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Catalysts
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Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes
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Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes

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

Deadline for manuscript submissions: 31 May 2024 | Viewed by 11301

Special Issue Editors

Dr. Ileana Daniela Lick

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Guest Editor
CINDECA (CCT La Plata-CONICET-UNLP), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Calle 47 N° 257, La Plata, Buenos Aires 1900, Argentina
Interests: heterogeneous catalysis; environmental catalysis; oxides; characterization of catalysts; catalytic combustion; biomass valorization; catalytic pyrolysis
Dr. Paula Osorio-Vargas

E-Mail Website
Guest Editor
CINDECA (CCT La Plata-CONICET-UNLP), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Calle 47 N° 257, La Plata, Buenos Aires 1900, Argentina
Interests: heterogeneous catalysis; environmental catalysis; characterization of catalysts; monometallic and bimetallic catalysts; steam reforming; H2 production; waste valorization; catalytic pyrolysis

Special Issue Information

Dear Colleagues,

In recent decades, scientific–technological efforts have been intensified to reduce the effect of pollutants on health, the environment, and consequent climate change. Heterogeneous catalysis has been successfully applied in various chemistry and chemical engineering fields such as traditional industrial processes, petrochemicals, environmental protection, obtaining fuels, and chemical products. Currently, the solution to several problems is addressed towards reactions and environmentally friendly processes. Various lines of research have been devoted to eliminating and controlling emissions and environmental remediation. On the other hand, and no less important, the study of reactions and processes allowing waste recovery and clean fuel obtention has been intensified. The growing demand for energy and using renewable sources as alternatives to fossil fuels has increased the interest in new fields and lines of research. To respond to the challenge, developing new active and selective catalysts and environmentally friendly catalytic processes for existing and new applications is essential.

This Special Issue of Catalysts aims to cover new research and trends in the development and application of catalytic materials for sustainable catalytic applications, including pollution control, clean energy production, fine chemical, biomass valorization, and environmental remediation. The Editors welcome contributions in the form of research papers, short communications, and reviews focusing on the design and development of catalysts for sustainable catalytic processes. Topics include but are not limited to the following:

  • Environmental catalysis;
  • Wastewater treatment;
  • Catalysis in green synthesis;
  • Catalysts for emission control and air pollution control;
  • Biomass conversion and biofuel production;
  • Waste conversion;
  • Biomass derivates sub-products valorization;
  • Catalytic Pyrolysis;
  • H2 production, CO2 conversion, gasification, Fischer–Tropsch synthesis;
  • New materials for catalytic applications;
  • In situ/operando characterization techniques for studying the catalyst;
  • Computational catalysis.

Dr. Ileana Daniela Lick
Dr. Paula Osorio-Vargas
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 submissions that pass pre-check are 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. Catalysts 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 2700 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
  • environmental catalysis
  • waste valorization
  • biofuel
  • energy

Published Papers (9 papers)

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Research

14 pages, 3327 KiB  
Article
Cobalt Nanoparticles Supported on TiO2 for Highly Selective Formation of N-Benzylideneanilines from Nitroarenes and Benzaldehyde via Reductive Imination Reaction
by Daniela González-Vera, Tatiana M. Bustamante, J. Noé Díaz de León, Cecilia C. Torres and Cristian H. Campos
Catalysts 2024, 14(4), 272; https://doi.org/10.3390/catal14040272 - 17 Apr 2024
Viewed by 201
Abstract
The search for active, inexpensive, and stable heterogeneous catalysts to produce desired imines in fine chemistry presents an ongoing challenge for both academia and industry. This work reports the utilization of Co nanoparticles supported on TiO2 derived from the H2-assisted [...] Read more.
The search for active, inexpensive, and stable heterogeneous catalysts to produce desired imines in fine chemistry presents an ongoing challenge for both academia and industry. This work reports the utilization of Co nanoparticles supported on TiO2 derived from the H2-assisted reduction of the perovskite-type mixed oxide CoTiO3. The entire preparation process is operationally simple and straightforward, enabling scalability for practical applications. The resulting catalyst comprises metallic cobalt nanoparticles responsible for the hydrogenation process, whereas the TiOx thin layer surrounding the cobalt promotes the adsorption of C=O, thereby enhancing the formation of desired products. Notably, at lower temperatures, the reaction yields the target imine product. Our study demonstrates a synergistic effect between nitrobenzene and benzaldehyde in the presence of a Co-TiOx interface, which reduces the apparent activation energy for the hydrogenation of the-NO2 group. Furthermore, under moderate reaction conditions, the catalytic system offers applicability to various nitrobenzene compounds substituted at the 4-position and benzaldehyde, resulting in high yields of the corresponding imines with electron-density-donating substituent groups. Finally, the catalyst exhibits facile separation for subsequent reuse, displaying moderate stability with minimal selectivity for the desired product. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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16 pages, 4110 KiB  
Article
Immobilization of the Lipase B from Candida antarctica on Urban Solid Waste
by Carlos R. Llerena Suster, Cynthia A. Fuentes, Jorge E. Sambeth and Carla José
Catalysts 2023, 13(10), 1324; https://doi.org/10.3390/catal13101324 - 26 Sep 2023
Viewed by 817
Abstract
The adsorption of the lipase B from Candida antarctica (CALB) over polyethylene terephthalate (PET), polypropylene (PP), and derivatives, abundant components of urban solid waste (USW), was investigated. The characterization of the supports and biocatalysts synthesized by SEM-EDS and FTIR is presented. Two immobilization [...] Read more.
The adsorption of the lipase B from Candida antarctica (CALB) over polyethylene terephthalate (PET), polypropylene (PP), and derivatives, abundant components of urban solid waste (USW), was investigated. The characterization of the supports and biocatalysts synthesized by SEM-EDS and FTIR is presented. Two immobilization strategies were evaluated, conventional and total adsorption. The adsorbed protein was determined by Bradford and through high-resolution inductively coupled plasma atomic emission spectroscopy (ICP-AES). In this sense, the adsorption of CALB in all the proposed supports was evidenced, obtaining the highest protein loads in bis-(2-hydroxyethyl) terephthalate (BHET). Subsequently, the biocatalysts were applied to the esterification of rac-ibuprofen with ethanol. CALB immobilized in BHET showed remarkable activity, achieving conversions of 30%. In this context, immobilization on this support was optimized, studying the addition of sorbitol-glycerol. Thus, in the presence of 0.91 g of polyols, a catalyst with a protein load of 33.3 mg·g−1 was obtained, achieving productivity of 0.298 mmol min−1 mg−1. Additionally, no differences were found when using BHET from USW bottles of various colors. This research shows the potential of materials derived from PET as enzymatic supports, unreported materials, that we can use as tools to achieve sustainable biotechnological applications. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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17 pages, 3407 KiB  
Article
Phosphotungstic Wells-Dawson Heteropolyacid as Potential Catalyst in the Transesterification of Waste Cooking Oil
by Paula S. Mateos, Claudia B. Ruscitti, Mónica L. Casella, Silvana R. Matkovic and Laura E. Briand
Catalysts 2023, 13(9), 1253; https://doi.org/10.3390/catal13091253 - 30 Aug 2023
Cited by 1 | Viewed by 894
Abstract
The esterification of oleic acid was applied in order to screen the suitability of a series of phosphotungstic-based Wells-Dawson types of compounds as potential catalysts in the heterogeneous transesterification of sunflower waste cooking oil. This test reaction indicated that the phosphotungstic Wells-Dawson heteropolyacid [...] Read more.
The esterification of oleic acid was applied in order to screen the suitability of a series of phosphotungstic-based Wells-Dawson types of compounds as potential catalysts in the heterogeneous transesterification of sunflower waste cooking oil. This test reaction indicated that the phosphotungstic Wells-Dawson heteropolyacid H6P2W18O62·xH2O, dispersed on titania oxide in a loading of 15 mg per m2 of oxide support (named 42% HPA/TiO2) and possessing exclusively Brønsted acid sites, was the most promising among the screened materials. In addition, the application of a nonlinear analysis methodology to find a surface that fits the specific activity of the oleic acid esterification with methanol at various temperatures, weights of catalyst, molar ratios of substrates, and stirring speeds, and also considering the active phase desorption out of the catalyst’s surface, allowed determining the optimum operative conditions that were applied in the transesterification of the waste cooking oil afterwards. The transesterification of the waste cooking oil at 60 °C and 1:9 WCO: methanol molar ratio in a batch reactor under stirring at 650 rpm for 3 h, catalyzed with 0.25 wt% of 42% HPA/TiO2 (20.0 g of oil and 49.6 mg of catalyst), presents 74.6% of conversion of glycerides and 74.4% yield towards fatty acid methyl esters. The catalyst was recovered and reused several times, maintaining a fairly constant catalytic performance. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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15 pages, 3252 KiB  
Article
Oxidation of Glycerol in Base-Free Aqueous Solution Using Carbon-Supported Pt and PtSn Catalyst
by María L. Faroppa, María E. Chiosso, Juan J. Musci, Marco A. Ocsachoque, Andrea B. Merlo and Mónica L. Casella
Catalysts 2023, 13(7), 1071; https://doi.org/10.3390/catal13071071 - 04 Jul 2023
Cited by 1 | Viewed by 1449
Abstract
In the present work, we studied the catalytic performance (activity and selectivity) of Pt supported on carbon systems and Pt modified with tin in the glycerol oxidation with H2O2 as the oxidising agent at atmospheric pressure, 60 °C, and base-free [...] Read more.
In the present work, we studied the catalytic performance (activity and selectivity) of Pt supported on carbon systems and Pt modified with tin in the glycerol oxidation with H2O2 as the oxidising agent at atmospheric pressure, 60 °C, and base-free conditions. The glycerol conversion obtained with monometallic Pt catalyst was 37% and remained unchanged with the addition of Sn in a ratio Sn/Pt = 0.4. The two bimetallic PtSn catalysts were able to oxidise commercial glycerol to dihydroxyacetone (DHA), and the selectivity to DHA reached 97% for the bimetallic catalyst with better conversion. In the reaction with crude glycerol, the conversion obtained was around 40% for the three catalysts, and the major product observed was glyceric acid. Both dihydroxyacetone and glyceric acid are high added value products with potential applications in different areas such as organic chemistry, medical and cosmetics industries. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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13 pages, 2684 KiB  
Article
DFT Studies of the Adsorption of Propane and Propene on Metallic Surfaces in Ag/ZrO2 Catalysts as a Model for Catalytic Combustion Reactions of Light Hydrocarbons
by José F. Ruggera, Marco A. Ocsachoque, Maia Montaña, Mónica L. Casella and Ileana D. Lick
Catalysts 2023, 13(7), 1068; https://doi.org/10.3390/catal13071068 - 03 Jul 2023
Viewed by 873
Abstract
Molecular modelling studies were carried out at the DFT level of the adsorption of propane and propene on Ag surfaces as a model of the interaction of light hydrocarbons with Ag/ZrO2 catalysts for catalytic combustion reactions. It was found that the most [...] Read more.
Molecular modelling studies were carried out at the DFT level of the adsorption of propane and propene on Ag surfaces as a model of the interaction of light hydrocarbons with Ag/ZrO2 catalysts for catalytic combustion reactions. It was found that the most stable mode of adsorption of propene through its π system on Ag atom has energies consistent with chemisorption and generates an elongation of the C1=C2 bond, which would explain the increase in the activity of the catalysts as a function of its metallic charge. The results obtained from the DFT calculations explain the different types of interactions between propene and propane with the metallic surface. The propene is chemisorbed on the Ag surface, distorting its bonds and generating its activation. This would imply that a higher metallic charge in the catalyst would increase the number of active sites in which this activation occurs, generating a higher activity. In addition, with the addition of O, the binding energy between the propene and the metal surface increased. On the other hand, the presence of a metallic surface is not enough for the activation of the propane molecule. This would explain why, by increasing the amount of metal in the catalyst, the activity for the combustion of propane is practically not affected. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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15 pages, 3691 KiB  
Article
Stable Sulfonic MCM-41 Catalyst for Furfural Production from Renewable Resources in a Biphasic System
by Yasnina Olivares, Carla Herrera, Juan Seguel, Catherine Sepúlveda, Carolina Parra and Gina Pecchi
Catalysts 2023, 13(6), 1024; https://doi.org/10.3390/catal13061024 - 20 Jun 2023
Cited by 1 | Viewed by 1224
Abstract
An MCM-41-SO3H catalyst with 14 wt% S was successfully synthesized to be used in furfural production from xylose and hemicellulose in a biphasic n-butanol/water system. The precursor MCM-41 and the acid-functionalized MCM-41-SO3H catalyst were characterized by XRD, FTIR, TEM, [...] Read more.
An MCM-41-SO3H catalyst with 14 wt% S was successfully synthesized to be used in furfural production from xylose and hemicellulose in a biphasic n-butanol/water system. The precursor MCM-41 and the acid-functionalized MCM-41-SO3H catalyst were characterized by XRD, FTIR, TEM, N2 physisorption, ICP-MS, TPD-NH3, and XPS. The characterization results indicated that the sulfonic process partially decreased the ordered mesoporous structure and increased the acid strength of the initial MCM-41. The catalytic performance of the xylose conversion was evaluated in a batch-type reactor using different biphasic ecological and renewable n-butanol/water ratios (1:1, 1.5:1, 2:1, and 2.5:1) as dissolvent at 170 °C. The effect of the dissolvent mixture was clearly seen from the larger initial reaction rate and TOF values for the 1.5:1 ratio. This catalytic behavior indicated that a proper proportion of n-butanol/water dissolvent mixture enhanced the solubility of the substrate in the n-butanol-rich mixture and prevented the deactivation of acidic sulfonated surface groups. To achieve transformation of lignocellulosic raw material to value-added products, the MCM-41-SO3H catalyst was also used for the production of furfural. The recycling evaluation tests indicated that for the recovered catalyst submitted to a sulfonation process, the yield of furfural was closer to the fresh catalyst. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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17 pages, 8440 KiB  
Article
Secondary Amines from Catalytic Amination of Bio-Derived Phenolics over Pd/C and Rh/C: Effect of Operation Parameters
by Maray Ortega, Raydel Manrique, Romel Jiménez, Miriam Parreño, Marcelo E. Domine and Luis E. Arteaga-Pérez
Catalysts 2023, 13(4), 654; https://doi.org/10.3390/catal13040654 - 27 Mar 2023
Cited by 1 | Viewed by 1810
Abstract
The production of renewable chemicals using lignocellulosic biomass has gained significant attention in green chemistry. Among biomass-derived chemicals, secondary amines have emerged as promising intermediates for synthetic applications. Here, we report a systematic study on the reductive amination of phenolics with cyclohexylamine using [...] Read more.
The production of renewable chemicals using lignocellulosic biomass has gained significant attention in green chemistry. Among biomass-derived chemicals, secondary amines have emerged as promising intermediates for synthetic applications. Here, we report a systematic study on the reductive amination of phenolics with cyclohexylamine using Pd/C and Rh/C as catalysts. The catalytic tests were performed in batch reactors under different reaction conditions (various: amine concentration (0.1–0.4 mol/L), hydrogen pressure (0–2.5 bar), temperature (80–160 °C), and substituted phenols (phenol, o-cresol, p-cresol, and methoxyphenol)) and using tert-amyl alcohol as a solvent. The experimental observations were consistent with a multi-step mechanism, where hydrogenation of phenol to cyclohexanone is followed by condensation of the ketone with cyclohexylamine to form an imine, which is finally hydrogenated to produce secondary amines. In addition, there was evidence of parallel self-condensation of the cyclohexylamine. The study also supported a limited dehydrogenation capacity of Rh/C, unlike Pd/C, which increases this capacity at higher temperatures generating a higher yield of cyclohexylaniline (up to 15%). The study of the alkylated phenols demonstrated that the nature and propensity of hydrogenation of the phenolic controls their amination. Kinetic analysis revealed reaction orders between 0.4 and 0.7 for H2, indicating its dissociative adsorption. Meanwhile, phenol’s order (between 1–1.8) suggests a single participation of this compound in the hydrogenation step. The order of 0.4 for cyclohexylamine suggests its participation as a surface-abundant species. The apparent activation energies derived from a power law approximation were of 37 kJ/mol and 10 kJ/mol on Pd/C and Rh/C, respectively. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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13 pages, 14234 KiB  
Article
The Quick Removal of Toxic Dye Molecules by an Efficient Adsorptive BiOI/Bi2MoO6 Heterostructure
by Tasie Ebenezer Onyedika, Mengying Xu, Yichao Deng, Yang Liu, Lian Li, Pier-Luc Tremblay and Tian Zhang
Catalysts 2023, 13(3), 457; https://doi.org/10.3390/catal13030457 - 21 Feb 2023
Cited by 2 | Viewed by 1374
Abstract
Adsorption is a low-energy, economical, and efficient method for pollutant removal from water. Because of their unique structure, large specific surface area (SSA), and non-toxicity, bismuth-based semiconductors, usually researched for the photodegradation of organic molecules, are also excellent for dark adsorption processes. Here, [...] Read more.
Adsorption is a low-energy, economical, and efficient method for pollutant removal from water. Because of their unique structure, large specific surface area (SSA), and non-toxicity, bismuth-based semiconductors, usually researched for the photodegradation of organic molecules, are also excellent for dark adsorption processes. Here, a three-dimensional adsorbent with a heterostructure with a hydrangea-like shape made of Bi2MoO6 (BMO) and BiOI (BOI) was synthesized by a one-pot solvothermal process and investigated for the adsorption of toxic dyes. BOI/BMO with an I-to-Mo ratio of 2.0 adsorbed 98.9% of the model pollutant rhodamine B (RhB) within 5 min with a maximum adsorption capacity of 72.72 mg/g in the dark at room temperature. When compared to pure BMO, the BOI2/BMO heterostructure was 14.1 times more performant because of its flower-like morphology with multiple planes, an SSA that was 1.6-fold larger, increased porosity, the formation of heterojunctions, and a negative surface charge attracting RhB. Further investigation indicated that adsorption by BOI2/BMO fitted the pseudo-second-order kinetic and the Langmuir isotherm models. In addition, the thermodynamic analysis showed that it was a spontaneous exothermic process probably relying on physisorption. Thus, the BOI/BMO adsorbent developed here is promising for the fast removal of toxic dyes from industrial wastewater. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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17 pages, 4528 KiB  
Article
Nickel and Cobalt Ilmenites-Based Catalysts for Upgrading Pyrolytic Oil during Pyrolysis of Waste Tires
by Daniela Correa-Muriel, Hoover Valencia-Sánchez, Héctor Cortes-Hernández, Daniela González-Vera, Javiera Herrera, Cristian H. Campos, Mónica L. Casella, Luis E. Arteaga-Perez and Paula Osorio-Vargas
Catalysts 2022, 12(11), 1437; https://doi.org/10.3390/catal12111437 - 15 Nov 2022
Cited by 1 | Viewed by 1883
Abstract
Pyrolysis as a waste treatment method has gained relevance because it can generate higher value-added products in addition to reducing the environment’s secondary pollution. In this study, the catalytic pyrolysis of waste tires was evaluated using NiTiO3 and CoTiO3 ilmenites as [...] Read more.
Pyrolysis as a waste treatment method has gained relevance because it can generate higher value-added products in addition to reducing the environment’s secondary pollution. In this study, the catalytic pyrolysis of waste tires was evaluated using NiTiO3 and CoTiO3 ilmenites as catalysts and precursors of metal catalysts with the aim to produce an oil enriched in high-value hydrocarbons, such as benzene, toluene, a xylenes mixture, and products less-reported, such as p-cymene and p-cymenene. The experiments were performed in an analytical pyrolyzer coupled to GC/MS. The effect of the nature of the catalysts on the product distribution was compared with the uncatalyzed reaction. The main products of uncatalyzed pyrolysis were D, L-limonene (~60%), and isoprene (~25%) due to the depolymerization of natural rubber. Meanwhile, Ni-ilmenites-based catalysts favored the formation of target compounds to expense D, L-limonene. Moreover, the presence of metal in reduced-ilmenite sharply enhanced the selectivity by ~50% concerning oxidized ilmenite and above 80% compared to the uncatalyzed reaction for p-cymene and p-cymenene. By contrast, the Co-ilmenites-based catalysts showed a marginal effect on secondary reactions. Finally, the feasibility of forming the aromatic terpenes, p-cymene, and p-cymenene from limonene in the non-catalytic pyrolysis was evaluated. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis for Environmentally Compatible Reactions and Processes)
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