Catalysts

12 pages, 3068 KiB

Open AccessArticle

Microporous Zeolites as Catalysts for the Preparation of Decyl Glucoside from Glucose with 1-Decanol by Direct Glucosidation

by Kyong-Hwan Chung¹, Hyunwoong Park², Ki-Joon Jeon³, Young-Kwon Park⁴ and Sang-Chul Jung^1,*

¹ Department of Environmental Engineering, Sunchon National University, 315 Maegok-Dong, Suncheon 540-742, Jeonnam, Korea

² School of Energy Engineering, Kyungpook National University, Daegu 702-701, Korea

³ Department of Environmental Engineering, Inha University, 100 Inha-ro, Nam-gu, Incheon 402-751, Korea

⁴ School of Environmental Engineering, University of Seoul, 163 Seoulsiripdaero, Dongdaemun-gu, Seoul 130-743, Korea

Catalysts 2016, 6(12), 216; https://doi.org/10.3390/catal6120216 - 21 Dec 2016

Cited by 6 | Viewed by 7275

Abstract

The catalytic properties of microporous zeolite catalysts were evaluated in the synthesis of decyl glucoside from glucose with 1-decanol by direct glucosidation. The effects of the acidic properties and pore structure of the zeolite catalysts on the glucose conversions and decyl glucoside yields [...] Read more.

The catalytic properties of microporous zeolite catalysts were evaluated in the synthesis of decyl glucoside from glucose with 1-decanol by direct glucosidation. The effects of the acidic properties and pore structure of the zeolite catalysts on the glucose conversions and decyl glucoside yields were investigated. The conversions of glucose on the H⁺ ion-exchanged FAU, MFI, and BEA zeolite catalysts were above 70%. The conversion increased with decreasing acid strength of the catalysts. The highest conversion and yield of decyl glucoside were exhibited on the H-FAU(3) zeolite catalyst. The catalytic activities were enhanced with increasing amounts of acid sites. The selectivity of decyl glucopyranoside increased with decreasing Si/Al values for the same zeolite catalysts. The pore structure of H-FAU zeolite would allow sufficient spatial restriction to produce decyl glucopyranoside through the isomerization of decyl glucofuranoside into decyl glucopyranoside in its extensive pore channels. The selectivities of the decyl glucoside isomers relied significantly on the restricted transition state to the primary products due to their pore topologies. Full article

(This article belongs to the Special Issue Heterogeneous Catalysis for Environmental Remediation)

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10 pages, 4029 KiB

Open AccessFeature PaperArticle

Aqueous-Phase Catalytic Chemical Reduction of p-Nitrophenol Employing Soluble Gold Nanoparticles with Different Shapes

by Francyelle Moura De Oliveira, Lucas Rafael Bezerra de Araújo Nascimento, Claudia Manuela Santos Calado, Mario Roberto Meneghetti^* and Monique Gabriella Angelo Da Silva^*

Grupo de Catálise e Reatividade Química, Instituto de Química e Biotecnologia, Universidade Federal de Alagoas, Av. Lourival de Melo Mota s/n, Cidade Universitária, 57072-900 Maceió-AL, Brazil

Catalysts 2016, 6(12), 215; https://doi.org/10.3390/catal6120215 - 21 Dec 2016

Cited by 34 | Viewed by 10199

Abstract

Gold nanoparticles with different shapes were prepared and used as catalysts in the reduction of p-nitrophenol (PNP) in the aqueous phase and in the presence of sodium borohydride (NaBH₄). Parameters such as the reaction temperature, substrate/NaBH₄ molar ratio, and [...] Read more.

Gold nanoparticles with different shapes were prepared and used as catalysts in the reduction of p-nitrophenol (PNP) in the aqueous phase and in the presence of sodium borohydride (NaBH₄). Parameters such as the reaction temperature, substrate/NaBH₄ molar ratio, and substrate/gold molar ratio were tested and evaluated. In this paper, we compare the catalytic reactivities of gold nanorods (AuNRs) and gold nanospheres (AuNSs), both synthesized by the seed-mediated method in the presence of cetyltrimethyl ammonium bromide (CTAB). Physical-chemical parameters such as the apparent rate constant (k_app) and activation energy (E_a) of the reactions were obtained for both systems. We observed that the catalytic system based on AuNRs is the most active. These colloidal dispersions were investigated and fully characterized by ultraviolet-visible absorption spectroscopy (UV–Vis) and transmission electron microscopy (TEM). Full article

(This article belongs to the Special Issue Soluble Nanoparticles in Catalytic Applications)

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8 pages, 7361 KiB

Open AccessArticle

CuO Nanorods-Decorated Reduced Graphene Oxide Nanocatalysts for Catalytic Oxidation of CO

by Yan Wang¹

, Zhihui Wen^1,*, Huoli Zhang², Guohua Cao², Qi Sun² and Jianliang Cao^2,*

¹ School of Safety Science and Engineering, State Key Laboratory Cultivation Base for Gas Geology and Gas Control, Henan Polytechnic University, Jiaozuo 454000, China

² School of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, China

Catalysts 2016, 6(12), 214; https://doi.org/10.3390/catal6120214 - 21 Dec 2016

Cited by 42 | Viewed by 9441

Abstract

Developing an efficient non-noble catalyst for CO oxidation with high catalytic activity remains a challenge for practical applications. In this work, CuO nanorods decorated reduced graphene oxide (RGO) nanocatalysts were prepared via a facile one-step hydrothermal method. The structure and morphology of the [...] Read more.

Developing an efficient non-noble catalyst for CO oxidation with high catalytic activity remains a challenge for practical applications. In this work, CuO nanorods decorated reduced graphene oxide (RGO) nanocatalysts were prepared via a facile one-step hydrothermal method. The structure and morphology of the as-prepared samples were characterized by XRD, Raman spectroscopy, SEM, TEM, and X-ray photoelectron spectroscopy (XPS). The analysis results show that CuO nanorods were successfully deposited on the surface of RGO sheets with the length of 250–500 nm. The catalytic properties of the as-prepared catalysts for CO oxidation were evaluated by using a microreactor-gas chromatograph (GC) system. The as-prepared RGO–CuO nanocatalysts exhibited high activity for CO oxidation, and the 10 wt % reduced graphene oxide content catalyst can achieve CO total oxidation at 165 °C. Full article

(This article belongs to the Special Issue Heterogeneous Catalysis for Environmental Remediation)

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11 pages, 3437 KiB

Open AccessFeature PaperArticle

P-Stereogenic Phosphines for the Stabilisation of Metal Nanoparticles. A Surface State Study

by Eva Raluy¹, Arnald Grabulosa²

, Pierre Lavedan³, Christian Pradel¹, Guillermo Muller²

, Isabelle Favier^1,* and Montserrat Gómez^1,*

¹ Université de Toulouse 3—Paul Sabatier, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), 118 Route de Narbonne, 31062 Toulouse CEDEX 9, France and CNRS, LHFA UMR 5069, 31062 Toulouse CEDEX 9, France

² Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain

³ Service Commun RMN, ICT, Université de Toulouse, UPS, 118 Route de Narbonne, 31062 Toulouse CEDEX 9, France

Catalysts 2016, 6(12), 213; https://doi.org/10.3390/catal6120213 - 20 Dec 2016

Cited by 6 | Viewed by 4982

Abstract

Palladium and ruthenium nanoparticles have been prepared following the organometallic precursor decomposition methodology, under dihydrogen pressure and in the presence of borane protected P-stereogenic phosphines. NMR (Nuclear Magnetic Resonance) monitoring of the corresponding syntheses has permitted to determine the optimal metal/ligand ratio [...] Read more.

Palladium and ruthenium nanoparticles have been prepared following the organometallic precursor decomposition methodology, under dihydrogen pressure and in the presence of borane protected P-stereogenic phosphines. NMR (Nuclear Magnetic Resonance) monitoring of the corresponding syntheses has permitted to determine the optimal metal/ligand ratio for leading to small and well-dispersed nanoparticles. Exchange ligand reactions of the as-prepared materials have proven the strong interaction of the phosphines with the metal surface; only oxidative treatment using hydrogen peroxide could release the phosphine-based stabiliser from the metal surface. Pd and Ru nanoparticles have been evaluated in hydrogenation reactions, confirming the robustness of the stabilisers, which selectively permitted the hydrogenation of exocyclic C=C bonds, preventing the coordination of the aromatic rings and as a result, their hydrogenation. Full article

(This article belongs to the Special Issue Soluble Nanoparticles in Catalytic Applications)

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16 pages, 2675 KiB

Open AccessArticle

N-acetylglucosamine 2-Epimerase from Pedobacter heparinus: First Experimental Evidence of a Deprotonation/Reprotonation Mechanism

by Su-Yan Wang¹, Pedro Laborda¹, Ai-Min Lu², Xu-Chu Duan¹, Hong-Yu Ma³, Li Liu^1,* and Josef Voglmeir^1,*

¹ Glycomics and Glycan Bioengineering Research Center (GGBRC), College of Food Science and Technology, Nanjing Agricultural University, Nanjing 210095, China

² College of Sciences, Nanjing Agricultural University, Nanjing 210095, China

³ Department of Plant Pathology, Nanjing Agricultural University, Nanjing 210095, China

Catalysts 2016, 6(12), 212; https://doi.org/10.3390/catal6120212 - 17 Dec 2016

Cited by 18 | Viewed by 9325

Abstract

The control of cellular N-acetylmannosamine (ManNAc) levels has been postulated to be an effective way to modulate the decoration of cell surfaces with sialic acid. N-acetylglucosamine 2-epimerase catalyzes the interconversion of N-acetylglucosamine (GlcNAc) and ManNAc. Herein, we describe the cloning, [...] Read more.

The control of cellular N-acetylmannosamine (ManNAc) levels has been postulated to be an effective way to modulate the decoration of cell surfaces with sialic acid. N-acetylglucosamine 2-epimerase catalyzes the interconversion of N-acetylglucosamine (GlcNAc) and ManNAc. Herein, we describe the cloning, expression, purification and biochemical characterization of an unstudied N-acetylglucosamine 2-epimerase from Pedobacter heparinus (PhGn2E). To further characterize the enzyme, several N-acylated glucosamine derivatives were chemically synthesized, and subsequently used to test the substrate specificity of PhGn2E. Furthermore, NMR studies of deuterium/hydrogen exchange at the anomeric hydroxy group and C-2 positions of the substrate in the reaction mixture confirmed for the first time the postulated epimerization reaction via ring-opening/enolate formation. Site-directed mutagenesis of key residues in the active site showed that Arg63 and Glu314 are directly involved in proton abstraction and re-incorporation onto the substrate. As all mechanistically relevant active site residues also occur in all mammalian isoforms, PhGn2E can serve as a model N-acetylglucosamine 2-epimerase for further elucidation of the active site mechanism in these enzymes. Full article

(This article belongs to the Special Issue Asymmetric and Selective Biocatalysis)

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14 pages, 2371 KiB

Open AccessArticle

A Microwave-Sensitive Solid Acid Catalyst Prepared from Sweet Potato via a Simple Method

by Hai-Ying Chen

and Zheng-Wei Cui^*

Jiangsu Key Laboratory of Advanced Food Manufacturing Equipment and Technology, School of Mechanical Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China

Catalysts 2016, 6(12), 211; https://doi.org/10.3390/catal6120211 - 17 Dec 2016

Cited by 17 | Viewed by 5738

Abstract

In this study, a microwave-sensitive solid acid catalyst was successfully synthesized from sweet potatoes via a simple process. The catalyst was proven to have superior microwave-sensitive and homogeneous properties. The physicochemical properties were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), Fourier-transform infrared spectra [...] Read more.

In this study, a microwave-sensitive solid acid catalyst was successfully synthesized from sweet potatoes via a simple process. The catalyst was proven to have superior microwave-sensitive and homogeneous properties. The physicochemical properties were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), Fourier-transform infrared spectra (FT-IR), thermogravimetric (TGA), scanning electron microscope (SEM) and elemental analysis (EA). Results showed that the total acid density and specific surface area for the catalyst were 6.35 mmol/g and 78.35 m²/g, respectively. The elemental sulfur content reached 7.449% after sulfonation and the catalytic activity could reach over 91% within 30 min with microwave power density of 1.0 W/mL. The catalytic reaction temperature should not exceed 200 °C, as shown in TGA curve, and the moisture content in the oil raw material should be within 1%–2%. The catalyst deactivated gradually to 64.38% after reutilization five times, but the catalytic activity could be simply regenerated by re-sulfonation, albeit slightly reduced (87.56%). The shift of diffraction peaks in the XRD patterns and new absorption peaks at 619.98 and 1190.49 cm⁻¹ of FT-IR spectra demonstrated that the –SO₃H group was effectively attached to the catalyst. The SEM images displayed a loose and porous amorphous structure in the end catalyst. Full article

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23 pages, 5882 KiB

Open AccessReview

Catalysis-Based Cataluminescent and Conductometric Gas Sensors: Sensing Nanomaterials, Mechanism, Applications and Perspectives

by Jinyun Liu^1,4,*, Tianli Han², Bai Sun¹, Lingtao Kong¹, Zhen Jin¹, Xingjiu Huang^1,3, Jinhuai Liu^1,3 and Fanli Meng^1,*

¹ Nanomaterials and Environmental Detection Laboratory, Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031, Anhui, China

² College of Chemistry and Material Engineering, Chaohu University, Chaohu 238000, Anhui, China

³ Department of Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, China

⁴ Frederick Seitz Materials Research Laboratory, Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA

Catalysts 2016, 6(12), 210; https://doi.org/10.3390/catal6120210 - 17 Dec 2016

Cited by 9 | Viewed by 7695

Abstract

Gas environment detection has become more urgent and significant, for both industrial manufacturing and environment monitoring. Gas sensors based on a catalytically-sensing mechanism are one of the most important types of devices for gas detection, and have been of great interest during the [...] Read more.

Gas environment detection has become more urgent and significant, for both industrial manufacturing and environment monitoring. Gas sensors based on a catalytically-sensing mechanism are one of the most important types of devices for gas detection, and have been of great interest during the past decades. However, even though many efforts have contributed to this area, some great challenges still remain, such as the development of sensitively and selectively sensing catalysts. In this review, two representative catalysis-based gas sensors, cataluminescent and conductometric sensors, the basis of optical and electric signal acquisition, respectively, are summarized comprehensively. The current challenges have been presented. Recent research progress on the working mechanism, sensing nanomaterials, and applications reported by our group and some other researchers have been discussed systematically. The future trends and prospects of the catalysis-based gas sensors have also been presented. Full article

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9 pages, 4759 KiB

Open AccessArticle

Hydrogen Evolution Reaction of γ-Mo_0.5W_0.5 C Achieved by High Pressure High Temperature Synthesis

by Yingfei Hu¹

, Gan Jia¹, Shuailing Ma², Jianqiang Hu¹, Pinwen Zhu^2,*, Tian Cui², Zhaosheng Li^1,* and Zhigang Zou^1,3

¹ Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Nanjing University, 22 Hankou Road, Nanjing 210093, China

² State Key Lab of Superhard Materials, College of Physics, Jilin University, 2699 Qianjin Street, Changchun 130012, China

³ Jiangsu Key Laboratory for Nano Technology, Department of Physics, Nanjing University, 22 Hankou Road, Nanjing 210093, China

Catalysts 2016, 6(12), 208; https://doi.org/10.3390/catal6120208 - 17 Dec 2016

Cited by 7 | Viewed by 5475

Abstract

For the first time, the hydrogen evolution reaction (HER) electrocatalytic performances of incompressible γ-Mo_0.5W_0.5C, prepared by high-pressure, high-temperature (HPHT) synthesis, were investigated in the electrolyte. The polarization curve of the γ-Mo_0.5W_0.5C cathode exhibits the current [...] Read more.

For the first time, the hydrogen evolution reaction (HER) electrocatalytic performances of incompressible γ-Mo_0.5W_0.5C, prepared by high-pressure, high-temperature (HPHT) synthesis, were investigated in the electrolyte. The polarization curve of the γ-Mo_0.5W_0.5C cathode exhibits the current density of 50 mA∙cm⁻² at an overpotential value of 320 mV. The corresponding Tafel slope of the incompressible γ-Mo_0.5W_0.5C is 74 mV∙dec⁻¹. After a 1000-cycle test, and then exposure to the air for six months, the γ-Mo_0.5W_0.5C electrode performed a current density of 50 mA∙cm⁻² at an overpotential of 354 mV, which was close to the initial one. Full article

(This article belongs to the Special Issue Heterogeneous Catalysis & Hydrogen Storage)

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15 pages, 2935 KiB

Open AccessArticle

Investigation of the Effect of Plasma Polymerized Siloxane Coating for Enzyme Immobilization and Microfluidic Device Conception

by Kalim Belhacene^1,2

, Adil Elagli^1,2, Céline Vivien¹, Anthony Treizebré¹, Pascal Dhulster², Philippe Supiot¹

and Renato Froidevaux^2,*

¹ Institut d’Electronique, de Microélectronique et de Nanotechnologie (IEMN)—UMR CNRS 8520, Université Lille Nord de France—Sciences et Technologies, Villeneuve 59650, d’Ascq, France

² EA 7394-ICV—Institut Charles Viollette, University of Lille, F-59000 Lille, France

Catalysts 2016, 6(12), 209; https://doi.org/10.3390/catal6120209 - 16 Dec 2016

Cited by 9 | Viewed by 5115

Abstract

This paper describes the impact of a physical immobilization methodology, using plasma polymerized 1,1,3,3, tetramethyldisiloxane, on the catalytic performance of β-galactosidase from Aspergillus oryzae in a microfluidic device. The β-galactosidase was immobilized by a polymer coating grown by Plasma Enhanced Chemical Vapor Deposition [...] Read more.

This paper describes the impact of a physical immobilization methodology, using plasma polymerized 1,1,3,3, tetramethyldisiloxane, on the catalytic performance of β-galactosidase from Aspergillus oryzae in a microfluidic device. The β-galactosidase was immobilized by a polymer coating grown by Plasma Enhanced Chemical Vapor Deposition (PEVCD). Combined with a microchannel patterned in the silicone, a microreactor was obtained with which the diffusion through the plasma polymerized layer and the hydrolysis of a synthetic substrate, the resorufin-β-d-galactopyranoside, were studied. A study of the efficiency of the immobilization procedure was investigated after several uses and kinetic parameters of immobilized β-galactosidase were calculated and compared with those of soluble enzyme. Simulation and a modelling approach were also initiated to understand phenomena that influenced enzyme behavior in the physical immobilization method. Thus, the catalytic performances of immobilized enzymes were directly influenced by immobilization conditions and particularly by the diffusion behavior and availability of substrate molecules in the enzyme microenvironment. Full article

(This article belongs to the Special Issue Immobilized Enzymes: Strategies for Enzyme Stabilization)

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16 pages, 3288 KiB

Open AccessArticle

Spatial Concentration Profiles for the Catalytic Partial Oxidation of Jet Fuel Surrogates in a Rh/Al₂O₃ Coated Monolith

by Julian N. Bär¹, Claudia Antinori², Lubow Maier² and Olaf Deutschmann^1,2,*

¹ Institute for Chemical Technology and Polymer Chemistry at Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe, Germany

² Institute of Catalysis Research and Technology at Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe, Germany

Catalysts 2016, 6(12), 207; https://doi.org/10.3390/catal6120207 - 14 Dec 2016

Cited by 5 | Viewed by 5831

Abstract

The catalytic partial oxidation (CPOX) of several hydrocarbon mixtures, containing n-dodecane (DD), 1,2,4-trimethylbenzene (TMB), and benzothiophene (BT) as a sulfur compound was studied over a Rh/Al₂O₃ honeycomb catalyst. The in-situ sampling technique SpaciPro was used in this study to [...] Read more.

The catalytic partial oxidation (CPOX) of several hydrocarbon mixtures, containing n-dodecane (DD), 1,2,4-trimethylbenzene (TMB), and benzothiophene (BT) as a sulfur compound was studied over a Rh/Al₂O₃ honeycomb catalyst. The in-situ sampling technique SpaciPro was used in this study to investigate the complex reaction system which consisted of total and partial oxidation, steam reforming, and the water gas shift reaction. The mixtures of 83 vol % DD, 17 vol % TMB with and without addition of the sulfur compound BT, as well as the pure hydrocarbons were studied at a molar C/O-ratio of 0.75. The spatially resolved concentration and temperature profiles inside a central channel of the catalyst revealed three reaction zones: an oxidation zone, an oxy-reforming zone, and a reforming zone. Hydrogen formation starts in the oxy-reforming zone, not directly at the catalyst inlet, contrary to methane CPOX on Rh. In the reforming zone, in which steam reforming is the predominant reaction, even small amounts of sulfur (10 mg S in 1 kg fuel) block active sites. Full article

(This article belongs to the Special Issue In Situ and Operando Characterization in Catalysis)

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15 pages, 3139 KiB

Open AccessReview

In Situ Spectroscopic Studies of Proton Transport in Zeolite Catalysts for NH₃-SCR

by Peirong Chen^* and Ulrich Simon^*

Institute of Inorganic Chemistry and Center for Automotive Catalytic Systems Aachen, RWTH Aachen University, 52074 Aachen, Germany

Catalysts 2016, 6(12), 204; https://doi.org/10.3390/catal6120204 - 14 Dec 2016

Cited by 9 | Viewed by 8651

Abstract

Proton transport is an elementary process in the selective catalytic reduction of nitrogen oxides by ammonia (DeNO_x by NH₃-SCR) using metal-exchanged zeolites as catalysts. This review summarizes recent advancements in the study of proton transport in zeolite catalysts using in [...] Read more.

Proton transport is an elementary process in the selective catalytic reduction of nitrogen oxides by ammonia (DeNO_x by NH₃-SCR) using metal-exchanged zeolites as catalysts. This review summarizes recent advancements in the study of proton transport in zeolite catalysts using in situ electrical impedance spectroscopy (IS) under NH₃-SCR reaction conditions. Different factors, such as the metal cation type, metal exchange level, zeolite framework type, or formation of intermediates, were found to influence the proton transport properties of zeolite NH₃-SCR catalysts. A combination of IS with diffuse reflection infrared Fourier transformation spectroscopy in situ (in situ IS-DRIFTS) allowed to achieve a molecular understanding of the proton transport processes. Several mechanistic aspects, such as the NH₃-zeolite interaction, NO-zeolite interaction in the presence of adsorbed NH₃, or formation of NH₄⁺ intermediates, have been revealed. These achievements indicate that IS-based in situ methods as complementary tools for conventional techniques (e.g., in situ X-ray absorption spectroscopy) are able to provide new perspectives for the understanding of NH₃-SCR on zeolite catalysts. Full article

(This article belongs to the Special Issue In Situ and Operando Characterization in Catalysis)

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15 pages, 2357 KiB

Open AccessReview

Nature Inspired Solutions for Polymers: Will Cutinase Enzymes Make Polyesters and Polyamides Greener?

by Valerio Ferrario¹, Alessandro Pellis²

, Marco Cespugli¹, Georg M. Guebitz^1,3 and Lucia Gardossi^1,*

¹ Laboratory of Applied and Computational Biocatalysis, Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Piazzale Europa 1, 34127 Trieste, Italy

² Department of Agrobiotechnology, University of Natural Resources and Life Sciences, Vienna, Konrad Lorenz Strasse 20, 3430 Tulln an der Donau, Austria

³ Division of enzymes & polymers, Austrian Centre of Industrial Biotechnology, Konrad Lorenz Strasse 20, 3430 Tulln an der Donau, Austria

Catalysts 2016, 6(12), 205; https://doi.org/10.3390/catal6120205 - 13 Dec 2016

Cited by 53 | Viewed by 9639

Abstract

The polymer and plastic sectors are under the urge of mitigating their environmental impact. The need for novel and more benign catalysts for polyester synthesis or targeted functionalization led, in recent years, to an increasing interest towards cutinases due to their natural ability [...] Read more.

The polymer and plastic sectors are under the urge of mitigating their environmental impact. The need for novel and more benign catalysts for polyester synthesis or targeted functionalization led, in recent years, to an increasing interest towards cutinases due to their natural ability to hydrolyze ester bonds in cutin, a natural polymer. In this review, the most recent advances in the synthesis and hydrolysis of various classes of polyesters and polyamides are discussed with a critical focus on the actual perspectives of applying enzymatic technologies for practical industrial purposes. More specifically, cutinase enzymes are compared to lipases and, in particular, to lipase B from Candida antarctica, the biocatalyst most widely employed in polymer chemistry so far. Computational and bioinformatics studies suggest that the natural role of cutinases in attacking natural polymers confer some essential features for processing also synthetic polyesters and polyamides. Full article

(This article belongs to the Special Issue Enzyme Catalysis)

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35 pages, 3778 KiB

Open AccessReview

Recent Breakthroughs in the Conversion of Ethanol to Butadiene

by Guillaume Pomalaza¹, Mickaël Capron¹, Vitaly Ordomsky^1,2 and Franck Dumeignil^1,*

¹ University Lille, CNRS, Centrale Lille, ENSCL, University Artois, UMR 8181-UCCS-Unité de Catalyse et Chimie du Solide, F-59000 Lille, France

² Eco-Efficient Products and Processes Laboratory (E2P2L), UMI 3464 CNRS-Solvay, Shanghai 201108, China

Catalysts 2016, 6(12), 203; https://doi.org/10.3390/catal6120203 - 13 Dec 2016

Cited by 115 | Viewed by 13084

Abstract

1,3-Butadiene is traditionally produced as a byproduct of ethylene production from steam crackers. What is unusual is that the alternative production route for this important commodity chemical via ethanol was developed a long time ago, before World War II. Currently, there is a [...] Read more.

1,3-Butadiene is traditionally produced as a byproduct of ethylene production from steam crackers. What is unusual is that the alternative production route for this important commodity chemical via ethanol was developed a long time ago, before World War II. Currently, there is a renewed interest in the production of butadiene from biomass due to the general trend to replace oil in the chemical industry. This review describes the recent progress in the production of butadiene from ethanol (ETB) by one or two-step process through intermediate production of acetaldehyde with an emphasis on the new catalytic systems. The different catalysts for butadiene production are compared in terms of structure-catalytic performance relationship, highlighting the key issues and requirements for future developments. The main difficulty in this process is that basic, acid and redox properties have to be combined in one single catalyst for the reactions of condensation, dehydration and hydrogenation. Magnesium and zirconium-based catalysts in the form of oxides or recently proposed silicates and zeolites promoted by metals are prevailing for butadiene synthesis with the highest selectivity of 70% at high ethanol conversion. The major challenge for further application of the process is to increase the butadiene productivity and to enhance the catalyst lifetime by suppression of coke deposition with preservation of active sites. Full article

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12 pages, 1566 KiB

Open AccessArticle

Photoassisted Oxidation of Sulfides Catalyzed by Artificial Metalloenzymes Using Water as an Oxygen Source

by Christian Herrero¹, Nhung Nguyen-Thi², Fabien Hammerer¹, Frédéric Banse¹, Donald Gagné², Nicolas Doucet²

, Jean-Pierre Mahy^1,* and Rémy Ricoux^1,*

¹ Institut de Chimie Moléculaire et des Matériaux d’Orsay UMR 8182 CNRS, Bâtiment 420, Université Paris Sud, Université Paris Saclay, F-91405 Orsay CEDEX, France

² Institut National de la Recherche Scientifique (INRS)-Institut Armand-Frappier, Université du Québec, 531 Boulevard des Prairies, Laval, QC H7V 1B7, Canada

Catalysts 2016, 6(12), 202; https://doi.org/10.3390/catal6120202 - 12 Dec 2016

Cited by 12 | Viewed by 7254

Abstract

The Mn(TpCPP)-Xln10A artificial metalloenzyme, obtained by non-covalent insertion of Mn(III)-meso-tetrakis(p-carboxyphenyl)porphyrin [Mn(TpCPP), 1-Mn] into xylanase 10A from Streptomyces lividans (Xln10A) as a host protein, was found able to catalyze the selective photo-induced oxidation of organic substrates in the presence of [Ru [...] Read more.

The Mn(TpCPP)-Xln10A artificial metalloenzyme, obtained by non-covalent insertion of Mn(III)-meso-tetrakis(p-carboxyphenyl)porphyrin [Mn(TpCPP), 1-Mn] into xylanase 10A from Streptomyces lividans (Xln10A) as a host protein, was found able to catalyze the selective photo-induced oxidation of organic substrates in the presence of [Ru^II(bpy)₃]²⁺ as a photosensitizer and [Co^III(NH₃)₅Cl]²⁺ as a sacrificial electron acceptor, using water as oxygen atom source. Full article

(This article belongs to the Special Issue Asymmetric and Selective Biocatalysis)

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9 pages, 4888 KiB

Open AccessArticle

N₂O Decomposition over Cu–Zn/γ–Al₂O₃ Catalysts

by Runhu Zhang¹

, Chao Hua^2,*, Bingshuai Wang³ and Yan Jiang³

¹ Department of Chemical Engineering, Kunming Metallurgy College, Kunming 650033, China

² Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

³ Liaoning Kelong Fine Chemical Co., Ltd., Liaoyang 111003, China

Catalysts 2016, 6(12), 200; https://doi.org/10.3390/catal6120200 - 12 Dec 2016

Cited by 10 | Viewed by 7635

Abstract

Cu–Zn/γ–Al₂O₃ catalysts were prepared by the impregnation method. Catalytic activity was evaluated for N₂O decomposition in a fixed bed reactor. The fresh and used catalysts were characterized by several techniques such as BET surface area, X-ray diffraction (XRD), [...] Read more.

Cu–Zn/γ–Al₂O₃ catalysts were prepared by the impregnation method. Catalytic activity was evaluated for N₂O decomposition in a fixed bed reactor. The fresh and used catalysts were characterized by several techniques such as BET surface area, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The Cu–Zn/γ–Al₂O₃ catalysts exhibit high activity and stability for N₂O decomposition in mixtures simulating real gas from adipic acid production, containing N₂O, O₂, NO, CO₂, and CO. Over the Cu–Zn/γ–Al₂O₃ catalysts, 100% of N₂O conversion was obtained at about 601 °C at a gas hourly space velocity (GHSV) of 7200 h⁻¹. Cu–Zn/γ–Al₂O₃ catalysts also exhibited considerably good durability, and no obvious activity loss was observed in the 100 h stability test. The Cu–Zn/γ–Al₂O₃ catalysts are promising for the abatement of this powerful greenhouse gas in the chemical industry, particularly in adipic acid production. Full article

(This article belongs to the Special Issue Heterogeneous Catalysis for Environmental Remediation)

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11 pages, 3280 KiB

Open AccessArticle

Synthesis of PtNi Alloy Nanoparticles on Graphene-Based Polymer Nanohybrids for Electrocatalytic Oxidation of Methanol

by Tung-Yuan Yung¹, Ting-Yu Liu^2,*, Kuan-Syun Wang², Che-Chun Liu², Shih-Hsuan Wang², Po-Tuan Chen³

and Chi-Yang Chao^4,*

¹ Nuclear Fuels and Materials Division, Institute of Nuclear Energy Research, Lontang, Taoyuan 325, Taiwan

² Department of Materials Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan

³ Guangzhou Wells Electronic Material Co. Ltd., Guangzhou 510530, China

⁴ Materials Science and Engineering, National Taiwan University, Taipei 106, Taiwan

Catalysts 2016, 6(12), 201; https://doi.org/10.3390/catal6120201 - 11 Dec 2016

Cited by 12 | Viewed by 6272

Abstract

We have successfully produced bimetallic PtNi alloy nanoparticles on poly(diallyldimethylammonium chloride) (PDDA)-modified graphene nanosheets (PtNi/PDDA-G) by the “one-pot” hydrothermal method. The size of PtNi alloy nanoparticles is approximately 2–5 nm. The PDDA-modified graphene nanosheets (PDDA-G) provides an anchored site for metal precursors; hence, [...] Read more.

We have successfully produced bimetallic PtNi alloy nanoparticles on poly(diallyldimethylammonium chloride) (PDDA)-modified graphene nanosheets (PtNi/PDDA-G) by the “one-pot” hydrothermal method. The size of PtNi alloy nanoparticles is approximately 2–5 nm. The PDDA-modified graphene nanosheets (PDDA-G) provides an anchored site for metal precursors; hence, the PtNi nanoparticles could be easily bond on the PDDA-G substrate. PtNi alloy nanoparticles (2–5 nm) display a homogenous alloy phase embedded on the PDDA-G substrate, evaluated by Raman, X-ray diffractometer (XRD), thermal gravity analysis (TGA), electron surface chemical analysis (ESCA), and electron energy loss spectroscopy (EELS). The Pt/Ni ratio of PtNi alloy nanoparticles is ~1.7, examined by the energy dispersive spectroscopy (EDS) spectra of transmitting electron microscopy (EDS/TEM spectra) and mapping technique. The methanol electro-oxidation of PtNi/PDDA-G was evaluated by cyclic voltammetry (CV) in 0.5 M of H₂SO₄ and 0.5 M of CH₃OH. Compared to Pt on carbon nanoparticles (Pt/C) and Pt on Graphene (Pt/G), the PtNi/PDDA-G exhibits the optimal electrochemical surface area (ECSA), methanol oxidation reaction (MOR) activity, and durability by chrono amperometry (CA) test, which can be a candidate for MOR in the electro-catalysis of direct methanol fuel cells (DMFC). Full article

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12 pages, 2170 KiB

Open AccessArticle

Selective Hydrogenation of Concentrated Vinyl Acetylene Mixed C4 by Modified Pd Catalysts: Effect of Cu

by Paisan Insorn¹ and Boonyarach Kitiyanan^1,2,*

¹ The Petroleum and Petrochemical College, Chulalongkorn University, Soi Chula 12, Phyathai Road, Pathumwan, Bangkok 10330, Thailand

² Center of Excellence on Petrochemical and Materials Technology, Chulalongkorn University, Bangkok 10330, Thailand

Catalysts 2016, 6(12), 199; https://doi.org/10.3390/catal6120199 - 9 Dec 2016

Cited by 10 | Viewed by 6767

Abstract

The Pd and Pd-Cu on alumina catalysts were tested for hydrogenation of vinyl acetylene in mixed C4 in a circulating tubular reactor. The results showed that adding proper amounts of Cu improved the reaction activity, but inhibited 1,3-butadiene selectivity. Moreover, the presence of [...] Read more.

The Pd and Pd-Cu on alumina catalysts were tested for hydrogenation of vinyl acetylene in mixed C4 in a circulating tubular reactor. The results showed that adding proper amounts of Cu improved the reaction activity, but inhibited 1,3-butadiene selectivity. Moreover, the presence of Cu retarded the carbon deposition on catalysts during the reaction. Temperature programmed oxidation (TPO), Temperature programmed reduction (TPR), H₂ chemisorption, and X-ray photoelectron spectroscopy (XPS) were utilized to characterize the catalysts. The characterization suggested both geometric and electronic modifications. Full article

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15 pages, 17705 KiB

Open AccessArticle

Facile Synthesis of MnPO₄·H₂O Nanowire/Graphene Oxide Composite Material and Its Application as Electrode Material for High Performance Supercapacitors

by Bo Yan¹, Duan Bin¹, Fangfang Ren^1,2,*, Zhiping Xiong¹, Ke Zhang¹, Caiqin Wang¹ and Yukou Du^1,3,*

¹ College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

² Analysis and Testing Center, Yancheng Normal University, Yancheng 224051, China

³ Tokyo University of Science Yamaguchi, SanyoOnoda-shi, Yamaguchi 756-0884, Japan

Catalysts 2016, 6(12), 198; https://doi.org/10.3390/catal6120198 - 9 Dec 2016

Cited by 32 | Viewed by 9114

Abstract

In this work, we reported a facile one-pot hydrothermal method to synthesize MnPO₄·H₂O nanowire/graphene oxide composite material with coated graphene oxide. Transmission electron microscopy and scanning electron microscope were employed to study its morphology information, and X-ray diffraction was [...] Read more.

In this work, we reported a facile one-pot hydrothermal method to synthesize MnPO₄·H₂O nanowire/graphene oxide composite material with coated graphene oxide. Transmission electron microscopy and scanning electron microscope were employed to study its morphology information, and X-ray diffraction was used to study the phase and structure of the material. Additionally, X-ray photoelectron spectroscopy was used to study the elements information. To measure electrochemical performances of electrode materials and the symmetry cell, cyclic voltammetry, chronopotentiometry and electrochemical impedance spectrometry were conducted on electrochemical workstation using 3 M KOH electrolytes. Importantly, electrochemical results showed that the as-prepared MnPO₄·H₂O nanowire/graphene oxide composite material exhibited high specific capacitance (287.9 F·g⁻¹ at 0.625 A·g⁻¹) and specific power (1.5 × 10⁵ W·kg⁻¹ at 2.271 Wh·kg⁻¹), which is expected to have promising applications as supercapacitor electrode material. Full article

(This article belongs to the Special Issue Graphene-Based Materials for Energy Conversion)

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21 pages, 2385 KiB

Open AccessReview

Proton Exchange Membrane Fuel Cell Reversal: A Review

by Congwei Qin^1,2, Jue Wang^1,2, Daijun Yang^1,2, Bing Li^1,2,* and Cunman Zhang^1,2,*

¹ School of Automotive Studies, Tongji University, Shanghai 201804, China

² Clean Energy Automotive Engineering Center, Tongji University, Shanghai 201804, China

Catalysts 2016, 6(12), 197; https://doi.org/10.3390/catal6120197 - 8 Dec 2016

Cited by 125 | Viewed by 16541

Abstract

The H₂/air-fed proton exchange membrane fuel cell (PEMFC) has two major problems: cost and durability, which obstruct its pathway to commercialization. Cell reversal, which would create irreversible damage to the fuel cell and shorten its lifespan, is caused by reactant starvation, [...] Read more.

The H₂/air-fed proton exchange membrane fuel cell (PEMFC) has two major problems: cost and durability, which obstruct its pathway to commercialization. Cell reversal, which would create irreversible damage to the fuel cell and shorten its lifespan, is caused by reactant starvation, load change, low catalyst performance, and so on. This paper will summarize the causes, consequences, and mitigation strategies of cell reversal of PEMFC in detail. A description of potential change in the anode and cathode and the differences between local starvation and overall starvation are reviewed, which gives a framework for comprehending the origins of cell reversal. According to the root factor of cell starvation, i.e., fuel cells do not satisfy the requirements of electrons and protons of normal anode and cathode chemical reactions, we will introduce specific methods to mitigate or prevent fuel cell damage caused by cell reversal in the view of system management strategies and component material modifications. Based on a comprehensive understanding of cell reversal, it is beneficial to operate a fuel cell stack and extend its lifetime. Full article

(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)

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24 pages, 682 KiB

Open AccessReview

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

by Shouyun Cheng

, Lin Wei^*, Xianhui Zhao and James Julson

Agricultural & Biosystems Engineering Department, South Dakota State University, 1400 North Campus Drive, Brookings, SD 57007, USA

Catalysts 2016, 6(12), 195; https://doi.org/10.3390/catal6120195 - 7 Dec 2016

Cited by 139 | Viewed by 13261

Abstract

The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO) are two [...] Read more.

The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO) are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction, and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided. Full article

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29 pages, 2803 KiB

Open AccessReview

New Frontiers in the Catalytic Synthesis of Levulinic Acid: From Sugars to Raw and Waste Biomass as Starting Feedstock

by Claudia Antonetti

, Domenico Licursi, Sara Fulignati

, Giorgio Valentini and Anna Maria Raspolli Galletti^*

Department of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi, 13, 56124 Pisa, Italy

Catalysts 2016, 6(12), 196; https://doi.org/10.3390/catal6120196 - 6 Dec 2016

Cited by 213 | Viewed by 16397

Abstract

Levulinic acid (LA) is one of the top bio-based platform molecules that can be converted into many valuable chemicals. It can be produced by acid catalysis from renewable resources, such as sugars, lignocellulosic biomass and waste materials, attractive candidates due to their abundance [...] Read more.

Levulinic acid (LA) is one of the top bio-based platform molecules that can be converted into many valuable chemicals. It can be produced by acid catalysis from renewable resources, such as sugars, lignocellulosic biomass and waste materials, attractive candidates due to their abundance and environmentally benign nature. The LA transition from niche product to mass-produced chemical, however, requires its production from sustainable biomass feedstocks at low costs, adopting environment-friendly techniques. This review is an up-to-date discussion of the literature on the several catalytic systems that have been developed to produce LA from the different substrates. Special attention has been paid to the recent advancements on starting materials, moving from simple sugars to raw and waste biomasses. This aspect is of paramount importance from a sustainability point of view, transforming wastes needing to be disposed into starting materials for value-added products. This review also discusses the strategies to exploit the solid residues always obtained in the LA production processes, in order to attain a circular economy approach. Full article

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21 pages, 6342 KiB

Open AccessFeature PaperReview

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

by Yajie Wang and Huimin Zhao^*

Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA

Catalysts 2016, 6(12), 194; https://doi.org/10.3390/catal6120194 - 5 Dec 2016

Cited by 60 | Viewed by 13012

Abstract

The application of biocatalysts in the synthesis of fine chemicals and medicinal compounds has grown significantly in recent years. Particularly, there is a growing interest in the development of one-pot tandem catalytic systems combining the reactivity of a chemical catalyst with the selectivity [...] Read more.

The application of biocatalysts in the synthesis of fine chemicals and medicinal compounds has grown significantly in recent years. Particularly, there is a growing interest in the development of one-pot tandem catalytic systems combining the reactivity of a chemical catalyst with the selectivity engendered by the active site of an enzyme. Such tandem catalytic systems can achieve levels of chemo-, regio-, and stereo-selectivities that are unattainable with a small molecule catalyst. In addition, artificial metalloenzymes widen the range of reactivities and catalyzed reactions that are potentially employable. This review highlights some of the recent examples in the past three years that combined transition metal catalysis with enzymatic catalysis. This field is still in its infancy. However, with recent advances in protein engineering, catalyst synthesis, artificial metalloenzymes and supramolecular assembly, there is great potential to develop more sophisticated tandem chemoenzymatic processes for the synthesis of structurally complex chemicals. Full article

(This article belongs to the Special Issue Asymmetric and Selective Biocatalysis)

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10 pages, 4847 KiB

Open AccessArticle

The Preparation of Cu-g-C₃N₄/AC Catalyst for Acetylene Hydrochlorination

by Wenli Zhao¹, Mingyuan Zhu^1,2,* and Bin Dai^1,2,*

¹ School of Chemistry and Chemical Engineering of Shihezi University, Shihezi 832000, Xinjiang, China

² Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, Shihezi 832000, Xinjiang, China

Catalysts 2016, 6(12), 193; https://doi.org/10.3390/catal6120193 - 5 Dec 2016

Cited by 38 | Viewed by 9244

Abstract

A novel catalyst based on g-C₃N₄/activated carbon was prepared by adding CuCl₂. The catalytic performance of the as-prepared catalyst was investigated in the acetylene hydrochlorination reaction. X-ray photoelectron spectroscopy, temperature programmed desorption, low temperature N₂ adsorption/desorption [...] Read more.

A novel catalyst based on g-C₃N₄/activated carbon was prepared by adding CuCl₂. The catalytic performance of the as-prepared catalyst was investigated in the acetylene hydrochlorination reaction. X-ray photoelectron spectroscopy, temperature programmed desorption, low temperature N₂ adsorption/desorption (Brunauer–Emmett–Teller), and thermal gravity analysis showed that Cu-g-C₃N₄/AC significantly enhanced the catalytic performance of the original catalyst by increasing the relative pyrrolic N content. Cu-g-C₃N₄/AC also affected the adsorption of hydrogen chloride and acetylene, as well as inhibited the coke deposition during acetylene hydrochlorination. Full article

(This article belongs to the Special Issue Heterogeneous Catalysis for Environmental Remediation)

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6 pages, 1052 KiB

Open AccessPerspective

Hidden but Possibly Fatal Misconceptions in Photocatalysis Studies: A Short Critical Review

by Bunsho Ohtani

Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan

Catalysts 2016, 6(12), 192; https://doi.org/10.3390/catal6120192 - 2 Dec 2016

Cited by 21 | Viewed by 7151

Abstract

This short review paper shows some misconceptions hidden in the discussion on the mechanism of heterogeneous photocatalysis, which may lead to fatal errors in conclusions. Topics described in this review are semiconductor photocatalysis, control experiments for proof of photocatalysis, and converse-proposition pitfalls in [...] Read more.

This short review paper shows some misconceptions hidden in the discussion on the mechanism of heterogeneous photocatalysis, which may lead to fatal errors in conclusions. Topics described in this review are semiconductor photocatalysis, control experiments for proof of photocatalysis, and converse-proposition pitfalls in discussion. Full article

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13 pages, 1643 KiB

Open AccessFeature PaperArticle

New Tailor-Made Alkyl-Aldehyde Bifunctional Supports for Lipase Immobilization

by Robson Carlos Alnoch^1,2

, Ricardo Rodrigues de Melo^1,3, Jose M. Palomo¹

, Emanuel Maltempi de Souza²

, Nadia Krieger⁴

and Cesar Mateo^1,*

¹ Departamento de Biocatálisis, Instituto de Catálisis y Petroleoquímica (CSIC), Marie Curie 2. Cantoblanco, Campus UAM, 28049 Madrid, Spain

² Departamento de Bioquímica e Biologia Molecular, Universidade Federal do Paraná, Cx. P. 19081 Centro Politécnico, 81531-980 Curitiba, Paraná, Brazil

³ Departamento de Ciência de Alimentos, Faculdade de Engenharia de Alimentos (FEA), Universidade Estadual de Campinas, 13083-862 Campinas, São Paulo, Brazil

⁴ Departamento de Química, Universidade Federal do Paraná, Cx. P. 19081 Centro Politécnico, 81531-980 Curitiba, Paraná, Brazil

Catalysts 2016, 6(12), 191; https://doi.org/10.3390/catal6120191 - 30 Nov 2016

Cited by 14 | Viewed by 6572

Abstract

Immobilized and stabilized lipases are important biocatalytic tools. In this paper, different tailor-made bifunctional supports were prepared for the immobilization of a new metagenomic lipase (LipC12). The new supports contained hydrophobic groups (different alkyl groups) to promote interfacial adsorption of the lipase and [...] Read more.

Immobilized and stabilized lipases are important biocatalytic tools. In this paper, different tailor-made bifunctional supports were prepared for the immobilization of a new metagenomic lipase (LipC12). The new supports contained hydrophobic groups (different alkyl groups) to promote interfacial adsorption of the lipase and aldehyde groups to react covalently with the amino groups of side chains of the adsorbed lipase. The best catalyst was 3.5-fold more active and 5000-fold more stable than the soluble enzyme. It was successfully used in the regioselective deacetylation of peracetylated d-glucal. The PEGylated immobilized lipase showed high regioselectivity, producing high yields of the C-3 monodeacetylated product at pH 5.0 and 4 °C. Full article

(This article belongs to the Special Issue Asymmetric and Selective Biocatalysis)

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16 pages, 2448 KiB

Open AccessArticle

Mechanistic and Structural Insight to an Evolved Benzoylformate Decarboxylase with Enhanced Pyruvate Decarboxylase Activity

by Forest H. Andrews¹, Cindy Wechsler², Megan P. Rogers¹, Danilo Meyer², Kai Tittmann² and Michael J. McLeish^1,*

¹ Department of Chemistry and Chemical Biology, Indiana University-Purdue University Indianapolis, Indianapolis, IN 46202, USA

² Göttingen Center for Molecular Biosciences, Georg-August-University Göttingen, Ernst-Caspari-Haus, Justus-von-Liebig-Weg 11, 37077 Göttingen, Germany

Catalysts 2016, 6(12), 190; https://doi.org/10.3390/catal6120190 - 30 Nov 2016

Cited by 3 | Viewed by 6152

Abstract

Benzoylformate decarboxylase (BFDC) and pyruvate decarboxylase (PDC) are thiamin diphosphate-dependent enzymes that share some structural and mechanistic similarities. Both enzymes catalyze the nonoxidative decarboxylation of 2-keto acids, yet differ considerably in their substrate specificity. In particular, the BFDC from P. putida exhibits very [...] Read more.

Benzoylformate decarboxylase (BFDC) and pyruvate decarboxylase (PDC) are thiamin diphosphate-dependent enzymes that share some structural and mechanistic similarities. Both enzymes catalyze the nonoxidative decarboxylation of 2-keto acids, yet differ considerably in their substrate specificity. In particular, the BFDC from P. putida exhibits very limited activity with pyruvate, whereas the PDCs from S. cerevisiae or from Z. mobilis show virtually no activity with benzoylformate (phenylglyoxylate). Previously, saturation mutagenesis was used to generate the BFDC T377L/A460Y variant, which exhibited a greater than 10,000-fold increase in pyruvate/benzoylformate substrate utilization ratio compared to that of wtBFDC. Much of this change could be attributed to an improvement in the K_m value for pyruvate and, concomitantly, a decrease in the k_cat value for benzoylformate. However, the steady-state data did not provide any details about changes in individual catalytic steps. To gain insight into the changes in conversion rates of pyruvate and benzoylformate to acetaldehyde and benzaldehyde, respectively, by the BFDC T377L/A460Y variant, reaction intermediates of both substrates were analyzed by NMR and microscopic rate constants for the elementary catalytic steps were calculated. Herein we also report the high resolution X-ray structure of the BFDC T377L/A460Y variant, which provides context for the observed changes in substrate specificity. Full article

(This article belongs to the Special Issue Asymmetric and Selective Biocatalysis)

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12 pages, 2832 KiB

Open AccessArticle

Continuous Packed Bed Reactor with Immobilized β-Galactosidase for Production of Galactooligosaccharides (GOS)

by Barbara Rodriguez-Colinas, Lucia Fernandez-Arrojo, Paloma Santos-Moriano, Antonio O. Ballesteros and Francisco J. Plou^*

Applied Biocatalysis Group, Instituto de Catálisis y Petroleoquímica, CSIC, 28049 Madrid, Spain

Catalysts 2016, 6(12), 189; https://doi.org/10.3390/catal6120189 - 30 Nov 2016

Cited by 46 | Viewed by 10379

Abstract

The β-galactosidase from Bacillus circulans was covalently attached to aldehyde-activated (glyoxal) agarose beads and assayed for the continuous production of galactooligosaccharides (GOS) in a packed-bed reactor (PBR). The immobilization was fast (1 h) and the activity of the resulting biocatalyst was 97.4 U/g [...] Read more.

The β-galactosidase from Bacillus circulans was covalently attached to aldehyde-activated (glyoxal) agarose beads and assayed for the continuous production of galactooligosaccharides (GOS) in a packed-bed reactor (PBR). The immobilization was fast (1 h) and the activity of the resulting biocatalyst was 97.4 U/g measured with o-nitrophenyl-β-d-galactopyranoside (ONPG). The biocatalyst showed excellent operational stability in 14 successive 20 min reaction cycles at 45 °C in a batch reactor. A continuous process for GOS synthesis was operated for 213 h at 0.2 mL/min and 45 °C using 100 g/L of lactose as a feed solution. The efficiency of the PBR slightly decreased with time; however, the maximum GOS concentration (24.2 g/L) was obtained after 48 h of operation, which corresponded to 48.6% lactose conversion and thus to maximum transgalactosylation activity. HPAEC-PAD analysis showed that the two major GOS were the trisaccharide Gal-β(1→4)-Gal-β(1→4)-Glc and the tetrasaccharide Gal-β(1→4)-Gal-β(1→4)-Gal-β(1→4)-Glc. The PBR was also assessed in the production of GOS from milk as a feed solution. The stability of the bioreactor was satisfactory during the first 8 h of operation; after that, a decrease in the flow rate was observed, probably due to partial clogging of the column. This work represents a step forward in the continuous production of GOS employing fixed-bed reactors with immobilized β-galactosidases. Full article

(This article belongs to the Special Issue Immobilized Enzymes: Strategies for Enzyme Stabilization)

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44 pages, 7772 KiB

Open AccessReview

The Applications of Morphology Controlled ZnO in Catalysis

by Yuhai Sun¹

, Limin Chen^1,2,*, Yunfeng Bao¹, Yujun Zhang¹, Jing Wang¹, Mingli Fu¹, Junliang Wu¹ and Daiqi Ye^1,2

¹ Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, China

² Guangdong Provincial Engineering and Technology Research Center for Environmental Risk Prevention and Emergency Disposal, South China University of Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, China

Catalysts 2016, 6(12), 188; https://doi.org/10.3390/catal6120188 - 30 Nov 2016

Cited by 151 | Viewed by 18182

Abstract

Zinc oxide (ZnO), with the unique chemical and physical properties of high chemical stability, broad radiation absorption range, high electrochemical coupling coefficient, and high photo-stability, is an attractive multifunctional material which has promoted great interest in many fields. What is more, its properties [...] Read more.

Zinc oxide (ZnO), with the unique chemical and physical properties of high chemical stability, broad radiation absorption range, high electrochemical coupling coefficient, and high photo-stability, is an attractive multifunctional material which has promoted great interest in many fields. What is more, its properties can be tuned by controllable synthesized morphologies. Therefore, after the success of the abundant morphology controllable synthesis, both the morphology-dependent ZnO properties and their related applications have been extensively investigated. This review concentrates on the properties of morphology-dependent ZnO and their applications in catalysis, mainly involved reactions on green energy and environmental issues, such as CO₂ hydrogenation to fuels, methanol steam reforming to generate H₂, bio-diesel production, pollutant photo-degradation, etc. The impressive catalytic properties of ZnO are associated with morphology tuned specific microstructures, defects or abilities of electron transportation, etc. The main morphology-dependent promotion mechanisms are discussed and summarized. Full article

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13 pages, 1797 KiB

Open AccessArticle

Composition, Structural Evolution and the Related Property Variations in Preparation of Mixed Cesium/Ammonium Acidic Salts of Heteropolyacids

by Heng Zhang^*, Tingting Wang, Xinxin Ma and Wancheng Zhu

School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China

Catalysts 2016, 6(12), 187; https://doi.org/10.3390/catal6120187 - 29 Nov 2016

Cited by 5 | Viewed by 4776

Abstract

The composition, structural evolution and the related property variations of mixed cesium/ammonium acidic salts of heteropolyacids were investigated in detail by tracking and analyzing the initial precipitates, evaporation residues and the calcined products in their preparation process. Results show that V cannot completely [...] Read more.

The composition, structural evolution and the related property variations of mixed cesium/ammonium acidic salts of heteropolyacids were investigated in detail by tracking and analyzing the initial precipitates, evaporation residues and the calcined products in their preparation process. Results show that V cannot completely enter the heteropolyanions in the initial precipitates when the Cs⁺ added amount is low, and the increase in Cs⁺ adding amount improves the substitution of V for Mo in the heteropolyanions. Both the initial precipitates and the evaporation residues are mixtures of cesium and ammonium salts of heteropolyacids before calcination. Thermal treatment causes the decomposition of the ammonium salts and the formation of single-phase solid solutions from mechanical mixtures. The calcined products of the initial precipitates and the evaporation residues vary greatly in textural properties. The determinants of the catalytic performance for the oxidation of methacrolein to methacrylic acid are acidity and specific surface area of the compounds. The increase in specific surface area mainly improves the conversion of methacrolein, but not the selectivity of methacrylic acid. Insufficient acidity caused by high Cs⁺ content in the compounds is responsible for the low selectivity. Full article

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23 pages, 7681 KiB

Open AccessFeature PaperReview

Micro/Mesoporous Zeolitic Composites: Recent Developments in Synthesis and Catalytic Applications

by Xuan Hoan Vu^1,2,*, Udo Armbruster³ and Andreas Martin^3,*

¹ Department for Management of Science and Technology Development, Ton Duc Thang University, Ho Chi Minh City 700000, Vietnam

² Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City 700000, Vietnam

³ Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a, 18059 Rostock, Germany

Catalysts 2016, 6(12), 183; https://doi.org/10.3390/catal6120183 - 29 Nov 2016

Cited by 57 | Viewed by 11936

Abstract

Micro/mesoporous zeolitic composites (MZCs) represent an important class of hierarchical zeolitic materials that have attracted increasing attention in recent years. By introducing an additional mesoporous phase interconnected with the microporosity of zeolites, a hierarchical porous system of MZCs is formed which facilitates molecular [...] Read more.

Micro/mesoporous zeolitic composites (MZCs) represent an important class of hierarchical zeolitic materials that have attracted increasing attention in recent years. By introducing an additional mesoporous phase interconnected with the microporosity of zeolites, a hierarchical porous system of MZCs is formed which facilitates molecular transport while preserving the intrinsic catalytic properties of zeolites. Thus, these materials offer novel perspectives for catalytic applications. Over the years, numerous synthesis strategies toward the formation of MZCs have been realized and their catalytic applications have been reported. In this review, the three main synthesis routes, namely direct synthesis using zeolite precursors, recrystallization of zeolites, and zeolitization of preformed mesoporous materials are thoroughly discussed, with focus on prior works and the most recent developments along with prominent examples given from the literature. In addition, the significant improvement in the catalytic properties of MZCs in a wide range of industrially relevant reactions is presented through several representative cases. Some perspectives for the future development of MZCs are also given. Full article

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