We investigate the use of a series of iron-based metal−organic frameworks as precursors for the manufacturing of isobutane dehydrogenation catalysts. Both the as-prepared and spent catalysts were characterized by PXRD, XPS, PDF, ICP-OES, and CHNS+O to determine the physicochemical properties of the materials and the active phases responsible for the catalytic activity. In contrast to the previous literature, our results indicate that (i) the formation of metallic Fe under reaction conditions results in secondary cracking and coke formation; (ii) the formation of iron carbide only contributes to coke formation; and (iii) the stabilization of the Fe 2+ species is paramount to achieve stable and selective catalysts. In this sense, promotion with potassium and incorporation of titanium improve the catalytic performance. While potassium is well known to improve the selectivity in iron-catalyzed dehydrogenation reactions, the unprecedented effect of titanium in the stabilization of a nanometric titanomaghemite phase, even under reductive reaction conditions, results in a moderately active and highly selective catalyst for several hours on stream with a remarkable resistance to coke formation.

Within the context of electron transfer during the catalytic water oxidation reaction, the Ir-based system is among the most active. The reaction, mimicking photosynthesis II, requires the use of an electron acceptor such the Ce4+ cation. This complex reaction, involving adsorbed water at the interface of the metal cation and Ce4+, has mostly been studied in homogenous systems. To address the ambiguity regarding the gradual transformation of a homogenous system into a heterogeneous one, we prepared and studied a heterogeneous catalyst system composed of IrO2, with a mean particle size ranging from about 5 Å to 10 Å, dispersed on a TiO2 anatase support, with the objective of probing into the different parameters of the reaction, as well as the compositional changes and rates. The system was stable for many of the runs that were conducted (five consecutive runs with 0.18 M of Ce4+ showed the same reaction rate with TON > 56,000) and, equally importantly, was stable without induction periods. Extraction of the reaction rates from the set of catalysts, with an attempt to normalize them with respect to Ir loading and, therefore, to obtain turnover frequencies (TOF), was conducted. While, within reasonable deviations, the TOF numbers extracted from TPR and XPS Ir4f were close, those extracted from the particle shape (HR-STEM) were considerably larger. The difference indicates that bulk Ir atoms contribute to the electron transfer reaction, which may indicate that the reaction rate is dominated by the reorganization energy between the redox couples involved. Therefore, the normalization of reaction rates with surface atoms may lead to an overestimation of the site activity.

The interaction between IrO2 and TiO2 (anatase) in non-isothermal reduction conditions has been studied by the temperature programmed reduction technique. IrO2 clusters are of sizes between 0.5 and 0.9 nm as determined from High Resolution Transmission Electron Microscopy (HRTEM). Largely, two main regions for reduction were found and modeled at ca. 100 and 230 °C. The first region is attributed to the partial reduction of IrO2 clusters, while the second one is due to reduction of the formed crystalline (rutile IrO2), during TPR, to Ir metal. Two methods for calculating kinetic parameters were tested. First, by applying different ramping rates on a 3.5 wt.% IrO2/TiO2 using Kissinger’s method. The apparent activation energy values for the first and second reduction regions were found to be ca. 35 and 100 kJ/mol, respectively. The second method was based on fitting different kinetic models for the experimental results in order to extract qualitative information on the nature of interaction during the reduction process. It was found that the first reduction is largely due to the amount of IrO2 (reactant concentration) while the second one involved phase boundary effect as well as nucleation.