Special Issue "Heterogeneous Catalytic Materials: Synthesis, Characterization and Applications for Energetic Purposes"

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: 31 December 2019.

Special Issue Editor

Guest Editor
Dr. Catia Cannilla Website E-Mail
Institute for Advanced Energy Technologies "Nicola Giordano" ITAE, Italian National Research Council (CNR) Messina, Italy
Interests: heterogenous catalysis (synthesis, chemico-physical characterization, structure-activity relationship); biofuels; additives for biofuels; green chemistry; reaction kinetics and mechanism; CO2 conversion

Special Issue Information

Dear Colleagues,

Solid catalytic materials play a key role in the development of industrial chemistry, showing important advantages over liquid materials thanks to their easier separation from the reaction liquid medium, their reusability and stability, and their environmentally-friendly character. This Special Issue is focused on the actual and potential application of heterogeneous catalysts for energetic purposes, as biofuels synthesis and H2 production through biomass, waste, biogas or CO2 conversion with specific interest towards innovative procedures of synthesis or catalytic formulations and chemicophysical characterization tecniques. For example, in situ and operando characterization techniques represent a suitable tool to identify and quantify the nature and functionality of surface adsorption active sites and, therefore, for correlating the catalytic behavior with the surface properties of the investigated systems. Based on this, by considering the importance of heterogeneous catalytic processes in the field of green chemistry, efficiency, sustainability, and environmental safety, it is my pleasure to invite you to submit original research papers or short reviews and communication for the Special Issue “Heterogeneous Catalytic Materials: Synthesis, Characterization and Applications for Energetic Purposes”.

Dr. Catia Cannilla
Guest Editor

Manuscript Submission Information

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Keywords

  • heterogenous catalysis
  • biomass conversion
  • H2 production
  • biofuels synthesis
  • CO2 conversion
  • waste
  • biogas
  • green processes
  • industrial chemistry

Published Papers (4 papers)

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Research

Open AccessArticle
Effect of Preparation Method on ZrO2-Based Catalysts Performance for Isobutanol Synthesis from Syngas
Catalysts 2019, 9(9), 752; https://doi.org/10.3390/catal9090752 - 06 Sep 2019
Abstract
Two types of amorphous ZrO2 (am-ZrO2) catalysts were prepared by different co-precipitation/reflux digestion methods (with ethylenediamine and ammonia as the precipitant respectively). Then, copper and potassium were introduced for modifying ZrO2 via an impregnation method to enhance the catalytic [...] Read more.
Two types of amorphous ZrO2 (am-ZrO2) catalysts were prepared by different co-precipitation/reflux digestion methods (with ethylenediamine and ammonia as the precipitant respectively). Then, copper and potassium were introduced for modifying ZrO2 via an impregnation method to enhance the catalytic performance. The obtained catalysts were further characterized by means of Brunauer-Emmett-Teller surface areas (BET), X-ray diffraction (XRD), H2-temperature-programmed reduction (H2-TPR), and In situ diffuse reflectance infrared spectroscopy (in situ DRIFTS). CO hydrogenation experiments were performed in a fixed-bed reactor for isobutanol synthesis. Great differences were observed on the distribution of alcohols over the two types of ZrO2 catalysts, which were promoted with the same content of Cu and K. The selectivity of isobutanol on K-CuZrO2 (ammonia as precipitant, A-KCZ) was three times higher than that on K-CuZrO2 (ethylenediamine as precipitant, E-KCZ). The characterization results indicated that the A-KCZ catalyst supplied more active hydroxyls (isolated hydroxyls) for anchoring and dispersing Cu. More importantly, it was found that bicarbonate species were formed, which were ascribed as important C1 species for isobutanol formation on the A-KCZ catalyst surface. These C1 intermediates had relatively stronger adsorption strength than those adsorbed on the E-KCZ catalyst, indicating that the bicarbonate species on the A-KCZ catalyst had a longer residence time for further carbon chain growth. Therefore, the selectivity of isobutanol was greatly enhanced. These findings would extend the horizontal of direct alcohols synthesis from syngas. Full article
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Open AccessArticle
Co-precipitation Synthesized MnOx-CeO2 Mixed Oxides for NO Oxidation and Enhanced Resistance to Low Concentration of SO2 by Metal Addition
Catalysts 2019, 9(6), 519; https://doi.org/10.3390/catal9060519 - 12 Jun 2019
Abstract
NO oxidation was conducted over MnOx-CeO2 catalysts, which were synthesized by the co-precipitation method. The calcination temperature and third metal doping were the main considerations. MnCe catalysts calcined at 350 °C and 450 °C attained the highest NO conversion efficiency, [...] Read more.
NO oxidation was conducted over MnOx-CeO2 catalysts, which were synthesized by the co-precipitation method. The calcination temperature and third metal doping were the main considerations. MnCe catalysts calcined at 350 °C and 450 °C attained the highest NO conversion efficiency, compared to 550 °C. XRD results suggested that the higher the calcination temperature, the higher the crystallization degree, which led to a negative effect on catalytic activity. Subsequently, Sn, Fe, Co, Cr, and Cu were separately doped into MnCe composites, but no improvement was observed for these trimetallic catalysts in NO conversion. Nevertheless, MnCeSn, MnCeFe, and MnCeCo still exhibited a desirable NO conversion efficiency, so they were tested under SO2 addition together with MnCe catalyst. Among them, MnCeFe exhibited the highest NO conversion after whole poisoning testing. XPS results indicated that Fe could protect Mn and Ce metal oxides from being reduced during SO2 poisoning process. Furthermore, in in-situ DRIFTS measurement, part of nitrate species maintained undestroyed on the MnCeFe catalyst surface after SO2 poisoning. These characteristics reinforced that Fe dropping would achieve better performance under SO2 atmosphere. Full article
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Open AccessCommunication
Ultra-Small Pd Nanoparticles on Ceria as an Advanced Catalyst for CO Oxidation
Catalysts 2019, 9(4), 385; https://doi.org/10.3390/catal9040385 - 24 Apr 2019
Abstract
In this study, we demonstrate the preparation and characterization of small palladium nanoparticles (Pd NPs) on modified ceria support (Pd/CeO2) using wet impregnation and further reduction in an H2/Ar flow. The obtained particles had a good dispersion, but their [...] Read more.
In this study, we demonstrate the preparation and characterization of small palladium nanoparticles (Pd NPs) on modified ceria support (Pd/CeO2) using wet impregnation and further reduction in an H2/Ar flow. The obtained particles had a good dispersion, but their small size made it difficult to analyze them by conventional techniques such as transmission electron microscopy (TEM) and X-ray powder diffraction (XRPD). The material demonstrated a high catalytic activity in the CO oxidation reaction: the 100% of CO conversion was achieved at ~50 °C, whereas for most of the cited literature, such a high conversion usually was observed near 100 °C or higher for Pd NPs. Diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy in combination with CO probe molecules was used to investigate the size and morphology of NPs and the ceria support. On the basis of the area ratio under the peaks attributed to bridged (B) and linear (L) carbonyls, high-dispersion Pd NPs was corroborated. Obtained results were in good agreement with data of X-ray absorption near edge structure analysis (XANES) and CO chemisorption measurements. Full article
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Open AccessArticle
Heteropolyacid Salt Catalysts for Methanol Conversion to Hydrocarbons and Dimethyl Ether: Effect of Reaction Temperature
Catalysts 2019, 9(4), 320; https://doi.org/10.3390/catal9040320 - 01 Apr 2019
Abstract
Phosphotungstic and silicotungstic acid salt catalysts (CuPW, CuSiW, FePW, FeSiW) were synthesized by substitution of protons with ferric and copper ions through a simple replacement reaction. The structure and thermal stability were characterized by IR, XRD and TG, and the salts showed a [...] Read more.
Phosphotungstic and silicotungstic acid salt catalysts (CuPW, CuSiW, FePW, FeSiW) were synthesized by substitution of protons with ferric and copper ions through a simple replacement reaction. The structure and thermal stability were characterized by IR, XRD and TG, and the salts showed a keggin structure and a thermal tolerance near 450 °C. Temperature programmed reactions indicated that the four catalysts showed similar trends in the change of methanol conversion, DME selectivity, and light olefins selectivity at 100–400 °C. Copper salt catalysts showed a 100% DME selectivity at temperatures ranging from 100–250 °C, while FeSiW and FePW catalysts had a 100% DME selectivity near 250 °C. Moreover, the heteropolyacid salt catalysts also produced a certain number of light olefins at the temperature ranging from 250–350 °C, and the CuSiW catalyst exhibited the highest ethylene and propylene selectivity of 44%. In the stability test evaluated at 200 °C, the catalysts showed different tendencies during the induction period and the same trends during the reduction period for the methanol conversion to DME, due to the differences in the strengths of the strong acid sites. Finally, the silicotungstic acid salt catalysts showed the longest lifetime of 120 h, much longer than the heteropolyacids. This approach provides an effective way to synthesize hydrocarbons through methanol, especially DME, at different temperatures using one catalyst. Full article
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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: Zr-based oxides for biofuels synthesis and H2 production
Author
: Dr. Nicola Scotti
Affiliation: ISTM-CNR, Italy
Abstract: Zr-based oxides are received increasing attention from the scientific community as heterogeneous catalysts and supports for metal nanoparticles, owing to their tunable phase composition, redox, and acid/base properties. High catalytic activity and selectivity have been reported for different classes of reactions such as hydrogenation with H2, transfer hydrogenation, dehydrogenation, dehydrogenative coupling, H2 production, and dehydration. In this view, the application of these kind of catalysts for biomass transformation for energy purpose is really promising, but requires a deep understating of their structure and activity in order to tune activity and selectivity and adapt the material for the desired application. In this review all these aspects will be discussed in a critical way.

Title: Metal oxide catalytic upgrading of microalgal biocrude by hydrothermal liquefaction
Authors: Alejandra Sánchez-Bayo1, Rosalía Rodríguez1, Victoria Morales2, Luis Fernando Bautista2, Gemma Vicente1*
Affiliations: 1 Department of Chemical, Energy and Mechanical Technology; Universidad Rey Juan Carlos, C/ Tulipán s/n, 28933 Móstoles, Spain
2 Department of Chemical and Environmental Technology; Universidad Rey Juan Carlos, C/ Tulipán s/n, 28933 Móstoles, Spain
Abstract: The yield and composition of the biocrude obtained by hydrothermal liquefaction (HTL) of Nannocloropsis gaditana using heterogeneous catalysts based on metal oxides (CaO, CeO2, La2O3, MnO2 and Al2O3) were evaluated. The reactions were performed in a batch autoclave reactor at 320oC during 10 min with a 1:10 (wt/wt) microalga:water ratio. These catalysts increased the yield of the liquefaction phase (from 94.3±0.9 wt% for La2O3 to 99.5±0.7 wt% for MnO2) as compared with the thermal reaction (92.6±0.7 wt%). Therefore, the conversion of the microalga improved, decreasing the solid fraction yields. Consequently, the biocrude yields also raised in the metal oxides catalyzed HTL, showing values remarkable higher for the CaO (50±1 wt%) in comparison to the HTL without catalyst (42.3±1 wt%). The nitrogen and oxygen content of the biocrude obtained from thermal HTL were 6.12±0.02 and 10.8±0.2 wt%, respectively. In this sense, the use of the metal oxides decreased the nitrogen content of the biocrude (4.17±0.03 - 5.3±0.01 wt%). However, these catalysts slightly increased its oxygen content (11±0.30 - 21.64±0.04 wt%).
Keywords: microalgae, hydrothermal liquefaction, biocrude, metal-oxide catalyst 

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Title: H2 photo-production: From materials to photo-reactors
Authors: Mario J. Muñoz-Batista*, et al.
Affiliation: University of Granada, Granada, Spain
Abstract: Photo-reforming of oxygenates is considered one of the most interesting process to produce H2 as a new clean energy vector and is mainly based on the potential utilization of sunlight or efficient illumination conditions and mind operation condition conditions. The process is strongly defined by the used semiconductor which must be optimized to provide the positive change photo-handling. This contribution focus on the utilization of two main groups of materials which have provided outstanding results in this reaction, named TiO2-based and g-C3N4-based materials. Traditional and advanced characterization approaches to understanding the process occurring under properly illumination condition are also reviewed. Special attention has been paid on in situ and operando studies. The work also summarize the main properties of photo-reactor setups in both liquid and gas media and describes a light-matter interaction modelling approach, which allows developing intrinsic kinetic modelling studies as well as the calculation of true quantum efficiency as main observable recommended by the IUPAC to analyze photocatalytic reactions.

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