Metal organic frameworks (MOFs), with their crystalline, porous structures, can be synthesized to incorporate a wide range of catalytically active metals in tailored surroundings. These materials have potential as catalysts for conversion of light alkanes, feedstocks available in large quantities from shale gas that are changing the economics of manufacturing commodity chemicals. Mononuclear high-spin (S = 2) Fe(II) sites situated in the nodes of the MOF MIL-100(Fe) convert propane via dehydrogenation, hydroxylation, and overoxidation pathways in reactions with the atomic oxidant N 2 O. Pair distribution function analysis, N 2 adsorption isotherms, X-ray diffraction patterns, and infrared and Raman spectra confirm the single-phase crystallinity and stability of MIL-100(Fe) under reaction conditions (523 K in vacuo, 378−408 K C 3 H 8 + N 2 O). Density functional theory (DFT) calculations illustrate a reaction mechanism for the formation of 2-propanol, propylene, and 1-propanol involving the oxidation of Fe(II) to Fe(III) via a high-spin Fe(IV)O intermediate. The speciation of Fe(II) and Fe(III) in the nodes and their dynamic interchange was characterized by in situ X-ray absorption spectroscopy and ex situ Mossbauer spectroscopy. The catalytic relevance of Fe(II) sites and the number of such sites were determined using in situ chemical titrations with NO. N 2 and C 3 H 6 production rates were found to be first-order in N 2 O partial pressure and zero-order in C 3 H 8 partial pressure, consistent with DFT calculations that predict the reaction of Fe(II) with N 2 O to be rate determining. DFT calculations using a broken symmetry method show that Fe-trimer nodes affecting reaction contain antiferromagnetically coupled iron species, and highlight the importance of stabilizing high-spin (S = 2) Fe(II) species for effecting alkane oxidation at low temperatures (<408 K).

The use of the non-negative matrix factorization (NMF) technique is validated for automatically extracting physically relevant components from atomic pair distribution function (PDF) data from time-series data such as in situ experiments. The use of two matrix-factorization techniques, principal component analysis and NMF, on PDF data is compared in the context of a chemical synthesis reaction taking place in a synchrotron beam, applying the approach to synthetic data where the correct composition is known and on measured PDFs from previously published experimental data. The NMF approach yields mathematical components that are very close to the PDFs of the chemical components of the system and a time evolution of the weights that closely follows the ground truth. Finally, it is discussed how this would appear in a streaming context if the analysis were being carried out at the beamline as the experiment progressed.

Short-lived reaction intermediates play a critical role in mediating material synthesis. Such short-lived species often elude characterization because of the mismatch between the time scale of measurements capable of describing them and their lifetimes. Thus, we have limited ability to probe, understand, and control the mechanism for material synthesis.Here we demonstrate a new approach to in situ X-ray pair distribution function (PDF) measurements of dynamic nanomaterials structure that yields an unprecedented combination of reaction time resolution and sensitivity. Reaction time is resolved spatially as a function of position along a flow path. By applying this approach to the well-studied aqueous reaction leading to FeS, mackinawite, we identify a novel metastable intermediate, FeS layer , that forms in the first second of the reaction and which can be described as individual FeS nanosheets. Recognizing these nanosheets as synthons in the reaction opens up the possibility to deliberately redirect this assembly of the nanosheet toward different phases, including novel heterostructures.

Unravelling the complex, competing pathways that can govern reactions in multicomponent systems is an experimental and technical challenge. We outline and apply a novel analytical toolkit that fully leverages the...

Probing short-lived reaction species is challenging owing to the need for both high signal-to-noise ratio, which can require long measurement time, and fast time resolution. Here, a novel in situ sample environment is presented that decouples time resolution from measurement time by distributing reaction time over space for the reaction under flow. In the mixing-flow reactor, precursor solutions are mixed at a specific position along the flow path, where the reaction is initiated. As the reaction mixture flows within a reaction capillary, the reaction time increases with distance from the mixing point. A measurement can be taken at a specific distance from the mixing point for as long as is needed to accumulate good statistics without compromising the time resolution of the measurement. Applications of the mixing-flow reactor for pair distribution function measurements of the initial nuclei formed during the hydrolysis of Al3+ at high pH are shown.