Unravelling the Molecular Structure and Confining Environment of an Organometallic Catalyst Heterogenized within Amorphous Porous Polymers.

The catalytic activity of multifunctional, microporous materials is directly linked to the spatial arrangement of their structural building blocks. Despite great achievements in the design and incorporation of isolated catalytically active metal complexes within such materials, a detailed understanding of their atomic-level structure and the local environment of the active species remains a fundamental challenge, especially when these latter are hosted in non-crystalline organic polymers. Here, we show that by combining computational chemistry with pair distribution function analysis, 129 Xe NMR, and Dynamic Nuclear Polarization enhanced NMR spectroscopy, a very accurate description of the molecular structure and confining surroundings of a catalytically active Rh-based organometallic complex incorporated inside the cavity of amorphous bipyridine-based porous polymers is obtained. Small, but significant, differences in the structural properties of the polymers are highlighted depending on their backbone motifs.

Speciation and Structures in Pt Surface Sites Stabilized by N-Heterocyclic Carbene Ligands Revealed by Dynamic Nuclear Polarization Enhanced Indirectly Detected 195Pt NMR Spectroscopic Signatures and Fingerprint Analysis.

N-Heterocyclic carbenes (NHCs) are widely used ligands in transition metal catalysis. Notably, they are increasingly encountered in heterogeneous systems. While a detailed knowledge of the possibly multiple metal environments would be essential to understand the activity of metal-NHC-based heterogeneous catalysts, only a few techniques currently have the ability to describe with atomic-resolution structures dispersed on a solid support. Here, we introduce a new dynamic nuclear polarization (DNP) surface-enhanced solid-state nuclear magnetic resonance (NMR) approach that, in combination with advanced density functional theory (DFT) calculations, allows the structure characterization of isolated silica-supported Pt-NHC sites. Notably, we demonstrate that the signal amplification provided by DNP in combination with fast magic angle spinning enables the implementation of sensitive 13C-195Pt correlation experiments. By exploiting 1J(13C-195Pt) couplings, 2D NMR spectra were acquired, revealing two types of Pt sites. For each of them, 1J(13C-195Pt) value was determined as well as 195Pt chemical shift tensor parameters. To interpret the NMR data, DFT calculations were performed on an extensive library of molecular Pt-NHC complexes. While one surface site was identified as a bis-NHC compound, the second site most likely contains a bidentate 1,5-cyclooctadiene ligand, pointing to various parallel grafting mechanisms. The methodology described here represents a new step forward in the atomic-level description of catalytically relevant surface metal-NHC complexes. In particular, it opens up innovative avenues for exploiting the spectral signature of platinum, one of the most widely used transition metals in catalysis, but whose use for solid-state NMR remains difficult. Our results also highlight the sensitivity of 195Pt NMR parameters to slight structural changes.

Redox Potentials of Magnetite Suspensions under Reducing Conditions.

Predicting the redox behavior of magnetite in reducing soils and sediments is challenging because there is neither agreement among measured potentials nor consensus on which Fe(III) | Fe(II) equilibria are most relevant. Here, we measured open-circuit potentials of stoichiometric magnetite equilibrated over a range of solution conditions. Notably, electron transfer mediators were not necessary to reach equilibrium. For conditions where ferrous hydroxide precipitation was limited, Nernstian behavior was observed with an EH vs pH slope of -179 ± 4 mV and an EH vs Fe(II)aq slope of -54 ± 4 mV. Our estimated EHo of 857 ± 8 mV closely matches a maghemite|aqueous Fe(II) EHo of 855 mV, suggesting that it plays a dominant role in poising the solution potential and that it's theoretical Nernst equation of EH[mV] = 855 - 177 pH - 59 log [Fe2+] may be useful in predicting magnetite redox behavior under these conditions. At higher pH values and without added Fe(II), a distinct shift in potentials was observed, indicating that the dominant Fe(III)|Fe(II) couple(s) poising the potential changed. Our findings, coupled with previous Mössbauer spectroscopy and kinetic data, provide compelling evidence that the maghemite/Fe(II)aq couple accurately predicts the redox behavior of stoichiometric magnetite suspensions in the presence of aqueous Fe(II) between pH values of 6.5 and 8.5.

Abiotic reduction of nitrite by Fe(II): a comparison of rates and N2O production.

Abiotic reduction of nitrite (NO2-) by Fe(II) species (i.e., chemodenitrification) has been demonstrated in a variety of natural environments and laboratory studies, and is a potentially significant source of atmospheric nitrous oxide (N2O) emissions. It is, however, unclear how chemodenitrification rates and N2O yields vary among heterogeneous Fe(II) species under similar conditions and whether abiotic reduction competes with biological NO2- reduction. Here, we measured rates of NO2- reduction and extents of N2O production by several Fe(II) species under consistent, environmentally relevant conditions (i.e., pH 7.0, bicarbonate buffer, and 0.1 mM NO2-). Nitrite reduction rates varied significantly among the heterogeneous Fe(II) species with half-lives (t1/2) ranging from as low as an hour to over two weeks following the trend of goethite/Fe(II) ∼ hematite/Fe(II) ∼ magnetites > maghemite/Fe(II) > sediment/Fe(II). Interestingly, we observed no clear trend of increasing NO2- reduction rates with higher magnetite stoichiometry (x = Fe2+/Fe3+). Nitrogen recovery as N2O also varied significantly among the Fe species ranging from 21% to 100% recovery. We further probed both chemodenitrification and biological denitrification in the absence and presence of added aqueous Fe(II) with a sediment collected from the floodplain of an agricultural watershed. While abiotic NO2- reduction by the sediment + Fe(II) was much slower than the laboratory Fe(II) species, we found near complete mass N balance during chemodenitrification, as well as evidence for both abiotic and biological NO2- reduction potentially occurring in the sediment under anoxic conditions. Our results suggest that in redox active sediments and soils both chemodenitrification and biological denitrification are likely to occur simultaneously, and that agricultural watersheds may be significant sources of N2O emissions.

Reduction of PCE and TCE by magnetite revisited.

Here we revisit whether the common mixed-valent Fe mineral, magnetite, is a viable reductant for the abiotic natural attenuation of perchloroethylene (PCE) and trichloroethylene (TCE) in anoxic groundwater plumes. We measured PCE and TCE reduction by stoichiometric magnetite as a function of pH and Fe(ii) concentration. In the absence of added Fe(ii), stoichiometric magnetite does not reduce PCE and TCE over a three month period under anoxic conditions. When Fe(ii) is added to magnetite suspensions, PCE and TCE are reduced under Fe(ii) and pH conditions that appear to be controlled by the solubility of ferrous hydroxide, Fe(OH)2(s). Reduction rates are slow with only 1 to 30% carbon products (primarily acetylene) accumulating over several months. We conducted a similar set of experiments with Fe(OH)2(s) alone and found that, compared to in the presence of magnetite, Fe(OH)2(s) reduces PCE and TCE only at Fe(ii) concentrations that are too high (≥13 mM, 726 mg L-1) to be representative of natural aquifer conditions. Our results suggest that magnetite present in aquifer sediments alone is unlikely to reduce PCE and TCE sufficiently fast to contribute to natural attenuation of PCE and TCE. The lack of compelling evidence for PCE and TCE reduction by magnetite raises important questions regarding the current application of using magnetic susceptibility as a potential indicator for abiotic natural attenuation. Dynamic conditions and high Fe(ii) concentrations that favor active precipitation of minerals, such as Fe(OH)2(s) in the presence of magnetite (or other Fe minerals), however, may lead to PCE and TCE reduction that could help attenuate PCE and TCE plumes.

International allied health education and cross-cultural perspectives.

International partnerships develop long-lasting friendships among colleagues. This is a dividend that is of immense value in this otherwise terribly divided globe with health care issues being a major concern. The framework and lessons learned proposed herein should be of value to individuals in colleges and universities to promote a true learning experience for both partners that are enduring and replicable models of international cooperation.