Special Issue "Advances in Heterocatalysis by Nanomaterials"

A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (31 August 2019).

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Prof. Dr. Ioannis V. Yentekakis
Website
Guest Editor
Physical Chemistry and Chemical Processes Laboratory, School of Environmental Engineering, TECHNICAL UNIVERSITY OF CRETE (TUC), Greece
Interests: physical chemistry; heterogeneous catalysi s; environmental catalysis; catalyst promotion; chemical reaction engineering and thermodynamics; surfaces and interfaces; electrochemistry; fuel cells; nanomaterials and nanotechnology
Special Issues and Collections in MDPI journals
Prof. Dr. Wei(Willy) Chu
Website
Guest Editor
Key Laboratory of Green Chemistry and Technology of Ministry of Education (MOE), College of Chemical Engineering, Sichuan University, Sichuan 610065, China
Interests: applied Catalysis; environmental catalysis and energy materials; nano functional materials; fischer tropsch synthesis and clean energy; heterogeneous catalysis; porphyrins and fine chemicals

Special Issue Information

Dear Colleagues,

Heterogeneous catalysis played, and will continue to play, a major key role in industrial processes for large-scale synthesis of commodity chemicals of global importance, and in catalytic systems that possess a critical role in energy generation and environmental protection approaches. Numerous eco-friendly and cost-efficient applications of heterogeneous catalysis involve, for example, De-NOx, De-N2O and VOCs emission control systems, waste treatment, photocatalytic, bio-refinery, CO2 utilization and fuel cells applications, as well as hydrocarbon processing for H2, added-value chemicals and liquid fuels production, among many others. 

Surface-induced and/or support-mediated promotion of catalytic performance through metal–metal and metal–support interactions, as well as surface morphology (size and shape of catalytic particles) are issues that have crucial role in determining and improving the efficiency and robustness of heterogeneous catalytic materials for specific applications. Great advances have been recorded on these issues as a result of the ongoing progress in nanotechnology that provides efficient approaches and routes for the design of nano-structured composite materials subjected to enhanced metal-metal and metal-support interactions; fine-tuning of critical physicochemical properties, such as electron affinity (work function), oxidation state and morphology of catalyst nanoparticles is therefore achieved, enabling catalytic activity, selectivity and time-on-stream stability optimization of the materials for reactions under consideration. 

The titled Special Issue aims to cover current experimental and/or computational (e.g., DFT calculations) studies, in the field of heterogeneous catalysis by nanomaterials. Advanced synthesis routes, characterizations, activity/stability evaluation and fundamental understanding of structure-activity relationships or possible metal–metal and metal–support interactions under desired reactions, are very welcome.

Prof. Dr. Ioannis V. Yentekakis
Prof. Dr. Wei(Willy) Chu
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Nanomaterials is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Heterogeneous catalysis
  • Nano-structured catalysts
  • Synthesis routes
  • Structural textural physicochemical characterizations
  • Catalysts promotion
  • Metal-metal and metal-support interactions
  • Nanomaterials for energy applications
  • Nanomaterials for emissions control applications
  • Environmental catalysis applications
  • Nano-structured photocatalysts
  • Electrocatalytic nanomaterials
  • Electrodes and fuel cells

Published Papers (11 papers)

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Editorial

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Open AccessEditorial
Advances in Heterocatalysis by Nanomaterials
Nanomaterials 2020, 10(4), 609; https://doi.org/10.3390/nano10040609 - 26 Mar 2020
Abstract
Heterogeneous catalysis played, plays, and will continue to play a major key role in industrial processes for the large-scale synthesis of commodity chemicals of global importance [...] Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available

Research

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Open AccessArticle
An Emerging Visible-Light Organic–Inorganic Hybrid Perovskite for Photocatalytic Applications
Nanomaterials 2020, 10(1), 115; https://doi.org/10.3390/nano10010115 - 07 Jan 2020
Cited by 2
Abstract
The development of visible-light active photocatalysts is a current challenge especially energy and environmental-related fields. Herein, methylammonium lead iodide perovskite (MAIPb) was chosen as the novel semiconductor material for its ability of absorbing visible-light. An easily reproducible and efficient method was employed to [...] Read more.
The development of visible-light active photocatalysts is a current challenge especially energy and environmental-related fields. Herein, methylammonium lead iodide perovskite (MAIPb) was chosen as the novel semiconductor material for its ability of absorbing visible-light. An easily reproducible and efficient method was employed to synthesize the as-mentioned material. The sample was characterized by various techniques and has been used as visible-light photocatalyst for degradation of two model pollutants: rhodamine B (RhB) and methylene-blue (MB). The photo-degradation of RhB was found to achieve about 65% after 180 min of treatment. Moreover, the efficiency was enhanced to 100% by assisting the process with a small amount of H2O2. The visible-light activity of the photocatalyst was attributed to its ability to absorb light as well as to enhance separation of photogenerated carriers. The main outcome of the present work is the investigation of a hybrid perovskite as photocatalyst for wastewater treatment. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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Open AccessCommunication
The Synergistic Effect of Acidic Properties and Channel Systems of Zeolites on the Synthesis of Polyoxymethylene Dimethyl Ethers from Dimethoxymethane and Trioxymethylene
Nanomaterials 2019, 9(9), 1192; https://doi.org/10.3390/nano9091192 - 23 Aug 2019
Cited by 1
Abstract
A series of zeolites with different topology structures, including SAPO-34, SUZ-4, ZSM-5, USY, MOR, and beta, were used to synthesize polyoxymethylene dimethyl ethers (PODEn) from dimethoxymethane (DMM) and trioxymethylene (TOM). The influence of acidic properties and channel systems were studied by [...] Read more.
A series of zeolites with different topology structures, including SAPO-34, SUZ-4, ZSM-5, USY, MOR, and beta, were used to synthesize polyoxymethylene dimethyl ethers (PODEn) from dimethoxymethane (DMM) and trioxymethylene (TOM). The influence of acidic properties and channel systems were studied by activity evaluation, characterization, and theoretical calculation. The results confirmed that pore mouth diameter larger than a TOM molecule was an essential prerequisite for the synthesis of PODEn over zeolites, and the synergistic effect between medium-strong Brønsted acid sites (Brønsted MAS) and the maximal space of zeolites available determined the catalytic performance of all studied zeolites. DMM and TOM were firstly decomposed into methoxymethoxy groups (MMZ) and monomer CH2O over Brønsted MAS. Subsequently, the steric constraint of the maximum included sphere, with an appropriate size in zeolite channels, can promote the combination of CH2O and MMZ to form transition species ZO(CH2O)nCH3, which reacted with the methyl-end group to form PODEn over Brønsted MAS. Moreover, the reaction temperature showed different effects on the product selectivity and distribution, which also mainly depends on the size of the maximum space available in zeolite channels. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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Open AccessArticle
Enzymatic Conversion of Oleuropein to Hydroxytyrosol Using Immobilized β-Glucosidase on Porous Carbon Cuboids
Nanomaterials 2019, 9(8), 1166; https://doi.org/10.3390/nano9081166 - 14 Aug 2019
Cited by 2
Abstract
In the present study, we developed novel β-glucosidase-based nano-biocatalysts for the bioconversion of oleuropein to hydroxytyrosol. Using non-covalent or covalent immobilization approaches, β-glucosidases from almonds and Thermotoga maritima were attached for the first time on oxidized and non-oxidized porous carbon cuboids [...] Read more.
In the present study, we developed novel β-glucosidase-based nano-biocatalysts for the bioconversion of oleuropein to hydroxytyrosol. Using non-covalent or covalent immobilization approaches, β-glucosidases from almonds and Thermotoga maritima were attached for the first time on oxidized and non-oxidized porous carbon cuboids (PCC). Various methods were used for the characterization of the bio-nanoconjugates, such as Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and fluorescence spectroscopy. The oxidation state of the nanο-support and the immobilization procedure play a key role for the immobilization efficiency or the catalytic activity of the immobilized β-glucosidases. The nano-biocatalysts were successfully used for the hydrolysis of oleuropein, which leads to the formation of its bioactive derivative, hydroxytyrosol (up to 2.4 g L−1), which is a phenolic compound with numerous health benefits. The bio-nanoconjugates exhibited high thermal and operational stability (up to 240 h of repeated use), which indicated that they are efficient tools for various bio-transformations. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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Open AccessArticle
MXene Boosted CoNi-ZIF-67 as Highly Efficient Electrocatalysts for Oxygen Evolution
Nanomaterials 2019, 9(5), 775; https://doi.org/10.3390/nano9050775 - 20 May 2019
Cited by 8
Abstract
Oxygen evolution reaction (OER) is a pivotal step for many sustainable energy technologies, and exploring inexpensive and highly efficient electrocatalysts is one of the most crucial but challenging issues to overcome the sluggish kinetics and high overpotentials during OER. Among the numerous electrocatalysts, [...] Read more.
Oxygen evolution reaction (OER) is a pivotal step for many sustainable energy technologies, and exploring inexpensive and highly efficient electrocatalysts is one of the most crucial but challenging issues to overcome the sluggish kinetics and high overpotentials during OER. Among the numerous electrocatalysts, metal-organic frameworks (MOFs) have emerged as promising due to their high specific surface area, tunable porosity, and diversity of metal centers and functional groups. It is believed that combining MOFs with conductive nanostructures could significantly improve their catalytic activities. In this study, an MXene supported CoNi-ZIF-67 hybrid ([email protected]3C2Tx) was synthesized through the in-situ growth of bimetallic CoNi-ZIF-67 rhombic dodecahedrons on the Ti3C2Tx matrix via a coprecipitation reaction. It is revealed that the inclusion of the MXene matrix not only produces smaller CoNi-ZIF-67 particles, but also increases the average oxidation of Co/Ni elements, endowing the [email protected]3C2Tx as an excellent OER electrocatalyst. The effective synergy of the electrochemically active CoNi-ZIF-67 phase and highly conductive MXene support prompts the hybrid to process a superior OER catalytic activity with a low onset potential (275 mV vs. a reversible hydrogen electrode, RHE) and Tafel slope (65.1 mV∙dec−1), much better than the IrO2 catalysts and the pure CoNi-ZIF-67. This work may pave a new way for developing efficient non-precious metal catalyst materials. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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Open AccessArticle
Synergistic Effect of Oxygen Vacancies and Ni Species on Tuning Selectivity of Ni/ZrO2 Catalyst for Hydrogenation of Maleic Anhydride into Succinic Anhydride and γ-Butyrolacetone
Nanomaterials 2019, 9(3), 406; https://doi.org/10.3390/nano9030406 - 11 Mar 2019
Cited by 4
Abstract
ZrO2 nanoparticles, ZrO2 (P) and ZrO2 (H), with different tetragonal phase contents, were prepared. ZrO2 (P) possessed higher tetragonal phase content than ZrO2 (H). Ni/ZrO2 catalysts (10% (w/w)), using ZrO2 (P) and [...] Read more.
ZrO2 nanoparticles, ZrO2 (P) and ZrO2 (H), with different tetragonal phase contents, were prepared. ZrO2 (P) possessed higher tetragonal phase content than ZrO2 (H). Ni/ZrO2 catalysts (10% (w/w)), using ZrO2 (P) and ZrO2 (H) as supports, were prepared using an impregnation method, and were characterized using XRD, Raman, H2-TPR, XPS, and H2-TPD techniques. Their catalytic performance in maleic anhydride hydrogenation was tested. The Ni/ZrO2 (P) catalyst exhibited stronger metal-support interactions than the Ni/ZrO2 (H) catalyst because of its higher number of oxygen vacancies and the low-coordinated oxygen ions on its surface. Consequently, smaller Ni crystallites and a higher C=C hydrogenation activity for maleic anhydride to succinic anhydride were obtained over a Ni/ZrO2 (P) catalyst. However, the C=O hydrogenation activity of Ni/ZrO2 (P) catalyst was much lower than that of the Ni/ZrO2 (H) catalyst. A 43.5% yield of γ-butyrolacetone was obtained over the Ni/ZrO2 (H) catalyst at 210 °C and 5 MPa of H2 pressure, while the yield of γ-butyrolactone was only 2.8% over the Ni/ZrO2 (P) catalyst under the same reaction conditions. In situ FT-IR characterization demonstrated that the high C=O hydrogenation activity for the Ni/ZrO2 (H) catalyst could be attributed to the surface synergy between active metallic nickel species and relatively electron-deficient oxygen vacancies. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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Open AccessArticle
Chitosan-MgO Nanocomposite: One Pot Preparation and Its Utility as an Ecofriendly Biocatalyst in the Synthesis of Thiazoles and [1,3,4]thiadiazoles
Nanomaterials 2018, 8(11), 928; https://doi.org/10.3390/nano8110928 - 08 Nov 2018
Cited by 7
Abstract
A chitosan-MgO hybrid nanocomposite was prepared using a simple chemical precipitation method and characterized using Fourier transform spectroscopy (FTIR), elemental analysis (EDX), and scanning electron microscopy (SEM). The nanocomposite was served as a powerful ecofriendly basic catalyst under microwave irradiation in the synthesis [...] Read more.
A chitosan-MgO hybrid nanocomposite was prepared using a simple chemical precipitation method and characterized using Fourier transform spectroscopy (FTIR), elemental analysis (EDX), and scanning electron microscopy (SEM). The nanocomposite was served as a powerful ecofriendly basic catalyst under microwave irradiation in the synthesis of two novel series of 5-arylazo-2-hydrazonothiazoles 4aj and 2-hydrazono[1,3,4]thiadiazoles 8ad, incorporating a sulfonamide group. The structures of the synthesized products were elucidated by spectral data and elemental analyses. Also, their yield percentages were calculated using triethylamine (as a traditional catalyst) and chitosan-MgO nanocomposite (as a green recyclable catalyst) in a comparative study. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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Open AccessArticle
One-Step Synthesis Heterostructured g-C3N4/TiO2 Composite for Rapid Degradation of Pollutants in Utilizing Visible Light
Nanomaterials 2018, 8(10), 842; https://doi.org/10.3390/nano8100842 - 16 Oct 2018
Cited by 13
Abstract
To meet the urgent need of society for advanced photocatalytic materials, novel visible light driven heterostructured composite was constructed based on graphitic carbon nitride (g-C3N4) and fibrous TiO2. The g-C3N4/TiO2 (CNT) composite [...] Read more.
To meet the urgent need of society for advanced photocatalytic materials, novel visible light driven heterostructured composite was constructed based on graphitic carbon nitride (g-C3N4) and fibrous TiO2. The g-C3N4/TiO2 (CNT) composite was prepared through electrospinning technology and followed calcination process. The state of the g-C3N4 and fibrous TiO2 was tightly coupled. The photocatalytic performance was measured by degrading the Rhodamine B. Compared to commercial TiO2 (P25®) and electrospun TiO2 nanofibers, the photocatalytic performance of CNT composite was higher than them. The formation of CNT heterostructures and the enlarged specific surface area enhanced the photocatalytic performance, suppressing the recombination rate of photogenerated carriers while broadening the absorption range of light spectrum. Our studies have demonstrated that heterostructured CNT composite with an appropriate proportion can rational use of visible light and can significantly promote the photogenerated charges transferred at the contact interface between g-C3N4 and TiO2. Full article
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Open AccessArticle
Fabrication of ZnO/Red Phosphorus Heterostructure for Effective Photocatalytic H2 Evolution from Water Splitting
Nanomaterials 2018, 8(10), 835; https://doi.org/10.3390/nano8100835 - 15 Oct 2018
Cited by 6
Abstract
Photocatalysis is a green technique that can convert solar energy to chemical energy, especially in H2 production from water splitting. In this study, ZnO and red phosphorus (ZnO/RP) heterostructures were fabricated through a facile calcination method for the first time, which showed [...] Read more.
Photocatalysis is a green technique that can convert solar energy to chemical energy, especially in H2 production from water splitting. In this study, ZnO and red phosphorus (ZnO/RP) heterostructures were fabricated through a facile calcination method for the first time, which showed the considerable photocatalytic activity of H2 evolution. The photocatalytic activities of heterostructures with different ratios of RP have been investigated in detail. Compared to bare ZnO, ZnO/RP heterostructures exhibit a 20.8-fold enhancement for H2 production and furthermore overcome the photocorrosion issue of ZnO. The improved photocatalytic activities highly depend on the synergistic effect of the high migration efficiency of photo-induced electron–hole pairs with the inhibited charge carrier recombination on the surface. The presented strategy can also be applied to other semiconductors for various optoelectronics applications. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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Open AccessArticle
Synthesis and Characterization of Rh/B–TNTs as a Recyclable Catalyst for Hydroformylation of Olefin Containing –CN Functional Group
Nanomaterials 2018, 8(10), 755; https://doi.org/10.3390/nano8100755 - 25 Sep 2018
Cited by 3
Abstract
The TiO2-based nanotubes (TNTs, B–TNTs) of different surface acidities and their supported Rh catalysts were designed and synthesized. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), tempera–ture–programmed desorption of [...] Read more.
The TiO2-based nanotubes (TNTs, B–TNTs) of different surface acidities and their supported Rh catalysts were designed and synthesized. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), tempera–ture–programmed desorption of ammonia (NH3–TPD), atomic emission spectrometer (ICP), and Brunauer–Emmett–Tellerv (BET) surface-area analyzers. Images of SEM and TEM showed that the boron-decorated TiO2 nanotubes (B–TNTs) had a perfect multiwalled tubular structure; their length was up to hundreds of nanometers and inner diameter was about 7 nm. The results of NH3-TPD analyses showed that B–TNTs had a stronger acid site compared with TNTs. For Rh/TNTs and Rh/B–TNTs, Rh nanoparticles highly dispersed on B–TNTs were about 2.79 nm in average diameter and much smaller than those on TNTs, which were about 4.94 nm. The catalytic performances of catalysts for the hydroformylation of 2-methyl-3-butennitrile (2M3BN) were also evaluated, and results showed that the existence of B in Rh/B–TNTs had a great influence on the catalytic performance of the catalysts. The Rh/B–TNTs displayed higher catalytic activity, selectivity for aldehydes, and stability than the Rh/TNTs. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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Open AccessArticle
Facile Synthesis of Magnetic Nitrogen-Doped Porous Carbon from Bimetallic Metal–Organic Frameworks for Efficient Norfloxacin Removal
Nanomaterials 2018, 8(9), 664; https://doi.org/10.3390/nano8090664 - 26 Aug 2018
Cited by 5
Abstract
Magnetic nitrogen-doped porous carbon (MNPC) has been prepared via self-catalytic pyrolysis of bimetallic metal-organic frameworks (MOFs). The as-obtained MNPC showed favorable features for antibiotics adsorption such as high specific surface area (871 m2 g−1), high pore volume (0.75 cm3 [...] Read more.
Magnetic nitrogen-doped porous carbon (MNPC) has been prepared via self-catalytic pyrolysis of bimetallic metal-organic frameworks (MOFs). The as-obtained MNPC showed favorable features for antibiotics adsorption such as high specific surface area (871 m2 g−1), high pore volume (0.75 cm3 g−1), porous structure, good graphitization degree, and rich N-doping. Moreover, the MNPC has magnetic properties due to the Co species, which is embedded with a high dispersion, so the absorbent can be easily separated. Based on the above excellent characteristics, the MNPC was used as the absorbent for norfloxacin (NOR) removal. The experimental maximum NOR adsorption capacity of MNPC was 55.12 mg g−1 at 298.15 K and a pH of 6.0 with an initial NOR concentration of 50 mg L−1. The data analysis of the kinetics revealed that the experimental data of NOR uptakes versus time agreed with the pseudo-second order model. The isotherm data analysis revealed the favorable application of the Freundlich model. Based on the adsorption results over a wide range of conditions, the dominant adsorption mechanisms were found to be pore-filling, electrostatic interaction, and the H-bond. Full article
(This article belongs to the Special Issue Advances in Heterocatalysis by Nanomaterials) Printed Edition available
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