Special Issue "Nanostructured Catalysts for Sustainable Applications"

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Energy and Catalysis".

Deadline for manuscript submissions: 31 October 2020.

Special Issue Editors

Dr. Marcelo E. Domine
Website1 Website2
Guest Editor
Instituto de Tecnología Química (UPV - CSIC). Universitat Politècnica de València. Consejo Superior de Investigaciones Científicas. Valencia, Spain
Interests: synthesis and characterization of multi-functional and nanostructured solid catalysts; catalysts application in sustainable chemical processes; biomass-derivatives transformations; wastes valorization into fuels and chemicals
Prof. Dr. Alberto Marinas Aramendía
Website
Guest Editor
Departamento de Química Orgánica, Instituto Universitario de Investigación en Química Fina y Nanoquímica IUIQFN, Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie, E-14071 Córdoba, Spain
Interests: heterogeneous (photo) catalysis applied to sustainable chemistry; biomass valorization; materials science; fine chemistry
Special Issues and Collections in MDPI journals

Special Issue Information

Dear Colleagues,

Different nano-structured solid materials with well-defined micro-, meso-, and hierarchical porosity and controlled catalytic properties (acid/base, redox) are capable of catalyzing a wide range of chemical reactions (e.g., oxidations, reductions, acid/base processes, etherifications, condensations, etc.) in the liquid and gas phases, interesting for the industrial production of chemicals, fuels, energy and energy vectors. The presence of isolated metallic species, homogeneously distributed in the form of nanoparticles on specific acid/base supports or adequately incorporated in the inorganic framework of well-structured materials, provides multi-functional capacities to afford catalytic transformations and multi-step reactions in “one-pot” or “cascade-type” processes, thus reducing reaction steps and operations costs and making processes more efficient and sustainable.

This Special Issue welcomes contributions devoted to the design, characterization, and application of novel nano-structured catalysts for sustainable chemical processes, mainly those focussed on the production of renewable energy and fuels or those related to the transformation of renewable raw materials, such as biomass and its derivatives into valuable products.

Dr. Marcelo E. Domine
Prof. Alberto Marinas
Guest Editors

Manuscript Submission Information

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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.

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Keywords

  • Nanomaterials
  • Nanostructured catalysts
  • Heterogeneous catalysis
  • Sustainable catalytic processes
  • Renewable chemicals
  • Renewable energy

Published Papers (9 papers)

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Research

Open AccessArticle
Potential of TiO2 with Various Au Nanoparticles for Catalyzing Mesotrione Removal from Wastewaters under Sunlight
Nanomaterials 2020, 10(8), 1591; https://doi.org/10.3390/nano10081591 - 13 Aug 2020
Abstract
Nowadays, great focus is given to the contamination of surface and groundwater because of the extensive usage of pesticides in agriculture. The improvements of commercial catalyst TiO2 activity using different Au nanoparticles were investigated for mesotrione photocatalytic degradation under simulated sunlight. The [...] Read more.
Nowadays, great focus is given to the contamination of surface and groundwater because of the extensive usage of pesticides in agriculture. The improvements of commercial catalyst TiO2 activity using different Au nanoparticles were investigated for mesotrione photocatalytic degradation under simulated sunlight. The selected system was 2.43 × 10−3% Au–S–CH2–CH2–OH/TiO2 (0.5 g/L) that was studied by transmission electron microscopy and ultraviolet-visible (UV-Vis) spectroscopy. It was found that TiO2 particles size was ~20 nm and ~50 nm, respectively. The Au nanoparticles were below 10 nm and were well distributed within the framework of TiO2. For 2.43 × 10−3% Au–S–CH2–CH2–OH/TiO2 (0.5 g/L), band gap energy was 2.45 eV. In comparison to the pure TiO2, addition of Au nanoparticles generally enhanced photocatalytic removal of mesotrione. By examining the degree of mineralization, it was found that 2.43 × 10−3% Au–S–CH2–CH2–OH/TiO2 (0.5 g/L) system was the most efficient for the removal of the mesotrione and intermediates. The effect of tert-butanol, NaF and ethylenediaminetetraacetic acid disodium salt on the transformation rate suggested that the relative contribution of various reactive species changed in following order: h+ > OHads > OHbulk. Finally, several intermediates that were formed during the photocatalytic treatment of mesotrione were identified. Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Open AccessArticle
Electrodeposition of Mesoporous Ni-Rich Ni-Pt Films for Highly Efficient Methanol Oxidation
Nanomaterials 2020, 10(8), 1435; https://doi.org/10.3390/nano10081435 - 23 Jul 2020
Abstract
The use of soft templates for the electrosynthesis of mesoporous materials has shown tremendous potential in energy and environmental domains. Among all the approaches that have been featured in the literature, block copolymer-templated electrodeposition had robustness and a simple method, but it practically [...] Read more.
The use of soft templates for the electrosynthesis of mesoporous materials has shown tremendous potential in energy and environmental domains. Among all the approaches that have been featured in the literature, block copolymer-templated electrodeposition had robustness and a simple method, but it practically cannot be used for the synthesis of mesoporous materials not based on Pt or Au. Nonetheless, extending and understanding the possibilities and limitations of block copolymer-templated electrodeposition to other materials and substrates is still challenging. Herein, a critical analysis of the role of the solution’s primary electroactive components and the applied potential were performed in order to understand their influences on the mesostructure of Ni-rich Ni-Pt mesoporous films. Among all the components, tetrahydrofuran and a platinum (IV) complex were shown to be crucial for the formation of a truly 3D mesoporous network. The electrosynthesized well-ordered mesoporous Ni-rich Ni-Pt deposits exhibit excellent electrocatalytic performance for methanol oxidation in alkaline conditions, improved stability and durability after 1000 cycles, and minimal CO poisoning. Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Open AccessArticle
Enhanced Photocatalytic Activity and Stability in Hydrogen Evolution of Mo6 Iodide Clusters Supported on Graphene Oxide
Nanomaterials 2020, 10(7), 1259; https://doi.org/10.3390/nano10071259 - 28 Jun 2020
Abstract
Catalytic properties of the cluster compound (TBA)2[Mo6Ii8(O2CCH3)a6] (TBA = tetrabutylammonium) and a new hybrid material (TBA)2Mo6Ii8@GO (GO = graphene oxide) in water [...] Read more.
Catalytic properties of the cluster compound (TBA)2[Mo6Ii8(O2CCH3)a6] (TBA = tetrabutylammonium) and a new hybrid material (TBA)2Mo6Ii8@GO (GO = graphene oxide) in water photoreduction into molecular hydrogen were investigated. New hybrid material (TBA)2Mo6Ii8@GO was prepared by coordinative immobilization of the (TBA)2[Mo6Ii8(O2CCH3)a6] onto GO sheets and characterized by spectroscopic, analytical, and morphological techniques. Liquid and, for the first time, gas phase conditions were chosen for catalytic experiments under UV–Vis irradiation. In liquid water, optimal H2 production yields were obtained after using (TBA)2[Mo6Ii8(O2CCH3)a6] and (TBA)2Mo6Ii8@GO) catalysts after 5 h of irradiation of liquid water. Despite these remarkable catalytic performances, “liquid-phase” catalytic systems have serious drawbacks: the cluster anion evolves to less active cluster species with partial hydrolytic decomposition, and the nanocomposite completely decays in the process. Vapor water photoreduction showed lower catalytic performance but offers more advantages in terms of cluster stability, even after longer radiation exposure times and recyclability of both catalysts. The turnover frequency (TOF) of (TBA)2Mo6Ii8@GO is three times higher than that of the microcrystalline (TBA)2[Mo6Ii8(O2CCH3)a6], in agreement with the better accessibility of catalytic cluster sites for water molecules in the gas phase. This bodes well for the possibility of creating {Mo6I8}4+-based materials as catalysts in hydrogen production technology from water vapor. Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Open AccessArticle
Olive Leaves as Biotemplates for Enhanced Solar-Light Harvesting by a Titania-Based Solid
Nanomaterials 2020, 10(6), 1057; https://doi.org/10.3390/nano10061057 - 30 May 2020
Cited by 1
Abstract
Olive leaves (by-product from olive oil production in olive mills) were used as biotemplates to synthesize a titania-based artificial olive leaf (AOL). Scanning electron microscopy (SEM) images of AOL showed the successful replication of trichomes and internal structure channels present in olive leaves. [...] Read more.
Olive leaves (by-product from olive oil production in olive mills) were used as biotemplates to synthesize a titania-based artificial olive leaf (AOL). Scanning electron microscopy (SEM) images of AOL showed the successful replication of trichomes and internal structure channels present in olive leaves. The BET surface area of AOL was 52 m2·g−1. X-ray diffraction (XRD) and Raman spectra revealed that the resulting solid was in the predominantly-anatase crystalline form (7.5 nm average particle size). Moreover, the synthesis led to a red-shift in light absorption as compared to reference anatase (gap energies of 2.98 and 3.2 eV, respectively). The presence of surface defects (as evidenced by X-ray photoelectron spectroscopy, XPS, and electron paramagnetic resonance spectroscopy, EPR) and doping elements (e.g., 1% nitrogen, observed by elemental analysis and XPS) could account for that. AOL was preliminarily tested as a catalyst for hydrogen production through glycerol photoreforming and exhibited an activity 64% higher than reference material Evonik P25 under solar irradiation and 144% greater under ultraviolet radiation (UV). Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Open AccessArticle
Mesoporous Tungsten Trioxide Photoanodes Modified with Nitrogen-Doped Carbon Quantum Dots for Enhanced Oxygen Evolution Photo-Reaction
Nanomaterials 2019, 9(10), 1502; https://doi.org/10.3390/nano9101502 - 22 Oct 2019
Cited by 3
Abstract
Nanostructured photoanodes are attractive materials for hydrogen production via water photo-electrolysis process. This study focused on the incorporation of carbon quantum dots doped with nitrogen as a photosensitizer into mesoporous tungsten trioxide photoanodes (N-CQD/meso-WO3) using a surfactant self-assembly [...] Read more.
Nanostructured photoanodes are attractive materials for hydrogen production via water photo-electrolysis process. This study focused on the incorporation of carbon quantum dots doped with nitrogen as a photosensitizer into mesoporous tungsten trioxide photoanodes (N-CQD/meso-WO3) using a surfactant self-assembly template approach. The crystal structure, composition, and morphology of pure and N-CQD- modified mesoporous WO3 photoanodes were investigated using scanning electron and transmission microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Due to their high surface area, enhanced optical absorption, and charge-carrier separation and transfer, the resulting N-CQD/meso-WO3 photoanodes exhibited a significantly enhanced photocurrent density of 1.45 mA cm−2 at 1.23 V vs. RHE under AM 1.5 G illumination in 0.5 M Na2SO4 without any co-catalysts or sacrificial reagent, which was about 2.23 times greater than its corresponding pure meso-WO3. Moreover, the oxygen evolution onset potential of the N-CQD/meso-WO3 photoanodes exhibited a negative shift of 95 mV, signifying that both the charge-carrier separation and transfer processes were promoted. Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Open AccessArticle
Electrochemical Synergies of Heterostructured Fe2O3-MnO Catalyst for Oxygen Evolution Reaction in Alkaline Water Splitting
Nanomaterials 2019, 9(10), 1486; https://doi.org/10.3390/nano9101486 - 18 Oct 2019
Cited by 2
Abstract
For efficient electrode development in an electrolysis system, Fe2O3, MnO, and heterojunction Fe2O3-MnO materials were synthesized via a simple sol–gel method. These particles were coated on a Ni-foam (NF) electrode, and the resulting material was [...] Read more.
For efficient electrode development in an electrolysis system, Fe2O3, MnO, and heterojunction Fe2O3-MnO materials were synthesized via a simple sol–gel method. These particles were coated on a Ni-foam (NF) electrode, and the resulting material was used as an electrode to be used during an oxygen evolution reaction (OER). A 1000-cycle OER test in a KOH alkaline electrolyte indicated that the heterojunction Fe2O3-MnO/NF electrode exhibited the most stable and highest OER activity: it exhibited a low overvoltage (n) of 370 mV and a small Tafel slope of 66 mV/dec. X-ray photoelectron spectroscopy indicated that the excellent redox performance contributed to the synergy of Mn and Fe, which enhanced the OER performance of the Fe2O3-MnO/NF electrode. Furthermore, the effective redox reaction of Mn and Fe indicated that the structure maintained stability even under 1000 repeated OER cycles. Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Open AccessArticle
Influence of Boron, Tungsten and Molybdenum Modifiers on Zirconia Based Pt Catalyst for Glycerol Valorization
Nanomaterials 2019, 9(4), 509; https://doi.org/10.3390/nano9040509 - 02 Apr 2019
Cited by 1
Abstract
The influence of boron, tungsten and molybdenum modifiers on zirconia-based Pt catalyst was studied for glycerol valorization. Zirconia modified supports were prepared by impregnation of ZrO2 with either boric, silicontungstic or phosphomolybdic acids to obtain supports with enhanced Brönsted acidic properties. The [...] Read more.
The influence of boron, tungsten and molybdenum modifiers on zirconia-based Pt catalyst was studied for glycerol valorization. Zirconia modified supports were prepared by impregnation of ZrO2 with either boric, silicontungstic or phosphomolybdic acids to obtain supports with enhanced Brönsted acidic properties. The modified supports were subsequently impregnated with chloroplatinic acid to obtain Pt-based catalysts. Pt incorporation resulted in the increase in Lewis acidity of the solids, being more significant for the Pt//W/ZrO2 catalyst. Reduced Pt catalysts were tested for the liquid-phase glycerol hydrogenolysis, observing a synergistic effect between catalyst acid sites and metal function that proved to be crucial in glycerol hydrogenolysis. The Pt//W/ZrO2 catalyst was the most active catalyst in this reaction, being the only leading to 1,3-PDO (45% sel., 160 °C) while Pt//Mo/ZrO2 is the best option for 1,2-PDO (49% sel., 180 °C). Reusability studies carried out for Pt//W/ZrO2 showed that catalytic activity dropped after the first use, remaining constant for the second and subsequent ones. Selectivity to reaction products also changes during reuses. Therefore, the selectivity to 1,2 PDO increases in the first reuse in detriment to the selectivity to n-propanol whereas the selectivity to 1,3-PDO remains constant along the uses. This behavior could be associated to the lixiviation of W species and/or catalyst fouling during reaction runs. Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Open AccessArticle
Engineering Charge Transfer Characteristics in Hierarchical Cu2S QDs @ ZnO Nanoneedles with p–n Heterojunctions: Towards Highly Efficient and Recyclable Photocatalysts
Nanomaterials 2019, 9(1), 16; https://doi.org/10.3390/nano9010016 - 23 Dec 2018
Cited by 8
Abstract
Equipped with staggered gap p-n heterojunctions, a new paradigm of photocatalysts based on hierarchically structured nano-match-shaped heterojunctions (NMSHs) Cu2S quantum dots (QDs)@ZnO nanoneedles (NNs) are successfully developed via engineering the successive ionic layer adsorption and reaction (SILAR). Under UV and visible [...] Read more.
Equipped with staggered gap p-n heterojunctions, a new paradigm of photocatalysts based on hierarchically structured nano-match-shaped heterojunctions (NMSHs) Cu2S quantum dots (QDs)@ZnO nanoneedles (NNs) are successfully developed via engineering the successive ionic layer adsorption and reaction (SILAR). Under UV and visible light illumination, the photocatalytic characteristics of Cu2[email protected] heterojunctions with different loading amounts of Cu2S QDs are evaluated by the corresponding photocatalytic degradation of rhodamine B (RhB) aqueous solution. The results elaborate that the optimized samples (S3 serial specimens with six cycles of SILAR reaction) by means of tailored the band diagram exhibit appreciable improvement of photocatalytic activities among all synthesized samples, attributing to the sensitization of a proper amount of Cu2S QDs. Such developed architecture not only could form p–n junctions with ZnO nanoneedles to facilitate the separation of photo-generated carries but also interact with the surface defects of ZnO NNs to reduce the electron and hole recombination probability. Moreover, the existence of Cu2S QDs could also extend the light absorption to improve the utilization rate of sunlight. Importantly, under UV light S3 samples demonstrate the remarkably enhanced RhB degradation efficiency, which is clearly testified upon the charge transfer mechanism discussions and evaluations in the present work. Further supplementary investigations illustrate that the developed nanoscale Cu2[email protected] heterostructures also possess an excellent photo-stability during our extensive recycling photocatalytic experiments, promising for a wide range of highly efficient and sustainably recyclable photocatalysts applications. Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Open AccessArticle
Vacuum Thermal Treated Ni-CeO2/SBA-15 Catalyst for CO2 Methanation
Nanomaterials 2018, 8(10), 759; https://doi.org/10.3390/nano8100759 - 26 Sep 2018
Cited by 6
Abstract
Ni-CeO2/SBA-15-V catalyst was prepared by the impregnation method with vacuum thermal treatment and used for CO2 methanation reaction. Compared with Ni-CeO2/SBA-15-air catalyst with thermal treatment in air, the reduced Ni-CeO2/SBA-15-V catalyst with vacuum thermal treatment exhibited [...] Read more.
Ni-CeO2/SBA-15-V catalyst was prepared by the impregnation method with vacuum thermal treatment and used for CO2 methanation reaction. Compared with Ni-CeO2/SBA-15-air catalyst with thermal treatment in air, the reduced Ni-CeO2/SBA-15-V catalyst with vacuum thermal treatment exhibited higher Ni dispersion and smaller Ni particle size. In CO2 methanation reaction, the Ni-CeO2/SBA-15-V catalyst was more active and selective than the Ni-CeO2/SBA-15-air catalyst. The good activity and selectivity of Ni-CeO2/SBA-15-V catalyst should be due to highly dispersed Ni in contact with small CeO2 particles. Full article
(This article belongs to the Special Issue Nanostructured Catalysts for Sustainable Applications)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Conversion of glycerol to value added products in a semi-continuous batch reactor using noble metals supported on ZSM-11 zeolite
Authors: Eliana Diguilio1, Marcelo E. Dómine2, Liliana B. Pierella1, M. Soledad Renzini1
Affiliation: 1 Centro de Investigación y Tecnologı́a Quı́mica (CITeQ), UE CONICET –Universidad Tecnológica Nacional, Facultad Regional Córdoba, Maestro Lopez esq Cruz Roja Argentina, Ciudad Universitaria, (5016) Córdoba; [email protected] 2 Instituto de Tecnologı́a Quı́mica (UPV-CSIC), Universitat Politècnica de València,Consejo Superior de Investigaciones Cientı́ficas, Avda. de los Naranjos s/n, 46022, Valencia, Spain; [email protected]
Abstract: Au, Pt and Pd supported on ZSM-11 microporous zeolite was investigated as catalysts for glycerol oxidation towards higher value-added products. ZSM-11 was synthesized by hydrothermal treatment at 140° C in autoclave. Subsequently, ion exchange with NH4Cl 1M was performed to recover acidic sites and then, Au, Pt and Pd were incorporated onto this material by wet impregnation at 80° C. Finally, thermal treatment of desorption and calcination at 500 °C was carried out. These materials were characterized by different techniques as XRD, ICP, TEM- XEDS, XPS and then, these were evaluated in glycerol oxidation reaction in alkaline medium by employing oxygen pure as oxidizing agent. The maximum conversion of glycerol (57%) was reached over the Pt–ZSM-11 catalyst with selectivity higher than 50% towards lactic acid in mild reaction conditions. The optimal reaction conditions were studied to maximize the selectivity towards this important product. Catalytic tests were carried out to find the optimal reaction conditions that maximize selectivity to LA, modifying temperature, reaction time and NaOH/GLY ratio.

Title: ZnO modified by high energy ball milling supported Cu nanoparticles as an efficient nanocatalyst for glycerol hydrogenolisis
Authors: Maria Karla López González, Maria Roxana Morales, Luis Eduardo Cadús
Affiliation: Instituto de Investigaciones en Tecnología Química (INTEQUI-CONICET), Universidad Nacional de San Luis (UNSL), Facultad de Química Bioquímica y Farmacia, Almirante Brown 1455, Capital, 5700 San Luis, Argentina
Abstract: In this work, ZnO unmodified (Cux/ZnO-0) and ZnO (Cux/ZnO-z) modified by high energy ball milling, were used as support for copper nanoparticles. The prepared samples were fully characterized by XRD, SBET, SEM-EDS, FT-IR, AA, Raman, isopropyl alcohol decomposition reaction of, CO2-TPD, XPS, RTP, N2O chemisorption and O2-TPD. The effect of high energy ball milling on the structural and physicochemical properties of ZnO were studied. Furthermore, these modifications introduced in the support were related to the size of metallic particles, their dispersion and the metal-support interaction, for each copper compositions. Both catalytic systems were evaluated in the oxidation of glycerol in liquid phase. The stability of copper nanoparticles under reaction conditions were studied by reuse cycles.

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