Next Issue
Previous Issue

Table of Contents

Catalysts, Volume 7, Issue 2 (February 2017)

  • Issues are regarded as officially published after their release is announced to the table of contents alert mailing list.
  • You may sign up for e-mail alerts to receive table of contents of newly released issues.
  • PDF is the official format for papers published in both, html and pdf forms. To view the papers in pdf format, click on the "PDF Full-text" link, and use the free Adobe Readerexternal link to open them.
Cover Story Transaminases are enzymes that catalyse transaminations i.e. enantioselective reactions leading to [...] Read more.
View options order results:
result details:
Displaying articles 1-36
Export citation of selected articles as:

Editorial

Jump to: Research, Review

Open AccessEditorial Catalysts—Looking Back and Peering Ahead
Catalysts 2017, 7(2), 41; doi:10.3390/catal7020041
Received: 23 January 2017 / Revised: 23 January 2017 / Accepted: 23 January 2017 / Published: 26 January 2017
PDF Full-text (362 KB) | HTML Full-text | XML Full-text
Abstract
I am pleased to report on the latest happenings at Catalysts.[...] Full article

Research

Jump to: Editorial, Review

Open AccessFeature PaperCommunication Stereoselective Chemoenzymatic Synthesis of Optically Active Aryl-Substituted Oxygen-Containing Heterocycles
Catalysts 2017, 7(2), 37; doi:10.3390/catal7020037
Received: 22 December 2016 / Revised: 16 January 2017 / Accepted: 17 January 2017 / Published: 25 January 2017
PDF Full-text (1316 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A two-step stereoselective chemoenzymatic synthesis of optically active α-aryl-substituted oxygen heterocycles was developed, exploiting a whole-cell mediated asymmetric reduction of α-, β-, and γ-chloroalkyl arylketones followed by a stereospecific cyclization of the corresponding chlorohydrins into the target heterocycles. Among the various whole cells
[...] Read more.
A two-step stereoselective chemoenzymatic synthesis of optically active α-aryl-substituted oxygen heterocycles was developed, exploiting a whole-cell mediated asymmetric reduction of α-, β-, and γ-chloroalkyl arylketones followed by a stereospecific cyclization of the corresponding chlorohydrins into the target heterocycles. Among the various whole cells screened (baker’s yeast, Kluyveromyces marxianus CBS 6556, Saccharomyces cerevisiae CBS 7336, Lactobacillus reuteri DSM 20016), baker’s yeast was the one providing the best yields and the highest enantiomeric ratios (up to 95:5 er) in the bioreduction of the above ketones. The obtained optically active chlorohydrins could be almost quantitatively cyclized in a basic medium into the corresponding α-aryl-substituted cyclic ethers without any erosion of their enantiomeric integrity. In this respect, valuable, chiral non-racemic functionalized oxygen containing heterocycles (e.g., (S)-styrene oxide, (S)-2-phenyloxetane, (S)-2-phenyltetrahydrofuran), amenable to be further elaborated on, can be smoothly and successfully generated from their prochiral precursors. Full article
(This article belongs to the Special Issue Asymmetric and Selective Biocatalysis)
Figures

Open AccessArticle A Comparison Reduction of 4-Nitrophenol by Gold Nanospheres and Gold Nanostars
Catalysts 2017, 7(2), 38; doi:10.3390/catal7020038
Received: 12 December 2016 / Revised: 18 January 2017 / Accepted: 19 January 2017 / Published: 24 January 2017
Cited by 4 | PDF Full-text (4632 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In order to investigate structure-property relationships, the catalytic properties of gold nanoparticles were evaluated in the reduction of 4-nitrophenol by NaBH4. Using catalyst suspensions with identical amounts of gold, the following key results were obtained: first, the nanostars showed increased activity
[...] Read more.
In order to investigate structure-property relationships, the catalytic properties of gold nanoparticles were evaluated in the reduction of 4-nitrophenol by NaBH4. Using catalyst suspensions with identical amounts of gold, the following key results were obtained: first, the nanostars showed increased activity as compared to spherical gold nanoparticles; second, larger gold nanostars showed higher activity, likely because of the abundance of flat/spiky features on these particles, which show high metal utilization; third, treatment of the nanostar colloid with cucurbit[7]uril can be used to balance catalyst stability and activity; fourth, as expected from the decreasing surface atom fraction, the specific activity of the spherical nanoparticles decreased with increasing particle size. Full article
(This article belongs to the Special Issue Soluble Nanoparticles in Catalytic Applications)
Figures

Figure 1

Open AccessArticle Mechanistic Analysis of Water Oxidation Catalyst cis-[Ru(bpy)2(H2O)2]2+: Effect of Dimerization
Catalysts 2017, 7(2), 39; doi:10.3390/catal7020039
Received: 27 November 2016 / Revised: 9 January 2017 / Accepted: 18 January 2017 / Published: 25 January 2017
Cited by 1 | PDF Full-text (1602 KB) | HTML Full-text | XML Full-text
Abstract
While the catalytic activity of some Ru-based polypyridine complexes in water oxidation is well established, the relationship between their chemical structure and activity is less known. In this work, the single site Ru complex [Ru(bpy)2(H2O)2]2+ (bpy
[...] Read more.
While the catalytic activity of some Ru-based polypyridine complexes in water oxidation is well established, the relationship between their chemical structure and activity is less known. In this work, the single site Ru complex [Ru(bpy)2(H2O)2]2+ (bpy = 2,2′-bipyridine)—which can exist as either a cis isomer or a trans isomer—is investigated. While a difference in the catalytic activity of these two isomers is well established, with cis-[Ru(bpy)2(H2O)2]2+ being much more active, no mechanistic explanation of this fact has been presented. The oxygen evolving capability of both isomers at multiple concentrations has been investigated, with cis-[Ru(bpy)2(H2O)2]2+ showing a second-order dependence of O2 evolution activity with increased catalyst concentration. Measurement of the electron paramagnetic resonance (EPR) spectrum of cis-[Ru(bpy)2(H2O)2]2+, shortly after oxidation with CeIV, showed the presence of a signal matching that of cis,cis-[RuIII(bpy)2(H2O)ORuIV(bpy)2(OH)]4+, also known as “blue dimer”. The formation of dimers is a concentration-dependent process, which could serve to explain the greater than first order increase in catalytic activity. The trans isomer showed a first-order dependence of O2 evolution on catalyst concentration. Behavior of [Ru(bpy)2(H2O)2]2+ isomers is compared with other Ru-based catalysts, in particular [Ru(tpy)(bpy)(H2O)]2+ (tpy = 2,2′;6,2′′-terpyridine). Full article
(This article belongs to the Special Issue Ruthenium Catalysts)
Figures

Open AccessArticle Sucrose Hydrolysis in a Bespoke Capillary Wall-Coated Microreactor
Catalysts 2017, 7(2), 42; doi:10.3390/catal7020042
Received: 14 November 2016 / Accepted: 24 January 2017 / Published: 27 January 2017
Cited by 4 | PDF Full-text (2440 KB) | HTML Full-text | XML Full-text
Abstract
Microscale technology has been increasingly used in chemical synthesis up to production scale, but in biocatalysis the implementation has been proceeding at a slower pace. In this work, the design of a low cost and versatile continuous flow enzyme microreactor is described that
[...] Read more.
Microscale technology has been increasingly used in chemical synthesis up to production scale, but in biocatalysis the implementation has been proceeding at a slower pace. In this work, the design of a low cost and versatile continuous flow enzyme microreactor is described that illustrates the potential of microfluidic reactors for both the development and characterization of biocatalytic processes. The core structure of the developed reactor consists of an array of capillaries with 450 μm of inner diameter with their inner surface functionalized with (3-aminopropyl)triethoxysilane (APTES) and glutaraldehyde where Saccharomyces cerevisiae invertase was covalently bound. The production of invert sugar syrup through enzymatic sucrose hydrolysis was used as model system. Once the microreactor assembly reproducibility and the immobilized enzyme behavior were established, the evaluation of the immobilized enzyme kinetic parameters was carried out at flow rates ranging from 20.8 to 219.0 μL·min−1 and substrate concentrations within 2.0%–10.0% (w/v). Despite the impact of immobilization on the kinetic parameters, viz. Km(app) was increased two fold and Kcat showed a 14-fold decrease when compared to solution phase invertase, the immobilization proved highly robust. For a mean residence time of 48.8 min, full conversion of 5.0% (w/v) sucrose was observed over 20 days. Full article
(This article belongs to the Special Issue Immobilized Enzymes: Strategies for Enzyme Stabilization)
Figures

Figure 1

Open AccessArticle Poisoning Effects of Water and Dyes on the [Bmim][BF4] Catalysis of Poly(Ethylene Terephthalate) (PET) Depolymerization under Supercritical Ethanol
Catalysts 2017, 7(2), 43; doi:10.3390/catal7020043
Received: 9 November 2016 / Revised: 11 January 2017 / Accepted: 12 January 2017 / Published: 28 January 2017
PDF Full-text (1619 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Open AccessArticle Aqueous and Surface Chemistries of Photocatalytic Fe-Doped CeO2 Nanoparticles
Catalysts 2017, 7(2), 45; doi:10.3390/catal7020045
Received: 7 November 2016 / Revised: 23 January 2017 / Accepted: 23 January 2017 / Published: 29 January 2017
Cited by 2 | PDF Full-text (4985 KB) | HTML Full-text | XML Full-text
Abstract
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 %
[...] Read more.
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
(This article belongs to the Special Issue Ceria-based Catalysts)
Figures

Figure 1

Open AccessArticle One-Pot Two-Step Organocatalytic Asymmetric Synthesis of Spirocyclic Piperidones via Wolff Rearrangement–Amidation–Michael–Hemiaminalization Sequence
Catalysts 2017, 7(2), 46; doi:10.3390/catal7020046
Received: 14 December 2016 / Revised: 18 January 2017 / Accepted: 22 January 2017 / Published: 4 February 2017
PDF Full-text (2142 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Metal-free Organocatalysis)
Figures

Open AccessArticle Morphology-Dependent Properties of Cu/CeO2 Catalysts for the Water-Gas Shift Reaction
Catalysts 2017, 7(2), 48; doi:10.3390/catal7020048
Received: 4 January 2017 / Revised: 20 January 2017 / Accepted: 26 January 2017 / Published: 5 February 2017
PDF Full-text (3701 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Ceria-based Catalysts)
Figures

Open AccessArticle Immobilization of Thermostable Lipase QLM on Core-Shell Structured Polydopamine-Coated Fe3O4 Nanoparticles
Catalysts 2017, 7(2), 49; doi:10.3390/catal7020049
Received: 9 December 2016 / Revised: 18 January 2017 / Accepted: 25 January 2017 / Published: 6 February 2017
PDF Full-text (4327 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Immobilized Enzymes: Strategies for Enzyme Stabilization)
Figures

Figure 1

Open AccessCommunication Aqueous Phase Hydrogenolysis of Bio-Derivable Furfuryl Alcohol to Pentanediols Using Copper Catalysts
Catalysts 2017, 7(2), 50; doi:10.3390/catal7020050
Received: 1 November 2016 / Revised: 11 January 2017 / Accepted: 22 January 2017 / Published: 7 February 2017
PDF Full-text (535 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Open AccessArticle The Synergy Effect of Ni-M (M = Mo, Fe, Co, Mn or Cr) Bicomponent Catalysts on Partial Methanation Coupling with Water Gas Shift under Low H2/CO Conditions
Catalysts 2017, 7(2), 51; doi:10.3390/catal7020051
Received: 6 January 2017 / Revised: 30 January 2017 / Accepted: 3 February 2017 / Published: 8 February 2017
Cited by 1 | PDF Full-text (7869 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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
[...] Read more.
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
Figures

Open AccessArticle A Comparative Discussion of the Catalytic Activity and CO2-Selectivity of Cu-Zr and Pd-Zr (Intermetallic) Compounds in Methanol Steam Reforming
Catalysts 2017, 7(2), 53; doi:10.3390/catal7020053
Received: 10 January 2017 / Accepted: 7 February 2017 / Published: 9 February 2017
Cited by 4 | PDF Full-text (6052 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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 ZrOxHy 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
(This article belongs to the Special Issue Reforming Catalysts)
Figures

Figure 1

Open AccessArticle Enantioselective Transamination in Continuous Flow Mode with Transaminase Immobilized in a Macrocellular Silica Monolith
Catalysts 2017, 7(2), 54; doi:10.3390/catal7020054
Received: 10 January 2017 / Accepted: 7 February 2017 / Published: 10 February 2017
Cited by 3 | PDF Full-text (2927 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Sol–Gel Chemistry: A Toolbox for Catalyst Preparation)
Figures

Open AccessArticle Production of Renewable Hydrogen from Glycerol Steam Reforming over Bimetallic Ni-(Cu,Co,Cr) Catalysts Supported on SBA-15 Silica
Catalysts 2017, 7(2), 55; doi:10.3390/catal7020055
Received: 11 December 2016 / Revised: 23 January 2017 / Accepted: 6 February 2017 / Published: 10 February 2017
Cited by 3 | PDF Full-text (4439 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Reforming Catalysts)
Figures

Open AccessArticle Mechanism of Water Oxidation Catalyzed by a Dinuclear Ruthenium Complex Bridged by Anthraquinone
Catalysts 2017, 7(2), 56; doi:10.3390/catal7020056
Received: 5 January 2017 / Revised: 2 February 2017 / Accepted: 6 February 2017 / Published: 10 February 2017
PDF Full-text (3982 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Water Oxidation Catalysis)
Figures

Open AccessArticle Photocatalytic TiO2 Nanorod Spheres and Arrays Compatible with Flexible Applications
Catalysts 2017, 7(2), 60; doi:10.3390/catal7020060
Received: 29 December 2016 / Revised: 31 January 2017 / Accepted: 7 February 2017 / Published: 14 February 2017
Cited by 4 | PDF Full-text (9697 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Titanium Dioxide Photocatalysis)
Figures

Open AccessArticle Electrochemical Removal of NOx on Ceria-Based Catalyst-Electrodes
Catalysts 2017, 7(2), 61; doi:10.3390/catal7020061
Received: 23 December 2016 / Revised: 3 February 2017 / Accepted: 8 February 2017 / Published: 16 February 2017
PDF Full-text (3587 KB) | HTML Full-text | XML Full-text
Abstract
This study reports the electrochemical properties for NOx 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 NOx. This catalytic layer was deposited
[...] Read more.
This study reports the electrochemical properties for NOx 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 NOx. 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 NOx 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 NOx 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
(This article belongs to the Special Issue Ceria-based Catalysts)
Figures

Figure 1

Open AccessArticle Reactor Design for CO2 Photo-Hydrogenation toward Solar Fuels under Ambient Temperature and Pressure
Catalysts 2017, 7(2), 63; doi:10.3390/catal7020063
Received: 27 December 2016 / Revised: 6 February 2017 / Accepted: 8 February 2017 / Published: 16 February 2017
Cited by 1 | PDF Full-text (5292 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Small Molecule Activation and Catalysis)
Figures

Open AccessArticle Synthesis of Ti4O7 Nanoparticles by Carbothermal Reduction Using Microwave Rapid Heating
Catalysts 2017, 7(2), 65; doi:10.3390/catal7020065
Received: 14 December 2016 / Accepted: 13 February 2017 / Published: 16 February 2017
PDF Full-text (2858 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Enabling Technologies toward Green Catalysis)
Figures

Open AccessArticle A Recyclable Fluorous Hydrazine‐1,2Bis(Carbothioate) Organocatalyst for the Synthesis of ꞵ‐Chloroethers with N‐Chlorosuccinimide
Catalysts 2017, 7(2), 66; doi:10.3390/catal7020066
Received: 14 January 2017 / Accepted: 15 February 2017 / Published: 16 February 2017
PDF Full-text (5459 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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.
[...] Read more.
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
(This article belongs to the Special Issue Metal-free Organocatalysis)
Figures

Open AccessFeature PaperArticle Improved CO Oxidation Activity of 3DOM Pr-Doped Ceria Catalysts: Something Other Than an Ordered Macroporous Structure
Catalysts 2017, 7(2), 67; doi:10.3390/catal7020067
Received: 10 January 2017 / Revised: 10 February 2017 / Accepted: 11 February 2017 / Published: 17 February 2017
Cited by 2 | PDF Full-text (3554 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Ceria-based Catalysts)
Figures

Figure 1

Open AccessCommunication Effect of CO Concentration on the α-Value of Plasma-Synthesized Co/C Catalyst in Fischer-Tropsch Synthesis
Catalysts 2017, 7(2), 69; doi:10.3390/catal7020069
Received: 28 December 2016 / Revised: 9 February 2017 / Accepted: 13 February 2017 / Published: 21 February 2017
Cited by 1 | PDF Full-text (3485 KB) | HTML Full-text | XML Full-text
Abstract
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 =
[...] Read more.
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
Figures

Open AccessArticle Novel Fe‐W‐Ce Mixed Oxide for the Selective Catalytic Reduction of NOx with NH3 at Low Temperatures
Catalysts 2017, 7(2), 71; doi:10.3390/catal7020071
Received: 16 January 2017 / Accepted: 16 February 2017 / Published: 20 February 2017
Cited by 3 | PDF Full-text (3556 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmental Remediation)
Figures

Figure 1

Review

Jump to: Editorial, Research

Open AccessReview How to Lengthen the Long-Term Stability of Enzyme Membranes: Trends and Strategies
Catalysts 2017, 7(2), 36; doi:10.3390/catal7020036
Received: 19 December 2016 / Revised: 17 January 2017 / Accepted: 19 January 2017 / Published: 24 January 2017
Cited by 2 | PDF Full-text (1661 KB) | HTML Full-text | XML Full-text
Abstract
In this review, factors that contribute to enhancing the stability of immobilized enzyme membranes have been indicated, and the solutions to each factor, based on examples, are discussed. The factors are divided into two categories: one is dependent on the improvement of enzyme
[...] Read more.
In this review, factors that contribute to enhancing the stability of immobilized enzyme membranes have been indicated, and the solutions to each factor, based on examples, are discussed. The factors are divided into two categories: one is dependent on the improvement of enzyme properties, and the other, on the development of supporting materials. Improvement of an enzyme itself would effectively improve its properties. However, some novel materials or novel preparation methods are required for improving the properties of supporting materials. Examples have been provided principally aimed at improvements in membrane stability. Full article
(This article belongs to the Special Issue Immobilized Enzymes: Strategies for Enzyme Stabilization)
Figures

Figure 1

Open AccessFeature PaperReview Trifluoromethanesulfonic Acid as Acylation Catalyst: Special Feature for C- and/or O-Acylation Reactions
Catalysts 2017, 7(2), 40; doi:10.3390/catal7020040
Received: 6 December 2016 / Revised: 13 January 2017 / Accepted: 18 January 2017 / Published: 28 January 2017
Cited by 1 | PDF Full-text (9609 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Open AccessReview Engineering Surface Ligands of Noble Metal Nanocatalysts in Tuning the Product Selectivity
Catalysts 2017, 7(2), 44; doi:10.3390/catal7020044
Received: 29 December 2016 / Revised: 25 January 2017 / Accepted: 25 January 2017 / Published: 28 January 2017
Cited by 2 | PDF Full-text (3489 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Open AccessReview Ruthenium–Platinum Catalysts and Direct Methanol Fuel Cells (DMFC): A Review of Theoretical and Experimental Breakthroughs
Catalysts 2017, 7(2), 47; doi:10.3390/catal7020047
Received: 23 November 2016 / Revised: 22 January 2017 / Accepted: 24 January 2017 / Published: 5 February 2017
Cited by 2 | PDF Full-text (3274 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Ruthenium Catalysts)
Figures

Open AccessFeature PaperReview Oxidation Catalysis by Enzymes in Microemulsions
Catalysts 2017, 7(2), 52; doi:10.3390/catal7020052
Received: 12 January 2017 / Revised: 27 January 2017 / Accepted: 4 February 2017 / Published: 8 February 2017
PDF Full-text (1606 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Open AccessReview Indoor Light Enhanced Photocatalytic Ultra-Thin Films on Flexible Non-Heat Resistant Substrates Reducing Bacterial Infection Risks
Catalysts 2017, 7(2), 57; doi:10.3390/catal7020057
Received: 14 January 2017 / Accepted: 7 February 2017 / Published: 13 February 2017
Cited by 6 | PDF Full-text (5030 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Open AccessReview Time Resolved Operando X-ray Techniques in Catalysis, a Case Study: CO Oxidation by O2 over Pt Surfaces and Alumina Supported Pt Catalysts
Catalysts 2017, 7(2), 58; doi:10.3390/catal7020058
Received: 26 September 2016 / Revised: 24 January 2017 / Accepted: 26 January 2017 / Published: 14 February 2017
Cited by 1 | PDF Full-text (7779 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue In Situ and Operando Characterization in Catalysis)
Figures

Figure 1

Open AccessFeature PaperReview Supported Catalysts for CO2 Methanation: A Review
Catalysts 2017, 7(2), 59; doi:10.3390/catal7020059
Received: 16 December 2016 / Revised: 7 February 2017 / Accepted: 8 February 2017 / Published: 13 February 2017
Cited by 12 | PDF Full-text (2171 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Open AccessReview Monoliths: A Review of the Basics, Preparation Methods and Their Relevance to Oxidation
Catalysts 2017, 7(2), 62; doi:10.3390/catal7020062
Received: 8 September 2016 / Revised: 22 November 2016 / Accepted: 5 December 2016 / Published: 16 February 2017
Cited by 1 | PDF Full-text (2176 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Figure 1

Open AccessFeature PaperReview Aluminum Alkyl Complexes Bearing Salicylaldiminato Ligands: Versatile Initiators in the Ring-Opening Polymerization of Cyclic Esters
Catalysts 2017, 7(2), 64; doi:10.3390/catal7020064
Received: 23 December 2016 / Revised: 7 February 2017 / Accepted: 13 February 2017 / Published: 16 February 2017
Cited by 2 | PDF Full-text (1830 KB) | HTML Full-text | XML Full-text
Abstract
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
[...] Read more.
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
Figures

Open AccessFeature PaperReview On Metal Segregation of Bimetallic Nanocatalysts Prepared by a One-Pot Method in Microemulsions
Catalysts 2017, 7(2), 68; doi:10.3390/catal7020068
Received: 28 December 2016 / Revised: 8 February 2017 / Accepted: 10 February 2017 / Published: 17 February 2017
Cited by 2 | PDF Full-text (1917 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
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
[...] Read more.
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
(This article belongs to the Special Issue Soluble Nanoparticles in Catalytic Applications)
Figures

Figure 1

Open AccessReview Development of Ni-Based Catalysts Derived from Hydrotalcite-Like Compounds Precursors for Synthesis Gas Production via Methane or Ethanol Reforming
Catalysts 2017, 7(2), 70; doi:10.3390/catal7020070
Received: 13 December 2016 / Revised: 6 February 2017 / Accepted: 16 February 2017 / Published: 20 February 2017
Cited by 4 | PDF Full-text (1083 KB) | HTML Full-text | XML Full-text
Abstract
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,
[...] Read more.
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
(This article belongs to the Special Issue Reforming Catalysts)
Figures

Figure 1

Back to Top