Catalysts

9 pages, 1721 KiB

Open AccessArticle

Cu₄₂Ge₂₄Na₄—A Giant Trimetallic Sesquioxane Cage: Synthesis, Structure, and Catalytic Activity

by Alena N. Kulakova^1,2, Alexey N. Bilyachenko^1,2,*, Victor N. Khrustalev^2,3

, Yan V. Zubavichus³

, Pavel V. Dorovatovskii³, Lidia S. Shul’pina¹

, Xavier Bantreil⁴, Frédéric Lamaty^4,*, Elena S. Shubina¹

, Mikhail M. Levitsky¹ and Georgiy B. Shul’pin^5,6,*

¹ A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova, 28, Moscow 119991, Russia

² People’s Friendship University of Russia, ul. Miklukho-Maklaya, dom 6, Moscow 117198, Russia

³ National Research Center “Kurchatov Institute”, pl. Akademika Kurchatova, dom 1, Moscow 123182, Russia

⁴ Institut des Biomolécules Max Mousseron (IBMM) UMR 5247, CNRS, Université de Montpellier, ENSCM, Université de Montpellier Campus Triolet Place Eugène Bataillon, 34095 Montpellier CEDEX 5, France

⁵ Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, Moscow 119991, Russia

⁶ Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow 117997, Russia

Catalysts 2018, 8(10), 484; https://doi.org/10.3390/catal8100484 - 22 Oct 2018

Cited by 17 | Viewed by 4218

Abstract

Unprecedented germanium-based sesquioxane exhibits an extremely high nuclearity (Cu₄₂Ge₂₄Na₄) and unusual encapsulation features. The compound demonstrated a high catalytic activity in the oxidative amidation of alcohols, with cost-effective catalyst loading down to 400 ppm of copper, and [...] Read more.

Unprecedented germanium-based sesquioxane exhibits an extremely high nuclearity (Cu₄₂Ge₂₄Na₄) and unusual encapsulation features. The compound demonstrated a high catalytic activity in the oxidative amidation of alcohols, with cost-effective catalyst loading down to 400 ppm of copper, and in the oxidation of cyclohexane and other alkanes with H₂O₂ in acetonitrile in the presence of nitric acid. Selectivity parameters and the mode of dependence of initial cyclohexane oxidation rate on initial concentration of the hydrocarbon indicate that the reaction occurs with the participation of hydroxyl radicals and alkyl hydroperoxides are formed as the main primary product. Alcohols have been transformed into the corresponding ketones by the catalytic oxidation with tert-butyl hydroperoxide. Full article

(This article belongs to the Section Catalytic Materials)

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21 pages, 3491 KiB

Open AccessReview

General and Prospective Views on Oxidation Reactions in Heterogeneous Catalysis

by Sabine Valange^1,* and Jacques C. Védrine^2,*

¹ Institut de Chimie, des Milieux et Matériaux de Poitiers (IC2MP), UMR CNRS 7285, Université de Poitiers, ENSI Poitiers, B1, 1 rue Marcel Doré, TSA41105, F-86073 Poitiers Cedex 9, France

² Sorbonne Université, Faculté des Sciences et Ingénierie, Laboratoire de Réactivité de Surface, UMR-CNRS 7197, 4 place Jussieu, F-75252 Paris, France

Catalysts 2018, 8(10), 483; https://doi.org/10.3390/catal8100483 - 22 Oct 2018

Cited by 48 | Viewed by 8922

Abstract

In this review paper, we have assembled the main characteristics of partial oxidation reactions (oxidative dehydrogenation and selective oxidation to olefins or oxygenates, as aldehydes and carboxylic acids and nitriles), as well as total oxidation, particularly for depollution, environmental issues and wastewater treatments. [...] Read more.

In this review paper, we have assembled the main characteristics of partial oxidation reactions (oxidative dehydrogenation and selective oxidation to olefins or oxygenates, as aldehydes and carboxylic acids and nitriles), as well as total oxidation, particularly for depollution, environmental issues and wastewater treatments. Both gas–solid and liquid–solid media have been considered with recent and representative examples within these fields. We have also discussed about their potential and prospective industrial applications. Particular attention has been brought to new raw materials stemming from biomass, as well as to liquid–solid catalysts cases. This review paper also summarizes the progresses made in the use of unconventional activation methods for performing oxidation reactions, highlighting the synergy of these technologies with heterogeneous catalysis. Focus has been centered on both usual catalysts activation methods and less usual ones, such as the use of ultrasounds, microwaves, grinding (mechanochemistry) and photo-activated processes, as well as their combined use. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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14 pages, 5003 KiB

Open AccessArticle

A Buoyant, Microstructured Polymer Substrate for Photocatalytic Degradation Applications

by John R. Bertram^1,2 and Matthew J. Nee^1,*

¹ Department of Chemistry, Western Kentucky University, 1906 College Heights Blvd., Bowling Green, KY 42101, USA

² Renewable and Sustainable Energy Institute, Materials Science and Engineering Program, University of Colorado, Boulder, CO 80303, USA

Catalysts 2018, 8(10), 482; https://doi.org/10.3390/catal8100482 - 22 Oct 2018

Cited by 5 | Viewed by 4187

Abstract

Microbubble fabrication of poly(dimethylsiloxane) (PDMS) beads with incorporated TiO₂ provides a low-density, microstructured photocatalyst that is buoyant in water. This approach surmounts many of the challenges traditionally encountered in the generation of buoyant photocatalysts, an area which is critical for the implementation [...] Read more.

Microbubble fabrication of poly(dimethylsiloxane) (PDMS) beads with incorporated TiO₂ provides a low-density, microstructured photocatalyst that is buoyant in water. This approach surmounts many of the challenges traditionally encountered in the generation of buoyant photocatalysts, an area which is critical for the implementation of widespread environmental cleaning of organic pollutants in water resources. Because the incorporation into the polymer bead surface is done at low temperatures, the crystal structure of TiO₂ is unaltered, ensuring high-quality photocatalytic activity, while PDMS is well-established as biocompatible, temperature stable, and simple to produce. The photocatalyst is shown to degrade methylene blue faster than other buoyant, TiO₂-based photocatalysts, and only an order of magnitude less than direct suspension of an equivalent amount of photocatalyst in solution, even though the photocatalyst is only present at the surface of the solution. The reusability of the TiO₂/PDMS beads is also strong, showing no depreciation in photocatalytic activity after five consecutive degradation trials. Full article

(This article belongs to the Special Issue Catalysts for Oxidative Destruction of Volatile Organic Compounds)

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12 pages, 3557 KiB

Open AccessArticle

Low Temperature Activation of Carbon Dioxide by Ammonia in Methane Dry Reforming—A Thermodynamic Study

by Anand Kumar

Department of Chemical Engineering, Qatar University, P. O. Box 2713, Doha, Qatar

Catalysts 2018, 8(10), 481; https://doi.org/10.3390/catal8100481 - 22 Oct 2018

Cited by 9 | Viewed by 5014

Abstract

Methane dry reforming (MDR) is an attractive alternative to methane steam reforming for hydrogen production with low harmful environmental emissions on account of utilizing carbon dioxide in the feed. However, carbon formation in the product stream has been the most challenging aspect of [...] Read more.

Methane dry reforming (MDR) is an attractive alternative to methane steam reforming for hydrogen production with low harmful environmental emissions on account of utilizing carbon dioxide in the feed. However, carbon formation in the product stream has been the most challenging aspect of MDR, as it leads to catalyst deactivation by coking, prevalent in hydrocarbon reforming reactions. Common strategies to limit coking have mainly targeted catalyst modifications, such as by doping with rare earth metals, supporting on refractory oxides, adding oxygen/steam in the feed, or operating at reaction conditions (e.g., higher temperature), where carbon formation is thermodynamically restrained. These methods do help in suppressing carbon formation; nonetheless, to a large extent, catalyst activity and product selectivity are also adversely affected. In this study, the effect of ammonia addition in MDR feed on carbon suppression is presented. Based on a thermodynamic equilibrium analysis, the most significant observation of ammonia addition is towards low temperature carbon dioxide activation to methane, along with carbon removal. Results indicate that ammonia not only helps in removing carbon formation, but also greatly enriches hydrogen production. Full article

(This article belongs to the Special Issue Catalytic Reforming of Methane)

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14 pages, 8756 KiB

Open AccessFeature PaperArticle

A New Tool in the Quest for Biocompatible Phthalocyanines: Palladium Catalyzed Aminocarbonylation for Amide Substituted Phthalonitriles and Illustrative Phthalocyanines Thereof

by Vanessa A. Tomé, Mário J. F. Calvete^*

, Carolina S. Vinagreiro

, Rafael T. Aroso and Mariette M. Pereira^*

Centro de Química de Coimbra (CQC), Department of Chemistry, University of Coimbra, Coimbra 3004-535, Portugal

Catalysts 2018, 8(10), 480; https://doi.org/10.3390/catal8100480 - 20 Oct 2018

Cited by 5 | Viewed by 4280

Abstract

The amide peptide bond type linkage is one of the most natural conjugations available, present in many biological synthons and pharmaceutical drugs. Hence, aiming the direct conjugation of potentially biologically active compounds to phthalocyanines, herein we disclose a new strategy for direct modulation [...] Read more.

The amide peptide bond type linkage is one of the most natural conjugations available, present in many biological synthons and pharmaceutical drugs. Hence, aiming the direct conjugation of potentially biologically active compounds to phthalocyanines, herein we disclose a new strategy for direct modulation of phthalonitriles, inspired by an attractive synthetic strategy for the preparation of carboxamides based on palladium-catalyzed aminocarbonylation of aryl halides in the presence of carbon monoxide (CO) which, to our knowledge, has never been used to prepare amide-substituted phthalonitriles, the natural precursors for the synthesis of phthalocyanines. Some examples of phthalocyanines prepared thereof are also reported, along with their full spectroscopic characterization and photophysical properties initial assessment. Full article

(This article belongs to the Special Issue Catalysis for Global Development. Contributions around the Iberoamerican Federation of Catalysis)

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23 pages, 3639 KiB

Open AccessArticle

A Novel Method of Affinity Tag Cleavage in the Purification of a Recombinant Thermostable Lipase from Aneurinibacillus thermoaerophilus Strain HZ

by Malihe Masomian^1,2, Raja Noor Zaliha Raja Abd Rahman^1,2,*

and Abu Bakar Salleh^1,3

¹ Enzyme and Microbial Technology Research Centre, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia

² Department of Microbiology, Faculty of Biotechnology and Biomolecular Science, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia

³ Department of Biochemistry, Faculty of Biotechnology and Biomolecular Science, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia

Catalysts 2018, 8(10), 479; https://doi.org/10.3390/catal8100479 - 20 Oct 2018

Cited by 10 | Viewed by 6062

Abstract

The development of an efficient and economical purification method is required to obtain a pure and mature recombinant protein in a simple process with high efficiency. Hence, a new technique was invented to cleave the tags from the N-terminal region of recombinant fusion [...] Read more.

The development of an efficient and economical purification method is required to obtain a pure and mature recombinant protein in a simple process with high efficiency. Hence, a new technique was invented to cleave the tags from the N-terminal region of recombinant fusion HZ lipase in the absence of protease treatment. The recombinant pET32b/rHZ lipase was overexpressed into E. coli BL21 (DE3). Affinity chromatography was performed as the first step of purification. The stability of the protein was then tested in different temperatures. The fused Trx-His-S-tags to the rHZ lipase was cleaved by treatment of the fusion protein at 20 °C in 100 mM Tris-HCl buffer, pH 8.0. The precipitated tag was removed, and the mature recombinant enzyme was further characterized to specify its properties. A purification yield of 78.9% with 1.3-fold and 21.8 mg total purified mature protein was obtained from 50 mL starting a bacterial culture. N-terminal sequencing of purified recombinant HZ lipase confirmed the elimination of the 17.4 kDa tag from one amino acid before the native start codon (Methionine) of the protein. The mature rHZ lipase was highly active at 65 °C and a pH of 7.0, with a half-life of 2 h 15 min at 55 °C and 45 min at 60 °C. The rHZ lipase showed a preference for the hydrolysis of natural oil with a long carbon chain (C18) and medium-size acyl chain p-nitrophenyl esters (C10). The enzyme remained stable in the presence of nonpolar organic solvents, and its activity was increased by polar organic solvents. This study thus demonstrates a simple and convenient purification method which resulted in the high yield of mature enzyme along with unique and detailed biochemical characterization of rHZ lipase, making the enzyme favorable in various industrial applications. Full article

(This article belongs to the Special Issue Biocatalysis for Industrial Applications)

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20 pages, 2965 KiB

Open AccessFeature PaperReview

Active Sites in Heterogeneous Catalytic Reaction on Metal and Metal Oxide: Theory and Practice

by Yanbo Pan

, Xiaochen Shen

, Libo Yao, Abdulaziz Bentalib and Zhenmeng Peng^*

Department of Chemical and Biomolecular Engineering, The University of Akron, Akron, OH 44325, USA

Catalysts 2018, 8(10), 478; https://doi.org/10.3390/catal8100478 - 20 Oct 2018

Cited by 74 | Viewed by 21856

Abstract

Active sites play an essential role in heterogeneous catalysis and largely determine the reaction properties. Yet identification and study of the active sites remain challenging owing to their dynamic behaviors during catalysis process and issues with current characterization techniques. This article provides a [...] Read more.

Active sites play an essential role in heterogeneous catalysis and largely determine the reaction properties. Yet identification and study of the active sites remain challenging owing to their dynamic behaviors during catalysis process and issues with current characterization techniques. This article provides a short review of research progresses in active sites of metal and metal oxide catalysts, which covers the past achievements, current research status, and perspectives in this research field. In particular, the concepts and theories of active sites are introduced. Major experimental and computational approaches that are used in active site study are summarized, with their applications and limitations being discussed. An outlook of future research direction in both experimental and computational catalysis research is provided. Full article

(This article belongs to the Special Issue Active Sites in Catalytic Reaction)

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10 pages, 2999 KiB

Open AccessArticle

Facile Synthesis of Bi₂MoO₆ Microspheres Decorated by CdS Nanoparticles with Efficient Photocatalytic Removal of Levfloxacin Antibiotic

by Shijie Li^1,*, Yanping Liu², Yunqian Long^1,*, Liuye Mo¹, Huiqiu Zhang¹ and Jianshe Liu³

¹ Key Laboratory of Key Technical Factors in Zhejiang Seafood Health Hazards, Institute of Innovation & Application, Zhejiang Ocean University, Zhoushan 316022, China

² Department of Environmental Engineering, Zhejiang Ocean University, Zhoushan 316022, China

³ State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, College of Environmental Science and Engineering, Donghua University, Shanghai 201620, China

Catalysts 2018, 8(10), 477; https://doi.org/10.3390/catal8100477 - 19 Oct 2018

Cited by 18 | Viewed by 5221

Abstract

Developing high-efficiency and stable visible-light-driven (VLD) photocatalysts for removal of toxic antibiotics is still a huge challenge at present. Herein, a novel CdS/Bi₂MoO₆ heterojunction with CdS nanoparticles decorated Bi₂MoO₆ microspheres has been obtained by a simple solvothermal-precipitation-calcination [...] Read more.

Developing high-efficiency and stable visible-light-driven (VLD) photocatalysts for removal of toxic antibiotics is still a huge challenge at present. Herein, a novel CdS/Bi₂MoO₆ heterojunction with CdS nanoparticles decorated Bi₂MoO₆ microspheres has been obtained by a simple solvothermal-precipitation-calcination method. 1.0CdS/Bi₂MoO₆ has stronger light absorption ability and highest photocatalytic activity with levofloxacin (LEV) degradation efficiency improving 6.2 or 12.6 times compared to pristine CdS or Bi₂MoO₆. CdS/Bi₂MoO₆ is very stable during cycling tests, and no appreciable activity decline and microstructural changes are observed. Results signify that the introduction of CdS could enhance the light absorption ability and dramatically boost the separation of charge carriers, leading to the excellent photocatalytic performance of the heterojunction. This work demonstrates that flower-like CdS/ Bi₂MoO₆ is an excellent photocatalyst for the efficient removal of the LEV antibiotic. Full article

(This article belongs to the Special Issue Novel Heterogeneous Catalysts for Advanced Oxidation Processes (AOPs))

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15 pages, 2782 KiB

Open AccessArticle

Characterization of a New Glyoxal Oxidase from the Thermophilic Fungus Myceliophthora thermophila M77: Hydrogen Peroxide Production Retained in 5-Hydroxymethylfurfural Oxidation

by Marco Antonio Seiki Kadowaki^1,2, Mariana Ortiz de Godoy^1,2, Patricia Suemy Kumagai¹

, Antonio José da Costa-Filho³, Andrew Mort², Rolf Alexander Prade^2,* and Igor Polikarpov^1,*

¹ São Carlos Institute of Physics, University of São Paulo, Av. Trabalhador São-Carlense, 400, São Carlos 13566-590, Brazil

² Departments of Biochemistry & Molecular Biology and Microbiology & Molecular Genetics, Oklahoma State University, Stillwater, OK 74078, USA

³ Department of Physics, Ribeirão Preto School of Philosophy, Sciences and Literature, University of São Paulo, Ribeirão Preto BR-14040901, Brazil

Catalysts 2018, 8(10), 476; https://doi.org/10.3390/catal8100476 - 19 Oct 2018

Cited by 23 | Viewed by 5264

Abstract

Myceliophthora thermophyla is a thermophilic industrially relevant fungus that secretes an assortment of hydrolytic and oxidative enzymes for lignocellulose degradation. Among them is glyoxal oxidase (MtGLOx), an extracellular oxidoreductase that oxidizes several aldehydes and α-hydroxy carbonyl substrates coupled to the reduction [...] Read more.

Myceliophthora thermophyla is a thermophilic industrially relevant fungus that secretes an assortment of hydrolytic and oxidative enzymes for lignocellulose degradation. Among them is glyoxal oxidase (MtGLOx), an extracellular oxidoreductase that oxidizes several aldehydes and α-hydroxy carbonyl substrates coupled to the reduction of O₂ to H₂O₂. This copper metalloprotein belongs to a class of enzymes called radical copper oxidases (CRO) and to the “auxiliary activities” subfamily AA5_1 that is based on the Carbohydrate-Active enZYmes (CAZy) database. Only a few members of this family have been characterized to date. Here, we report the recombinant production, characterization, and structure-function analysis of MtGLOx. Electron Paramagnetic Resonance (EPR) spectroscopy confirmed MtGLOx to be a radical-coupled copper complex and small angle X-ray scattering (SAXS) revealed an extended spatial arrangement of the catalytic and four N-terminal WSC domains. Furthermore, we demonstrate that methylglyoxal and 5-hydroxymethylfurfural (HMF), a fermentation inhibitor, are substrates for the enzyme. Full article

(This article belongs to the Special Issue Recent Advances in Biocatalysis and Metabolic Engineering for Biomanufacturing)

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9 pages, 4055 KiB

Open AccessArticle

Heteroatom (Nitrogen/Sulfur)-Doped Graphene as an Efficient Electrocatalyst for Oxygen Reduction and Evolution Reactions

by Jian Zhang¹, Jia Wang², Zexing Wu², Shuai Wang^2,*

, Yumin Wu^1,* and Xien Liu²

¹ College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao 266042, China

² State Key Laboratory Base of Eco-Chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science & Technology, Qingdao 266042, China

Catalysts 2018, 8(10), 475; https://doi.org/10.3390/catal8100475 - 19 Oct 2018

Cited by 21 | Viewed by 4622

Abstract

Carbon nanomaterials are potential materials with their intrinsic structure and property in energy conversion and storage. As the electrocatalysts, graphene is more remarkable in electrochemical reactions. Additionally, heteroatoms doping with metal-free materials can obtain unique structure and demonstrate excellent electrocatalytic performance. In this [...] Read more.

Carbon nanomaterials are potential materials with their intrinsic structure and property in energy conversion and storage. As the electrocatalysts, graphene is more remarkable in electrochemical reactions. Additionally, heteroatoms doping with metal-free materials can obtain unique structure and demonstrate excellent electrocatalytic performance. In this work, we proposed a facile method to prepare bifunctional electrocatalyst which was constructed by nitrogen, sulfur doped graphene (NSG), which demonstrate superior properties with high activity and excellent durability compared with Pt/C and IrO₂ for oxygen reduction (OR) and oxygen evolution (OE) reactions. Accordingly, these phenomena are closely related to the synergistic effect of doping with nitrogen and sulfur by rationally regulating the polarity of carbon in graphene. The current work expands the method towards carbon materials with heteroatom dopants for commercialization in energy-related reactions. Full article

(This article belongs to the Special Issue Immobilized Non-Precious Electrocatalysts for Advanced Energy Devices)

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12 pages, 6191 KiB

Open AccessArticle

Water: Friend or Foe in Catalytic Hydrogenation? A Case Study Using Copper Catalysts

by Alisa Govender^1,2, Abdul S. Mahomed¹

and Holger B. Friedrich^1,*

¹ School of Chemistry and Physics, University of KwaZulu-Natal, Durban 4041, South Africa

² Group Technology, Research & Technology, Sasol South Africa (Pty) Ltd., 1 Klasie Havenga Road, Sasolburg 1947, South Africa

Catalysts 2018, 8(10), 474; https://doi.org/10.3390/catal8100474 - 19 Oct 2018

Cited by 8 | Viewed by 3887

Abstract

Copper oxide supported on alumina and copper chromite were synthesized, characterized, and subsequently tested for their catalytic activity toward the hydrogenation of octanal. Thereafter, the impact of water addition on the conversion and selectivity of the catalysts were investigated. The fresh catalysts were [...] Read more.

Copper oxide supported on alumina and copper chromite were synthesized, characterized, and subsequently tested for their catalytic activity toward the hydrogenation of octanal. Thereafter, the impact of water addition on the conversion and selectivity of the catalysts were investigated. The fresh catalysts were characterized using X-ray diffraction (XRD), BET surface area and pore volume, SEM, TEM, TGA-DSC, ICP, TPR, and TPD. An initial catalytic testing study was carried out using the catalysts to optimize the temperature and the hydrogen-to-aldehyde ratio—which were found to be 160 °C and 2, respectively—to obtain the best conversion and selectivity to octanol prior to water addition. Water impact studies were carried out under the same conditions. The copper chromite catalyst showed no deactivation or change in octanol selectivity when water was added to the feed. The alumina-supported catalyst showed no change in conversion, but the octanol selectivity improved marginally when water was added. Full article

(This article belongs to the Special Issue Catalysts Deactivation, Poisoning and Regeneration)

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11 pages, 2578 KiB

Open AccessFeature PaperReview

α-Glucan Phosphorylase-Catalyzed Enzymatic Reactions Using Analog Substrates to Synthesize Non-Natural Oligo- and Polysaccharides

by Jun-ichi Kadokawa

Department of Chemistry, Biotechnology, and Chemical Engineering, Graduate School of Science and Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima 860-0065, Japan

Catalysts 2018, 8(10), 473; https://doi.org/10.3390/catal8100473 - 19 Oct 2018

Cited by 20 | Viewed by 5314

Abstract

As natural oligo- and polysaccharides are important biomass resources and exhibit vital biological functions, non-natural oligo- and polysaccharides with a well-defined structure can be expected to act as new functional materials with specific natures and properties. α-Glucan phosphorylase (GP) is one of the [...] Read more.

As natural oligo- and polysaccharides are important biomass resources and exhibit vital biological functions, non-natural oligo- and polysaccharides with a well-defined structure can be expected to act as new functional materials with specific natures and properties. α-Glucan phosphorylase (GP) is one of the enzymes that have been used as catalysts for practical synthesis of oligo- and polysaccharides. By means of weak specificity for the recognition of substrates by GP, non-natural oligo- and polysaccharides has precisely been synthesized. GP-catalyzed enzymatic glycosylations using several analog substrates as glycosyl donors have been carried out to produce oligosaccharides having different monosaccharide residues at the non-reducing end. Glycogen, a highly branched natural polysaccharide, has been used as the polymeric glycosyl acceptor and primer for the GP-catalyzed glycosylation and polymerization to obtain glycogen-based non-natural polysaccharide materials. Under the conditions of removal of inorganic phosphate, thermostable GP-catalyzed enzymatic polymerization of analog monomers occurred to give amylose analog polysaccharides. Full article

(This article belongs to the Section Biocatalysis)

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14 pages, 769 KiB

Open AccessArticle

Bacterial Biodegradation of 4-Monohalogenated Diphenyl Ethers in One-Substrate and Co-Metabolic Systems

by Amanda Pacholak¹

, Wojciech Smułek^1,*

, Agata Zdarta¹

, Agnieszka Zgoła-Grześkowiak²

and Ewa Kaczorek¹

¹ Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, 60-965 Poznan, Poland

² Institute of Chemistry and Technical Electrochemistry, Poznan University of Technology, Berdychowo 4, 60-965 Poznan Poland

Catalysts 2018, 8(10), 472; https://doi.org/10.3390/catal8100472 - 19 Oct 2018

Cited by 11 | Viewed by 3132

Abstract

The use of diphenyl ether (DE) and its 4-monohalogenated derivatives (4-HDE) as flame retardants, solvents, and substrates in biocide production significantly increases the risk of ecosystem contamination. Their removal is important from the point of view of environmental protection. The aim of this [...] Read more.

The use of diphenyl ether (DE) and its 4-monohalogenated derivatives (4-HDE) as flame retardants, solvents, and substrates in biocide production significantly increases the risk of ecosystem contamination. Their removal is important from the point of view of environmental protection. The aim of this study was to evaluate the degradation processes of DE and 4-HDE by enzymes of the environmental bacterial strains under one-substrate and co-metabolic conditions. The study is focused on the biodegradation of DE and 4-HDE, the enzymatic activity of microbial strains, and the cell surface properties after contact with compounds. The results show that the highest biodegradation (96%) was observed for 4-chlorodiphenyl ether in co-metabolic culture with P. fluorescens B01. Moreover, the activity of 1,2-dioxygenase during degradation of 4-monohalogenated diphenyl ethers was higher than that of 2,3-dioxygenase for each strain tested. The presence of a co-substrate provoked changes in dioxygenase activity, resulting in the increased activity of 1,2-dioxygenase. Moreover, the addition of phenol as a co-substrate allowed for increased biodegradation of the diphenyl ethers and noticeable modification of the cell surface hydrophobicity during the process. All observations within the study performed have led to a deeper understanding of the contaminants’ biodegradation processes catalyzed by environmental bacteria. Full article

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23 pages, 6711 KiB

Open AccessArticle

Rice Husk as an Inexpensive Renewable Immobilization Carrier for Biocatalysts Employed in the Food, Cosmetic and Polymer Sectors

by Marco Cespugli¹, Simone Lotteria¹, Luciano Navarini², Valentina Lonzarich², Lorenzo Del Terra², Francesca Vita³, Marina Zweyer⁴, Giovanna Baldini⁴, Valerio Ferrario¹, Cynthia Ebert¹ and Lucia Gardossi^1,*

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

² illycaffè S.p.A., via Flavia 110, 34147 Trieste, Italy

³ Department of Life Science, University of Trieste, 34127 Trieste, Italy

⁴ Department of Medical, Surgical, and Health Sciences, University of Trieste, 34149 Trieste, Italy

Catalysts 2018, 8(10), 471; https://doi.org/10.3390/catal8100471 - 19 Oct 2018

Cited by 38 | Viewed by 6489

Abstract

The high cost and environmental impact of fossil-based organic carriers represent a critical bottleneck to their use in large-scale industrial processes. The present study demonstrates the applicability of rice husk as inexpensive renewable carrier for the immobilization of enzymes applicable sectors where the [...] Read more.

The high cost and environmental impact of fossil-based organic carriers represent a critical bottleneck to their use in large-scale industrial processes. The present study demonstrates the applicability of rice husk as inexpensive renewable carrier for the immobilization of enzymes applicable sectors where the covalent anchorage of the protein is a pre-requisite for preventing protein contamination while assuring the recyclability. Rice husk was oxidized and then functionalized with a di-amino spacer. The morphological characterization shed light on the properties that affect the functionalization processes. Lipase B from Candida antarctica (CaLB) and two commercial asparaginases were immobilized covalently achieving higher immobilization yield than previously reported. All enzymes were immobilized also on commercial epoxy methacrylic resins and the CaLB immobilized on rice husk demonstrated a higher efficiency in the solvent-free polycondensation of dimethylitaconate. CaLB on rice husk appears particularly suitable for applications in highly viscous processes because of the unusual combination of its low density and remarkable mechanical robustness. In the case of the two asparaginases, the biocatalyst immobilized on rice husk performed in aqueous solution at least as efficiently as the enzyme immobilized on methacrylic resins, although the rice husk loaded a lower amount of protein. Full article

(This article belongs to the Special Issue Immobilization of Enzymes)

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12 pages, 2745 KiB

Open AccessArticle

Development of Biotransamination Reactions towards the 3,4-Dihydro-2H-1,5-benzoxathiepin-3-amine Enantiomers

by Daniel González-Martínez¹, Nerea Fernández-Sáez², Carlos Cativiela³, Joaquín M. Campos^2,4,*

and Vicente Gotor-Fernández^1,*

¹ Organic and Inorganic Chemistry Department, University of Oviedo, Avenida Julián Clavería 8, 33006 Oviedo, Spain

² Departamento de Química Farmacéutica y Orgánica, Facultad de Farmacia, c/Campus de Cartuja s/n, 18071 Granada, Spain

³ Departamento de Química Orgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC–Universidad de Zaragoza, 50009 Zaragoza, Spain

⁴ Instituto de Investigación Biosanitaria ibs.GRANADA, Complejo Hospitalario Universitario de Granada/Universidad de Granada, 18071 Granada, Spain

Catalysts 2018, 8(10), 470; https://doi.org/10.3390/catal8100470 - 19 Oct 2018

Cited by 6 | Viewed by 3862

Abstract

The stereoselective synthesis of chiral amines is an appealing task nowadays. In this context, biocatalysis plays a crucial role due to the straightforward conversion of prochiral and racemic ketones into enantiopure amines by means of a series of enzyme classes such as amine [...] Read more.

The stereoselective synthesis of chiral amines is an appealing task nowadays. In this context, biocatalysis plays a crucial role due to the straightforward conversion of prochiral and racemic ketones into enantiopure amines by means of a series of enzyme classes such as amine dehydrogenases, imine reductases, reductive aminases and amine transaminases. In particular, the stereoselective synthesis of 1,5-benzoxathiepin-3-amines have attracted particular attention since they possess remarkable biological profiles; however, their access through biocatalytic methods is unexplored. Amine transaminases are applied herein in the biotransamination of 3,4-dihydro-2H-1,5-benzoxathiepin-3-one, finding suitable enzymes for accessing both target amine enantiomers in high conversion and enantiomeric excess values. Biotransamination experiments have been analysed, trying to optimise the reaction conditions in terms of enzyme loading, temperature and reaction times. Full article

(This article belongs to the Special Issue Biocatalysis and Pharmaceuticals: A Smart Tool for Sustainable Development)

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18 pages, 5074 KiB

Open AccessArticle

Catalytic Performance of Gold Supported on Mn, Fe and Ni Doped Ceria in the Preferential Oxidation of CO in H₂-Rich Stream

by Shuna Li^1,2

, Huaqing Zhu², Zhangfeng Qin^2,*

, Yagang Zhang^2,3, Guofu Wang², Zhiwei Wu², Weibin Fan² and Jianguo Wang^2,*

¹ Key Laboratory for Surface Engineering and Remanufacturing in Shaanxi Province, School of Chemical Engineering, Xi’an University, Xi’an 710065, China

² State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan 030001, China

³ Department of Chemistry and Chemical Engineering, Xi’an University of Science and Technology, Xi’an 710054, China

Catalysts 2018, 8(10), 469; https://doi.org/10.3390/catal8100469 - 18 Oct 2018

Cited by 11 | Viewed by 4323

Abstract

Ceria supported metal catalysts often exhibit high activity in the preferential oxidation (PROX) of CO in H₂-rich stream and doping the ceria support with other metals proves to be rather effective in further enhancing their catalytic performance. Therefore, in this work, [...] Read more.

Ceria supported metal catalysts often exhibit high activity in the preferential oxidation (PROX) of CO in H₂-rich stream and doping the ceria support with other metals proves to be rather effective in further enhancing their catalytic performance. Therefore, in this work, a series of ceria materials doped with Mn, Fe and Ni (CeM, where M = Mn, Fe and Ni; M/Ce = 1/8) were synthesized by a modified hydrothermal method; with the doped ceria materials (CeM) as the support, various supported gold catalysts (Au/CeM) were prepared by the colloidal deposition method. The influence of metal dopant on the performance of these ceria materials supported with gold catalysts in CO PROX was then investigated in detail with the help of various characterization measures such as N₂ sorption, XRD, TEM, Raman spectroscopy, H₂-TPR, XPS and XAS. The results indicate that the incorporation of Mn, Fe and Ni metal ions into ceria can remarkably increase the amount of oxygen vacancies in the doped ceria support, which is beneficial for enhancing the reducibility of ceria, the metal-support interaction and the dispersion of gold species. Although the gold catalysts supported on various doped ceria are similar in the size and state of Au nanoparticles, the CO conversions for CO PROX over Au/CeMn, Au/CeFe and Au/CeNi catalysts are 65.6%, 93.0% and 48.2%, respectively, much higher than the value of 33.6% over the undoped Au/CeO₂ catalyst at ambient temperature. For CO PROX over the Au/CeNi catalyst, the conversion of CO remains near 100% at 60–130 °C, with a PROX selectivity to CO₂ of higher than 50%. The excellent performance of Au/CeNi catalyst can be ascribed to its large amount of oxygen vacancies and high reducibility on account of Ni incorporation. The insight shown in this work helps to clarify the doping effect of other metals on the physicochemical properties of ceria, which is then beneficial to building a structure-performance relation for ceria supported gold catalyst as well as developing a better catalyst for removing trace CO in the hydrogen stream and producing high purity hydrogen. Full article

(This article belongs to the Special Issue Heterogeneous Catalysis for Energy Conversion)

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10 pages, 3239 KiB

Open AccessArticle

Preparation of a Flower-Like Immobilized D-Psicose 3-Epimerase with Enhanced Catalytic Performance

by Lu Zheng¹, Yining Sun¹, Jing Wang², He Huang¹, Xin Geng¹, Yi Tong^3,* and Zhi Wang^1,*

¹ Key Laboratory of Molecular Enzymology and Engineering of Ministry of Education, College of Life Science, Jilin University, Changchun 130012, China

² Nutrition & Health Research Institute, COFCO Corporation, Beijing 102209, China

³ Jilin COFCO Biochemistry Co., Ltd. (National Engineering Research Center of Corn Deep Processing), Changchun 130033, China

Catalysts 2018, 8(10), 468; https://doi.org/10.3390/catal8100468 - 18 Oct 2018

Cited by 41 | Viewed by 5784

Abstract

In this present study, we proposed a smart biomineralization method for creating hybrid organic–inorganic nanoflowers using a Co²⁺-dependent enzyme (D-psicose 3-epimerase; DPEase) as the organic component and cobalt phosphate as the inorganic component. The prepared nanoflowers have many separated [...] Read more.

In this present study, we proposed a smart biomineralization method for creating hybrid organic–inorganic nanoflowers using a Co²⁺-dependent enzyme (D-psicose 3-epimerase; DPEase) as the organic component and cobalt phosphate as the inorganic component. The prepared nanoflowers have many separated petals that have a nanometer size. Under optimum conditions (60 °C and pH of 8.5), the nanoflower can display its maximum activity (36.2 U/mg), which is about 7.2-fold higher than free DPEase. Furthermore, the immobilized DPEase presents enhanced pH and thermal stabilities. The DPEase-nanoflower maintained about 90% of its activity after six reaction cycles, highlighting its excellent reusability. Full article

(This article belongs to the Special Issue Immobilization of Enzymes)

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12 pages, 1847 KiB

Open AccessArticle

Selective Dehydration of Glucose into 5-Hydroxymethylfurfural by Ionic Liquid-ZrOCl₂ in Isopropanol

by Yubo Ma^1,2, Lei Wang^1,3, Hongyi Li^4,*, Tianfu Wang^2,* and Ronghui Zhang⁵

¹ School of Chemical Engineering, Chongqing Chemical Industry Vocational College, Chongqing 401220, China

² Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi 830011, China

³ Department of chemistry and Chemical Engineering, Xinjiang University, Urumqi 830001, China

⁴ Xinjiang Quality of Products Supervision & Inspection Institute of Technology, Urumqi 830001, China

⁵ Guangdong Key Laboratory of Intelligent Transportation System, School of Engineering, Sun Yat-Sen University, Guangzhou 510275, China

Catalysts 2018, 8(10), 467; https://doi.org/10.3390/catal8100467 - 18 Oct 2018

Cited by 10 | Viewed by 4688

Abstract

In this work, a heterogeneous catalytic system consisting of [HO₂CMMIm]Cl and ZrOCl₂ in isopropanol is demonstrated to be effective for 5-hydroxymethylfurfural (HMF) synthesis with glucose as the feedstock. Various reaction conditions for HMF synthesis by glucose dehydration were investigated systematically. [...] Read more.

In this work, a heterogeneous catalytic system consisting of [HO₂CMMIm]Cl and ZrOCl₂ in isopropanol is demonstrated to be effective for 5-hydroxymethylfurfural (HMF) synthesis with glucose as the feedstock. Various reaction conditions for HMF synthesis by glucose dehydration were investigated systematically. Under optimized reaction conditions, as high as 43 mol% HMF yield could be achieved. Increasing the water content to a level below 3.17% led to the production of HMF with a higher yield, while a lower HMF yield was observed when the water content was increased above 3.17%. In addition, the data also showed that ZrOCl₂ could not only effectively convert glucose into intermediate species (which were not fructose, in contrast to the literature) but also catalyze the intermediate species’ in situ dehydration into HMF. [HO₂CMMIm]Cl was used to catalyze the intermediate species’ in situ conversion to HMF. The kinetics data showed that a temperature increase accelerated the intermediate species’ dehydration reaction rate. The reaction of glucose dehydration was a strong endothermal reaction. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass-Derived Molecules to Chemicals and Fuels)

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19 pages, 7438 KiB

Open AccessArticle

Comparing Photocatalytic Degradation of Gaseous Ethylbenzene Using N-doped and Pure TiO₂ Nano-Catalysts Coated on Glass Beads under Both UV and Visible Light Irradiation

by Morteza Kamaei^1,2, Hamid Rashedi^1,*, Seyed Mohammad Mehdi Dastgheib² and Saeideh Tasharrofi³

¹ School of Chemical Engineering, College of Engineering, University of Tehran, Tehran 1417614418, Iran

² Microbiology and Biotechnology Group, Environment and Biotechnology Research Division, Research Institute of Petroleum Industry, Tehran 1485733111, Iran

³ Ecology and Environmental Pollution Control Research Group, Environment and Biotechnology Research Division, Research Institute of Petroleum Industry, Tehran 1485733111, Iran

Catalysts 2018, 8(10), 466; https://doi.org/10.3390/catal8100466 - 18 Oct 2018

Cited by 37 | Viewed by 4414

Abstract

Volatile Organic Compounds (VOCs) are within the main industrial air pollutants whose release into the atmosphere is harmful to the ecosystem and human health. Gas-phase photocatalytic degradation of ethylbenzene, an aromatic VOC emitted from various sources, has been investigated in this study using [...] Read more.

Volatile Organic Compounds (VOCs) are within the main industrial air pollutants whose release into the atmosphere is harmful to the ecosystem and human health. Gas-phase photocatalytic degradation of ethylbenzene, an aromatic VOC emitted from various sources, has been investigated in this study using TiO₂ nanoparticle-coated glass beads in an annular photoreactor. To use visible light irradiation, TiO₂ nanoparticles were doped by nitrogen using urea. The results showed that nitrogen doping significantly increased the removal efficiency of ethylbenzene under visible light irradiation compared with the pure TiO₂, so that the removal efficiencies between 75–100% could be yielded for the initial ethylbenzene concentrations up to 0.13 g/m³ under visible light which could be useful for improving indoor air quality. The UV irradiated reactor needed less residence time and much higher removal efficiencies could be yielded at high initial concentrations. When the residence time under UV irradiation was one third of the same under visible light, the removal efficiency was more than 80% for the inlet concentrations up to 0.6 g/m³, whereas the removal efficiency under visible light was about 25% at this inlet concentration. Langmuir-Hinshelwood kinetic model could be well fitted to the photocatalytic reaction in both irradiation systems. Full article

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15 pages, 5854 KiB

Open AccessArticle

The Modification of Pt/Graphene Composites with Oxophilic Metal Bi (Bi₂O₃) and Its Dual-Functional Electro-Photo Catalytic Performance

by Yingli Wu^1,†, Xiuyun Duan^1,†, Zhongshui Li^1,2, Shuhong Xu¹, Yixin Xie¹, Yufei Lai¹ and Shen Lin^1,2,*

¹ College of Chemistry & Materials Science, Fujian Normal University, Fuzhou 350007, China

² Fujian Provincial Key Laboratory of Advanced Materials Oriented Chemical Engineering, Fuzhou 350007, China

^† These authors contributed equally to this work.

Catalysts 2018, 8(10), 465; https://doi.org/10.3390/catal8100465 - 17 Oct 2018

Cited by 7 | Viewed by 4806

Abstract

The Pt-Bi (Bi₂O₃)/GNs (PVP) composite was synthesized using aqueous solution synthesis and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and Raman spectroscopy. It was found that the [...] Read more.

The Pt-Bi (Bi₂O₃)/GNs (PVP) composite was synthesized using aqueous solution synthesis and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and Raman spectroscopy. It was found that the water-soluble polyvinyl pyrrolidone (PVP) helped to tune the particles’ morphology, resulting in a uniform distribution of Pt-Bi nanoclusters on the surface of graphene. Cyclic voltammetry, chronoamperometry and linear scanning voltammetry (LSV) were used to study the electrocatalytic properties towards a methanol oxidation reaction (MOR) and an oxygen reduction reaction (ORR). The results show that Pt-Bi (Bi₂O₃)/GNs (PVP) exhibits superior bifunctional electrocatalytic properties for both MOR and ORR, mainly due to the introduction of oxophilic Bi species and the better dispersion of the Pt-Bi nanoclusters. In particular, the electro-photo catalysis for both MOR and ORR occurred under simulated sunlight irradiation due to the existence of photo-responsive Bi species, which is helpful for converting solar energy into electric energy during a traditional electrocatalytic process. Full article

(This article belongs to the Special Issue Recent Advances in Pt-Based Catalysts: Theoretical and Experimental Results)

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17 pages, 1448 KiB

Open AccessPerspective

Oxidative Cleavage of Fatty Acid Derivatives for Monomer Synthesis

by Ana Soutelo-Maria^1,*, Jean-Luc Dubois^2,*

, Jean-Luc Couturier¹ and Giancarlo Cravotto³

¹ Arkema France, Centre de Recherche Rhône-Alpes, Rue Henri Moisson, F-69493 Pierre Bénite, France

² Arkema France, Rue d’Estienne d’Orves, F-92705 Colombes, France

³ Dipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Via P. Giuria 9, I-10125 Torino, Italy

Catalysts 2018, 8(10), 464; https://doi.org/10.3390/catal8100464 - 17 Oct 2018

Cited by 32 | Viewed by 12852

Abstract

Oxidative cleavage of fatty acids and fatty acid derivatives is a practical way to obtain bifunctional molecules that can be used in polycondensation reactions. Diacids, hydroxyacids, and amino acids can then be used to produce polyesters or polyamides and also a large range [...] Read more.

Oxidative cleavage of fatty acids and fatty acid derivatives is a practical way to obtain bifunctional molecules that can be used in polycondensation reactions. Diacids, hydroxyacids, and amino acids can then be used to produce polyesters or polyamides and also a large range of other products, such as lubricants and plasticizers. Ozonolysis has long been the sole industrial process for oxidative cleavage, but recently, routes using hydrogen peroxide as a clean oxidant have regained interest. Hydrogen peroxide is easier to use, but the kinetics of the catalyzed reactions are still slow. Although several catalytic systems have been described in the literature, tungsten-based catalysts are still the preferred choices. Different catalysts can trigger different mechanisms, such as a radical mechanism instead of a catalytic reaction. In addition, some side products and co-products often disregarded in the literature, such as shorted cleavage products, indicate the presence of side reactions that affect the quality of the final products. The oxidative cleavages in continuous and batch processes have significant differences, which are discussed with an illustration of our understanding of the process used by Matrica S.p.A. Full article

(This article belongs to the Special Issue New Developments in Heterogeneous Partial and Total Oxidation Catalysis)

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13 pages, 1757 KiB

Open AccessArticle

Interface-Controlled Pd Nanodot-Au Nanoparticle Colloids for Efficient Visible-Light-Induced Photocatalytic Suzuki-Miyaura Coupling Reaction

by Eunmi Kang, Hyeon Ho Shin and Dong-Kwon Lim^*

KU-KIST Graduate School of Converging Science and Technology, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Korea

Catalysts 2018, 8(10), 463; https://doi.org/10.3390/catal8100463 - 17 Oct 2018

Cited by 13 | Viewed by 4894

Abstract

Plasmonic nanostructures can be employed for performing photocatalytic reactions with visible-light illumination involving two different possible mechanisms, namely, the near-field enhancement and/or direct hot-electron transfer to the conduction band of an active catalyst. In this study, we demonstrate the significant contribution of a [...] Read more.

Plasmonic nanostructures can be employed for performing photocatalytic reactions with visible-light illumination involving two different possible mechanisms, namely, the near-field enhancement and/or direct hot-electron transfer to the conduction band of an active catalyst. In this study, we demonstrate the significant contribution of a graphene interface layer present between plasmonic nanoparticles and active catalysts (Pd nanodots) in enhancing the photocatalytic efficiency of Pd nanodots through an accelerated electron transfer process. The well-defined Pd-nanodot-modified gold nanoparticles with or without a graphene interface layer were prepared using a wet-chemical synthetic method. The role of the graphene interface was investigated by performing wavelength-dependent reduction studies using potassium hexacyanoferrate (III) in the presence of Pd-nanodot-modified cysteamine-modified AuNPs (Pd-cys-AuNPs), Pd-nanodot-modified graphene oxide (GO)-coated AuNPs (Pd-GO-AuNPs), and Pd-nanodot-modified reduced GO (rGO)-coated AuNPs (Pd-rGO-AuNPs). The fastest rate for the reduction of Fe³⁺ to Fe²⁺ was obtained with Pd-rGO-AuNPs because of the fast electron transfer achieved in the presence of the reduced graphene oxide layer. The highest catalytic activity for the visible-light induced C-C coupling reaction was obtained with Pd-rGO-AuNPs, indicating the role of the graphene interface layer. These results indicate that the design and use of engineered interfaces are of importance to achieve enhanced catalytic activity with plasmonic hybrid nanomaterials. Full article

(This article belongs to the Special Issue Catalysts for Suzuki–Miyaura Coupling Reaction)

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15 pages, 4784 KiB

Open AccessArticle

Atmospheric Air Plasma Treated SnS Films: An Efficient Electrocatalyst for HER

by Po-Chia Huang¹

, Sanjaya Brahma¹, Po-Yen Liu¹, Jow-Lay Huang^1,2,3, Sheng-Chang Wang^4,*, Shao-Chieh Weng¹

and Muhammad Omar Shaikh⁴

¹ Department of Materials Science and Engineering, National Cheng Kung University, Tainan 70101, Taiwan

² Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 70101, Taiwan

³ Hierarchical Green-Energy Materials (Hi-GEM) Research Center, National Cheng Kung University, Tainan 70101, Taiwan

⁴ Department of Mechanical Engineering, Southern Taiwan University of Science and Technology, Tainan 710, Taiwan

Catalysts 2018, 8(10), 462; https://doi.org/10.3390/catal8100462 - 17 Oct 2018

Cited by 7 | Viewed by 4121

Abstract

Here, we demonstrate the enhanced water-splitting performance (I = 10 mA/cm², Tafel slope = 60 mV/dec, onset potential = −80 mV) of atmospheric air plasma treated (AAPT) SnS thin films by the hydrogen evolution reaction (HER). The as prepared SnS films [...] Read more.

Here, we demonstrate the enhanced water-splitting performance (I = 10 mA/cm², Tafel slope = 60 mV/dec, onset potential = −80 mV) of atmospheric air plasma treated (AAPT) SnS thin films by the hydrogen evolution reaction (HER). The as prepared SnS films were subjected to Atmospheric Air Plasma Treatment (AAPT) which leads to formation of additional phases of Sn and SnO₂ at plasma powers of 150 W and 250 W, respectively. The AAPT treatment at 150 W leads to the evaporation of the S atoms as SO₂ generates a number of S-vacancies and Sn active edge sites over the surface of the SnS thin film. S-vacancies also create Sn active edge sites, surface p-type pinning that tunes the suitable band positions, and a hydrophilic surface which is beneficial for hydrogen adsorption/desorption. At high plasma power (250 W), the surface of the SnS films becomes oxidized and degrades the HER performance. These results demonstrate that AAPT (150 W) is capable of improving the HER performance of SnS thin films and our results indicate that SnS thin films can work as efficient electrocatalysts for HER. Full article

(This article belongs to the Special Issue Platinum-Free Electrocatalysts)

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15 pages, 3234 KiB

Open AccessArticle

Oxygen Reduction Reaction Electrocatalysis in Alkaline Electrolyte on Glassy-Carbon-Supported Nanostructured Pr₆O₁₁ Thin-Films

by Rakesh K. Sharma¹, Verónica Müller¹, Marian Chatenet^1,2,*

and Elisabeth Djurado^1,*

¹ LEPMI, Université Grenoble Alpes, CNRS, Grenoble-INP (Institute of Engineering Univ. Grenoble Alpes), LEPMI, F-38000 Grenoble, France

² Institut Universitaire de France, IUF, 75231 Paris Cedex 05, France

Catalysts 2018, 8(10), 461; https://doi.org/10.3390/catal8100461 - 17 Oct 2018

Cited by 7 | Viewed by 4733

Abstract

In this work, hierarchical nanostructured Pr₆O₁₁ thin-films of brain-like morphology were successfully prepared by electrostatic spray deposition (ESD) on glassy-carbon substrates. These surfaces were used as working electrodes in the rotating disk electrode (RDE) setup and characterized in alkaline electrolyte [...] Read more.

In this work, hierarchical nanostructured Pr₆O₁₁ thin-films of brain-like morphology were successfully prepared by electrostatic spray deposition (ESD) on glassy-carbon substrates. These surfaces were used as working electrodes in the rotating disk electrode (RDE) setup and characterized in alkaline electrolyte (0.1 M NaOH at 25 ± 2 °C) for the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR) for their potential application in alkaline electrolyzers or in alkaline fuel cells. The electrochemical performances of these electrodes were investigated as a function of their crystallized state (amorphous versus crystalline). Although none of the materials display spectacular HER and OER activity, the results show interesting performances of the crystallized sample towards the ORR with regards to this class of non-Pt group metal (non-PGM) electrocatalysts, the activity being, however, still far from a benchmark Pt/C electrocatalyst. Full article

(This article belongs to the Special Issue Catalysts for Polymer Membrane Fuel Cells)

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20 pages, 2202 KiB

Open AccessReview

Combined Cross-Linked Enzyme Aggregates as Biocatalysts

by Meng-Qiu Xu¹, Shuang-Shuang Wang², Li-Na Li¹, Jian Gao^2,* and Ye-Wang Zhang^1,2,*

¹ School of Pharmacy, United Pharmaceutical Institute of Jiangsu University and Shandong Tianzhilvye Biotechnology Co. Ltd., Jiangsu University, Zhenjiang 212013, China

² College of Petroleum and Chemical Engineering, Qinzhou University, Qinzhou 535011, China

Catalysts 2018, 8(10), 460; https://doi.org/10.3390/catal8100460 - 17 Oct 2018

Cited by 78 | Viewed by 9022

Abstract

Enzymes are efficient biocatalysts providing an important tool in many industrial biocatalytic processes. Currently, the immobilized enzymes prepared by the cross-linked enzyme aggregates (CLEAs) have drawn much attention due to their simple preparation and high catalytic efficiency. Combined cross-linked enzyme aggregates (combi-CLEAs) including [...] Read more.

Enzymes are efficient biocatalysts providing an important tool in many industrial biocatalytic processes. Currently, the immobilized enzymes prepared by the cross-linked enzyme aggregates (CLEAs) have drawn much attention due to their simple preparation and high catalytic efficiency. Combined cross-linked enzyme aggregates (combi-CLEAs) including multiple enzymes have significant advantages for practical applications. In this review, the conditions or factors for the preparation of combi-CLEAs such as the proportion of enzymes, the type of cross-linker, and coupling temperature were discussed based on the reaction mechanism. The recent applications of combi-CLEAs were also reviewed. Full article

(This article belongs to the Special Issue Recent Advances in Biocatalysis and Metabolic Engineering for Biomanufacturing)

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4 pages, 155 KiB

Open AccessEditorial

Selective Catalytic Reduction of NO_x

by Oliver Kröcher

Bioenergy and Catalysis Laboratory, Paul Scherrer Institut (PSI), 5232 Villigen, Switzerland

Catalysts 2018, 8(10), 459; https://doi.org/10.3390/catal8100459 - 17 Oct 2018

Cited by 24 | Viewed by 4153

Abstract

n/a Full article

(This article belongs to the Special Issue Selective Catalytic Reduction of NO_x)

64 pages, 21630 KiB

Open AccessReview

Recent Progress in the Transition Metal Catalyzed Synthesis of Indoles

by Raffaella Mancuso^*

and Renato Dalpozzo^*

Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87030 Arcavacata di Rende (Cs), Italy

Catalysts 2018, 8(10), 458; https://doi.org/10.3390/catal8100458 - 16 Oct 2018

Cited by 66 | Viewed by 11049

Abstract

Indole is the most frequently found heterocyclic core structures in pharmaceuticals, natural products, agrochemicals, dyes and fragrances. For about 150 years, chemists were absorbed in finding new and easier synthetic strategies to build this nucleus. Many books and reviews have been written, but [...] Read more.

Indole is the most frequently found heterocyclic core structures in pharmaceuticals, natural products, agrochemicals, dyes and fragrances. For about 150 years, chemists were absorbed in finding new and easier synthetic strategies to build this nucleus. Many books and reviews have been written, but the number of new syntheses that appear in the literature, make necessary continuous updates. This reviews aims to give a comprehensive overview on indole synthesis catalyzed by transition metals appeared in the literature in the years 2016 and 2017. Full article

(This article belongs to the Section Catalytic Materials)

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9 pages, 2329 KiB

Open AccessArticle

Ultrasonic-Assisted Synthesis of 2D α-Fe₂O₃@g-C₃N₄ Composite with Excellent Visible Light Photocatalytic Activity

by Huoli Zhang¹, Changxin Zhu¹, Jianliang Cao^1,*

, Qingjie Tang¹, Man Li¹, Peng Kang², Changliang Shi^1,* and Mingjie Ma¹

¹ School of Chemistry and Chemical Engineering, Henan Key Laboratory of Coal Green Conversion, The Collaboration Innovation Center of Coal Safety Production of Henan Province, Henan Polytechnic University, Jiaozuo 454003, China

² College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Catalysts 2018, 8(10), 457; https://doi.org/10.3390/catal8100457 - 16 Oct 2018

Cited by 33 | Viewed by 5387

Abstract

In this study, α-Fe₂O₃@g-C₃N₄ photocatalyst was synthesized using an ultrasonic assisted self-assembly preparation method. The α-Fe₂O₃@g-C₃N₄ photocatalyst had a stronger optical absorption in the visible light region than pure [...] Read more.

In this study, α-Fe₂O₃@g-C₃N₄ photocatalyst was synthesized using an ultrasonic assisted self-assembly preparation method. The α-Fe₂O₃@g-C₃N₄ photocatalyst had a stronger optical absorption in the visible light region than pure graphitic carbon nitride (g-C₃N₄). The Z-Scheme heterojunction between α-Fe₂O₃ and g-C₃N₄ significantly inhibited the recombination of electrons and holes. The photocatalytic performances of α-Fe₂O₃@g-C₃N₄ photocatalyst were excellent in degradation of Rhodamine B (RhB) under visible light irradiation. The results indicated that 5 wt.% α-Fe₂O₃/g-C₃N₄ had the optimal photocatalytic activity because two-dimension (2D) α-Fe₂O₃ nanosheets can be well-dispersed on the surface of g-C₃N₄ layers by ultrasonic assisted treatment. A possible photocatalytic mechanism is also discussed. Full article

(This article belongs to the Special Issue Semiconductor Catalysis)

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13 pages, 3395 KiB

Open AccessArticle

Oligomerization of Butene Mixture over NiO/Mesoporous Aluminosilicate Catalyst

by Donggun Lee¹, Hyeona Kim¹, Young-Kwon Park² and Jong-Ki Jeon^1,*

¹ Department of Chemical Engineering, Kongju National University, Cheonan 31080, Korea

² School of Environmental Engineering, University of Seoul, Seoul 02504, Korea

Catalysts 2018, 8(10), 456; https://doi.org/10.3390/catal8100456 - 16 Oct 2018

Cited by 8 | Viewed by 4442

Abstract

This study is aimed at preparing C₈–C₁₆ alkene through oligomerization of a butene mixture using nickel oxide supported on mesoporous aluminosilicate. Mesoporous aluminosilicate with an ordered structure was successfully synthesized from HZSM-5 zeolite by combining a top-down and a bottom-up [...] Read more.

This study is aimed at preparing C₈–C₁₆ alkene through oligomerization of a butene mixture using nickel oxide supported on mesoporous aluminosilicate. Mesoporous aluminosilicate with an ordered structure was successfully synthesized from HZSM-5 zeolite by combining a top-down and a bottom-up method. MMZ_ZSM-5 catalyst showed much higher butene conversion and C₈–C₁₆ yield in the butene oligomerization reaction than those with HZSM-5. This is attributed to the pore geometry of MMZ_ZSM-5, which is more beneficial for internal diffusion of reactants, reaction intermediates, and products. The ordered channel-like mesopores were maintained after the nickel-loading on MMZ_ZSM-5. The yield for C₈–C₁₆ hydrocarbons over NiO/MMZ_ZSM-5 was higher than that of MMZ_ZSM-5 catalyst, which seemed to be due to higher acid strength from a higher ratio of Lewis acid to Brønsted acid. The present study reveals that a mesoporous NiO/MMZ_ZSM-5 catalyst with a large amount of Lewis acid sites is one of the potential catalysts for efficient generation of aviation fuel through the butene oligomerization. Full article

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10 pages, 1806 KiB

Open AccessFeature PaperArticle

Photoelectrocatalytic vs. Photocatalytic Degradation of Organic Water Born Pollutants

by Ioannis Papagiannis¹, Georgia Koutsikou², Zacharias Frontistis³

, Ioannis Konstantinou², George Avgouropoulos¹

, Dionissios Mantzavinos³

and Panagiotis Lianos^3,*

¹ Department of Materials Science, University of Patras, 26500 Patras, Greece

² Department of Chemistry, University of Ioannina, 45110 Ioannina, Greece

³ Department of Chemical Engineering, University of Patras, 26500 Patras, Greece

Catalysts 2018, 8(10), 455; https://doi.org/10.3390/catal8100455 - 15 Oct 2018

Cited by 27 | Viewed by 4603

Abstract

The azo dye Basic Blue 41 was subjected to photocatalytic and photoelectrocatalytic degradation using nanopararticulate titania films deposited on either glass slides or Fluorine doped Tin Oxide (FTO) transparent electrodes. The degradation was carried out by irradiating titania films with weak ultraviolet (UVA) [...] Read more.

The azo dye Basic Blue 41 was subjected to photocatalytic and photoelectrocatalytic degradation using nanopararticulate titania films deposited on either glass slides or Fluorine doped Tin Oxide (FTO) transparent electrodes. The degradation was carried out by irradiating titania films with weak ultraviolet (UVA) radiation. The degradation was faster when using FTO as a titania support even without bias and was further accelerated under forward electric bias. This result was explained by enhanced electron-hole separation even in the case of the unbiased titania/FTO combination. This system for organic material photocatalytic degradation was also successfully applied to the degradation of the anti-inflammatory drug piroxicam, which demonstrated a well distinguished degradation behavior in going from a plain glass support to unbiased and biased FTO. The degradation pathway of piroxicam has been additionally studied using liquid chromatography-accurate mass spectrometry analysis. Full article

(This article belongs to the Special Issue New Trends in the Photocatalytic Removal of Organic Dyes)

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Catalysts, Volume 8, Issue 10 (October 2018) – 80 articles

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