Iron-/Nitrogen-Doped Electrocatalytically Active Carbons for the Oxygen Reduction Reaction with Low Amounts of Cobalt.

Transition-metal-doped carbon catalysts are promising Pt-free alternatives for low-temperature fuel cells. They are frequently obtained from sacrificial N-rich zeolitic imidazolate frameworks (ZIFs) doped with Co and Fe. The optimal low loading of metals has to be achieved to guarantee the competitive efficiency and facilitate an inquiry into the mechanism of their catalytic activity. We report on microwave-assisted solvothermal synthesis of Zn,Co-ZIFs with a relatively low (1-15 mol %) Co loading, which were further enriched with Fe(II). Materials were pyrolyzed at 700 °C to form catalytically active carbons bearing metal nanoparticles confined in structured carbon. The electrochemistry test of carbons for the oxygen reduction reaction (ORR) in perchloric acid demonstrated their high efficiency even at low cobalt contents. The initial loading of 10 mol % was found efficient, leading to the production of catalytically active carbons allowing for four-electron path of ORR.

DFT Study of the CNS Ligand Effect on the Geometry, Spin-State, and Absorption Spectrum in Ruthenium, Iron, and Cobalt Quaterpyridine Complexes.

Geometry parameters, total energy of the system in different spin states, harmonic vibrational frequencies, and absorption spectra were computed for a range of mononuclear quaterpyridine Ru(II), Fe(III/II), and Co(III/II) complexes with two axial ambidentate CNS ligands by using density functional theory (DFT) and time-dependent DFT calculations. Both structural and electronic properties were found to be correlating with the type of the binding atom in the CNS ligand (isomerization differs by 4-13 kcal·mol-1). The N-bonding of CNS ligands is energetically favored. It was also found that the low spin (LS) state is the ground state for both Ru(II) and Co(III) complexes regardless of the CNS arrangement. The other complexes are the high-spin (HS) ground-state ones with the only exception of the S-bonded CNS isomer of the Fe(III) complex. The dependencies of energy differences between the HS and LS states versus C demonstrated stabilization of the HS state with an increasing amount of the exact exchange admixture (C) for iron and cobalt complexes. An opposite behavior was observed for ruthenium complexes. The best match in harmonic vibrational frequencies between the experimental and calculated values has been reached at C = 0.15 for all the complexes. The absorption profile of the Fe(II) complex with the alternatively bonded CNS ligands strongly depends on the angle between them. The light-harvesting efficiency of the Fe(II) complexes is very similar (∼0.4) and sufficiently close to that of the Ru(II) complexes. The iron-based coordination compounds are considered as a prospective dye for dye-sensitized solar cells. The results of calculations were completed with experimental reference data, thus providing a systematic compendium for practical use.

Partial and Complete Substitution of the 1,4-Benzenedicarboxylate Linker in UiO-66 with 1,4-Naphthalenedicarboxylate: Synthesis, Characterization, and H2-Adsorption Properties.

We describe the synthesis and corresponding full characterization of the set of UiO-66 metal-organic frameworks (MOFs) with 1,4-benzenedicarboxylate (C6H4(COOH)2, hereafter H2BDC) and 1,4-naphthalenedicarboxylate (C10H6(COOH)2, hereafter H2NDC) mixed linkers with NDC contents of 0, 25, 50, and 100%. Their structural (powder X-ray diffraction, PXRD), adsorptive (N2, H2, and CO2), vibrational (IR/Raman), and thermal stability (thermogravimetric analysis, TGA) properties quantitatively correlate with the NDC content in the material. The UiO-66 phase topology is conserved at all relative fractions of BDC/NDC. The comparison between the synchrotron radiation PXRD and 77 K N2-adsorption isotherms obtained on the 50:50 BDC/NDC sample and on a mechanical mixture of the pure BDC and NDC samples univocally proves that in the mixed linkers of the MOFs the BDC and NDC linkers are shared in each MOF crystal, discarding the hypothesis of two independent phases, where each crystal contains only BDC or NDC linkers. The careful tuning of the NDC content opens a way for controlled alteration of the sorption properties of the resulting material as testified by the H2-adsorption experiments, showing that the relative ranking of the materials in H2 adsorption is different in different equilibrium-pressure ranges: at low pressures, 100NDC is the most efficient sample, while with increasing pressure, its relative performance progressively declines; at high pressures, the ranking follows the BDC content, reflecting the larger internal pore volume available in the MOFs with a higher fraction of smaller linkers. The H2-adsorption isotherms normalized by the sample Brunauer-Emmett-Teller specific surface area show, in the whole pressure range, that the surface-area-specific H2-adsorption capabilities in UiO-66 MOFs increase progressively with increasing NDC content. Density functional theory calculations, using the hybrid B3LYP exchange correlation functional and quadruple-ζ with four polarization functions (QZ4P) basis set, show that the interaction of H2 with the H2NDC linker results in an adsorption energy larger by about 15% with respect to that calculated for adsorption on the H2BDC linker.

Water as a structure-driving agent between the UiO-66 and MIL-140A metal-organic frameworks.

We report a careful investigation of a selective phase formation in the zirconium-terephthalic acid system during solvothermal synthesis, which could result in the UiO-66 (Zr6O6(OH)4(BDC)6) or MIL-140A (ZrO(BDC)) metal-organic frameworks (MOFs). The introduction of water varies the phase from MIL-140A to UiO-66 by producing at the nucleation stage tetragonal ZrO2 nanoparticles, where the local arrangement of Zr and O atoms is similar to that in the UiO-66 SBU.