Lithium-Directed Transformation of Amorphous Iridium (Oxy)hydroxides To Produce Active Water Oxidation Catalysts.

The oxygen evolution reaction (OER) is crucial to future energy systems based on water electrolysis. Iridium oxides are promising catalysts due to their resistance to corrosion under acidic and oxidizing conditions. Highly active iridium (oxy)hydroxides prepared using alkali metal bases transform into low activity rutile IrO2 at elevated temperatures (>350 °C) during catalyst/electrode preparation. Depending on the residual amount of alkali metals, we now show that this transformation can result in either rutile IrO2 or nano-crystalline Li-intercalated IrOx. While the transition to rutile results in poor activity, the Li-intercalated IrOx has comparative activity and improved stability when compared to the highly active amorphous material despite being treated at 500 °C. This highly active nanocrystalline form of lithium iridate could be more resistant to industrial procedures to produce PEM membranes and provide a route to stabilize the high populations of redox active sites of amorphous iridium (oxy)hydroxides.

Stable amorphous georgeite as a precursor to a high-activity catalyst.

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable--and hence little known and largely ignored--georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions--a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

Sulfur Promotion in Au/C Catalyzed Acetylene Hydrochlorination.

The formation of highly active and stable acetylene hydrochlorination catalysts is of great industrial importance. The successful replacement of the highly toxic mercuric chloride catalyst with gold has led to a flurry of research in this area. One key aspect, which led to the commercialization of the gold catalyst is the use of thiosulphate as a stabilizing ligand. This study investigates the use of a range of sulfur containing compounds as promoters for production of highly active Au/C catalysts. Promotion is observed across a range of metal sulfates, non-metal sulfates, and sulfuric acid treatments. This observed enhancement can be optimized by careful consideration of either pre- or post-treatments, concentration of dopants used, and modification of washing steps. Pre-treatment of the carbon support with sulfuric acid (0.76 m) resulted in the most active Au/C in this series with an acetylene conversion of ≈70% at 200 °C.

Operando potassium K-edge X-ray absorption spectroscopy: investigating potassium catalysts during soot oxidation.

The chemical and structural nature of potassium compounds involved in catalytic soot oxidation have been studied by a combination of temperature programmed oxidation and operando potassium K-edge X-ray absorption spectroscopy experiments. These experiments are the first known operando studies using tender X-rays (∼3.6 keV) under high temperature oxidation reaction conditions. X-ray absorption near edge structure analysis of K2CO3/Al2O3 catalysts during heating shows that, at temperatures between 100 and 200 °C, potassium species undergo a structural change from an initial hydrated K2CO3·xH2O and KHCO3 mixture to well-defined K2CO3. As the catalyst is heated from 200 °C to 600 °C, a feature associated with multiple scattering shifts to lower energy, indicating increased K2CO3 dispersion, due to its mobility at high reaction temperature. This shift was noted to be greater in samples containing soot than in control experiments without soot and can be attributed to enhanced mobility of the K2CO3, due to the interaction between soot and potassium species. No potassium species except K2CO3 could be defined during reactions, which excludes a potential reaction mechanism in which carbonate ions are the active soot-oxidising species. Simulations of K-edge absorption near edge structures were performed to rationalise the observed changes seen. Findings showed that cluster size, unit cell distortions and variation in the distribution of potassium crystallographic sites influenced the simulated spectra of K2CO3. While further simulation studies are required for a more complete understanding, the current results support the hypothesis that changes in the local structure on dispersion can influence the observed spectra. Ex situ characterisation was carried out on the fresh and used catalyst, by X-ray diffraction and X-ray photoelectron spectroscopy, which indicated changes to the carbonate species, in line with the X-ray absorption spectroscopy experiments.

Enhancing the understanding of the glycerol to lactic acid reaction mechanism over AuPt/TiO2 under alkaline conditions.

The oxidation of glycerol under alkaline conditions in the presence of a heterogeneous catalyst can be tailored to the formation of lactic acid, an important commodity chemical. Despite recent advances in this area, the mechanism for its formation is still a subject of contention. In this study, we use a model 1 wt. % AuPt/TiO2 catalyst to probe this mechanism by conducting a series of isotopic labeling experiments with 1,3-13C glycerol. Optimization of the reaction conditions was first conducted to ensure high selectivity to lactic acid in the isotopic labeling experiments. Selectivity to lactic acid increased with temperature and concentration of NaOH, but increasing the O2 pressure appeared to influence only the rate of reaction. Using 1,3-13C glycerol, we demonstrate that conversion of pyruvaldehyde to lactic acid proceeds via a base-promoted 1,2-hydride shift. There was no evidence to suggest that this occurs via a 2,1-methide shift under the conditions used in this study.

Solvent-Activated Hafnium-Containing Zeolites Enable Selective and Continuous Glucose-Fructose Isomerisation.

The isomerisation of glucose to fructose is a critical step towards manufacturing petroleum-free chemicals from lignocellulosic biomass. Herein we show that Hf-containing zeolites are unique catalysts for this reaction, enabling true thermodynamic equilibrium to be achieved in a single step during intensified continuous operation, which no chemical or biological catalyst has yet been able to achieve. Unprecedented single-pass yields of 58 % are observed at a fructose selectivity of 94 %, and continuous operation for over 100 hours is demonstrated. The unexpected performance of the catalyst is realised following a period of activation within the reactor, during which time interaction with the solvent generates a state of activity that is absent in the synthesised catalyst. Mechanistic studies by X-ray absorption spectroscopy, chemisorption FTIR, operando UV/Vis and 1 H-13 C HSQC NMR spectroscopy indicate that activity arises from isolated HfIV atoms with monofunctional acidic properties.

The effect of sodium species on methanol synthesis and water-gas shift Cu/ZnO catalysts: utilising high purity zincian georgeite.

The effect of sodium species on the physical and catalytic properties of Cu/ZnO catalysts derived from zincian georgeite has been investigated. Catalysts prepared with <100 ppm to 2.1 wt% Na+, using a supercritical CO2 antisolvent technique, were characterised and tested for the low temperature water-gas shift reaction and also CO2 hydrogenation to methanol. It was found that zincian georgeite catalyst precursor stability was dependent on the Na+ concentration, with the 2.1 wt% Na+-containing sample uncontrollably ageing to malachite and sodium zinc carbonate. Samples with lower Na+ contents (<100-2500 ppm) remained as the amorphous zincian georgeite phase, which on calcination and reduction resulted in similar CuO/Cu particle sizes and Cu surface areas. The aged 2.1 wt% Na+ containing sample, after calcination and reduction, was found to comprise of larger CuO crystallites and a lower Cu surface area. However, calcination of the high Na+ sample immediately after precipitation (before ageing) resulted in a comparable CuO/Cu particle size to the lower (<100-2500 ppm) Na+ containing samples, but with a lower Cu surface area, which indicates that Na+ species block Cu sites. Activity of the catalysts for the water-gas shift reaction and methanol yields in the methanol synthesis reaction correlated with Na+ content, suggesting that Na+ directly poisons the catalyst. In situ XRD analysis showed that the ZnO crystallite size and consequently Cu crystallite size increased dramatically in the presence of water in a syn-gas reaction mixture, showing that stabilisation of nanocrystalline ZnO is required. Sodium species have a moderate effect on ZnO and Cu crystallite growth rate, with lower Na+ content resulting in slightly reduced rates of growth under reaction conditions.

The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site.

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology.

An investigation of the effect of carbon support on ruthenium/carbon catalysts for lactic acid and butanone hydrogenation.

A series of ruthenium catalysts supported on two different carbons were tested for the hydrogenation of lactic acid to 1,2-propanediol and butanone to 2-butanol. The properties of the carbon supports were investigated by inelastic neutron scattering and correlated with the properties of the ruthenium deposited onto the carbons by wet impregnation or sol-immobilisation. It was noted that the rate of butanone hydrogenation was highly dependent on the carbon support, while no noticeable difference in rates was observed between different catalysts for the hydrogenation of lactic acid.

The use of carbon monoxide as a probe molecule in spectroscopic studies for determination of exposed gold sites on TiO2.

The sol immobilisation technique, in which a stabilising ligand (such as polyvinyl alcohol or polyvinyl pyridine) can be used to tune metal particle size and composition, has become a valuable method of making supported nanoparticle catalysts. An unfortunate consequence of the stabilising ligand is that often access of reactant molecules to the metal nanoparticle surface is impeded. Several methods have been proposed for the removal of these ligands, though determination of the degree of their success is difficult. Here, we demonstrate the use of in situ infrared and UV-Vis spectroscopy to elucidate the access of carbon monoxide to the surface of Au/TiO2 catalysts before and after various ligand removal treatments. These were contrasted with a catalyst prepared by deposition precipitation prepared in the absence of stabilising ligand as a control. Changes were observed in the infrared spectrum, with the wavenumber of carbon monoxide linearly bonded to Au for catalysts shifting before and after ligand removal, which correlated well with the activity of the catalyst for carbon monoxide oxidation. Also the extent of shifting of the Au surface resonance plasmon band on the addition of carbon monoxide, observed by UV-Vis, also correlated well with catalyst activity. These simple methods can be used to determine the quantity of exposed metal sites after a ligand removal treatment and so determine the treatments effectiveness.

Partial oxidation of ethane to oxygenates using Fe- and Cu-containing ZSM-5.

Iron and copper containing ZSM-5 catalysts are effective for the partial oxidation of ethane with hydrogen peroxide giving combined oxygenate selectivities and productivities of up to 95.2% and 65 mol kgcat(-1) h(-1), respectively. High conversion of ethane (ca. 56%) to acetic acid (ca. 70% selectivity) can be observed. Detailed studies of this catalytic system reveal a complex reaction network in which the oxidation of ethane gives a range of C2 oxygenates, with sequential C-C bond cleavage generating C1 products. We demonstrate that ethene is also formed and can be subsequently oxidized. Ethanol can be directly produced from ethane, and does not originate from the decomposition of its corresponding alkylperoxy species, ethyl hydroperoxide. In contrast to our previously proposed mechanism for methane oxidation over similar zeolite catalysts, the mechanism of ethane oxidation involves carbon-based radicals, which lead to the high conversions we observe.

Selective catalytic oxidation using supported gold-platinum and palladium-platinum nanoalloys prepared by sol-immobilisation.

Supported nano-alloys have been prepared using the sol-immobilisation method for two bimetallic combinations, namely gold-platinum and palladium-platinum, using activated carbon and titania as supports. Some of the materials were prepared using a method where both metals are simultaneously reduced, thereby leading to homogeneous alloys being formed. In addition, sequential reduction of the metal combinations has also been investigated to facilitate the formation of core-shell structures. The materials have been characterized using X-ray photoelectron spectroscopy and aberration-corrected scanning transmission electron microscopy. The supported nanoparticles have been tested for a two selective oxidation reactions, namely the oxidation of toluene and benzyl alcohol using tertiary butyl hydroperoxide at 80 °C, in order to elucidate any potential structure-activity relationships.

In situ spectroscopic investigation of oxidative dehydrogenation and disproportionation of benzyl alcohol.

In the solvent free oxidation of benzyl alcohol, using supported gold-palladium nanoalloys, toluene is often one of major by-products and it is formed by the disproportionation of benzyl alcohol. Gold-palladium catalysts on acidic supports promote both the disproportionation of benzyl alcohol and oxidative dehydrogenation to form benzaldehyde. Basic supports completely switch off disproportionation and the gold-palladium nanoparticles catalyse the oxidative dehydrogenation reaction exclusively. In an attempt to provide further details on the course of these reactions, we have utilized in situ ATR-IR, in situ DRIFT and inelastic neutron scattering spectroscopic methods, and in this article we present the results of these in situ spectroscopic studies.

In situ K-edge X-ray absorption spectroscopy of the ligand environment of single-site Au/C catalysts during acetylene hydrochlorination.

The replacement of HgCl2/C with Au/C as a catalyst for acetylene hydrochlorination represents a significant reduction in the environmental impact of this industrial process. Under reaction conditions atomically dispersed cationic Au species are the catalytic active site, representing a large-scale application of heterogeneous single-site catalysts. While the metal nuclearity and oxidation state under operating conditions has been investigated in catalysts prepared from aqua regia and thiosulphate, limited studies have focused on the ligand environment surrounding the metal centre. We now report K-edge soft X-ray absorption spectroscopy of the Cl and S ligand species used to stabilise these isolated cationic Au centres in the harsh reaction conditions. We demonstrate the presence of three distinct Cl species in the materials; inorganic Cl-, Au-Cl, and C-Cl and how these species evolve during reaction. Direct evidence of Au-S interactions is confirmed in catalysts prepared using thiosulfate precursors which show high stability towards reduction to inactive metal nanoparticles. This stability was clear during gas switching experiments, where exposure to C2H2 alone did not dramatically alter the Au electronic structure and consequently did not deactivate the thiosulfate catalyst.

Facile synthesis of precious-metal single-site catalysts using organic solvents.

Single-site catalysts can demonstrate high activity and selectivity in many catalytic reactions. The synthesis of these materials by impregnation from strongly oxidizing aqueous solutions or pH-controlled deposition often leads to low metal loadings or a range of metal species. Here, we demonstrate that simple impregnation of the metal precursors onto activated carbon from a low-boiling-point, low-polarity solvent, such as acetone, results in catalysts with an atomic dispersion of cationic metal species. We show the generality of this method by producing single-site Au, Pd, Ru and Pt catalysts supported on carbon in a facile manner. Single-site Au/C catalysts have previously been validated commercially to produce vinyl chloride, and here we show that this facile synthesis method can produce effective catalysts for acetylene hydrochlorination in the absence of the highly oxidizing acidic solvents previously used.

Oxidative Carboxylation of 1-Decene to 1,2-Decylene Carbonate.

Cyclic carbonates are valuable chemicals for the chemical industry and thus, their efficient synthesis is essential. Commonly, cyclic carbonates are synthesised in a two-step process involving the epoxidation of an alkene and a subsequent carboxylation to the cyclic carbonate. To couple both steps into a direct oxidative carboxylation reaction would be desired from an economical view point since additional work-up procedures can be avoided. Furthermore, the efficient sequestration of CO2, a major greenhouse gas, would also be highly desirable. In this work, the oxidative carboxylation of 1-decene is investigated using supported gold catalysts for the epoxidation step and tetrabutylammonium bromide in combination with zinc bromide for the cycloaddition of carbon dioxide in the second step. The compatibility of the catalysts for both steps is explored and a detailed study of catalyst deactivation using X-ray photoelectron spectroscopy and scanning electron microscopy is reported. Promising selectivity of the 1,2-decylene carbonate is observed using a one-pot two-step approach.

Faraday Discussions meeting Catalysis for Fuels.

Welcome to Africa was the motto when after more than 100 years the flag ship conference series of the Royal Society of Chemistry, the Faraday Discussions was hosted for the first time on the African Continent. Under the fitting topic 'Catalysis for Fuels' over 120 delegates followed the invitation by the conference chair Prof. Graham Hutchings FRS (Cardiff Catalysis Institute), his organizing committee and the co-organizing DST-NRF Centre of Excellence in Catalysis c*change (). In the presentations of 21 invited speakers and 59 posters, cutting edge research in the field of catalysis for fuels, designing new catalysts for synthetic fuels, hydrocarbon conversion in the production of synthetic fuels and novel photocatalysis was presented over the two-day meeting. The scene was set by the opening lecture of Prof. Enrique Iglesias (UC Berkeley) and wrapped-up with the concluding remarks by Philip Gibson (SASOL).

Acetylene hydrochlorination using Au/carbon: a journey towards single site catalysis.

The replacement of mercuric chloride in the production of vinyl chloride monomer, a precursor to PVC, would greatly reduce the environmental impact of this large scale industrial process. The validation of single Au cations supported on carbon as the best catalyst for this reaction at an industrial scale has resulted from nearly 35 years of research. In this feature article we review the development of this catalyst system and address the limitations of a range of characterisation techniques used previously which may induce damage to the fresh catalyst. Following our latest findings using X-ray absorption spectroscopy, we show that under operating conditions the catalyst is atomically dispersed and can be classed as a single site catalyst, we give a perspective on future directions in single atom catalysis.

The Effects of Secondary Oxides on Copper-Based Catalysts for Green Methanol Synthesis.

Catalysts for methanol synthesis from CO2 and H2 have been produced by two main methods: co-precipitation and supercritical anti-solvent (SAS) precipitation. These two methods are compared, along with the behaviour of copper supported on Zn, Mg, Mn, and Ce oxides. Although the SAS method produces initially active material with high Cu specific surface area, they appear to be unstable during reaction losing significant amounts of surface area and hence activity. The CuZn catalysts prepared by co-precipitation, however, showed much greater thermal and reactive stability than the other materials. There appeared to be the usual near-linear dependence of activity upon Cu specific area, though the initial performance relationship was different from that post-reaction, after some loss of surface area. The formation of the malachite precursor, as reported before, is important for good activity and stability, whereas if copper oxides are formed during the synthesis and ageing process, then a detrimental effect on these properties is seen.

Supercritical Antisolvent Precipitation of Amorphous Copper-Zinc Georgeite and Acetate Precursors for the Preparation of Ambient-Pressure Water-Gas-Shift Copper/Zinc Oxide Catalysts.

A series of copper-zinc acetate and zincian georgeite precursors have been produced by supercritical CO2 antisolvent (SAS) precipitation as precursors to Cu/ZnO catalysts for the water gas shift (WGS) reaction. The amorphous materials were prepared by varying the water/ethanol volumetric ratio in the initial metal acetate solutions. Water addition promoted georgeite formation at the expense of mixed metal acetates, which are formed in the absence of the water co-solvent. Optimum SAS precipitation occurs without water to give high surface areas, whereas high water content gives inferior surface areas and copper-zinc segregation. Calcination of the acetates is exothermic, producing a mixture of metal oxides with high crystallinity. However, thermal decomposition of zincian georgeite resulted in highly dispersed CuO and ZnO crystallites with poor structural order. The georgeite-derived catalysts give superior WGS performance to the acetate-derived catalysts, which is attributed to enhanced copper-zinc interactions that originate from the precursor.