Tim A. Wezendonk

Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts

Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

A self-assembled delivery platform with post-production tunable release rate.

Self-assembly of three molecular components results in a delivery platform, the release rate of which can be tuned after its production. A fluorophore-conjugated gelator can be hydrolyzed by an enzyme, resulting in the release of a fluorescent small molecule. To allow the release to be tunable, the enzyme is entrapped in liposomes and can be liberated by heating the system for a short period. Crucially, the heating time determines the amount of enzyme liberated; with that, the release rate can be tuned by the time of heating.

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes

The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.

Iridium-based double perovskites for efficient water oxidation in acid media

The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2.

Metal organic frameworks as precursors for the manufacture of advanced catalytic materials

The use of metal organic frameworks as hard templates for the preparation of heterogeneous catalysts is thoroughly reviewed. In this critical article, the main factors to consider when using a MOF as a sacrificial template are first discussed. Then, the existing literature on the topic is reviewed, classifying the different examples according to the MOF metal. Finally, the main advantages, limitations and perspectives of the so-called MOF mediated synthesis are outlined.

Shaping Covalent Triazine Frameworks for the Hydrogenation of Carbon Dioxide to Formic Acid

A facile one‐step method to shape covalent triazine frameworks (CTFs) for catalytic applications is reported. Phase inversion of the CTF powder by using a polyimide as a binder in a microfluidic device results in the formation of composite spheres with accessible CTF porosity and a high mechanical and thermal stability. The fabricated spheres can be used to host organometallic complexes. The obtained shaped catalysts, Ir@CTF spheres, are active and fully recyclable in the direct hydrogenation of carbon dioxide into formic acid under mild reaction conditions (20 bar and 50–90 °C) and in the dehydrogenation of formic acid.

Determination of early warning signs for photocatalytic degradation of titanium white oil paints by means of surface analysis

Titanium white (TiO2) has been widely used as a pigment in the 20th century. However, its most photocatalytic form (anatase) can cause severe degradation of the oil paint in which it is contained. UV light initiates TiO2-photocatalyzed processes in the paint film, degrading the oil binder into volatile components resulting in chalking of the paint. This will eventually lead to severe changes in the appearance of a painting. To date, limited examples of degraded works of art containing titanium white are known due to the relatively short existence of the paintings in question and the slow progress of the degradation process. However, UV light will inevitably cause degradation of paint in works of art containing photocatalytic titanium white. In this work, a method to detect early warning signs of photocatalytic degradation of unvarnished oil paint is proposed, using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Consequently, a four-stage degradation model was developed through in-depth study of TiO2-containing paint films in various stages of degradation. The XPS surface analysis proved very valuable for detecting early warning signs of paint degradation, whereas the AFM results provide additional confirmation and are in good agreement with bulk gloss reduction.

Formulation and catalytic performance of MOF-derived Fe@C/Al composites for high temperature Fischer–Tropsch synthesis

High productivity towards C2–C4 olefins together with high catalyst stability are key for optimum operation in high temperature Fischer–Tropsch synthesis (HT-FTS). Here, we report the fabrication of Fe@C/Al composites that combine both the outstanding catalytic properties of the Fe–BTC MOF-derived Fe catalyst and the excellent mechanical resistance and textural properties provided by the inorganic AlOOH binder. The addition of AlOOH to Fe–BTC followed by pyrolysis in N2 atmosphere at 500 °C results in composites with a large mesoporosity, a high Fe/Fe3O4 ratio, 10–35 nm average Fe crystallite size and coordinatively unsaturated Al3+ sites. In catalytic terms, the addition of AlOOH binder gives rise to enhanced C2–C4 selectivity and catalyst mechanical stability in HT-FTS, but at high Al contents the activity decreases. Altogether, the productivity of these Fe@C/Al composites is well above most known Fe catalysts for this process.

Effects of Substrate and Polymer Encapsulation on CO2 Electroreduction by Immobilized Indium(III) Protoporphyrin

Heterogenization of molecular catalysts for CO2 electroreduction has attracted significant research activity, due to the combined advantages of homogeneous and heterogeneous catalysts. In this work, we demonstrate the strong influence of the nature of the substrate on the selectivity and reactivity of electrocatalytic CO2 reduction, as well as on the stability of the studied immobilized indium(III) protoporphyrin IX, for electrosynthesis of formic acid. Additionally, we investigate strategies to improve the CO2 reduction by tuning the chemical functionality of the substrate surface by means of electrochemical and plasma treatment and by catalyst encapsulation in polymer membranes. We point out several underlying factors that affect the performance of electrocatalytic CO2 reduction. The insights gained here allow one to optimize heterogenized molecular systems for enhanced CO2 electroreduction without modification of the catalyst itself.

MnOx/IrOx as Selective Oxygen Evolution Electrocatalyst in Acidic Chloride Solution

The oxygen evolution reaction (OER) and chlorine evolution reaction (CER) are electrochemical processes with high relevance to water splitting for (solar) energy conversion and industrial production of commodity chemicals, respectively. Carrying out the two reactions separately is challenging, since the catalytic intermediates are linked by scaling relations. Optimizing the efficiency of OER over CER in acidic media has proven especially difficult. In this regard, we have investigated the OER versus CER selectivity of manganese oxide (MnOx), a known OER catalyst. Thin films (∼5–20 nm) of MnOx were electrodeposited on glassy carbon-supported hydrous iridium oxide (IrOx/GC) in aqueous chloride solutions of pH ∼0.9. Using rotating ring–disk electrode voltammetry and online electrochemical mass spectrometry, it was found that deposition of MnOx onto IrOx decreases the CER selectivity of the system in the presence of 30 mM Cl– from 86% to less than 7%, making it a highly OER-selective catalyst. Detailed studies of the CER mechanism and ex-situ structure studies using SEM, TEM, and XPS suggest that the MnOx film is in fact not a catalytically active phase, but functions as a permeable overlayer that disfavors the transport of chloride ions.