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Catalytic Applications of Clay Minerals and Hydrotalcites

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

Deadline for manuscript submissions: closed (15 April 2021) | Viewed by 18061

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Special Issue Editors

Dr. Juan Antonio Cecilia

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Guest Editor

Departamento de Química Inorgánica, Cristalografía y Mineralogía, Universidad de Málaga, 29071 Málaga, Spain
Interests: adsorption; biomass valorization; heterogeneous catalysis; high-added value products
Special Issues, Collections and Topics in MDPI journals

Dr. Carmen Pilar Jiménez Gómez

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Guest Editor

Departamento de Química Inorgánica, Cristalografía y Mineralogía, Universidad de Málaga, 29071 Málaga, Spain
Interests: characterization; hydrotalcites; clay minerals; catalysis; biomass valorization
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Clay minerals are inexpensive and available materials with a wide range of applications (adsorbent, ion exchanger, support, catalyst, paper coating, ceramic, and pharmaceutical, among others). Clay minerals could be easily modified through acid/basic treatment, through the insertion of bulky ions or pillars in the interlayer spacing, as well as through acid treatment, improving their physicochemical properties.

Considering their low cost and high availability, clay minerals display a relatively high specific surface area in such a way that they have a great potential to be used as catalytic supports, since they can disperse expensive active phases as noble metals on the porous structure of their surface. In addition, the low cost of these supports allows their implementation on an industrial scale more easily than other supports, which are only feasible for the laboratory scale.

Hydrotalcites (considered as anionic or basic clays) are also inexpensive materials with a great potential to be used as catalysts, since their textural properties could also be modified easily through the insertion of anions in their interlayer spacing. In the same way, these hydrotalcites, formed by layered double hydroxides, can lead to their respective mixed oxides after thermal treatment. These mixed oxides are considered basic catalysts with a high surface area, so they can also be used as catalytic support.

Taking into account the great potential of clay minerals and hydrotalcites, the editors think that the catalytic applications of both materials are worthy of a Special Issue in the journal Catalysts.

Dr. Juan Antonio Cecilia
Dr. Carmen Pilar Jiménez Gómez
Guest Editors

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Keywords

Caracterization
Clay mineral
Hydrotalcites
Mixed oxides
Catalytic support
Heterogeneous catalysis

Published Papers (7 papers)

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Editorial

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4 pages, 212 KiB

Open AccessEditorial

Catalytic Applications of Clay Minerals and Hydrotalcites

by Juan Antonio Cecilia and Carmen Pilar Jiménez-Gómez

Catalysts 2021, 11(1), 68; https://doi.org/10.3390/catal11010068 - 06 Jan 2021

Cited by 7 | Viewed by 1738

Abstract

Clay minerals are the most abundant minerals on the surface of Earth [...] Full article

(This article belongs to the Special Issue Catalytic Applications of Clay Minerals and Hydrotalcites)

Research

Jump to: Editorial

11 pages, 4078 KiB

Open AccessCommunication

An Efficient Catalyst Prepared from Residual Kaolin for the Esterification of Distillate from the Deodorization of Palm Oil

by Alex de Nazaré de Oliveira, Irlon Maciel Ferreira, David Esteban Quintero Jimenez, Fernando Batista Neves, Linéia Soares da Silva, Ana Alice Farias da Costa, Erika Tallyta Leite Lima, Luíza Helena de Oliveira Pires, Carlos Emmerson Ferreira da Costa, Geraldo Narciso da Rocha Filho and Luís Adriano Santos do Nascimento

Catalysts 2021, 11(5), 604; https://doi.org/10.3390/catal11050604 - 07 May 2021

Cited by 8 | Viewed by 2455

Abstract

The distillate from the deodorization of palm oil (DDPO) is an agro-industrial residue, approximately 84% of which consists of free fatty acids (FFAs), which can be used for the production of fatty acid ethyl esters (FAEE). A catalyst (10HPMo/AlSiM) obtained from a waste material, Amazon flint kaolin, was applied in the esterification of the DDPO, reaching a conversion index of 94%, capable of maintaining satisfactory activity (>75%) after four consecutive cycles. Flint kaolin is therefore proven to be an efficient option in the search for new heterogeneous low-cost catalysts obtained from industrial by-products, contributing to the reduction of environmental impact and adding value to widely available wastes that would otherwise be discarded directly into the environment. Based on the catalytic results, esterification of DDPO using 10HPMo/AlSiM can be a cheaper alternative for the production of sustainable fuels. Full article

(This article belongs to the Special Issue Catalytic Applications of Clay Minerals and Hydrotalcites)

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12 pages, 21120 KiB

Open AccessArticle

MgF₂-Modified Hydrotalcite-Derived Composites Supported Pt-In Catalysts for Isobutane Direct Dehydrogenation

by Zhen Song, Jiameng Wang, Fanji Liu, Xiqing Zhang, Énio Matusse and Lihong Zhang

Catalysts 2021, 11(4), 478; https://doi.org/10.3390/catal11040478 - 08 Apr 2021

Cited by 2 | Viewed by 2245

Abstract

Here, a simple method was developed to prepare an MgF₂-modified hydrotalcite-derived composite, which was used as support for the Pt-In catalyst for isobutane direct dehydrogenation. The catalysts, composites, and their precursors were characterized by numerous characterization techniques. The results provided evidence for the MgF₂ promoter effect on the physical–chemical properties and dehydrogenation performance of the supported Pt-In catalysts. The catalyst with MgF₂ shows exceptional isobutene selectivity that can be stabilized at 95%, and the conversion increases from 50% to 58% during the reaction process. Moreover, the existence of MgF₂ plays an important role in the resistance to coke formation and Pt sintering by improving the Pt dispersion, inhibiting the reduction of the In³⁺ species, and adjusting the acidity of the catalyst. Full article

(This article belongs to the Special Issue Catalytic Applications of Clay Minerals and Hydrotalcites)

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12 pages, 3854 KiB

Open AccessArticle

Easily Recycled CuMgFe Catalysts Derived from Layered Double Hydroxides for Hydrogenolysis of Glycerol

by Xiaopeng Yu, Fubao Zhang, Yi Wang and Dejun Cheng

Catalysts 2021, 11(2), 232; https://doi.org/10.3390/catal11020232 - 09 Feb 2021

Cited by 4 | Viewed by 1790

Abstract

A series of CuMgFe catalysts with different (Cu + Mg)/Fe molar ratios derived from hydrotalcites were prepared by coprecipitation for the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO). X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), vibrating sample magnetometer (VSM), hydrogen temperature-programmed reduction (H₂-TPR), CO₂-TPD, and H₂-TPD (temperature-programmed desorption of CO₂ and H₂) were used to investigate the physicochemical properties of the catalysts. The CuMgFe-layered double oxides (CuMgFe-4LDO) catalyst with (Cu + Mg)/Fe molar ratio of 4 exhibited superior activity and stability. The high glycerol conversion and 1,2-propanediol selectivity over CuMgFe-4LDO catalyst were attributed to its strong basicity, excellent H₂ activation ability, and an increase in the surface Cu content. The CuMgFe catalysts could be easily recycled with the assistance of an external magnetic field due to their magnetism. Full article

(This article belongs to the Special Issue Catalytic Applications of Clay Minerals and Hydrotalcites)

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22 pages, 6292 KiB

Open AccessFeature PaperArticle

Gas-Phase Hydrogenation of Furfural to Furfuryl Alcohol over Cu-ZnO-Al₂O₃ Catalysts Prepared from Layered Double Hydroxides

by Guillermo R. Bertolini, Carmen P. Jiménez-Gómez, Juan Antonio Cecilia and Pedro Maireles-Torres

Catalysts 2020, 10(5), 486; https://doi.org/10.3390/catal10050486 - 29 Apr 2020

Cited by 15 | Viewed by 3036

Abstract

Several layered double hydroxides (LDHs) with general chemical composition (Cu,Zn)_1−xAl_x(OH)₂(CO₃)_x/2·mH₂O have been synthesized by the co-precipitation method, maintaining a (M²⁺/M³⁺) molar ratio of 3, and varying the Cu²⁺/Zn²⁺ molar ratio between 0.2 and 6.0. After calcination and reduction steps, Cu/ZnO/Al₂O₃ catalysts were synthesized. These catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), H₂ thermoprogrammed reduction (H₂-TPR), N₂ adsorption-desorption at −196 °C, N₂O titration, X-ray photoelectron miscroscopy (XPS), NH₃-thermoprogramed desorption (NH₃-TPD) and CO₂- thermoprogrammed desorption (CO₂-TPD). The characterization data revealed that these catalysts are mainly meso-and macroporous, where Cu, ZnO and Al₂O₃ are well dispersed. The catalytic results show that these catalysts are active in the gas-phase hydrogenation of furfural, being highly selective to furfuryl alcohol (FOL) and reaching the highest FOL yield for the catalyst with a Cu²⁺/Zn²⁺ molar ratio of 1. In an additional study, the influence of the aging time on the synthesis of the LDHs was also evaluated. The catalytic data revealed that the use of shorter aging time in the formation of the LDH has a beneficial effect on the catalytic behavior, since more disordered structures with a higher amount of available Cu sites is obtained, leading to a higher yield towards FOL (71% after 5 h of time-on-stream at 210 °C). Full article

(This article belongs to the Special Issue Catalytic Applications of Clay Minerals and Hydrotalcites)

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15 pages, 3292 KiB

Open AccessArticle

Effect of Reduction Atmosphere on Structure and Catalytic Performance of PtIn/Mg(Al)O/ZnO for Propane Dehydrogenation

by Ming Zhang, Zhen Song, Mengquan Guo, Xiangxiang Li, Yanjun Lin and Lihong Zhang

Catalysts 2020, 10(5), 485; https://doi.org/10.3390/catal10050485 - 29 Apr 2020

Cited by 8 | Viewed by 2437

Abstract

The effect of reduction atmospheres, H₂/N₂, C₃H₈/H₂/N₂, C₃H₈ and CO, on the structure and propane direct dehydrogenation performance of PtIn/Mg(Al)O/ZnO catalyst derived from ZnO-supported PtIn-hydrotalcite was studied. The physicochemical properties of the as-prepared and used catalytic system were characterized by various characterization methods. The results show that the dehydrogenation performance, especially the stability of the PtIn/Mg(Al)O/ZnO catalyst, was significantly improved along with the change in reduction atmosphere. The highest catalytic activity (51% of propane conversion and 97% propylene selectivity), resistance toward coke deposition, and stability for more than 30 h were achieved with the H₂/N₂-reduced catalyst. The optimal dehydrogenation performance and coke resistance are mainly related to the high Pt dispersion and In⁰/In³⁺ molar ratio, strong Pt–In interaction and small metal particle size, depending on the nature of the reduction atmospheres. The reconstruction of meixnerite favors the stability and coke resistance to some extent. Full article

(This article belongs to the Special Issue Catalytic Applications of Clay Minerals and Hydrotalcites)

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17 pages, 9008 KiB

Open AccessArticle

Hierarchical PtIn/Mg(Al)O Derived from Reconstructed PtIn-hydrotalcite-like Compounds for Highly Efficient Propane Dehydrogenation

by Jiaxin Li, Ming Zhang, Zhen Song, Shuo Liu, Jiameng Wang and Lihong Zhang

Catalysts 2019, 9(9), 767; https://doi.org/10.3390/catal9090767 - 12 Sep 2019

Cited by 17 | Viewed by 3229

Abstract

The challenges facing propane dehydrogenation are to solve the Pt sintering and carbon deposition. This paper provides a new way to disperse and stabilize Pt species and resist carbon deposition. Highly dispersed Pt species were topologically transformed from reconstructed PtIn-hydrotalcite-like precursors in a flower-like hierarchical microstructure. The lattice confinement of reconstructed hydrotalcite-like precursor is in favor of stabilizing the highly dispersed Pt species, and the hierarchical microstructure is an important factor to prolong its lifetime by enhancing tolerance to carbon deposition. In propane dehydrogenation, the propene selectivity decreases in the sequences of catalyst in flower-like > single-plate > block mass with small, flakeys. A propene selectivity of >97% with a conversion of 48% at 600 °C has been achieved over a flower-like PtIn/Mg(Al)O catalyst. Additionally, no visible Pt sintering can even be observed on this catalyst after a reaction time of 190 h. This strategy provides an effective and feasible alternative for the facile preparation of highly dispersed metal catalysts. Full article

(This article belongs to the Special Issue Catalytic Applications of Clay Minerals and Hydrotalcites)

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