrimer with carboxylate surface groups (generation 3.5) could react with Ni(II) ions to form a precatalyst for OER. During electrochemical OER, this precatalyst converted to Ni-Fe LDH, which is an efficient catalyst toward OER in the presence of Fe(III) ions. The catalyst was characterized by a number of methods and applied for OER using fluorine-doped tin oxide (FTO), Au, Pt, Ni foam, and glassy carbon electrodes. The catalyst shows a current density of 100 mA/cm2 on the surface of the Ni foam, using only 297 mV overpotential and with the Tafel slope of 60.8 mV/decade. A current density of 50 mA/cm2 on the surface of Au or Pt requires 333 and 317 mV overpotentials, respectively. The slopes of the Tafel plots for the catalyst on Au, GC, and Pt are 52.5, 47.1, and 37.4 mV/decade, respectively. The dendrimer resulted in a large dispersibility and an increase in active sites of Ni-Fe LDH, as well as the formation of Ni-Fe LDH.

Aggregated manganese complex-nanolayered manganese oxide: a new hybrid molecular-inorganic material.

Layered materials such as clays, layered double hydroxides, and layered hydroxides are promising compounds for material science applications because, in addition to their structural and functional properties, the aggregation of these compounds with others results in new structural and functional characteristics. Notably, the aggregation of a metal complex and nanolayered material leads to new structures and properties. Mn oxides and complexes are different compounds, which show promising properties. Herein, a new hybrid molecular-inorganic material was synthesized by the aggregation of a manganese complex with a 2,4,6-tris(2-pyridyl)-1,3,5-triazine ligand and monolayers of Mn oxide. This new hybrid molecular-inorganic material was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis, microanalysis, UV-Vis spectroscopy, nitrogen adsorption-desorption isotherm, magnetic properties, and electron paramagnetic resonance spectroscopy. All these methods showed that the aggregation of the manganese complex and layered Mn oxide occurred. A larger extent of aggregation for this hybrid molecular-inorganic material was observed compared to monolayered Mn oxide. The new material constitutes a new family of hybrid molecular-inorganic materials, in which transition metal complexes could be placed in a new environment.