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Catalysts, Volume 7, Issue 10 (October 2017)

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Cover Story (view full-size image) Brookite - the once least known TiO2 polymorph - is now recognized as an active phase with peculiar [...] Read more.
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Open AccessArticle Activated Carbon-Supported Tetrapropylammonium Perruthenate Catalysts for Acetylene Hydrochlorination
Catalysts 2017, 7(10), 311; https://doi.org/10.3390/catal7100311
Received: 13 October 2017 / Revised: 20 October 2017 / Accepted: 20 October 2017 / Published: 24 October 2017
Cited by 3 | PDF Full-text (2728 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The Ru-based catalysts, including Ru/AC (activated carbon), TPAP (tetrapropylammonium perruthenate)/AC, TPAP/AC-HNO3, and TPAP/AC-HCl, were prepared and assessed for the direct synthesis of vinyl chloride monomer. The results indicate that the TPAP/AC-HCl catalyst exhibits the best performance with the conversion falling from
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The Ru-based catalysts, including Ru/AC (activated carbon), TPAP (tetrapropylammonium perruthenate)/AC, TPAP/AC-HNO3, and TPAP/AC-HCl, were prepared and assessed for the direct synthesis of vinyl chloride monomer. The results indicate that the TPAP/AC-HCl catalyst exhibits the best performance with the conversion falling from 97% to 91% in 48 hours’ reaction under the conditions of 180 °C, a GHSV(C2H2) of 180 h−1, and the feed ratio VHCl/VC2H2 of 1.15. The substitution of RuCl3 precursor with high valent TPAP species leads to more ruthenium oxides active species in the catalysts; the acidification treatment of carrier in TPAP/AC catalyst can produce an enhanced interaction between the active species and the modified functional groups on the carrier, and it is beneficial to inhibit the carbon deposition and sintering of ruthenium species in the reaction process, greatly increase the adsorption ability of reactants, and further increase the amount of dominating active species in the catalysts, thus improving the catalytic performance. This also provides a promising strategy to explore high efficient and economic mercury-free catalysts for the hydrochlorination of acetylene. Full article
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Open AccessArticle Water–Gas Shift Reaction over Ni/CeO2 Catalysts
Catalysts 2017, 7(10), 310; https://doi.org/10.3390/catal7100310
Received: 28 August 2017 / Revised: 2 October 2017 / Accepted: 7 October 2017 / Published: 20 October 2017
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Abstract
This paper reports the results of a study of a water–gas shift reaction over nickel–ceria catalysts with different metal loading. Within this study, the overall CO conversion and observed kinetic behavior were investigated over the temperature range of 250–550 °C in different reactor
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This paper reports the results of a study of a water–gas shift reaction over nickel–ceria catalysts with different metal loading. Within this study, the overall CO conversion and observed kinetic behavior were investigated over the temperature range of 250–550 °C in different reactor configurations (fixed-bed and microchannel reactors). The quasi-steady state kinetics of the CO water–gas shift reaction was studied for fractions of Ni-containing cerium oxide catalysts in fixed-bed experiments at lab-scale level using a very dilute gas (1% CO + 1.8% H2O in Не). A set of experiments with a microchannel reactor was performed using the feed composition (CO:H2O:H2:N2 = 1:2:2:2), representing a product gas from methane partial oxidation. The results were interpreted using computational models. The kinetic parameters were determined by regression analysis, while mechanistic aspects were considered only briefly. Simulation of the WGS reaction in the microreactor was also carried out by using the COMSOL Multiphysics program. Full article
(This article belongs to the Special Issue Nanostructured Materials for Applications in Heterogeneous Catalysis)
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Open AccessArticle Synthesis of Biolubricant Basestocks from Epoxidized Soybean Oil
Catalysts 2017, 7(10), 309; https://doi.org/10.3390/catal7100309
Received: 5 August 2017 / Revised: 27 September 2017 / Accepted: 13 October 2017 / Published: 19 October 2017
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Abstract
This work deals with the preparation of biolubricant basestocks through the ring-opening reaction of epoxidized soybean oil (ESO) by alcohols in presence of solid acid catalysts (SAC-13 resin). To this end, different experimental runs were carried out in a lab-scale reactor, analyzing the
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This work deals with the preparation of biolubricant basestocks through the ring-opening reaction of epoxidized soybean oil (ESO) by alcohols in presence of solid acid catalysts (SAC-13 resin). To this end, different experimental runs were carried out in a lab-scale reactor, analyzing the effect of the alcohol (methanol, ethanol, 2-propanol, 2-butanol), catalyst mass loading (from 1 to 10 wt % with respect to the oil mass) and operating temperature (60–90 °C). The main focus of investigation was oxirane conversion. The study was complemented by FT-IR, 1H NMR and kinematic viscosity characterization of the different products of the ring-opening reaction. Experimental conversion data were fitted through a suitable kinetic model. Values of the best-fitting parameters in terms of rate constant, activation energy and catalyst reaction order were obtained, and were potentially useful for the design of an industrial process. Full article
(This article belongs to the Special Issue Catalytic Sustainable Processes in Biorefineries)
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Open AccessArticle Alcohol Dehydrogenation on Kraft Lignin-Derived Chars with Surface Basicity
Catalysts 2017, 7(10), 308; https://doi.org/10.3390/catal7100308
Received: 27 September 2017 / Revised: 13 October 2017 / Accepted: 15 October 2017 / Published: 19 October 2017
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Abstract
The properties of lignin and its potential as a renewable source make it an ideal precursor for carbon products. Specifically, the high content of Na observed in Kraft lignin makes this industrial by-product an interesting precursor for the preparation of catalysts for different
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The properties of lignin and its potential as a renewable source make it an ideal precursor for carbon products. Specifically, the high content of Na observed in Kraft lignin makes this industrial by-product an interesting precursor for the preparation of catalysts for different applications. In this work, basic activated carbons with different textural properties and surface chemistry were obtained from Kraft lignin by direct carbonization at various temperatures. The influence of a further washing treatment and partial gasification with CO2 was also evaluated. The carbon catalysts were tested as catalysts for the alcohol decomposition reaction. In this sense, 2-propanol, a molecule widely used for testing the acidic-basic character of heterogeneous catalysts, was selectively transformed into acetone, meanwhile, ethanol and methanol yielded mainly acetaldehyde and formaldehyde, respectively. Full article
(This article belongs to the Special Issue Catalytic Sustainable Processes in Biorefineries)
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Open AccessArticle Concept of Vaporized Urea Dosing in Selective Catalytic Reduction
Catalysts 2017, 7(10), 307; https://doi.org/10.3390/catal7100307
Received: 7 September 2017 / Revised: 28 September 2017 / Accepted: 13 October 2017 / Published: 19 October 2017
Cited by 1 | PDF Full-text (2148 KB) | HTML Full-text | XML Full-text
Abstract
This work tried to identify the influence of dosing vaporized urea solution in a selective catalytic reduction (SCR) system. In the SCR method, optimising the urea evaporation and mixing properties can significantly improve the NOx conversion efficiency in the catalyst. It can
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This work tried to identify the influence of dosing vaporized urea solution in a selective catalytic reduction (SCR) system. In the SCR method, optimising the urea evaporation and mixing properties can significantly improve the NOx conversion efficiency in the catalyst. It can also exert a positive effect on the uniformity of NH3 concentration distribution across the catalyst face. The concept of an electrically evaporated urea-dosing system was investigated and it was found that urea pre-heating prior to introduction into the exhaust gas is favourable for enhancing NOx removal under steady-state and transient engine operation. In the urea evaporating system the heating chamber was of a cylindrical tube shape and the urea vapour was introduced into the exhaust by means of a Venturi orifice. The concept urea dosing was only a custom-made solution, but proved to be superior to the regular dosing system operating in the liquid phase. Full article
(This article belongs to the Special Issue Selective Catalytic Reduction of NOx)
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Open AccessFeature PaperReview Application of Artificial Neural Networks for Catalysis: A Review
Catalysts 2017, 7(10), 306; https://doi.org/10.3390/catal7100306
Received: 28 September 2017 / Revised: 14 October 2017 / Accepted: 16 October 2017 / Published: 18 October 2017
Cited by 19 | PDF Full-text (7318 KB) | HTML Full-text | XML Full-text
Abstract
Machine learning has proven to be a powerful technique during the past decades. Artificial neural network (ANN), as one of the most popular machine learning algorithms, has been widely applied to various areas. However, their applications for catalysis were not well-studied until recent
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Machine learning has proven to be a powerful technique during the past decades. Artificial neural network (ANN), as one of the most popular machine learning algorithms, has been widely applied to various areas. However, their applications for catalysis were not well-studied until recent decades. In this review, we aim to summarize the applications of ANNs for catalysis research reported in the literature. We show how this powerful technique helps people address the highly complicated problems and accelerate the progress of the catalysis community. From the perspectives of both experiment and theory, this review shows how ANNs can be effectively applied for catalysis prediction, the design of new catalysts, and the understanding of catalytic structures. Full article
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Open AccessFeature PaperReview Recent Advances in Graphene Based TiO2 Nanocomposites (GTiO2Ns) for Photocatalytic Degradation of Synthetic Dyes
Catalysts 2017, 7(10), 305; https://doi.org/10.3390/catal7100305
Received: 24 August 2017 / Revised: 3 October 2017 / Accepted: 10 October 2017 / Published: 16 October 2017
Cited by 7 | PDF Full-text (3009 KB) | HTML Full-text | XML Full-text
Abstract
Synthetic dyes are widely used in textile, paper, food, cosmetic, and pharmaceutical industries. During industrial processes, some of these dyes are released into the wastewater and their successive release into rivers and lakes produces serious environmental problems. TiO2 is one of the
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Synthetic dyes are widely used in textile, paper, food, cosmetic, and pharmaceutical industries. During industrial processes, some of these dyes are released into the wastewater and their successive release into rivers and lakes produces serious environmental problems. TiO2 is one of the most widely studied and used photocatalysts for environmental remediation. However, it is mainly active under UV-light irradiation due to its band gap of 3.2 eV, while it shows low efficiency under the visible light spectrum. Regarding the exploration of TiO2 activation in the visible light region of the total solar spectrum, the incorporation of carbon nanomaterials, such as graphene, in order to form carbon-TiO2 composites is a promising area. Graphene, in fact, has a large surface area which makes it a good adsorbent for organic pollutants removal through the combination of electrostatic attraction and π-π interaction. Furthermore, it has a high electron mobility and therefore it reduces the electron-hole pair recombination, improving the photocatalytic activity of the semiconductor. In recent years, there was an increasing interest in the preparation of graphene-based TiO2 photocatalysts. The present short review describes the recent advances in TiO2 photocatalyst coupling with graphene materials with the aim of extending the light absorption of TiO2 from UV wavelengths into the visible region, focusing on recent progress in the design and applications in the photocatalytic degradation of synthetic dyes. Full article
(This article belongs to the Special Issue Nanomaterials for Environmental Purification and Energy Conversion)
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Open AccessFeature PaperArticle Flame-Made Cu/TiO2 and Cu-Pt/TiO2 Photocatalysts for Hydrogen Production
Catalysts 2017, 7(10), 301; https://doi.org/10.3390/catal7100301
Received: 8 September 2017 / Revised: 29 September 2017 / Accepted: 11 October 2017 / Published: 16 October 2017
Cited by 2 | PDF Full-text (2103 KB) | HTML Full-text | XML Full-text
Abstract
The effect of Cu or Cu-Pt nanoparticles in TiO2 photocatalysts prepared by flame spray pyrolysis in one step was investigated in hydrogen production from methanol photo-steam reforming. Two series of titanium dioxide photocatalysts were prepared, containing either (i) Cu nanoparticles (0.05–0.5 wt%)
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The effect of Cu or Cu-Pt nanoparticles in TiO2 photocatalysts prepared by flame spray pyrolysis in one step was investigated in hydrogen production from methanol photo-steam reforming. Two series of titanium dioxide photocatalysts were prepared, containing either (i) Cu nanoparticles (0.05–0.5 wt%) or (ii) both Cu (0 to 0.5 wt%) and Pt (0.5 wt%) nanoparticles. In addition, three photocatalysts obtained either by grafting copper and/or by depositing platinum by wet methods on flame-made TiO2 were also investigated. High hydrogen production rates were attained with copper-containing photocatalysts, though their photoactivity decreased with increasing Cu loading, whereas the photocatalysts containing both Cu and Pt nanoparticles exhibit a bell-shaped photoactivity trend with increasing copper content, the highest hydrogen production rate being attained with the photocatalyst containing 0.05 wt% Cu. Full article
(This article belongs to the Special Issue Titanium Dioxide Photocatalysis)
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Open AccessFeature PaperReview Brookite: Nothing New under the Sun?
Catalysts 2017, 7(10), 304; https://doi.org/10.3390/catal7100304
Received: 2 October 2017 / Revised: 11 October 2017 / Accepted: 11 October 2017 / Published: 13 October 2017
Cited by 1 | PDF Full-text (2104 KB) | HTML Full-text | XML Full-text
Abstract
Advances in the synthesis of pure brookite and brookite-based TiO2 materials have opened the way to fundamental and applicative studies of the once least known TiO2 polymorph. Brookite is now recognized as an active phase, in some cases showing enhanced performance
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Advances in the synthesis of pure brookite and brookite-based TiO2 materials have opened the way to fundamental and applicative studies of the once least known TiO2 polymorph. Brookite is now recognized as an active phase, in some cases showing enhanced performance with respect to anatase, rutile or their mixture. The peculiar structure of brookite determines its distinct electronic properties, such as band gap, charge–carrier lifetime and mobility, trapping sites, surface energetics, surface atom arrangements and adsorption sites. Understanding the relationship between these properties and the photocatalytic performances of brookite compared to other TiO2 polymorphs is still a formidable challenge, because of the interplay of many factors contributing to the observed efficiency of a given photocatalyst. Here, the most recent advances in brookite TiO2 material synthesis and applications are summarized, focusing on structure/activity relation studies of phase and morphology-controlled materials. Many questions remain unanswered regarding brookite, but one answer is clear: Is it still worth studying such a hard-to-synthesize, elusive TiO2 polymorph? Yes. Full article
(This article belongs to the Special Issue Titanium Dioxide Photocatalysis)
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Open AccessReview Reactivity of Trapped and Accumulated Electrons in Titanium Dioxide Photocatalysis
Catalysts 2017, 7(10), 303; https://doi.org/10.3390/catal7100303
Received: 20 September 2017 / Revised: 5 October 2017 / Accepted: 8 October 2017 / Published: 13 October 2017
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Abstract
Electrons, photogenerated in conduction bands (CB) and trapped in electron trap defects (Tids) in titanium dioxide (TiO2), play crucial roles in characteristic reductive reactions. This review summarizes the recent progress in the research on electron transfer in photo-excited TiO
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Electrons, photogenerated in conduction bands (CB) and trapped in electron trap defects (Tids) in titanium dioxide (TiO2), play crucial roles in characteristic reductive reactions. This review summarizes the recent progress in the research on electron transfer in photo-excited TiO2. Particularly, the reactivity of electrons accumulated in CB and trapped at Tids on TiO2 is highlighted in the reduction of molecular oxygen and molecular nitrogen, and the hydrogenation and dehalogenation of organic substrates. Finally, the prospects for developing highly active TiO2 photocatalysts are discussed. Full article
(This article belongs to the Special Issue Titanium Dioxide Photocatalysis)
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Open AccessArticle Improved Catalytic Performance of Lipase Supported on Clay/Chitosan Composite Beads
Catalysts 2017, 7(10), 302; https://doi.org/10.3390/catal7100302
Received: 11 August 2017 / Revised: 29 September 2017 / Accepted: 11 October 2017 / Published: 13 October 2017
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Abstract
Clay/chitosan composite beads were prepared and used as the carrier to support lipase by adsorption, to improve the activity and stability of lipase in the hydrolysis of olive oil. Under conditions of pH 6.0, 25 °C and adsorption for 10 h, immobilized lipases
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Clay/chitosan composite beads were prepared and used as the carrier to support lipase by adsorption, to improve the activity and stability of lipase in the hydrolysis of olive oil. Under conditions of pH 6.0, 25 °C and adsorption for 10 h, immobilized lipases on chitosan bead (CB–lipase) and three clay/chitosan composite beads, at different clay to chitosan proportions of 1:8 (CCB-8-lipase), 1:5 (CCB-5-lipase) and 1:3 (CCB-3-lipase), were prepared. By comparing the activity of these immobilized lipases, CCB-5-lipase showed the highest activity, followed by CCB-8-lipase > CCB-3-lipase > CB-lipase; this improvement was attributed to the synergetic effect of enrichment of olive oil by clay at the reaction surface and better biocompatibility of chitosan with lipase molecules. The optimum pH and temperature in the reaction respectively changed from 7.0 and 30 °C for free lipase to 7.5 and 35 °C for immobilized forms. Furthermore, the thermal stability and repeated usability of these immobilized lipases were sequenced as CCB-3-lipase > CCB-5-lipase > CCB-8-lipase > CB–lipase, due to greater rigidity of immobilized lipase with the addition of clay, which was further confirmed by SEM. The study shows that the incorporation of clay with chitosan creates a good synergetic effect to improve the catalytic performance of immobilized lipase on clay/chitosan composite. Full article
(This article belongs to the Special Issue Biocatalysis and Biotransformations)
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Open AccessArticle PEG1000-Based Dicationic Acidic Ionic Liquid/Solvent-Free Conditions: An Efficient Catalytic System for the Synthesis of Bis(Indolyl)methanes
Catalysts 2017, 7(10), 300; https://doi.org/10.3390/catal7100300
Received: 18 September 2017 / Revised: 5 October 2017 / Accepted: 7 October 2017 / Published: 11 October 2017
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Abstract
An efficient procedure has been researched for the solvent-free synthesis of bis(indolyl)methanes via a one-pot reaction of indoles and aldehydes or ketones promoted by PEG1000-based dicationic acidic ionic liquid (PEG1000-DAIL). The catalyst PEG1000-DAIL could be reused seven
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An efficient procedure has been researched for the solvent-free synthesis of bis(indolyl)methanes via a one-pot reaction of indoles and aldehydes or ketones promoted by PEG1000-based dicationic acidic ionic liquid (PEG1000-DAIL). The catalyst PEG1000-DAIL could be reused seven times with excellent results. Furthermore, through this method, a highly chemoselective reaction of benzaldehyde and acetophenone with indole could be achieved. Full article
(This article belongs to the Special Issue Organocatalysis in Ionic Liquids)
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Open AccessArticle Biotransformation of Ergostane Triterpenoid Antcin K from Antrodia cinnamomea by Soil-Isolated Psychrobacillus sp. AK 1817
Catalysts 2017, 7(10), 299; https://doi.org/10.3390/catal7100299
Received: 22 September 2017 / Revised: 2 October 2017 / Accepted: 3 October 2017 / Published: 11 October 2017
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Abstract
Antcin K is one of the major ergostane triterpenoids from the fruiting bodies of Antrodia cinnamomea, a parasitic fungus that grows only on the inner heartwood wall of the aromatic tree Cinnamomum kanehirai Hay (Lauraceae). To search for strains that have the
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Antcin K is one of the major ergostane triterpenoids from the fruiting bodies of Antrodia cinnamomea, a parasitic fungus that grows only on the inner heartwood wall of the aromatic tree Cinnamomum kanehirai Hay (Lauraceae). To search for strains that have the ability to biotransform antcin K, a total of 4311 strains of soil bacteria were isolated, and their abilities to catalyze antcin K were determined by ultra-performance liquid chromatography analysis. One positive strain, AK 1817, was selected for functional studies. The strain was identified as Psychrobacillus sp., based on the DNA sequences of the 16S rRNA gene. The biotransformation metabolites were purified with the preparative high-performance liquid chromatography method and identified as antcamphin E and antcamphin F, respectively, based on the mass and nuclear magnetic resonance spectral data. The present study is the first to report the biotransformation of triterpenoids from A. cinnamomea (Antrodia cinnamomea). Full article
(This article belongs to the Special Issue Catalyzed Synthesis of Natural Products)
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Open AccessReview A Review on the Production and Purification of Biomass-Derived Hydrogen Using Emerging Membrane Technologies
Catalysts 2017, 7(10), 297; https://doi.org/10.3390/catal7100297
Received: 28 August 2017 / Revised: 25 September 2017 / Accepted: 27 September 2017 / Published: 6 October 2017
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Abstract
Hydrogen energy systems are recognized as a promising solution for the energy shortage and environmental pollution crises. To meet the increasing demand for hydrogen, various possible systems have been investigated for the production of hydrogen by efficient and economical processes. Because of its
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Hydrogen energy systems are recognized as a promising solution for the energy shortage and environmental pollution crises. To meet the increasing demand for hydrogen, various possible systems have been investigated for the production of hydrogen by efficient and economical processes. Because of its advantages of being renewable and environmentally friendly, biomass processing has the potential to become the major hydrogen production route in the future. Membrane technology provides an efficient and cost-effective solution for hydrogen separation and greenhouse gas capture in biomass processing. In this review, the future prospects of using gas separation membranes for hydrogen production in biomass processing are extensively addressed from two perspectives: (1) the current development status of hydrogen separation membranes made of different materials and (2) the feasibility of using these membranes for practical applications in biomass-derived hydrogen production. Different types of hydrogen separation membranes, including polymeric membranes, dense metal membranes, microporous membranes (zeolite, metal-organic frameworks (MOFs), silica, etc.) are systematically discussed in terms of their fabrication methods, gas permeation performance, structure stability properties, etc. In addition, the application feasibility of these membranes in biomass processing is assessed from both practical and economic perspectives. The benefits and possibilities of using membrane reactors for hydrogen production in biomass processing are also discussed. Lastly, we summarize the limitations of the currently available hydrogen membranes as well as the gaps between research achievements and industrial application. We also propose expected research directions for the future development of hydrogen gas membrane technology. Full article
(This article belongs to the Special Issue Catalytic Sustainable Processes in Biorefineries)
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Open AccessArticle HDO of Methyl Palmitate over Silica-Supported Ni Phosphides: Insight into Ni/P Effect
Catalysts 2017, 7(10), 298; https://doi.org/10.3390/catal7100298
Received: 30 July 2017 / Revised: 19 September 2017 / Accepted: 30 September 2017 / Published: 4 October 2017
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Abstract
Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO)2
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Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO)2) and ((NH4)2HPO4) as a precursor. The NixPy/SiO2 catalysts were characterized using chemical analysis N2 physisorption, XRD, TEM, 31P MAS NMR. Methyl palmitate hydrodeoxygenation (HDO) was performed in a trickle-bed reactor at 3 MPa and 290 °C with LHSV ranging from 0.3 to 16 h−1. The Ni/P ratio was found to affect the nickel phosphide phase composition, POx groups content and catalytic properties in methyl palmitate HDO with the TOF increased along with a decline of Ni/P ratio and a growth of POx groups’ content. Taking into account the possible routes of methyl palmitate conversion (metal-catalyzed hydrogenolysis or acid-catalyzed hydrolysis), we proposed that the enhancement of acid POx groups’ content with the Ni/P ratio decrease provides an enhancement of the rate of methyl palmitate conversion through the acceleration of acid-catalyzed hydrolysis. Full article
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