Highly dispersed Ptδ+ on TixCe(1−x)O2 as an active phase in preferential oxidation of CO

Structure–activity relationships for 1 wt.% Pt catalysts were investigated for a series of TixCe(1−x)O2 (x = 1, 0.98, 0.9, 0.5, 0.2 and 0) supports prepared by the sol–gel method. The catalysts prepared by impregnation were characterized in detail by applying a wide range of techniques as N2-isotherms, XRF, XRD, Raman, XPS, H2-TPR, Drifts, UV–vis, etc. and tested in the preferential oxidation of CO in the presence of H2. Also several reaction conditions were deeply analyzed. A strong correlation between catalyst performance and the electronic properties let us to propose, based in all the experimental results, a plausible reaction mechanism where several redox cycles are involved.Financial support from Generalitat Valenciana and Ministerio de Economía y Competitividad (Spain) through projects PROME-TEOII/2014/004 and MAT2010-21147 is gratefully acknowledged. EOJ also thanks the CNPq – Brazil for her grant. EVRF gratefully acknowledge the Ministerio de Economía y Competitividad (Spain) for his Ramon y Cajal grant (RYC-2012-11427)

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

Controlled formation of iron carbides and their performance in Fischer-Tropsch synthesis

Iron carbides are unmistakably associated with the active phase for Fischer-Tropsch synthesis (FTS). The formation of these carbides is highly dependent on the catalyst formulation, the activation method and the operational conditions. Because of this highly dynamic behavior, studies on active phase performance often lack the direct correlation between catalyst performance and iron carbide phase. For the above reasons, an extensive in situ Mössbauer spectroscopy study on highly dispersed Fe on carbon catalysts (Fe@C) produced through pyrolysis of a Metal Organic Framework was coupled to their FTS performance testing. The preparation of Fe@C catalysts via this MOF mediated synthesis allows control over the active phase formation and therefore provides an ideal model system to study the performance of different iron carbides. Reduction of fresh Fe@C followed by low-temperature Fischer-Tropsch (LTFT) conditions resulted in the formation of the ε′-Fe2.2C, whereas carburization of the fresh catalysts under high-temperature Fischer-Tropsch (HTFT) resulted in the formation of χ-Fe5C2. Furthermore, the different activation methods did not alter other important catalyst properties, as pre- and post-reaction transmission electron microscopy (TEM) characterization confirmed that the iron nanoparticle dispersion was preserved. The weight normalized activities (FTY) of χ-Fe5C2 and ε′-Fe2.2C are virtually identical, whilst it is found that ε′-Fe2.2C is a better hydrogenation catalyst than χ-Fe5C2. The absence of differences under subsequent HTFT experiments, where χ-Fe5C2 is the dominating phase, is a strong indication that the iron carbide phase is responsible for the differences in selectivity

Controlled formation of iron carbides and their performance in Fischer-Tropsch synthesis

\u3cp\u3eIron carbides are unmistakably associated with the active phase for Fischer-Tropsch synthesis (FTS). The formation of these carbides is highly dependent on the catalyst formulation, the activation method and the operational conditions. Because of this highly dynamic behavior, studies on active phase performance often lack the direct correlation between catalyst performance and iron carbide phase. For the above reasons, an extensive in situ Mössbauer spectroscopy study on highly dispersed Fe on carbon catalysts (Fe@C) produced through pyrolysis of a Metal Organic Framework was coupled to their FTS performance testing. The preparation of Fe@C catalysts via this MOF mediated synthesis allows control over the active phase formation and therefore provides an ideal model system to study the performance of different iron carbides. Reduction of fresh Fe@C followed by low-temperature Fischer-Tropsch (LTFT) conditions resulted in the formation of the ε′-Fe\u3csub\u3e2.2\u3c/sub\u3eC, whereas carburization of the fresh catalysts under high-temperature Fischer-Tropsch (HTFT) resulted in the formation of χ-Fe\u3csub\u3e5\u3c/sub\u3eC\u3csub\u3e2\u3c/sub\u3e. Furthermore, the different activation methods did not alter other important catalyst properties, as pre- and post-reaction transmission electron microscopy (TEM) characterization confirmed that the iron nanoparticle dispersion was preserved. The weight normalized activities (FTY) of χ-Fe\u3csub\u3e5\u3c/sub\u3eC\u3csub\u3e2\u3c/sub\u3e and ε′-Fe\u3csub\u3e2.2\u3c/sub\u3eC are virtually identical, whilst it is found that ε′-Fe\u3csub\u3e2.2\u3c/sub\u3eC is a better hydrogenation catalyst than χ-Fe\u3csub\u3e5\u3c/sub\u3eC\u3csub\u3e2\u3c/sub\u3e. The absence of differences under subsequent HTFT experiments, where χ-Fe\u3csub\u3e5\u3c/sub\u3eC\u3csub\u3e2\u3c/sub\u3e is the dominating phase, is a strong indication that the iron carbide phase is responsible for the differences in selectivity.\u3c/p\u3

MnO_x/IrO_x 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 (MnO_x), a known OER catalyst. Thin films (∼5–20 nm) of MnO_x were electrodeposited on glassy carbon-supported hydrous iridium oxide (IrO_x/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 MnO_x onto IrO_<i>x</i> 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 <i>ex-situ</i> structure studies using SEM, TEM, and XPS suggest that the MnO_x film is in fact not a catalytically active phase, but functions as a permeable overlayer that disfavors the transport of chloride ions

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

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

Elucidating the Nature of Fe Species during Pyrolysis of the Fe-BTC MOF into Highly Active and Stable Fischer–Tropsch Catalysts

In this combined <i>in situ</i> XAFS, DRIFTS, and Mössbauer study, we elucidate the changes in structural, electronic, and local environments of Fe during pyrolysis of the metal organic framework Fe-BTC toward highly active and stable Fischer–Tropsch synthesis (FTS) catalysts (Fe@C). Fe-BTC framework decomposition is characterized by decarboxylation of its trimesic acid linker, generating a carbon matrix around Fe nanoparticles. Pyrolysis of Fe-BTC at 400 °C (Fe@C-400) favors the formation of highly dispersed epsilon carbides (ε′-Fe_2.2C, <i>d</i>_p = 2.5 nm), while at temperatures of 600 °C (Fe@C-600), mainly Hägg carbides are formed (χ-Fe₅C₂, <i>d</i>_p = 6.0 nm). Extensive carburization and sintering occur above these temperatures, as at 900 °C the predominant phase is cementite (θ-Fe₃C, <i>d</i>_p = 28.4 nm). Thus, the loading, average particle size, and degree of carburization of Fe@C catalysts can be tuned by varying the pyrolysis temperature. Performance testing in high-temperature FTS (HT-FTS) showed that the initial turnover frequency (TOF) of Fe@C catalysts does not change significantly for pyrolysis temperatures up to 600 °C. However, methane formation is minimized when higher pyrolysis temperatures are applied. The material pyrolyzed at 900 °C showed longer induction periods and did not reach steady state conversion under the conditions studied. None of the catalysts showed deactivation during 80 h time on stream, while maintaining high Fe time yield (FTY) in the range of 0.19–0.38 mmol_CO g_Fe^–1 s^–1, confirming the outstanding activity and stability of this family of Fe-based FTS catalysts

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.ChemE/Catalysis Engineerin