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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (31 December 2018) | Viewed by 56631

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Dr. Giuseppe Bonura

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Institute for Advanced Energy Technologies "Nicola Giordano" ITAE, Italian National Research Council (CNR), 98126 Messina, Italy
Interests: heterogeneous catalysis; CO₂ hydrogenation; methanol/DME synthesis; temperature-programmed characterization; oxyfuels
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Special Issue Information

Dear Colleagues,

Supported materials represent effective catalysts for many catalytic reactions, including reforming processes, hydrocarbon conversion, hydrotreating, hydrogenation/dehydrogenation, selective oxidation, photocatalysis, pollution abatement, etc. Recent advances in creating hybrid/multifunctional or nanostructured supported materials also provide new possibilities in catalysis. Therefore, research is more and more interested in disclosing the new potentials of these materials for catalysis and the different routes available to tune their electronic states and active sites.

This Special Issue aims to encompass original research work and reviews on supported materials featuring innovative catalytic formulations, methodologies of synthesis, as well as peculiar catalytic applications, characterized by unusual activity-selectivity patterns, as the keys for enhanced energy efficiency, also meeting the pressing needs of sustainability process both from an environmental and economic point of view. The current and future challenges faced by these catalytic materials in terms of fundamental understanding and the development of novel industrial applications are also explored.

On the basis of such an outstanding topic, it is my pleasure to invite you to submit original papers, short communications and reviews for this Special Issue "Supported Materials for Catalytic Applications".

Dr. Giuseppe Bonura
Guest Editor

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Keywords

supported materials
catalytic applications
solid catalysts
innovative processes

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Published Papers (12 papers)

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Research

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11 pages, 2271 KiB

Open AccessArticle

Highly Efficient Liquid-Phase Hydrogenation of Naringin Using a Recyclable Pd/C Catalyst

by Jiamin Zhao, Ying Yuan, Xiuhong Meng, Linhai Duan and Rujin Zhou

Materials 2019, 12(1), 46; https://doi.org/10.3390/ma12010046 - 24 Dec 2018

Cited by 5 | Viewed by 4121

Abstract

A highly efficient liquid-phase hydrogenation reaction using a recyclable palladium on carbon (Pd/C) catalyst has been used for the transformation of naringin to its corresponding dihydrochalcone. The effects of various solvents on the hydrogenation process were studied, with water being identified as the optimal solvent. The analysis also revealed that sodium hydroxide (NaOH) can accumulate on the surface of the Pd/C catalyst in alcoholic solvents, leading to its inactivation. The higher solubility of NaOH in water implies that it remains in solution and does not accumulate on the Pd/C catalyst surface, ensuring the catalytic activity and stability. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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12 pages, 9212 KiB

Open AccessFeature PaperArticle

Copper Tridentate Schiff Base Complex Supported on SBA-15 as Efficient Nanocatalyst for Three-Component Reactions under Solventless Conditions

by Elham Sadat Diarjani, Fatemeh Rajabi, Asieh Yahyazadeh, Alain R. Puente-Santiago and Rafael Luque

Materials 2018, 11(12), 2458; https://doi.org/10.3390/ma11122458 - 4 Dec 2018

Cited by 15 | Viewed by 3764

Abstract

The anchorage of a supported copper Schiff base complex on SBA-15 materials provides highly efficient heterogeneous catalysts towards the solvent-free synthesis of dihydropyrimidinones derivatives via the Biginelli condensation reaction. The novel nanocatalysts exhibited a highly ordered mesostructure with a surface area of 346 m²g⁻¹ and an average pore diameter of 8.6 nm. Additionally, the supported copper nanocatalysts were reused at least ten times, remaining almost unchanged from the initial activity. Both the mesoporous scaffold and the tridentate Schiff base ligand contributed to the stabilization of copper species. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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11 pages, 4447 KiB

Open AccessArticle

Nanostructure Design and Catalytic Performance of Mo/ZnAl-LDH in Cationic Orchid X-BL Removal

by Yin Xu, Tingjiao Liu, Yang Li, Yun Liu and Fei Ge

Materials 2018, 11(12), 2390; https://doi.org/10.3390/ma11122390 - 27 Nov 2018

Cited by 9 | Viewed by 3496

Abstract

The nanostructure of ZnAl-layered double hydroxide (ZnAl-LDH) was designed to promote the catalytic performance of Mo-based ZnAl-LDH (Mo/ZnAl-LDH) catalysts, in a catalytic wet air oxidation (CWAO) process, under room temperature and pressure, in degradation of dye wastewater. Four most commonly used preparation methods, traditional precipitation (TP), hydrothermal synthesis (HS), sol-gel (SG), and urea co-precipitation (UC) were employed to prepare the ZnAl-LDH. The resulting Mo/ZnAl-LDH samples were contrasted through surface area, crystal structure, chemical state, and morphology. The degradation of cationic orchid X-BL, under room temperature and pressure, was developed to determine the catalytic activity of these Mo/ZnAl-LDH samples. The results showed that the nanostructure of ZnAl-LDH, prepared by HS, enhanced the adhesion of the catalytic active component, thus Mo/ZnAl-LDH had the highest catalytic activity of 84.2% color removal efficiency and 73.9% total organic carbon removal efficiency. Specific Mo species, such as Na₂Mo₂O₇, Mo dispersion, and O²⁻ ions were proved to be related with catalytic performance. These findings preliminarily clarified that LDHs preparation methods make a difference in the performance of Mo/LDHs. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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14 pages, 2708 KiB

Open AccessArticle

In Situ FT-IR Characterization of CuZnZr/Ferrierite Hybrid Catalysts for One-Pot CO₂-to-DME Conversion

by Ivana Miletto, Enrico Catizzone, Giuseppe Bonura, Chiara Ivaldi, Massimo Migliori, Enrica Gianotti, Leonardo Marchese, Francesco Frusteri and Girolamo Giordano

Materials 2018, 11(11), 2275; https://doi.org/10.3390/ma11112275 - 14 Nov 2018

Cited by 32 | Viewed by 4363

Abstract

CO₂ hydrogenation to dimethyl ether (DME) is a promising strategy to drive the current chemical industry towards a low-carbon scenario since DME can be used as an eco-friendly fuel as well as a platform molecule for chemical production. A Cu‒ZnO‒ZrO₂/ferrierite (CZZ/FER) hybrid grain was recently proposed as a catalyst for CO₂-to-DME one-pot conversion exhibiting high DME productivity thanks to the unique shape-selectivity offered by ferrierite zeolite. Nevertheless, such a catalyst deactivates but no direct evidence has been reported of activity loss over time. In this work, CZZ/FER catalysts with different acidity levels were characterized with the FTIR technique before and after reactions, aiming to give new insights about catalyst deactivation. Results show that activity loss can be related to both (i) copper particle sintering, which decreases CO₂ activation towards methanol, and (ii) acidity loss due to H⁺/Cu²⁺ ion exchange. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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11 pages, 8639 KiB

Open AccessCommunication

A Rational Design of the Sintering-Resistant Au-CeO₂ Nanoparticles Catalysts for CO Oxidation: The Influence of H₂ Pretreatments

by Yuqi Sun, Wei Liu, Miao Tian, Liguo Wang and Zhongpeng Wang

Materials 2018, 11(10), 1952; https://doi.org/10.3390/ma11101952 - 12 Oct 2018

Cited by 16 | Viewed by 3287

Abstract

The redox pretreatment of samples is one of the crucial ways of altering the catalytic properties of the supported noble metal materials in many heterogeneous reactions. Here, H₂-reducing pretreatment is reported to enhance the thermal stability of Au-CeO₂ catalysts prepared by the deposition–precipitation method and calcination at 600 °C for CO oxidation. In order to understand the improved activity and thermal stability, a series of techniques were used to characterize the physico-chemical changes of the catalyst samples. H₂ pretreatment may lead to: (i) a strong metal–support interaction (SMSI) between Au nanoparticles (NPs) and CeO₂, evidenced by the particular coverage of Au NPs by CeO₂, electronic interactions and CO adsorption changes. (ii) the production of surface bicarbonates which can accelerate CO oxidation. As a result, the H₂ pretreatment makes the Au NPs more resistant to sintering at high temperature and enhances the CO oxidation activity. Furthermore, this reduction pretreatment strategy may provide a potential approach to enhance the thermal-stability of other supported noble metal catalysts. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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24 pages, 5871 KiB

Open AccessArticle

Study of PtO_x/TiO₂ Photocatalysts in the Photocatalytic Reforming of Glycerol: The Role of Co-Catalyst Formation

by Katalin Majrik, Zoltán Pászti, László Korecz, László Trif, Attila Domján, Giuseppe Bonura, Catia Cannilla, Francesco Frusteri, András Tompos and Emília Tálas

Materials 2018, 11(10), 1927; https://doi.org/10.3390/ma11101927 - 10 Oct 2018

Cited by 22 | Viewed by 3982

Abstract

In this study, relationships between preparation conditions, structure, and activity of Pt-containing TiO₂ photocatalysts in photoinduced reforming of glycerol for H₂ production were explored. Commercial Aerolyst^® TiO₂ (P25) and homemade TiO₂ prepared by precipitation-aging method were used as semiconductors. Pt co-catalysts were prepared by incipient wetness impregnation from aqueous solution of Pt(NH₃)₄(NO₃)₂ and activated by calcination, high temperature hydrogen, or nitrogen treatments. The chemico-physical and structural properties were evaluated by XRD, ¹H MAS NMR, ESR, XPS, TG-MS and TEM. The highest H₂ evolution rate was observed over P25 based samples and the H₂ treatment resulted in more active samples than the other co-catalyst formation methods. In all calcined samples, reduction of Pt occurred during the photocatalytic reaction. Platinum was more easily reducible in all of the P25 supported samples compared to those obtained from the more water-retentive homemade TiO₂. This result was related to the negative effect of the adsorbed water content of the homemade TiO₂ on Pt reduction and on particle growth during co-catalyst formation. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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15 pages, 6862 KiB

Open AccessArticle

Tungsten-Embedded Graphene: Theoretical Study on a Potential High-Activity Catalyst toward CO Oxidation

by Guoliang Dai, Lei Chen and Xin Zhao

Materials 2018, 11(10), 1848; https://doi.org/10.3390/ma11101848 - 28 Sep 2018

Cited by 14 | Viewed by 2914

Abstract

The oxidation mechanism of CO on W-embedded graphene was investigated by M06-2X density functional theory. Two models of tungsten atom embedded in single and double vacancy (W-SV and W-DV) graphene sheets were considered. It was found that over W-SV-graphene and W-DV-graphene, the oxidation of CO prefers to Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanism, respectively. The two surfaces exhibit different catalytic activity during different reaction stages. The present results imply that W-embedded graphene is a promising catalyst for CO oxidation, which provides a useful reference for the design of a high-efficiency catalyst in detecting and removing of toxic gases. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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13 pages, 1887 KiB

Open AccessArticle

In Situ DRIFTS Studies of NH₃-SCR Mechanism over V₂O₅-CeO₂/TiO₂-ZrO₂ Catalysts for Selective Catalytic Reduction of NO_x

by Yaping Zhang, Xiupeng Yue, Tianjiao Huang, Kai Shen and Bin Lu

Materials 2018, 11(8), 1307; https://doi.org/10.3390/ma11081307 - 28 Jul 2018

Cited by 47 | Viewed by 5866

Abstract

TiO₂-ZrO₂ (Ti-Zr) carrier was prepared by a co-precipitation method and 1 wt. % V₂O₅ and 0.2 CeO₂ (the Mole ratio of Ce to Ti-Zr) was impregnated to obtain the V₂O₅-CeO₂/TiO [...] Read more.

TiO₂-ZrO₂ (Ti-Zr) carrier was prepared by a co-precipitation method and 1 wt. % V₂O₅ and 0.2 CeO₂ (the Mole ratio of Ce to Ti-Zr) was impregnated to obtain the V₂O₅-CeO₂/TiO₂-ZrO₂ catalyst for the selective catalytic reduction of NO_x by NH₃. The transient activity tests and the in situ DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) analyses were employed to explore the NH₃-SCR (selective catalytic reduction) mechanism systematically, and by designing various conditions of single or mixing feeding gas and pre-treatment ways, a possible pathway of NO_x reduction was proposed. It was found that NH₃ exhibited a competitive advantage over NO in its adsorption on the catalyst surface, and could form an active intermediate substance of -NH₂. More acid sites and intermediate reaction species (-NH₂), at lower temperatures, significantly promoted the SCR activity of the V₂O₅-0.2CeO₂/TiO₂-ZrO₂ catalyst. The presence of O₂ could promote the conversion of NO to NO₂, while NO₂ was easier to reduce. The co-existence of NH₃ and O₂ resulted in the NH₃ adsorption strength being lower, as compared to tests without O₂, since O₂ could occupy a part of the active site. Due to CeO_2’s excellent oxygen storage-release capacity, NH₃ adsorption was weakened, in comparison to the 1 wt. % V₂O₅-0.2CeO₂/TiO₂-ZrO₂ catalyst. If NO_x were to be pre-adsorbed in the catalyst, the formation of nitrate and nitro species would be difficult to desorb, which would greatly hinder the SCR reaction. All the findings concluded that NH₃-SCR worked mainly through the Eley-Rideal (E-R) mechanism. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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14 pages, 6007 KiB

Open AccessArticle

Metal/Carbon Hybrid Nanostructures Produced from Plasma-Enhanced Chemical Vapor Deposition over Nafion-Supported Electrochemically Deposited Cobalt Nanoparticles

by Mohammad Islam, Amine Achour, Khalid Saeed, Mohammed Boujtita, Sofia Javed and Mohamed Abdou Djouadi

Materials 2018, 11(5), 687; https://doi.org/10.3390/ma11050687 - 27 Apr 2018

Cited by 4 | Viewed by 4330

Abstract

In this work, we report development of hybrid nanostructures of metal nanoparticles (NP) and carbon nanostructures with strong potential for catalysis, sensing, and energy applications. First, the etched silicon wafer substrates were passivated for subsequent electrochemical (EC) processing through grafting of nitro phenyl groups using para-nitrobenzene diazonium (PNBT). The X-ray photoelectron spectroscope (XPS) and atomic force microscope (AFM) studies confirmed presence of few layers. Cobalt-based nanoparticles were produced over dip or spin coated Nafion films under different EC reduction conditions, namely CoSO₄ salt concentration (0.1 M, 1 mM), reduction time (5, 20 s), and indirect or direct EC reduction route. Extensive AFM examination revealed NP formation with different attributes (size, distribution) depending on electrochemistry conditions. While relatively large NP with >100 nm size and bimodal distribution were obtained after 20 s EC reduction in H₃BO₃ following Co²⁺ ion uptake, ultrafine NP (<10 nm) could be produced from EC reduction in CoSO₄ and H₃BO₃ mixed solution with some tendency to form oxides. Different carbon nanostructures including few-walled or multiwalled carbon nanotubes (CNT) and carbon nanosheets were grown in a C₂H₂/NH₃ plasma using the plasma-enhanced chemical vapor deposition technique. The devised processing routes enable size controlled synthesis of cobalt nanoparticles and metal/carbon hybrid nanostructures with unique microstructural features. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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16 pages, 6517 KiB

Open AccessArticle

Catalytic Oxidation of Soot on a Novel Active Ca-Co Dually-Doped Lanthanum Tin Pyrochlore Oxide

by Lijie Ai, Zhongpeng Wang, Chenchen Cui, Wei Liu and Liguo Wang

Materials 2018, 11(5), 653; https://doi.org/10.3390/ma11050653 - 24 Apr 2018

Cited by 20 | Viewed by 3971

Abstract

A novel active Ca-Co dually-doping pyrochlore oxide La_2−xCa_xSn_2−yCo_yO₇ catalyst was synthesized by the sol-gel method for catalytic oxidation of soot particulates. The microstructure, atomic valence, reduction, and adsorption performance were investigated by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), H₂-TPR (temperature-programmed reduction), and in situ diffuse reflection infrared Fourier transformed (DRIFTS) techniques. Temperature programmed oxidation (TPO) tests were performed with the mixture of soot-catalyst under tight contact conditions to evaluate the catalytic activity for soot combustion. Synergetic effect between Ca and Co improved the structure and redox properties of the solids, increased the surface oxygen vacancies, and provided a suitable electropositivity for oxide, directly resulting in the decreased ignition temperature for catalyzed soot oxidation as low as 317 °C. The presence of NO in O₂ further promoted soot oxidation over the catalysts with the ignition temperature decreased to about 300 °C. The DRIFTS results reveal that decomposition of less stable surface nitrites may account for NO₂ formation in the ignition period of soot combustion, which thus participate in the auxiliary combustion process. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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Review

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22 pages, 1474 KiB

Open AccessReview

Butanol Synthesis Routes for Biofuel Production: Trends and Perspectives

by Beata Kolesinska, Justyna Fraczyk, Michal Binczarski, Magdalena Modelska, Joanna Berlowska, Piotr Dziugan, Hubert Antolak, Zbigniew J. Kaminski, Izabela A. Witonska and Dorota Kregiel

Materials 2019, 12(3), 350; https://doi.org/10.3390/ma12030350 - 23 Jan 2019

Cited by 96 | Viewed by 9885

Abstract

Butanol has similar characteristics to gasoline, and could provide an alternative oxygenate to ethanol in blended fuels. Butanol can be produced either via the biotechnological route, using microorganisms such as clostridia, or by the chemical route, using petroleum. Recently, interest has grown in the possibility of catalytic coupling of bioethanol into butanol over various heterogenic systems. This reaction has great potential, and could be a step towards overcoming the disadvantages of bioethanol as a sustainable transportation fuel. This paper summarizes the latest research on butanol synthesis for the production of biofuels in different biotechnological and chemical ways; it also compares potentialities and limitations of these strategies. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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15 pages, 2592 KiB

Open AccessReview

A Review on Flexible and Transparent Energy Storage System

by Jie Li, Qianqian Jiang, Nannan Yuan and Jianguo Tang

Materials 2018, 11(11), 2280; https://doi.org/10.3390/ma11112280 - 14 Nov 2018

Cited by 25 | Viewed by 5665

Abstract

Due to the broad application prospect, flexible and transparent electronic device has been widely used in portable wearable devices, energy storage smart window and other fields, which owns many advantages such as portable, foldable, small-quality, low-cost, good transparency, high performance and so on. All these electronic devices are inseparable from the support of energy storage device. Energy storage device, like lithium-ion battery and super capacitor, also require strict flexibility and transparency as the energy supply equipment of electronic devices. Here, we demonstrate the development and applications of flexible and transparent lithium-ion battery and super capacitor. In particular, carbon nanomaterials are widely used in flexible and transparent electronic device, due to their excellent optical and electrical properties and good mechanical properties. For example, carbon nanotubes with high electrical conductivity and low density have been widely reported by researchers. Otherwise, graphene as an emerging two-dimensional material with electrical conductivity and carrier mobility attracts comparatively more attention than that of other carbon nanomaterials. Substantial effort has been put on the research for graphene-based energy storage system by researchers from all over the world. But, there is still a long way to accomplish this goal of improving the performance for stretchable and transparent electronic device due to the existing technical conditions. Full article

(This article belongs to the Special Issue Supported Materials for Catalytic Application)

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