Catalysts, Volume 7, Issue 2 (February 2017) – 36 articles

A plasma-synthesized cobalt catalyst supported on carbon (Co/C) was tested for Fischer-Tropsch synthesis (FTS) in a 3-phase continuously-stirred tank slurry reactor (3-φ-CSTSR) operated isothermally at 220 °C (493 K), and 2 MPa pressure. Initial syngas feed stream of H₂:CO ratio = 2 with molar composition of 0.6 L/L (60 vol %) H₂ and 0.3 L/L (30 vol %) CO, balanced in 0.1 L/L (10 vol %) Ar was used, flowing at hourly space velocity (GHSV) of 3600 cm³·h⁻¹·g⁻¹ of catalyst. Similarly, other syngas feed compositions of H₂:CO ratio = 1.5 and 1.0 were used. Results showed ~40% CO conversion with early catalyst selectivity inclined towards formation of gasoline (C₄–C₁₂) and diesel (C₁₃–C₂₀) fractions. With prolonged time-on-stream (TOS), catalyst selectivity escalated towards the heavier molecular-weight fractions such as waxes (C₂₁₊). The catalyst’s α-value, which signifies the probability of the hydrocarbon chain growth was empirically determined to be in the range of 0.85–0.87 (at H₂:CO ratio = 2), demonstrating prevalence of the hydrocarbon-chain propagation, with particular predisposition for wax production. The inhibiting CO effect towards FTS was noted at molar H₂:CO ratio of 1.0 and 1.5, giving only ~10% and ~20% CO conversion respectively, although with a high α-value of 0.93 in both cases, which showed predominant production of the heavier molecular weight fractions. Full article

A set of novel iron doped cerium‐tungsten catalysts were prepared by sol‐gel method with a view to their application for low temperature selective catalytic reduction (SCR) of NOx with NH3 in power plants. With a molar ratio Fe/W/Ce of 0.5:1:1, a NOx reduction of >90% at 200 °C was achieved. In Fe-W-Ce catalysts with low iron oxide content, it was found that the iron compounds were highly dispersed and formed a solid solution within the cerium oxide lattice, which promoted the SCR activity. Large amounts of iron in the catalysts might form a layer of Fe2O3 on the catalyst surface, which induced the synergistic inhibition effect among Fe, Ce and W species. Moreover, the Fe‐W‐Ce catalysts possessed a high resistance to changed operation parameters as well as to deactivation by SO2 and/or H2O. The novel catalyst showed to be competitive among recently developed low‐temperature SCR catalysts. Full article

As a favorably clean fuel, syngas (synthesis gas) production has been the focus of concern in past decades. Substantial literatures reported the syngas production by various catalytic reforming reactions particularly in methane or ethanol reforming. Among the developed catalysts in these reforming processes, Ni-based catalysts from hydrotalcite-like compounds (HTLcs) precursors have drawn considerable attention for their preferable structural traits. This review covers the recent literature reporting syngas production with Ni-based catalysts from HTLc precursors via methane or ethanol reforming. The discussion was initiated with catalyst preparation (including conventional and novel means), followed by subsequent thermal treatment processes, then composition design and the addition of promoters in these catalysts. As Ni-based catalysts have thermodynamic potential to deactivate because of carbon deposition or metal sintering, measures for dealing with these problems were finally summarized. To obtain optimal catalytic performances and resultantly better syngas production, based on analyzing the achievements of the references, some perspectives were finally proposed. Full article

A comparative study on different bimetallic nanocatalysts prepared from microemulsions using a one-pot method has been carried out. The analysis of experimental observations, complemented by simulation studies, provides detailed insight into the factors affecting nanoparticle architecture: (1) The metal segregation in a bimetallic nanocatalysts is the result of the combination of three main kinetic parameters: the reduction rate of metal precursors (related to reduction standard potentials), the material intermicellar exchange rate (determined by microemulsion composition), and the metal precursors concentration; (2) A minimum difference between the reduction standard potentials of the two metals of 0.20 V is needed to obtain a core-shell structure. For values ∆ε⁰ smaller than 0.20 V the obtaining of alloys cannot be avoided, neither by changing the microemulsion nor by increasing metal concentration; (3) As a rule, the higher the film flexibility around the micelles, the higher the degree of mixture in the nanocatalyst; (4) A minimum concentration of metal precursors is required to get a core-shell structure. This minimum concentration depends on the microemulsion flexibility and on the difference in reduction rates. Full article

It is demonstrated that the synthesis procedure for preparing three-dimensionally ordered macroporous (3DOM) Pr-doped ceria catalysts using a polymethylmethacrylate (PMMA) template not only affects the porous structure, but also the chemistry of the ceria surface. The PMMA template does not affect the crystalline features (type of phases, crystallite size, and cell parameter) of Pr-doped ceria, Ce and Pr location into the particles, and the bulk reduction of the Ce-Pr mixed oxide catalysts. On the contrary, the utilization of the PMMA template improves both the porosity and surface redox properties. 3DOM Ce-Pr mixed oxide catalysts combine micro, meso, and macropores, the most area being in the macropore range, while a reference unshaped catalyst presents poor porosity in all ranges. However, the catalyzed CO oxidation rates do not correlate with the surface area of the catalysts (neither micro nor meso/macro). The Ce-Pr-3DOM catalyst also presents improved surface reducibility with regards to the counterpart reference material prepared without the template, and improved redox behavior under reaction conditions; that is, it has a higher area and this area is reduced and reoxidized more easily. X-ray photoelectron spectroscopy analysis evidences that this is mainly attributed to praseodymium cations, which accomplish redox cycles more easily than cerium cations. Full article

A novel fluorous hydrazine‐1,2‐bis(carbothioate) was prepared. It showed good catalytic activity in the synthesis of ꞵ‐chloroethers with N‐chlorosuccinimide under mild reaction conditions. This fluorous organocatalyst could be recovered and recycled several times with good purity. Full article

The polymer electrolyte fuel cell (PEFC) is an attractive power generation method from the perspective of environmental protection. Carbon is usually used as a catalyst support in PEFC, but it is oxidized under high electrical potential conditions. Ti₄O₇ is expected as a new catalyst support because of its high electrical conductivity and chemical resistivity. Though Ti₄O₇ as a catalyst support must have a high specific surface area for a high performance, it is difficult to synthesize nanostructured Ti₄O₇. In this research, Ti₄O₇ nanoparticles with a size of about 60 nm were synthesized by carbothermal reduction of TiO₂ nanoparticles with polyvinylpyrrolidone (carbon source) using 2.45 GHz microwave irradiation. The experiment condition was at 950 °C for 30 min and the samples synthesized by conventional heating showed a grain growth. The findings of this study suggest that microwave processing can drastically reduce the total processing time for the synthesis of nanostructured Ti₄O₇. Full article

Linear aliphatic polyesters are degradable thermoplastic polymers, which can be obtained by ring-opening polymerization (ROP) of cyclic esters through a coordination-insertion mechanism. Aluminum based organometallic complexes have a leading position as efficient catalysts for this polymerization process. Aluminumalkyl complexes bearing salicylaldiminato ligands, although less explored, have been shown to be efficient and versatile catalysts for the ROP of various cyclic esters. These species have the potential to function as active catalysts in the ROP because of their less coordinatively saturated nature with respect to analogous SALEN-type complexes. They have been used as efficient catalysts in the ROP of commercially available cyclic esters, such as ε-caprolactone, l-lactide, rac-lactide, and glycolide. Moreover, they resulted in efficient catalysts for the ROP of cyclic esters with large ring-size and for the ROP of functionalized lactide. Furthermore, they have been used in the co- and ter-polymerization of various cyclic esters affording well controlled polymerization and a plethora of microstructural architectures, ranging from random to block to multiblock. Full article

Photo-hydrogenation of carbon dioxide (CO₂) is a green and promising technology and has received much attention recently. This technique could convert solar energy under ambient temperature and pressure into desirable and sustainable solar fuels, such as methanol (CH₃OH), methane (CH₄), and formic acid (HCOOH). It is worthwhile to mention that this direction can not only potentially depress atmospheric CO₂, but also weaken dependence on fossil fuel. Herein, 1 wt % Pt/CuAlGaO₄ photocatalyst was successfully synthesized and fully characterized by ultraviolet-visible light (UV-vis) spectroscopy, X-ray diffraction (XRD), Field emission scanning electron microscopy using energy dispersive spectroscopy analysis (FE-SEM/EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET), respectively. Three kinds of experimental photo-hydrogenation of CO₂ in the gas phase, liquid phase, and gas-liquid phase, correspondingly, were conducted under different H₂ partial pressures. The remarkable result has been observed in the gas-liquid phase. Additionally, increasing the partial pressure of H₂ would enhance the yield of product. However, when an extra amount of H₂ is supplied, it might compete with CO₂ for occupying the active sites, resulting in a negative effect on CO₂ photo-hydrogenation. For liquid and gas-liquid phases, CH₃OH is the major product. Maximum total hydrocarbons 8.302 µmol·g⁻¹ is achieved in the gas-liquid phase. Full article

Considerable research has been conducted on monolithic catalysts for various applications. Strategies toward coating monoliths are of equal interest and importance. In this paper, the preparation of monoliths and monolithic catalysts have been summarized. More specifically, a brief explanation for the manufacturing of ceramic and metallic monoliths has been provided. Also, different methods for coating γ-alumina, as a secondary support, are included. Techniques used to deposit metal-based species, zeolites and carbon onto monoliths are discussed. Furthermore, monoliths extruded with metal oxides, zeolites and carbon are described. The main foci are on the reasoning and understanding behind the preparation of monolithic catalysts. Ideas and concerns are also contributed to encourage better approaches when designing these catalysts. More importantly, the relevance of monolithic structures to reactions, such as the selective oxidation of alkanes, catalytic combustion for power generation and the preferential oxidation of carbon monoxide, has been described. Full article

This study reports the electrochemical properties for NO_x reduction of a ceria-based mixed ionic electronic conducting porous electrode promoted by Pt nanoparticles, as efficient catalyst for NO oxidation, and BaO, as sorbent to store NO_x. This catalytic layer was deposited by screen-printing on a dense membrane of gadolinia-doped ceria, an O²⁻ ionic conductor. The targeted Ba and Pt loadings were 150 and 5 μg/cm², respectively. The NO_x selective electrochemical reduction was performed between 400 °C and 500 °C with and without oxygen in the feed. Variations of the open-circuit voltage with time were found to be a good sensor of the NO_x storage process on the ceria-based catalyst-electrode. However, no N₂ production was observed in the presence of O₂ phase in spite of nitrates formation. Full article

In the present study, titanium dioxide nanostructures were synthesized through microwave irradiation. In a typical microwave synthesis, nanorod spheres in the powder form were simultaneously produced with nanorod arrays grown on polyethylene terephthalate (PET) substrates. The syntheses were performed in water or ethanol with limited temperature at 80 °C and 200 °C. A simple and low-cost approach was used for the arrays growth, which involved a PET substrate with a zinc oxide seed layer deposited by spin-coating. X-ray diffraction (XRD) and Raman spectroscopy revealed that synthesis in water result in a mixture of brookite and rutile phases, while using ethanol as solvent it was only observed the rutile phase. Scanning electron microscopy (SEM) showed that the synthesized spheres were in the micrometer range appearing as aggregates of fine nanorods. The arrays maintained the sphere nanorod aggregate structures and the synthesis totally covered the flexible substrates. Transmission electron microscopy (TEM) was used to identify the brookite structure. The optical band gaps of all materials have been determined from diffuse reflectance spectroscopy. Photocatalytic activity was assessed from rhodamine B degradation with remarkable degradability performance under ultraviolet (UV) radiation. Reusability experiments were carried out for the best photocatalyst, which also revealed notable photocatalytic activity under solar radiation. The present study is an interesting and competitive alternative for the photocatalysts existing nowadays, as it simultaneously results in highly photoactive powders and flexible materials produced with low-cost synthesis routes such as microwave irradiation. Full article

The catalytic oxidation of CO by O₂ to form CO₂ over Pt surfaces and supported catalysts is one of the most studied catalytic reactions from both fundamental and applied points of view. This review aims to show how the application of a range of time resolved, X-ray based techniques, such as X-ray diffraction (XRD), Surface X-ray diffraction (SXRD), total X-ray scattering/pair distribution function (PDF), X-ray absorption (XAFS), X-ray emission (XES), and X-ray photoelectron spectroscopies (XPS), applied under operando conditions and often coupled to adjunct techniques (for instance mass spectrometry (MS) and infrared spectroscopy (IR)) have shed new light on the structures and mechanisms at work in this most studied of systems. The aim of this review is therefore to demonstrate how a fusion of the operando philosophy with the ever augmenting capacities of modern synchrotron sources can lead to new insight and catalytic possibilities, even in the case of a process that has been intensely studied for almost 100 years. Full article

CO₂ methanation is a well-known reaction that is of interest as a capture and storage (CCS) process and as a renewable energy storage system based on a power-to-gas conversion process by substitute or synthetic natural gas (SNG) production. Integrating water electrolysis and CO₂ methanation is a highly effective way to store energy produced by renewables sources. The conversion of electricity into methane takes place via two steps: hydrogen is produced by electrolysis and converted to methane by CO₂ methanation. The effectiveness and efficiency of power-to-gas plants strongly depend on the CO₂ methanation process. For this reason, research on CO₂ methanation has intensified over the last 10 years. The rise of active, selective, and stable catalysts is the core of the CO₂ methanation process. Novel, heterogeneous catalysts have been tested and tuned such that the CO₂ methanation process increases their productivity. The present work aims to give a critical overview of CO₂ methanation catalyst production and research carried out in the last 50 years. The fundamentals of reaction mechanism, catalyst deactivation, and catalyst promoters, as well as a discussion of current and future developments in CO₂ methanation, are also included. Full article

Photocatalytic antibacterial sol-gel coated substrates have been reported to kill bacteria under light or in the dark. These coatings showed non-uniform distribution, poor adhesion to the substrate and short effective lifetime as antibacterial surfaces. These serious limitations to the performance/stability retard the potential application of antibacterial films on a wide range of surfaces in hospital facilities and public places. Here, the preparation, testing and performance of flexible ultra-thin films prepared by direct current magnetron sputtering (DCMS) at different energies are reviewed. This review reports the recent advancements in the preparation of highly adhesive photocatalytic coatings prepared by up to date sputtering technology: High Power Impulse Magnetron Sputtering (HIPIMS). These latter films demonstrated an accelerated antibacterial capability compared to thicker films prepared by DCMS leading to materials saving. Nanoparticulates of Ti and Cu have been shown during the last decades to possess high oxidative redox potentials leading to bacterial inactivation kinetics in the minute range. In the case of TiO2CuOx films, the kinetics of abatement of Escherichia coli (E. coli) and methicillin resistant Staphylococcus aureus (MRSA) were enhanced under indoor visible light and were perceived to occur within few minutes. Oligodynamic effect was seen to be responsible for bacterial inactivation by the small amount of released material in the dark and/or under light as detected by inductively-coupled plasma mass spectrometry (ICP-MS). The spectral absorbance (detected by Diffuse Reflectance Spectroscopy (DRS)) was also seen to slightly shift to the visible region based on the preparation method. Full article

We synthesized 1,8-bis(2,2′:6′,2″-terpyrid-4′-yl)anthraquinone (btpyaq) as a new dimerizing ligand and determined its single crystal structure by X-ray analysis. The dinuclear Ruthenium complex [Ru2(µ-Cl)(bpy)2(btpyaq)](BF4)3 ([3](BF4)3, bpy = 2,2′-bipyridine) was used as a catalyst for water oxidation to oxygen with (NH4)2[Ce(NO3)6] as the oxidant (turnover numbers = 248). The initial reaction rate of oxygen evolution was directly proportional to the concentration of the catalyst and independent of the oxidant concentration. The cyclic voltammogram of [3](BF4)3 in water at pH 1.3 showed an irreversible catalytic current above +1.6 V (vs. SCE), with two quasi-reversible waves and one irreversible wave at E1/2 = +0.62, +0.82 V, and Epa = +1.13 V, respectively. UV-vis and Raman spectra of [3](BF4)3 with controlled-potential electrolysis at +1.40 V revealed that [Ru(IV)=O O=Ru(IV)]4+ is stable under electrolysis conditions. [Ru(III), Ru(II)] species are recovered after dissociation of an oxygen molecule from the active species in the catalytic cycle. These results clearly indicate that an O–O bond is formed via [Ru(V)=O O=Ru(IV)]5+. Full article

Glycerol steam reforming (GSR) is a promising alternative to obtain renewable hydrogen and help the economics of the biodiesel industry. Nickel-based catalysts are typically used in reforming reactions. However, the choice of the catalyst greatly influences the process, so the development of bimetallic catalysts is a research topic of relevant interest. In this work, the effect of adding Cu, Co, and Cr to the formulation of Ni/SBA-15 catalysts for hydrogen production by GSR has been studied, looking for an enhancement of its catalytic performance. Bimetallic Ni-M/SBA-15 (M: Co, Cu, Cr) samples were prepared by incipient wetness co-impregnation to reach 15 wt % of Ni and 4 wt % of the second metal. Catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), N2-physisorption, X-ray powder diffraction (XRD), hydrogen temperature programmed reduction (H2-TPR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TGA), and tested in GSR at 600 °C and atmospheric pressure. The addition of Cu, Co, and Cr to the Ni/SBA-15 catalyst helped to form smaller crystallites of the Ni phase, this effect being more pronounced in the case of the Ni-Cr/SBA-15 sample. This catalyst also showed a reduction profile shifted towards higher temperatures, indicating stronger metal-support interaction. As a consequence, the Ni-Cr/SBA-15 catalyst exhibited the best performance in GSR in terms of glycerol conversion and hydrogen production. Additionally, Ni-Cr/SBA-15 achieved a drastic reduction in coke formation compared to the Ni/SBA-15 material. Full article

ω-Transaminases have been immobilized on macrocellular silica monoliths and used as heterogeneous biocatalysts in a continuous flow mode enantioselective transamination reaction. The support was prepared by a sol-gel method based on emulsion templating. The enzyme was immobilized on the structured silica monoliths both by adsorption, and by covalent grafting using amino-functionalized silica monoliths and glutaraldehyde as a coupling agent. A simple reactor set-up based on the use of a heat-shrinkable Teflon tube is presented and successfully used for the continuous flow kinetic resolution of a chiral amine, 4-bromo-α-methylbenzylamine. The porous structure of the supports ensures effective mass transfer and the reactor works in the plug flow regime without preferential flow paths. When immobilized in the monolith and used in the flow reactor, transaminases retain their activity and their enantioselectivity. The solid biocatalyst is also shown to be stable both on stream and during storage. These essential features pave the way to the successful development of an environmentally friendly process for chiral amines production. Full article

The activation and catalytic performance of two representative Zr-containing intermetallic systems, namely Cu-Zr and Pd-Zr, have been comparatively studied operando using methanol steam reforming (MSR) as test reaction. Using an inverse surface science and bulk model catalyst approach, we monitored the transition of the initial metal/intermetallic compound structures into the eventual active and CO₂-selective states upon contact to the methanol steam reforming mixture. For Cu-Zr, selected nominal stoichiometries ranging from Cu:Zr = 9:2 over 2:1 to 1:2 have been prepared by mixing the respective amounts of metallic Cu and Zr to yield different Cu-Zr bulk phases as initial catalyst structures. In addition, the methanol steam reforming performance of two Pd-Zr systems, that is, a bulk system with a nominal Pd:Zr = 2:1 stoichiometry and an inverse model system consisting of CVD-grown ZrO_xH_y layers on a polycrystalline Pd foil, has been comparatively assessed. While the CO₂-selectivity and the overall catalytic performance of the Cu-Zr system is promising due to operando formation of a catalytically beneficial Cu-ZrO₂ interface, the case for Pd-Zr is different. For both Pd-Zr systems, the low-temperature coking tendency, the high water-activation temperature and the CO₂-selectivity spoiling inverse WGS reaction limit the use of the Pd-Zr systems for selective MSR applications, although alloying of Pd with Zr opens water activation channels to increase the CO₂ selectivity. Full article

Microemulsions are regarded as “the ultimate enzyme microreactors” for liquid oxidations. Their structure, composed of water nanodroplets dispersed in a non-polar medium, provides several benefits for their use as media for enzymatic transformations. They have the ability to overcome the solubility limitations of hydrophobic substrates, enhance the enzymatic activity (superactivity phenomenon) and stability, while providing an interface for surface-active enzymes. Of particular interest is the use of such systems to study biotransformations catalyzed by oxidative enzymes. Nanodispersed biocatalytic media are perfect hosts for liquid oxidation reactions catalyzed by many enzymes such as heme peroxidases, phenoloxidases, cholesterol oxidase, and dehydrogenases. The system’s composition and structural properties are important for better understanding of nanodispersion-biocatalyst interactions. Full article

Ni-M (M = Mo, Fe, Co, Mn or Cr) bicomponent catalysts were prepared through the co-impregnation method for upgrading low H₂/CO ratio biomass gas into urban gas through partial methanation coupling with water gas shift (WGS). The catalysts were characterized by N₂ isothermal adsorption, X-ray diffraction (XRD), H₂ temperature programmed reduction (H₂-TPR), H₂ temperature programmed desorption (H₂-TPD), scanning electron microscopy (SEM) and thermogravimetry (TG). The catalytic performances demonstrated that Mn and Cr were superior to the other three elements due to the increased fraction of reducible NiO particles, promoted dispersion of Ni nanoparticles and enhanced H₂ chemisorption ability. The comparative study on Mn and Cr showed that Mn was more suitable due to its smaller carbon deposition rate and wider adaptability to various H₂/CO and H₂O/CO conditions, indicating its better synergy effect with Ni. A nearly 100 h, the lifetime test and start/stop cycle test further implied that 15Ni-3Mn was stable for industrial application. Full article

In the context of sustainable production processes based on bio-derivable feedstocks, the hydrogenolysis of furfuryl alcohol gives access to two important diols. This work evaluates the performance of commercial copper catalysts in the aqueous phase hydrogenolysis reaching a selectivity towards 1,2-pentanediol of up to 34%. In contrast to noble metal catalysts such as supported ruthenium, the selectivity of the hydrogenation product, tetrahydrofurfuryl alcohol, is significantly lower, so the desired diols are now the main products of this reaction. Catalysis experiments show that the performance is correlated to the catalyst composition rather than the free copper surface, indicating a strong influence of the supporting material. Although the formation of oligomeric and polymeric side products is still perturbing, copper catalysts represent promising candidates for this reaction due to their low cost and wide availability. Full article

Here, core-shell structured polydopamine-coated Fe₃O₄ nanoparticles were constructed to immobilize thermostable lipase QLM from Alcaligenes sp. Systematical characterization indicated that lipase QLM was successfully immobilized on the surface of nanoparticles with an enzyme loading of 21.4 ± 1.47 mg/g immobilized enzyme. Then, the immobilized enzyme was demonstrated to possess favorable catalytic activity and stability in the ester hydrolysis, using p-nitrophenyl caprylate as the substrate. Further, it was successfully employed in the kinetic resolution of (R, S)-2-octanol, and satisfactory enantioselectivity and recyclability could be obtained with an enantiomeric ratio (E) of 8–15 over 10 cycle reactions. Thus, core-shell structured polydopamine-coated Fe₃O₄ nanoparticles can be potentially used as a carrier for enzyme immobilization to improve their activity, stability, and reusability, which is beneficial for constructing efficient catalysts for industrial biocatalysis. Full article

CeO₂ nanooctahedrons, nanorods, and nanocubes were prepared by the hydrothermal method and were then used as supports of Cu-based catalysts for the water-gas shift (WGS) reaction. The chemical and physical properties of these catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption/desorption, UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H₂-TPR) and in situ diffuse reflectance infra-red fourier transform spectroscopy (DRIFTS) techniques. Characterization results indicate that the morphology of the CeO₂ supports, originating from the selective exposure of different crystal planes, has a distinct impact on the dispersion of Cu and the catalytic properties. The nanooctahedron CeO₂ catalyst (Cu-CeO₂-O) showed the best dispersion of Cu, the largest amount of moderate copper oxide, and the strongest Cu-support interaction. Consequently, the Cu-CeO₂-O catalyst exhibited the highest CO conversion at the temperature range of 150–250 °C when compared with the nanocube and nanorod Cu-CeO₂ catalysts. The optimized Cu content of the Cu-CeO₂-O catalysts is 10 wt % and the CO conversion reaches 91.3% at 300 °C. A distinctive profile assigned to the evolution of different types of carbonate species was observed in the 1000–1800 cm⁻¹ region of the in situ DRIFTS spectra and a particular type of carbonate species was identified as a potential key reaction intermediate at low temperature. Full article

The increasing miniaturization of devices creates the need for adequate power sources and direct methanol fuel cells (DMFC) are a strong option in the various possibilities under current development. DMFC catalysts are mostly based on platinum, for its outperformance in three key areas (activity, selectivity and stability) within methanol oxidation framework. However, platinum poisoning with products of methanol oxidation led to the use of alloys. Ruthenium–platinum alloys are preferred catalysts active phases for methanol oxidation from an industrial point of view and, indeed, ruthenium itself is a viable catalyst for this reaction. In addition, the route of methanol decomposition is crucial in the goal of producing H₂ from water reaction with methanol. However, the reaction pathway remains elusive and new approaches, namely in computational methods, have been ensued to determine it. This article reviews the various recent theoretical approaches for determining the pathway of methanol decomposition, and systematizes their validation with experimental data, within methodological context. Full article

A highly enantioselective organocatalytic Wolff rearrangement–amidation–Michael–hemiaminalization stepwise reaction is described involving a cyclic 2-diazo-1,3-diketone, primary amine and α,β-unsaturated aldehyde. Product stereocontrol can be achieved by adjusting the sequence of steps in this one-pot multicomponent reaction. This approach was used to synthesize various optically active spirocyclic piperidones with three stereogenic centers and multiple functional groups in good yields up to 76%, moderate diastereoselectivities of up to 80:20 and high enantioselectivities up to 97%. Full article

The present work describes the effects of water on Fe-doped nanoparticulate CeO₂, produced by flame spray pyrolysis, which is a critical environmental issue because CeO₂ is not stable in typical atmospheric conditions. It is hygroscopic and absorbs ~29 wt % water in the bulk when exposed to water vapor but, more importantly, it forms a hydrated and passivating surface layer when immersed in liquid water. In the latter case, CeO₂ initially undergoes direct and/or reductive dissolution, followed by the establishment of a passivating layer calculated to consist of ~69 mol % solid CeO₂·2H₂O and ~30 mol % gelled Ce(OH)₄. Under static flow conditions, a saturated boundary layer also forms but, under turbulent flow conditions, this is removed. While the passivating hydrated surface layer, which is coherent probably owing to the continuous Ce(OH)₄ gel, would be expected to eliminate the photoactivity, this does not occur. This apparent anomaly is explained by the calculation of (a) the thermodynamic stability diagrams for Ce and Fe; (b) the speciation diagrams for the Ce⁴⁺-H₂O, Ce³⁺-H₂O, Fe³⁺-H₂O, and Fe²⁺-H₂O systems; and (c) the Pourbaix diagrams for the Ce-H₂O and Fe-H₂O systems. Furthermore, consideration of the probable effects of the localized chemical and redox equilibria owing to the establishment of a very low pH (<0) at the liquid-solid interface also is important to the interpretation of the phenomena. These factors highlight the critical importance of the establishment of the passivating surface layer and its role in photocatalysis. A model for the mechanism of photocatalysis by the CeO₂ component of the hydrated phase CeO₂·2H₂O is proposed, explaining the observation of the retention of photocatalysis following the apparent alteration of the surface of CeO₂ upon hydration. The model involves the generation of charge carriers at the outer surface of the hydrated surface layer, followed by the formation of radicals, which decompose organic species that have diffused through the boundary layer, if present. Full article

Nanosized noble metal catalysts supported on high-surface-area support are of great importance for numerous industrial chemical processes to mediate reaction pathways in heterogeneous catalysis. Control of surface area and surface energy of nanocatalysts is a key to achieving high activity and selectivity for desired products. In the past decade, new synthetic methodologies for noble metal nanocatalysts with well-defined nanostructures have been developed. Wet-chemical preparation of noble metal nanocatalysts usually involves the utilization of specific surfactants that can bind the surface of nanocatalysts as ligands to control the nanostructures and prevent the coalescence of nanocatalysts. Surface ligands that form a densely packed self-assembled monolayer offer a facile solution to tune the surface energy of nanocatalysts, and, therefore, the selectivity of products. In this minireview, we highlight the recent advances in understanding the role of surface ligands in control over the product selectivity in a multi-product reaction using noble metal nanocatalysts. The review is outlined according to the three possible roles of surface ligands, including steric effect, orientation effect and surface charge state, in varying the adsorption/binding of reactants/transition states. Full article

Supercritical ethanolysis (scEtOH) is a method that allows the production of monomers, e.g., diethyl terephthalate (DET), from Polyethylene terephthalate PET chemical recycling. The use of the ionic liquids (ILs) such as 1-n-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF₄]) as a catalyst has advantages in such processes by enhancing the yield at reduced times, as shown in previous work from our lab. However, the effects of water and dyes (from the coloured PET-bottles) regarding those advantages have not been investigated. Here, a study of the effects of water and dyes on IL-catalysis is provided. Results showed that the yield related to DET formation was 98% when anhydrous ethanol was employed, but decreased to 30% (or less) when water was present in the reaction even in low amounts. Furthermore, the DET-formation yield also decreased to 66% or to 21% if 2-aminoanthraquinone or zinc phthalocyanine were present, respectively, even in anhydrous conditions. Poisoning effect on the IL-catalysis was observed in both cases. Thus, these data are relevant for expanding the study of ILs as catalysts in this and other reaction systems. Full article

Trifluoromethanesulfonic acid (TfOH) is one of the superior catalysts for acylation. The catalytic activity of TfOH in C- and/or O-acylation has broadened the use of various substrates under mild and neat or forced conditions. In this review, the salient catalytic features of TfOH are summarized, and the unique controllability of its catalytic activity in the tendency of C-acylation and/or O-acylation is discussed. Full article