Heterogeneous Catalytic Materials: Synthesis, Characterization and Applications for Energetic Purposes, 2nd Edition

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

Deadline for manuscript submissions: closed (15 June 2023) | Viewed by 8946

Special Issue Editor

Institute for Advanced Energy Technologies "Nicola Giordano" ITAE, Italian National Research Council (CNR), 98126 Messina, Italy
Interests: heterogenous catalysis (synthesis, chemico-physical characterization, structure–activity relationship); biofuels; additives for biofuels; green chemistry; reaction kinetics and mechanisms; CO2 conversion
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Special Issue Information

Dear Colleagues, 

Solid catalytic materials play a key role in the development of industrial chemistry, showing important advantages over liquid materials due 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 applications of heterogeneous catalysts for energetic purposes, such as biofuels synthesis and H2 production, through biomass, waste, biogas, or CO2 conversion with specific interest in innovative procedures of synthesis or catalytic formulations and chemico-physical characterization techniques. 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, 2nd Edition”.

Dr. Catia Cannilla
Guest Editor

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Keywords

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

Published Papers (5 papers)

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Research

16 pages, 2685 KiB  
Article
Reaction Pathways of Gamma-Valerolactone Hydroconversion over Co/SiO2 Catalyst
by Gyula Novodárszki, Ferenc Lónyi, Magdolna R. Mihályi, Anna Vikár, Róbert Barthos, Blanka Szabó, József Valyon and Hanna E. Solt
Catalysts 2023, 13(7), 1144; https://doi.org/10.3390/catal13071144 - 23 Jul 2023
Viewed by 984
Abstract
The hydroconversion of γ-valerolactone (GVL) over Co/SiO2 catalyst proceeds in a complex reaction network, resulting in 2-methyltetrahydrofuran (2-MTHF) as the main product, and C4–C5 alcohol and alkane side-products. The catalyst was shown to contain Co0 sites and Lewis [...] Read more.
The hydroconversion of γ-valerolactone (GVL) over Co/SiO2 catalyst proceeds in a complex reaction network, resulting in 2-methyltetrahydrofuran (2-MTHF) as the main product, and C4–C5 alcohol and alkane side-products. The catalyst was shown to contain Co0 sites and Lewis acid (Co2+ ion)/Lewis base (O2− ion) pair sites, active for hydrogenation/dehydrogenation and dehydration reactions, respectively. The initial reaction step was confirmed to be the hydrogenation of GVL to key intermediate 1,4-pentanediol (1,4-PD). Cyclodehydration of 1,4-PD led to the main product 2-MTHF, whereas its dehydration/hydrogenation gave 1-pentanol and 2-pentanol side-products, with about the same yield. In contrast, 2-pentanol was the favored alcohol product of 2-MTHF hydrogenolysis. 2-Butanol was formed by decarbonylation of 4-hydroxypentanal intermediate. The latter was the product of 1,4-PD dehydrogenation. Alkanes were formed from the alcohol side-products via dehydration/hydrogenation reactions. Full article
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17 pages, 7078 KiB  
Article
Titanium Carbide Composite Hollow Cobalt Sulfide Heterojunction with Function of Promoting Electron Migration for Efficiency Photo-Assisted Electro-Fenton Cathode
by Fengjiang Chen, Fan Yang, Sai Che, Hongchen Liu, Neng Chen, Zhijie Wu and Yongfeng Li
Catalysts 2023, 13(2), 253; https://doi.org/10.3390/catal13020253 - 22 Jan 2023
Cited by 1 | Viewed by 1742
Abstract
Constructing heterostructure within electrocatalysts proves to be an attractive approach to adjust the interfacial charge redistribution to promote the adsorption of reactive species and accelerate the charge transfer. Herein, we present the one-pot solvothermal synthesis of Ti3C2 supported hollow CoS [...] Read more.
Constructing heterostructure within electrocatalysts proves to be an attractive approach to adjust the interfacial charge redistribution to promote the adsorption of reactive species and accelerate the charge transfer. Herein, we present the one-pot solvothermal synthesis of Ti3C2 supported hollow CoS2/CoS microsphere heterostructure with uneven charge distribution as the cathodic catalyst, which displays a superior quasi-first-order degradation rate (0.031 min−1) for sulfamethazine (SMT) in photo-assisted electric–Fenton (EF) process. CoS2/CoS/Ti3C2 is proven to favor the 2e oxygen reduction reaction (ORR), with H2O2 selectivity up to 76%. The built-in potential present in the heterojunction helps to accelerate electron transfer, thus promoting the production of H2O2. Subsequently, H2O2 is rapidly activated to produce ∙OH due to the synergistic effect of Co and S. Notably, CoS2/CoS/Ti3C2 exhibits enhanced photo-assisted EF (PEF) performance under light. The excellent photocatalysis properties of CoS2/CoS/Ti3C2 are attributed to that the unique hollow microsphere structure of catalyst improves the light absorption, and the uneven charge distribution of CoS2/CoS heterojunctions promotes the separation of photo-generated holes and electrons. Given the above advantages, CoS2/CoS/Ti3C2 cathode delivers a high degradation rate of 98.5%, 91.8%, and 94.5% for SMT, bisphenol A, and sulfadiazine, respectively, with TOC removal efficiency of 76% for SMT with 120 min. This work provides a novel light of the design and construction of efficient PEF cathodes for the treatment of antibiotic wastewater. Full article
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19 pages, 3536 KiB  
Article
Effect of Modulation and Functionalization of UiO-66 Type MOFs on Their Surface Thermodynamic Properties and Lewis Acid–Base Behavior
by Ali Ali-Ahmad, Tayssir Hamieh, Thibault Roques-Carmes, Mohamad Hmadeh and Joumana Toufaily
Catalysts 2023, 13(1), 205; https://doi.org/10.3390/catal13010205 - 16 Jan 2023
Cited by 2 | Viewed by 2050
Abstract
In this study, we investigated the surface thermodynamic properties of four MOF structures of the UiO-66 series, by employing seven molecular models, a thermal model, and three other methods using the inverse gas chromatography (IGC) technique at infinite dilution. We first determined the [...] Read more.
In this study, we investigated the surface thermodynamic properties of four MOF structures of the UiO-66 series, by employing seven molecular models, a thermal model, and three other methods using the inverse gas chromatography (IGC) technique at infinite dilution. We first determined the effect of the modulation of UiO-66 by an acid (e.g., formic acid and acetic acid) and on the other hand, we studied the effect of the functionalization of the organic linker by an amine group (NH2) on their dispersive component of the surface energy and on their Lewis acid–base properties. We found that all the studied MOFs presented an amphoteric character with a strong acidity whose acidity/basicity ratio is greater than 1 using all the models and methods in IGC. Moreover, the introduction of a modulator such as acetic acid or formic acid in the synthesis of these MOFs increased the number of structural defects and therefore increased the acidity of these MOFs. Similarly, the functionalization of the MOF by the NH2 group leads to an increase in the basicity constant of the functionalized MOF while remaining smaller than their acidity constant. In addition, the use of acids as modulators and amine groups as functional groups resulted in an increase in the dispersive component of the surface energy of the MOFs. Finally, comparing the results obtained by the different models and methods and based on the increasing order of the acidity of each MOF, it was clear that the thermal model resulted in more exact and precise values than the others. Our findings pave the way for the design and development of new acid catalysts based on UiO-66 structures. Full article
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10 pages, 2126 KiB  
Article
Differentiating the Reactivity of ZrO2-Bound Formates Formed on Cu/ZrO2 during CO2 Hydrogenation
by Frederic C. Meunier, Isaac Dansette, Kimleang Eng and Yves Schuurman
Catalysts 2022, 12(7), 793; https://doi.org/10.3390/catal12070793 - 19 Jul 2022
Cited by 9 | Viewed by 1687
Abstract
The surface species formed during the hydrogenation of CO2 with H2 over a ZrO2-supported Cu catalyst were investigated by operando diffuse reflectance FT-IR spectroscopy at 220 °C and 3 bar. The reactivity of two different formates located on zirconia [...] Read more.
The surface species formed during the hydrogenation of CO2 with H2 over a ZrO2-supported Cu catalyst were investigated by operando diffuse reflectance FT-IR spectroscopy at 220 °C and 3 bar. The reactivity of two different formates located on zirconia could be unraveled. The data pointed to ZrO2 hydroxyl groups at 3755 cm−1 as the sites on which carbonates and then formates were hydrogenated to methoxy species. Formate hydrogenation appeared as the slowest step. The most reactive ZrO2-bound formates exhibited a rate constant of reaction about 65 times higher than that of the slower formate. Full article
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16 pages, 6240 KiB  
Article
Copper and Iron Cooperation on Micro-Spherical Silica during Methanol Synthesis via CO2 Hydrogenation
by Serena Todaro, Francesco Frusteri, Dariusz Wawrzyńczak, Izabela Majchrzak-Kucęba, Juan-Francisco Pérez-Robles, Catia Cannilla and Giuseppe Bonura
Catalysts 2022, 12(6), 603; https://doi.org/10.3390/catal12060603 - 31 May 2022
Cited by 2 | Viewed by 1861
Abstract
A series of mono- and bi-metallic copper and iron samples were prepared by impregnation method on micro-spherical silica and used for the synthesis of methanol via CO2 hydrogenation. Compared with conventional carrier oxides, micro-spherical silica has obvious advantages in terms of absorption [...] Read more.
A series of mono- and bi-metallic copper and iron samples were prepared by impregnation method on micro-spherical silica and used for the synthesis of methanol via CO2 hydrogenation. Compared with conventional carrier oxides, micro-spherical silica has obvious advantages in terms of absorption capacity and optimal distribution of active phases on its surface, also exhibiting excellent heat resistance properties and chemical stability. The prepared catalysts were characterized by various techniques including XRF, XRD, SEM, TEM, H2-TPR and CO2-TPD techniques, while catalytic measurements in CO2 hydrogenation reaction to methanol were performed in a fixed bed reactor at a reaction pressure of 30 bar and temperature ranging from 200 to 260 °C. The obtained results revealed that the mutual interaction of copper–iron induces promotional effects on the formation of methanol, especially on systems where Fe enrichment on the silica support favours the presence of a larger concentration of oxygen vacancies, consequently responsible for higher CO2 adsorption and selective methanol production. Surface reconstruction phenomena rather than coke or metal sintering were responsible for the slight loss of activity recorded on the catalyst samples during the initial phase of reaction; however, with no appreciable change on the product selectivity. Full article
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