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Volume 10
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Catalysts, Volume 10, Issue 11 (November 2020) – 142 articles

Cover Story (view full-size image): Municipal solid waste is typically treated by mechanical and biological methods, resulting in the production of biogas and compost. However, compost is not economically attractive, and its production exceeds its demand for agricultural applications. Novel strategies are thus proposed to valorize compost into low-cost catalysts for the treatment of wastewater. View this paper
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22 pages, 8064 KiB  
Article
A Dynamic Model Incorporated with Delay Estimation and Variable Selection for Control of SCR De-NOx Process
by Ze Dong, Ling Li, Laiqing Yan, Ming Sun and Jinsong Li
Catalysts 2020, 10(11), 1364; https://doi.org/10.3390/catal10111364 - 23 Nov 2020
Cited by 7 | Viewed by 2646
Abstract
In order to control NH3 injection for the selective catalytic reduction of nitrogen oxide (NOx) denitration (SCR de-NOx) process, a model that can accurately and quickly predict outlet NOx emissions is required. This paper presents a dynamic [...] Read more.
In order to control NH3 injection for the selective catalytic reduction of nitrogen oxide (NOx) denitration (SCR de-NOx) process, a model that can accurately and quickly predict outlet NOx emissions is required. This paper presents a dynamic kernel partial least squares (KPLS) model incorporated with delay estimation and variable selection for outlet NOx emission and investigated control strategy for NH3 injection. First, k-nearest neighbor mutual information (KNN_MI) was used for delay estimation, and the effect of historical data lengths on KNN_MI was taken into account. Bidirectional search based on the change rate of KNN_MI (KNN_MI_CR) was used for variable selection. Delay–time difference update algorithm and feedback correction strategy were proposed. Second, the NH3 injection compensator (NIC) and the outlet NOx emission model constituted a correction controller. Then, its output and the output of the existing controller are added up to suitable NH3 injection. Finally, the KNN_MI_CR method was compared with different algorithms by benchmark dataset. The field data results showed that the KNN_MI_CR method could improve model accuracy for reconstructed samples. The final model can predict outlet NOx emissions in different operating states accurately. The control result not only meets the NOx emissions standard (50 mg/m3) but also keeps high de-NOx efficiency (80%). NH3 injection and NH3 escape are reduced by 11% and 39%. Full article
(This article belongs to the Special Issue Selective Catalytic Reduction: From Basic Science to deNOx Applications)
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12 pages, 4391 KiB  
Article
Mesoporous Silica-Supported Ionic Liquids as Catalysts for Styrene Carbonate Synthesis from CO2
by Agnieszka Siewniak, Adrianna Forajter and Katarzyna Szymańska
Catalysts 2020, 10(11), 1363; https://doi.org/10.3390/catal10111363 - 23 Nov 2020
Cited by 12 | Viewed by 3023
Abstract
Various types of mesoporous silica were used as carriers to synthesize a series of immobilized imidazolium-based ionic liquids. Their activity was tested in the synthesis of styrene carbonate from CO2 and styrene. This is one-pot process, whereby two stages are carried out [...] Read more.
Various types of mesoporous silica were used as carriers to synthesize a series of immobilized imidazolium-based ionic liquids. Their activity was tested in the synthesis of styrene carbonate from CO2 and styrene. This is one-pot process, whereby two stages are carried out in one reactor and there is no need to isolate the intermediate product, epoxide. A systematic study on the influence of parameters such as temperature, the reaction time, CO2 pressure, as well as the amount and type of catalyst used was carried out. A strong synergistic catalytic effect of ionic liquid and Lewis acid was observed in promoting this reaction. The addition sequence of regents and amount of immobilized catalyst were considered crucial for the synthesis of styrene carbonate from CO2 and styrene. The tested silica-supported ionic liquids gave an easily-recyclable system which under the most favorable conditions ([mtespim]Cl/@SiO2; ZnBr2, 0.1 mol%; 110 °C, 4 h, 1 MPa) can be reused without a significant loss of catalytic activity nor selectivity. Full article
(This article belongs to the Section Catalysis in Organic and Polymer Chemistry)
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14 pages, 3780 KiB  
Article
New Approach to Synthesis of Tetralin via Naphthalene Hydrogenation in Supercritical Conditions Using Polymer-Stabilized Pt Nanoparticles
by Alexey V. Bykov, Daria V. Alekseeva, Galina N. Demidenko, Alexandre L. Vasiliev, Linda Nikoshvili and Lioubov Kiwi-Minsker
Catalysts 2020, 10(11), 1362; https://doi.org/10.3390/catal10111362 - 23 Nov 2020
Cited by 17 | Viewed by 3354
Abstract
Supercritical (SC) fluid technologies are well-established methods in modern green chemical synthesis. Using SC fluids as solvents instead of traditional liquids gives benefits of higher diffusivity and lower viscosity, which allows mass transfer intensification and, thus, an increased production rate of chemical transformations. [...] Read more.
Supercritical (SC) fluid technologies are well-established methods in modern green chemical synthesis. Using SC fluids as solvents instead of traditional liquids gives benefits of higher diffusivity and lower viscosity, which allows mass transfer intensification and, thus, an increased production rate of chemical transformations. Therefore, a conjugation of heterogeneous catalysis with SC media is a large step toward a green chemistry. Tetralin (TL) is an important hydrogen donor solvent used for biomass liquefaction. In industry, TL is obtained via catalytic hydrogenation of naphthalene (NL). Herein, for the first time we have demonstrated the NL hydrogenation with close to 100% selectivity to TL at almost full conversion in the SC hexane. The observed transformation rates in SC hexane were much higher allowing process intensification. The downstream processes can be also facilitated since hexane after depressurisation can be easily separated from the reaction products via simple rectification. The TL synthesis was studied in a batch reactor at variation of reaction temperature and overall pressure. For the first time for this process, low Pt-loaded (1 wt.%) nanoparticles stabilized within hyper-cross-linked aromatic polymer (HAP) were applied. The Pt/HAP catalyst was stable under reaction conditions (250 °C, 6 MPa) allowing its recovery and reuse. Full article
(This article belongs to the Special Issue Heterogeneous Catalysis in Green Chemistry)
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18 pages, 2447 KiB  
Article
Redox Isomerization of Allylic Alcohols Catalyzed by New Water-Soluble Rh(I)-N-Heterocyclic Carbene Complexes
by Csilla Enikő Czégéni, Marianna Fekete, Eszter Tóbiás, Antal Udvardy, Henrietta Horváth, Gábor Papp and Ferenc Joó
Catalysts 2020, 10(11), 1361; https://doi.org/10.3390/catal10111361 - 23 Nov 2020
Cited by 7 | Viewed by 3134
Abstract
New water-soluble, N-heterocyclic carbene (NHC) or mixed NHC/tertiary phosphine complexes [RhCl(cod)(sSIMes)], Na2[Rh(bmim)(cod)(mtppts)], and [Rh(bmim)(cod)(pta)]BF4 were synthetized and applied for the first time as catalysts in redox isomerization of allylic alcohols in aqueous media. [RhCl(cod)(sSIMes)] (with added sulfonated [...] Read more.
New water-soluble, N-heterocyclic carbene (NHC) or mixed NHC/tertiary phosphine complexes [RhCl(cod)(sSIMes)], Na2[Rh(bmim)(cod)(mtppts)], and [Rh(bmim)(cod)(pta)]BF4 were synthetized and applied for the first time as catalysts in redox isomerization of allylic alcohols in aqueous media. [RhCl(cod)(sSIMes)] (with added sulfonated triphenylphosphine) and [Rh(bmim)(cod)(pta)]BF4 catalyzed selectively the transformation of allylic alcohols to the corresponding ketones. The highest catalytic activity, TOF = 152 h−1 (TOF = (mol reacted substrate) × (mol catalyst × time)−1) was observed in redox isomerization of hept-1-en-3-ol ([S]/[cat] = 100). The catalysts were reused in the aqueous phase at least three times, with only modest loss of the catalytic activity and selectivity. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis)
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10 pages, 2075 KiB  
Communication
A Highly Active Au/In2O3-ZrO2 Catalyst for Selective Hydrogenation of CO2 to Methanol
by Zhe Lu, Kaihang Sun, Jing Wang, Zhitao Zhang and Changjun Liu
Catalysts 2020, 10(11), 1360; https://doi.org/10.3390/catal10111360 - 23 Nov 2020
Cited by 44 | Viewed by 5513
Abstract
A novel gold catalyst supported by In2O3-ZrO2 with a solid solution structure shows a methanol selectivity of 70.1% and a methanol space–time yield (STY) of 0.59 gMeOH h−1 gcat−1 for CO2 hydrogenation to [...] Read more.
A novel gold catalyst supported by In2O3-ZrO2 with a solid solution structure shows a methanol selectivity of 70.1% and a methanol space–time yield (STY) of 0.59 gMeOH h−1 gcat−1 for CO2 hydrogenation to methanol at 573 K and 5 MPa. The ZrO2 stabilizes the structure of In2O3, increases oxygen vacancies, and enhances CO2 adsorption, causing the improved activity. Full article
(This article belongs to the Special Issue Feature Papers to Celebrate “Environmental Catalysis”—Trends & Outlook)
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13 pages, 5504 KiB  
Article
Rh Particles Supported on Sulfated g-C3N4: A Highly Efficient and Recyclable Heterogeneous Catalyst for Alkene Hydroformylation
by Yukun Shi, Yang Lu, Tongxin Ren, Jie Li, Qiqige Hu, Xiaojing Hu, Baolin Zhu and Weiping Huang
Catalysts 2020, 10(11), 1359; https://doi.org/10.3390/catal10111359 - 23 Nov 2020
Cited by 11 | Viewed by 3119
Abstract
The hydroformylation of alkenes with CO and H2 to manufacture aldehydes is one of the most large-scale chemical reactions. However, an efficient and recyclable heterogeneous catalyst for alkene hydroformylation is extremely in demand in academia and industry. In this study, a sulfated [...] Read more.
The hydroformylation of alkenes with CO and H2 to manufacture aldehydes is one of the most large-scale chemical reactions. However, an efficient and recyclable heterogeneous catalyst for alkene hydroformylation is extremely in demand in academia and industry. In this study, a sulfated carbon nitride supported rhodium particle catalyst (Rh/S-g-C3N4) was successfully synthesized via an impregnation-borohydride reduction method and applied in the hydroformylation of alkenes. The catalysts were characterized by XRD, FTIR, SEM, TEM, XPS, and nitrogen adsorption. The influence of the sulfate content, pressure of syngas, temperature, and reaction time, as well as the stability of Rh/S-g-C3N4, on the hydroformylation was examined in detail. The delocalized conjugated structure in g-C3N4 can lead to the formation of electron-deficient aromatic intermediates with alkenes. The sulphate g-C3N4 has a defected surface owing to the formation of oxygen vacancies, which increased the adsorption and dispersion of RhNPs on the surface of g-C3N4. Therefore, Rh/S-g-C3N4 exhibited an outstanding catalytic performance for styrene hydroformylation (TOF = 9000 h−1), the conversion of styrene could reach 99.9%, and the regioselectivity for the branched aldehyde was 52% under the optimized reaction conditions. The catalytic properties of Rh/S-g-C3N4 were also studied in the hydroformylation of various alkenes and displayed an excellent catalytic performance. Furthermore, the reuse of Rh/S-g-C3N4 was tested for five recycling processes, without an obvious decrease in the activity and selectivity under the optimum reaction conditions. These findings demonstrated that Rh/S-g-C3N4 is a potential catalyst for heterogeneous hydroformylation. Full article
(This article belongs to the Special Issue The Design and Development of Precious Metal Catalysts)
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39 pages, 8804 KiB  
Review
Non-Thermal Plasma for Process and Energy Intensification in Dry Reforming of Methane
by Rufat Sh. Abiev, Dmitry A. Sladkovskiy, Kirill V. Semikin, Dmitry Yu. Murzin and Evgeny V. Rebrov
Catalysts 2020, 10(11), 1358; https://doi.org/10.3390/catal10111358 - 22 Nov 2020
Cited by 46 | Viewed by 7874
Abstract
Plasma-assisted dry reforming of methane (DRM) is considered as a potential way to convert natural gas into fuels and chemicals under near ambient temperature and pressure; particularly for distributed processes based on renewable energy. Both catalytic and photocatalytic technologies have been applied for [...] Read more.
Plasma-assisted dry reforming of methane (DRM) is considered as a potential way to convert natural gas into fuels and chemicals under near ambient temperature and pressure; particularly for distributed processes based on renewable energy. Both catalytic and photocatalytic technologies have been applied for DRM to investigate the CH4 conversion and the energy efficiency of the process. For conventional catalysis; metaldoped Ni-based catalysts are proposed as a leading vector for further development. However; coke deposition leads to fast deactivation of catalysts which limits the catalyst lifetime. Photocatalysis in combination with non-thermal plasma (NTP), on the other hand; is an enabling technology to convert CH4 to more reactive intermediates. Placing the catalyst directly in the plasma zone or using post-plasma photocatalysis could generate a synergistic effect to increase the formation of the desired products. In this review; the recent progress in the area of NTP-(photo)catalysis applications for DRM has been described; with an in-depth discussion of novel plasma reactor types and operational conditions including employment of ferroelectric materials and nanosecond-pulse discharges. Finally, recent developments in the area of optical diagnostic tools for NTP, such as optical emission spectroscopy (OES), in-situ FTIR, and tunable diode laser absorption spectroscopy (TDLAS), are reviewed. Full article
(This article belongs to the Special Issue Photo- and Electro-Catalysis of Nanomaterials for Energy Conversion and Storage)
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13 pages, 2726 KiB  
Article
Enhancement of Ni Catalyst Using CeO2–Al2O3 Support Prepared with Magnetic Inducement for ESR
by Pumiwat Vacharapong, Sirintra Arayawate, Sasimas Katanyutanon, Pisanu Toochinda, Luckhana Lawtrakul and Sumittra Charojrochkul
Catalysts 2020, 10(11), 1357; https://doi.org/10.3390/catal10111357 - 21 Nov 2020
Cited by 7 | Viewed by 2547
Abstract
The effect of magnetic inducement in support preparation was studied to reduce coke and improve the activity of Ni catalysts for ethanol steam reforming (ESR) at 550–650 °C. Magnetic inducement was introduced to prepare 5 mol % CeO2 in Al2O [...] Read more.
The effect of magnetic inducement in support preparation was studied to reduce coke and improve the activity of Ni catalysts for ethanol steam reforming (ESR) at 550–650 °C. Magnetic inducement was introduced to prepare 5 mol % CeO2 in Al2O3 support in order to control the composition and the distribution of Ce in Al2O3. The results show that using CeO2–Al2O3 support with magnetic inducement affects both hydrogen production and coke reduction, where Ni/CeO2–Al2O3 support prepared under magnetic inducement with N–N pole arrangement (Ni/CeO2–Al2O3 (N–N)) exhibited the highest hydrogen production and the lowest coke formation among the catalysts used in this work. Compared with Ni/CeO2–Al2O3 (no magnet), Ni/CeO2–Al2O3 (N–N) catalysts yield 14.0% higher H2 production and 31.7% less coke production. The modified catalyst preparation process used in this study could create catalysts for hydrogen production from ESR which are high in performance and stability but low in preparation cost. Full article
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16 pages, 5798 KiB  
Article
Solar-Driven Chemical Looping Methane Reforming Using ZnO Oxygen Carrier for Syngas and Zn Production in a Cavity-Type Solar Reactor
by Srirat Chuayboon and Stéphane Abanades
Catalysts 2020, 10(11), 1356; https://doi.org/10.3390/catal10111356 - 21 Nov 2020
Cited by 7 | Viewed by 2615
Abstract
Converting sunlight into chemical fuels and metal commodities, via solar thermochemical conversion processes, is an attractive prospect for the long-term storage of renewable energy. In this study, the combined methane reforming and ZnO reduction in a single reaction for co-production of hydrogen-rich syngas [...] Read more.
Converting sunlight into chemical fuels and metal commodities, via solar thermochemical conversion processes, is an attractive prospect for the long-term storage of renewable energy. In this study, the combined methane reforming and ZnO reduction in a single reaction for co-production of hydrogen-rich syngas and metallic Zn was demonstrated in a flexible solar thermochemical reactor prototype, driven by highly concentrated sunlight. Using solar energy as the process heat source in chemical-looping methane reforming with the ZnO/Zn oxygen carrier is a means to reduce the dependence on conventional energy resources and to reduce emissions of CO2 and other pollutants, while upgrading the calorific value of the feedstock for the production of energy-intensive and high-value chemical fuels and materials. On-sun experiments were carried out with different operating parameters including operating temperatures (800–1000 °C), inlet methane flow-rates (0.1–0.4 NL/min), and inlet ZnO feeding-rates (0.5–1.0 g/min) both in batch and continuous modes under reduced (0.15 and 0.45 bar) and atmospheric pressures (0.90 bar), thereby demonstrating solar reactor flexibility and reliability. As a result, increasing the temperature promoted net ZnO conversion at the expense of favored methane cracking reaction, which can be lowered by decreasing pressure to vacuum conditions. Diminishing total pressure improved the net ZnO conversion but favored CO2 yield due to insufficient gas residence time. Rising ZnO feeding rate under a constant over-stoichiometric CH4/ZnO molar ratio of 1.5 enhanced ZnO and methane consumption rates, which promoted Zn and syngas yields. However, an excessively high ZnO feeding rate may be detrimental, as ZnO could accumulate when the ZnO feeding rate is higher than the ZnO consumption rate. In comparison, continuous operation demonstrated greater performance regarding higher ZnO conversion (XZnO) and lower methane cracking than batch operation. High-purity metallic Zn with a well-crystallized structure and of micrometric size was produced from both batch and continuous tests under vacuum and atmospheric pressures, demonstrating suitable reactor performance for the solar thermochemical methane-driven ZnO reduction process. The produced Zn metal can be further re-oxidized with H2O or CO2 in an exothermic reaction to produce pure H2 or CO by chemical-looping. Full article
(This article belongs to the Special Issue Chemical Looping for Catalysis)
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14 pages, 1575 KiB  
Article
On Catalytic Behavior of Bulk Mo2C in the Hydrodenitrogenation of Indole over a Wide Range of Conversion Thereof
by Marek Lewandowski, Rafał Janus, Mariusz Wądrzyk, Agnieszka Szymańska-Kolasa, Céline Sayag and Gérald Djéga-Mariadassou
Catalysts 2020, 10(11), 1355; https://doi.org/10.3390/catal10111355 - 21 Nov 2020
Cited by 6 | Viewed by 2556
Abstract
The catalytic activity of bulk molybdenum carbide (Mo2C) in the hydrodenitrogenation (HDN) of indole was studied. The catalyst was synthesized using a temperature-programmed reaction of the respective oxide precursor (MoO3) with the carburizing gas mixture of 10 vol.\% CH [...] Read more.
The catalytic activity of bulk molybdenum carbide (Mo2C) in the hydrodenitrogenation (HDN) of indole was studied. The catalyst was synthesized using a temperature-programmed reaction of the respective oxide precursor (MoO3) with the carburizing gas mixture of 10 vol.\% CH4/H2. The resultant material was characterized using X-ray diffraction, CO chemisorption, and nitrogen adsorption. The catalytic activity was studied in the HDN of indole over a wide range of conversion thereof and in the presence of a low amount of sulfur (50 ppm), which was used to simulate the processing of real petroleum intermediates. The molybdenum carbide has shown high activity under the tested operating conditions. Apparently, the bulk molybdenum carbide turned out to be selective towards the formation of aromatic products such as ethylbenzene, toluene, and benzene. The main products of HDN were ethylbenzene and ethylcyclohexane. After 99% conversion of indole HDN was reached (i.e., lack of N-containing compounds in the products was observed), the hydrogenation of ethylbenzene to ethylcyclohexane took place. Thus, the catalytic behavior of bulk molybdenum carbide for the HDN of indole is completely different compared to previously studied sulfide-based systems. Full article
(This article belongs to the Special Issue Catalysts in Environmental and Climate Protection)
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20 pages, 8673 KiB  
Article
Supported Bimetallic Catalysts for the Solvent-Free Hydrogenation of Levulinic Acid to γ-Valerolactone: Effect of Metal Combination (Ni-Cu, Ni-Co, Cu-Co)
by Mahlet N. Gebresillase, Reibelle Q. Raguindin, Hern Kim and Jeong Gil Seo
Catalysts 2020, 10(11), 1354; https://doi.org/10.3390/catal10111354 - 21 Nov 2020
Cited by 19 | Viewed by 4023
Abstract
γ-valerolactone (GVL) is an important value-added chemical with potential applications as a fuel additive, a precursor for valuable chemicals, and polymer synthesis. Herein, different monometallic and bimetallic catalysts supported on γ-Al2O3 nanofibers (Ni, Cu, Co, Ni-Cu, Ni-Co, Cu-Co) were prepared [...] Read more.
γ-valerolactone (GVL) is an important value-added chemical with potential applications as a fuel additive, a precursor for valuable chemicals, and polymer synthesis. Herein, different monometallic and bimetallic catalysts supported on γ-Al2O3 nanofibers (Ni, Cu, Co, Ni-Cu, Ni-Co, Cu-Co) were prepared by the incipient wetness impregnation method and employed in the solvent-free hydrogenation of levulinic acid (LA) to GVL. The influence of metal loading, metal combination, and ratio on the activity and selectivity of the catalysts was investigated. XRD, SEM-EDS, TEM, H2-TPR, XPS, NH3-TPD, and N2 adsorption were used to examine the structure and properties of the catalysts. In this study, GVL synthesis involves the single-step dehydration of LA to an intermediate, followed by hydrogenation of the intermediate to GVL. Ni-based catalysts were found to be highly active for the reaction. [2:1] Ni-Cu/Al2O3 catalyst showed 100.0% conversion of LA with >99.0% selectivity to GVL, whereas [2:1] Ni-Co/Al2O3 yielded 100.0% conversion of LA with 83.0% selectivity to GVL. Moreover, reaction parameters such as temperature, H2 pressure, time, and catalyst loading were optimized to obtain the maximum GVL yield. The solvent-free hydrogenation process described in this study propels the future industrial production of GVL from LA. Full article
(This article belongs to the Special Issue Catalysts in Sustainable, Industrial Processes in Biorefinery and Bioeconomy)
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12 pages, 1409 KiB  
Article
Optimization of the Catalytic Layer for Alkaline Fuel Cells Based on Fumatech Membranes and Ionomer
by David Sebastián, Giovanni Lemes, José M. Luque-Centeno, María V. Martínez-Huerta, Juan I. Pardo and María J. Lázaro
Catalysts 2020, 10(11), 1353; https://doi.org/10.3390/catal10111353 - 20 Nov 2020
Cited by 17 | Viewed by 4758
Abstract
Polymer electrolyte fuel cells with alkaline anion exchange membranes (AAEMs) have gained increasing attention because of the faster reaction kinetics associated with the alkaline environment compared to acidic media. While the development of anion exchange polymer membranes is increasing, the catalytic layer structure [...] Read more.
Polymer electrolyte fuel cells with alkaline anion exchange membranes (AAEMs) have gained increasing attention because of the faster reaction kinetics associated with the alkaline environment compared to acidic media. While the development of anion exchange polymer membranes is increasing, the catalytic layer structure and composition of electrodes is of paramount importance to maximize fuel cell performance. In this work, we examine the preparation procedures for electrodes by catalyst-coated substrate to be used with a well-known commercial AAEM, Fumasep® FAA-3, and a commercial ionomer of the same nature (Fumion), both from Fumatech GmbH. The anion exchange procedure, the ionomer concentration in the catalytic layer and also the effect of membrane thickness, are investigated as they are very relevant parameters conditioning the cell behavior. The best power density was achieved upon ion exchange of the ionomer by submerging the electrodes in KCl (isopropyl alcohol/water solution) for at least one hour, two exchange steps, followed by treatment in KOH for 30 min. The optimum ionomer (Fumion) concentration was found to be close to 50 wt%, with a relatively narrow interval of functioning ionomer percentages. These results provide a practical guide for electrode preparation in AAEM-based fuel cell research. Full article
(This article belongs to the Special Issue Electro-Catalysts for Energy Conversion and Storage Devices)
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13 pages, 4881 KiB  
Article
Efficient Photocatalytic CO2 Reduction with MIL-100(Fe)-CsPbBr3 Composites
by Ruolin Cheng, Elke Debroye, Johan Hofkens and Maarten B. J. Roeffaers
Catalysts 2020, 10(11), 1352; https://doi.org/10.3390/catal10111352 - 20 Nov 2020
Cited by 29 | Viewed by 4445
Abstract
Bromide-based metal halide perovskites (MHPs) are promising photocatalysts with strong blue-green light absorption. Composite photocatalysts of MHPs with MIL-100(Fe), as a powerful photocatalyst itself, have been investigated to extend the responsiveness towards red light. The composites, with a high specific surface area, display [...] Read more.
Bromide-based metal halide perovskites (MHPs) are promising photocatalysts with strong blue-green light absorption. Composite photocatalysts of MHPs with MIL-100(Fe), as a powerful photocatalyst itself, have been investigated to extend the responsiveness towards red light. The composites, with a high specific surface area, display an enhanced solar light response, and the improved charge carrier separation in the heterojunctions is employed to maximize the photocatalytic performance. Optimization of the relative composition, with the formation of a dual-phase CsPbBr3 to CsPb2Br5 perovskite composite, shows an excellent photocatalytic performance with 20.4 μmol CO produced per gram of photocatalyst during one hour of visible light irradiation. Full article
(This article belongs to the Special Issue MOFs for Advanced Applications)
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21 pages, 5655 KiB  
Article
Physical and Chemical Synthesis of Au/CeO2 Nanoparticle Catalysts for Room Temperature CO Oxidation: A Comparative Study
by Khaled Mohammad Saoud and Mohamed Samy El-Shall
Catalysts 2020, 10(11), 1351; https://doi.org/10.3390/catal10111351 - 20 Nov 2020
Cited by 14 | Viewed by 4135
Abstract
In many heterogeneous catalytic reactions, such as low-temperature CO oxidation, the preparation conditions, and the role of the CeO2 support (oxygen vacancies and redox properties) in the dispersion and the chemical state of Au, are considered critical factors for obtaining gold nanoparticle [...] Read more.
In many heterogeneous catalytic reactions, such as low-temperature CO oxidation, the preparation conditions, and the role of the CeO2 support (oxygen vacancies and redox properties) in the dispersion and the chemical state of Au, are considered critical factors for obtaining gold nanoparticle catalysts with high catalytic performance. In this work, the physical and chemical preparation methods were compared, aiming at understanding how the preparation method influences the catalytic activity. The Au/CeO2 nanoparticle catalysts with 5% Au loading were prepared via the Physical Laser Vaporization Controlled Condensation method (LVCC), and the chemical Deposition-Precipitation method (DP) was used to investigate the effect of synthesis methods on the structure and the catalytic activity toward the CO oxidation. In this manuscript, we compare the activity of nanostructured Au/CeO2 catalysts. The structure and the redox properties of the catalysts were investigated by the XRD, SEM, TEM, TPR, and XPS. The catalytic activity for low-temperature CO oxidation was studied using a custom-built quartz tube flow reactor coupled with an infrared detector system at atmospheric pressure. The study reveals that the prepared CeO2-supported Au nanoparticles’ catalytic activity was highly dependent on the preparation methods. It showed that the sample prepared by the DP method exhibits higher catalytic efficiency toward CO oxidation when compared with the sample prepared by the LVCC method. The high catalytic activity could be attributed to the small particle size and shape, slightly higher Au concentration at the surface, surface-active Au species such as Au1+, along with the large interface between Au and CeO2. This study suggests that the stability, dispersion of Au nanoparticles on CeO2, and strong interaction between Au and CeO2 lead to strong oxidation ability even below room temperature. Considering the universal character of different physical and chemical methods for Au/CeO2 preparation, this study may also provide a base for supported Au-based catalysts for many oxidation reactions in energy and environmental applications. Full article
(This article belongs to the Section Environmental Catalysis)
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19 pages, 4974 KiB  
Article
Modified Hydrothermal Route for Synthesis of Photoactive Anatase TiO2/g-CN Nanotubes from Sludge Generated TiO2
by Sayed Mukit Hossain, Heeju Park, Hui-Ju Kang, Jong Seok Mun, Leonard Tijing, Inkyu Rhee, Jong-Ho Kim, Young-Si Jun and Ho Kyong Shon
Catalysts 2020, 10(11), 1350; https://doi.org/10.3390/catal10111350 - 19 Nov 2020
Cited by 8 | Viewed by 2888
Abstract
Titania nanotube was prepared from sludge generated TiO2 (S-TNT) through a modified hydrothermal route and successfully composited with graphitic carbon nitride (g-CN) through a simple calcination step. Advanced characterization techniques such as X-ray diffraction, scanning and transmission electron microscopy, infrared spectroscopy, X-ray [...] Read more.
Titania nanotube was prepared from sludge generated TiO2 (S-TNT) through a modified hydrothermal route and successfully composited with graphitic carbon nitride (g-CN) through a simple calcination step. Advanced characterization techniques such as X-ray diffraction, scanning and transmission electron microscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, UV/visible diffuse reflectance spectroscopy, and photoluminescence analysis were utilized to characterize the prepared samples. A significant improvement in morphological and optical bandgap was observed. The effective surface area of the prepared composite increased threefold compared with sludge generated TiO2. The optical bandgap was narrowed to 3.00 eV from 3.18 in the pristine sludge generated TiO2 nanotubes. The extent of photoactivity of the prepared composites was investigated through photooxidation of NOx in a continuous flow reactor. Because of extended light absorption of the as-prepared composite, under visible light, 19.62% of NO removal was observed. On the other hand, under UV irradiation, owing to bandgap narrowing, although the light absorption was compromised, the impact on photoactivity was compensated by the increased effective surface area of 153.61 m2/g. Hence, under UV irradiance, the maximum NO removal was attained as 32.44% after 1 h of light irradiation. The proposed facile method in this study for the heterojunction of S-TNT and g-CN could significantly contribute to resource recovery from water treatment plants and photocatalytic atmospheric pollutant removal. Full article
(This article belongs to the Special Issue Commemorative Issue in Honor of Professor Akira Fujishima)
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10 pages, 3114 KiB  
Article
Visible-Light-Responsive Antibacterial Property of Boron-Doped Titania Films
by Ming-Show Wong, Man-Ting Sun, Der-Shan Sun and Hsin-Hou Chang
Catalysts 2020, 10(11), 1349; https://doi.org/10.3390/catal10111349 - 19 Nov 2020
Cited by 10 | Viewed by 2484
Abstract
Pure titanium dioxide TiO2 photocatalytic substrates exhibit antibacterial activity only when they are irradiated with ultraviolet light, which comprises high-energy wavelengths that damage all life. Impurity doping of TiO2-related materials enables visible light to stimulate photocatalytic activity, which enhances opportunities [...] Read more.
Pure titanium dioxide TiO2 photocatalytic substrates exhibit antibacterial activity only when they are irradiated with ultraviolet light, which comprises high-energy wavelengths that damage all life. Impurity doping of TiO2-related materials enables visible light to stimulate photocatalytic activity, which enhances opportunities for TiO2 to be used as a disinfectant in living environments. Boron-doped TiO2 displays visible-light-responsive bactericidal properties. However, because boron-derived compounds also exert notable antibacterial effects, most reports did not clearly demonstrate the extent to which the bactericidal property of boron-doped TiO2 is contributed by visible-light-stimulated photocatalysis. In addition, TiO2 thin films have considerable potential for applications in equipment that requires sterilization; however, the antibacterial properties of boron-doped TiO2 thin films have been examined by only a few studies. We found that boron-doped TiO2 thin films displayed visible-light-driven antibacterial properties. Moreover, because boron compounds may have intrinsic antibacterial properties, using control groups maintained in the dark, we clearly demonstrated that visible light stimulated the photocatalysis of boron-doped TiO2 thin films but not the residue boron compounds display antibacterial property. The bactericidal effects induced by visible light are equally potent for the elimination of the model organism Escherichia coli and human pathogens, such as Acinetobacter baumannii, Staphylococcus aureus, and Streptococcus pyogenes. The antibacterial applications of boron-doped TiO2 thin films are described, and relevant perspectives discussed. Full article
(This article belongs to the Special Issue TiO2-Based Materials for (Photo)Catalysis)
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13 pages, 2488 KiB  
Article
One-Pot Synthesis of B-Aryl Carboranes with Sensitive Functional Groups Using Sequential Cobalt- and Palladium-Catalyzed Reactions
by Sergey A. Anufriev, Akim V. Shmal’ko, Kyrill Yu. Suponitsky and Igor B. Sivaev
Catalysts 2020, 10(11), 1348; https://doi.org/10.3390/catal10111348 - 19 Nov 2020
Cited by 5 | Viewed by 2876
Abstract
The simple and efficient method was developed for the one-pot synthesis of B-substituted aryl derivatives of ortho-carborane with functional groups sensitive to organolithium and organomagnesium reagents using 9-iodo-ortho-carborane and generated in situ organozinc compounds. The method proposed was used [...] Read more.
The simple and efficient method was developed for the one-pot synthesis of B-substituted aryl derivatives of ortho-carborane with functional groups sensitive to organolithium and organomagnesium reagents using 9-iodo-ortho-carborane and generated in situ organozinc compounds. The method proposed was used to prepare a series of 9-aryl-ortho-carboranes, including those containing nitrile and ester groups, 9-RC6H4-1,2-C2B10H11 (R = p-Me, p-NMe2, p-OCH2OMe, o-OMe, p-OMe, o-CN, p-CN, o-COOEt, m-COOEt, and p-COOEt). It was demonstrated that the same approach can be used for synthesis of diaryl derivatives of ortho-carborane 9,12-(RC6H4)2-1,2-C2B10H10 (R = H, p-Me). The solid-state structures of 9-RC6H4-1,2-C2B10H11 (R = p-NMe2, p-OCH2OMe, o-OMe, o-CN, p-CN, m-COOEt, and p-COOEt) and 9,12-(p-MeC6H4)2-1,2-C2B10H10 were determined by single crystal X-ray diffraction. Full article
(This article belongs to the Special Issue Transition Metal Complexes as Catalysts in Organic Chemistry)
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12 pages, 3065 KiB  
Article
Liquid-Phase and Ultrahigh-Frequency-Acoustofluidics-Based Solid-Phase Synthesis of Biotin-Tagged 6′/3′-Sialyl-N-Acetylglucosamine by Sequential One-Pot Multienzyme System
by Mengge Gong, Tiechuan Li, Lina Wu, Zhenxing Zhang, Lishi Ren, Xuexin Duan, Hongzhi Cao, Meishan Pei, Jian-Jun Li and Yuguang Du
Catalysts 2020, 10(11), 1347; https://doi.org/10.3390/catal10111347 - 19 Nov 2020
Cited by 3 | Viewed by 2262
Abstract
6′/3′-Sialylated N-acetyllactosamine (6′/3′-SLN) is important for discrimination of the source (human or avian) of influenza virus strains. Biotinylated oligosaccharides have been widely used for analysis and quick detection. The development of efficient strategies to synthesize biotin-tagged 6′/3′-SLN have become necessary. Effective mixing [...] Read more.
6′/3′-Sialylated N-acetyllactosamine (6′/3′-SLN) is important for discrimination of the source (human or avian) of influenza virus strains. Biotinylated oligosaccharides have been widely used for analysis and quick detection. The development of efficient strategies to synthesize biotin-tagged 6′/3′-SLN have become necessary. Effective mixing is essential for enzymatic solid-phase oligosaccharide synthesis (SPOS). In the current study, newly developed technology ultrahigh-frequency-acoustofluidics (UHFA), which can provide a powerful source for efficient microfluidic mixing, solid-phase oligosaccharide synthesis and one-pot multienzyme (OPME) system, were used to develop a new strategy for oligosaccharide synthesis. Firstly, biotinylated N-acetylglucosamine was designed and chemically synthesized through traditional approaches. Secondly, biotinylated 6′- and 3′-sialyl-N-acetylglucosamines were prepared in solution through two sequential OPME modules in with a yield of ~95%. Thirdly, 6′-SLN was also prepared through UHFA-based enzymatic solid-phase synthesis on magnetic beads with a yield of 64.4%. The current strategy would be potentially used for synthesis of functional oligosaccharides. Full article
(This article belongs to the Special Issue Emerging Technologies and Novel Approaches for Enzymatic Catalysis)
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17 pages, 4421 KiB  
Article
Unravelling the Structural Modification (Meso-Nano-) of Cu/ZnO-Al2O3 Catalysts for Methanol Synthesis by the Residual NaNO3 in Hydroxycarbonate Precursors
by Rut Guil-López, Noelia Mota, Jorge Llorente, Elena Millan, Bárbara G. Pawelec, Jose Luis G. Fierro and Rufino M. Navarro
Catalysts 2020, 10(11), 1346; https://doi.org/10.3390/catal10111346 - 19 Nov 2020
Cited by 5 | Viewed by 2581
Abstract
The effects of residual NaNO3 on the modification of Cu/ZnO-Al2O3 catalysts have been extensively documented, but the modification mechanism is so far unclear. This work studies in detail the influence of the residual sodium nitrate present in the hydroxycarbonate [...] Read more.
The effects of residual NaNO3 on the modification of Cu/ZnO-Al2O3 catalysts have been extensively documented, but the modification mechanism is so far unclear. This work studies in detail the influence of the residual sodium nitrate present in the hydroxycarbonate precursors on their decomposition during calcination and how it affects to the formation and configuration of the final active sites of the Cu/ZnO-Al2O3 catalysts. Different samples with varying sodium content after washing (from 0.01 to 7.3 wt%) were prepared and studied in detail after calcination and reduction steps. The results of this work demonstrated that NaNO3 affects the decomposition mechanism of the hydroxycarbonate precursors during calcination and produces its decarbonation at low temperature. The enhancement of the decarbonation by NaNO3 leads to segregation and crystallization of CuO and ZnO with loss of mesostructure and surface area in the calcined catalysts. The loss of mesostructure in calcined catalysts affects the subsequent reduction step, decreasing the reducibility and damaging the nanostructure of the reduced catalysts forming large Cu particles in poor contact with ZnOx that results in a significant decrease in the intrinsic activity of the copper active sites for methanol synthesis. Full article
(This article belongs to the Special Issue Catalysts for Production and Conversion of Syngas)
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17 pages, 5420 KiB  
Article
Combined Reforming of Clean Biogas over Nanosized Ni–Rh Bimetallic Clusters
by Nicola Schiaroli, Carlo Lucarelli, Maria Carmela Iapalucci, Giuseppe Fornasari, Antonio Crimaldi and Angelo Vaccari
Catalysts 2020, 10(11), 1345; https://doi.org/10.3390/catal10111345 - 19 Nov 2020
Cited by 7 | Viewed by 3314
Abstract
The combined steam/dry reforming of clean biogas (CH4/CO2 = 50/50 v/v) represents an innovative way to produce synthesis gas (CO + H2) using renewable feeds, avoiding to deplete the fossil resources and increase CO2 pollution. The [...] Read more.
The combined steam/dry reforming of clean biogas (CH4/CO2 = 50/50 v/v) represents an innovative way to produce synthesis gas (CO + H2) using renewable feeds, avoiding to deplete the fossil resources and increase CO2 pollution. The reaction was carried out to optimize the reaction conditions for the production of a syngas with a H2/CO ratio suitable for the production of methanol or fuels without any further upgrading. Ni-Rh/Mg/Al/O catalysts obtained from hydrotalcite-type precursors showed high performances in terms of clean biogas conversion due to the formation of very active and resistant Ni-Rh bimetallic nanoparticles. Through the utilization of a {Ni10Rh(CO)19}{(CH3CH2)4N}3 cluster as a precursor of the active particles, it was possible to promote the Ni-Rh interaction and thus obtain low metal loading catalysts composed by highly dispersed bimetallic nanoparticles supported on the MgO, MgAl2O4 matrix. The optimization of the catalytic formulation improved the size and the distribution of the active sites, leading to a better catalyst activity and stability, with low carbon deposition with time-on-stream. Full article
(This article belongs to the Special Issue Catalysts for Reforming of Methane)
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20 pages, 3483 KiB  
Article
Copper-Containing Mixed Metal Oxides (Al, Fe, Mn) for Application in Three-Way Catalysis
by Tim Van Everbroeck, Radu-George Ciocarlan, Wouter Van Hoey, Myrjam Mertens and Pegie Cool
Catalysts 2020, 10(11), 1344; https://doi.org/10.3390/catal10111344 - 19 Nov 2020
Cited by 18 | Viewed by 4171
Abstract
Mixed oxides were synthesized by co-precipitation of a Cu source in combination with Al, Fe or Mn corresponding salts as precursors. The materials were calcined at 600 and 1000 °C in order to crystallize the phases and to mimic the reaction conditions of [...] Read more.
Mixed oxides were synthesized by co-precipitation of a Cu source in combination with Al, Fe or Mn corresponding salts as precursors. The materials were calcined at 600 and 1000 °C in order to crystallize the phases and to mimic the reaction conditions of the catalytic application. At 600 °C a mixed spinel structure was only formed for the combination of Cu and Mn, while at 1000 °C all the materials showed mixed spinel formation. The catalysts were applied in three-way catalysis using a reactor with a gas mixture containing CO, NO and O2. All the materials calcined at 600 °C displayed the remarkable ability to oxidize CO with O2 but also to reduce NO with CO, while the pure oxides such as CuO and MnO2 were not able to. The high catalytic activity at 600 °C was attributed to small supported CuO particles present and imperfections in the spinel structure. Calcination at 1000 °C crystallized the structure further which led to a dramatic loss in catalytic activity, although CuAl2O4 and CuFe2O4 still converted some NO. The materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, H2-Temperatrue Programmed Reduction (H2-TPR), N2-sorption and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX). Full article
(This article belongs to the Special Issue Nanotechnology in Catalysis)
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11 pages, 2070 KiB  
Review
Catalysis with Silver: From Complexes and Nanoparticles to MORALs and Single-Atom Catalysts
by Mario Pagliaro, Cristina Della Pina, Francesco Mauriello and Rosaria Ciriminna
Catalysts 2020, 10(11), 1343; https://doi.org/10.3390/catal10111343 - 19 Nov 2020
Cited by 24 | Viewed by 5448
Abstract
Silver catalysis has a rich and versatile chemistry now expanding from processes mediated by silver complexes and silver nanoparticles to transformations catalyzed by silver metal organic alloys and single-atom catalysts. Focusing on selected recent advances, we identify the key advantages offered by these [...] Read more.
Silver catalysis has a rich and versatile chemistry now expanding from processes mediated by silver complexes and silver nanoparticles to transformations catalyzed by silver metal organic alloys and single-atom catalysts. Focusing on selected recent advances, we identify the key advantages offered by these highly selective heterogeneous catalysts. We conclude by offering seven research and educational guidelines aimed at further progressing the field of new generation silver-based catalytic materials. Full article
(This article belongs to the Special Issue Single-Atom Catalysts Seeking Practical Application: Achievements and Challenges)
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18 pages, 2706 KiB  
Article
Influence of Topology and Brønsted Acid Site Presence on Methanol Diffusion in Zeolites Beta and MFI
by Cecil H. Botchway, Richard Tia, Evans Adei, Alexander J. O’Malley, Nelson Y. Dzade, Carlos Hernandez-Tamargo and Nora H. de Leeuw
Catalysts 2020, 10(11), 1342; https://doi.org/10.3390/catal10111342 - 18 Nov 2020
Cited by 16 | Viewed by 3901
Abstract
Detailed insight into molecular diffusion in zeolite frameworks is crucial for the analysis of the factors governing their catalytic performance in methanol-to-hydrocarbons (MTH) reactions. In this work, we present a molecular dynamics study of the diffusion of methanol in all-silica and acidic zeolite [...] Read more.
Detailed insight into molecular diffusion in zeolite frameworks is crucial for the analysis of the factors governing their catalytic performance in methanol-to-hydrocarbons (MTH) reactions. In this work, we present a molecular dynamics study of the diffusion of methanol in all-silica and acidic zeolite MFI and Beta frameworks over the range of temperatures 373–473 K. Owing to the difference in pore dimensions, methanol diffusion is more hindered in H-MFI, with diffusion coefficients that do not exceed 10 × 10−10 m2s−1. In comparison, H-Beta shows diffusivities that are one to two orders of magnitude larger. Consequently, the activation energy of translational diffusion can reach 16 kJ·mol−1 in H-MFI, depending on the molecular loading, against a value for H-Beta that remains between 6 and 8 kJ·mol−1. The analysis of the radial distribution functions and the residence time at the Brønsted acid sites shows a greater probability for methylation of the framework in the MFI structure compared to zeolite Beta, with the latter displaying a higher prevalence for methanol clustering. These results contribute to the understanding of the differences in catalytic performance of zeolites with varying micropore dimensions in MTH reactions. Full article
(This article belongs to the Special Issue Advances in Zeolite Catalysts)
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12 pages, 1674 KiB  
Article
Characterization of Anaerobic Biofilms Growing on Carbon Felt Bioanodes Exposed to Air
by Raúl M. Alonso, Guillermo Pelaz, María Isabel San-Martín, Antonio Morán and Adrián Escapa
Catalysts 2020, 10(11), 1341; https://doi.org/10.3390/catal10111341 - 18 Nov 2020
Cited by 2 | Viewed by 2284
Abstract
The role of oxygen in anodic biofilms is still a matter of debate. In this study, we tried to elucidate the structure and performance of an electrogenic biofilm that develops on air-exposed, carbon felt electrodes, commonly used in bioelectrochemical systems. By simultaneously recording [...] Read more.
The role of oxygen in anodic biofilms is still a matter of debate. In this study, we tried to elucidate the structure and performance of an electrogenic biofilm that develops on air-exposed, carbon felt electrodes, commonly used in bioelectrochemical systems. By simultaneously recording the current density produced by the bioanode and dissolved oxygen concentration, both inside and in the vicinity of the biofilm, it was possible to demonstrate the influence of a protective aerobic layer present in the biofilm (mainly formed by Pseudomonas genus bacteria) that prevents electrogenic bacteria (such as Geobacter sp.) from hazardous exposure to oxygen during its normal operation. Once this protective barrier was deactivated for a long period of time, the catalytic capacity of the biofilm was severely affected. In addition, our results highlighted the importance of the material’s porous structure for oxygen penetration in the electrode. Full article
(This article belongs to the Special Issue Environmental Friendly Catalysts for Energy and Pollution Control Applications)
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14 pages, 3634 KiB  
Article
Investigating Light-Induced Processes in Covalent Dye-Catalyst Assemblies for Hydrogen Production
by Sebastian Bold, Tatiana Straistari, Ana B. Muñoz-García, Michele Pavone, Vincent Artero, Murielle Chavarot-Kerlidou and Benjamin Dietzek
Catalysts 2020, 10(11), 1340; https://doi.org/10.3390/catal10111340 - 18 Nov 2020
Cited by 10 | Viewed by 2746
Abstract
The light-induced processes occurring in two dye-catalyst assemblies for light-driven hydrogen production were investigated by ultrafast transient absorption spectroscopy. These dyads consist of a push-pull organic dye based on a cyclopenta[1,2-b:5,4-b’]dithiophene (CPDT) bridge, covalently linked to two different H2-evolving cobalt catalysts. [...] Read more.
The light-induced processes occurring in two dye-catalyst assemblies for light-driven hydrogen production were investigated by ultrafast transient absorption spectroscopy. These dyads consist of a push-pull organic dye based on a cyclopenta[1,2-b:5,4-b’]dithiophene (CPDT) bridge, covalently linked to two different H2-evolving cobalt catalysts. Whatever the nature of the latter, photoinduced intramolecular electron transfer from the excited state of the dye to the catalytic center was never observed. Instead, and in sharp contrast to the reference dye, a fast intersystem crossing (ISC) populates a long-lived triplet excited state, which in turn non-radiatively decays to the ground state. This study thus shows how the interplay of different structures in a dye-catalyst assembly can lead to unexpected excited state behavior and might open up new possibilities in the area of organic triplet sensitizers. More importantly, a reductive quenching mechanism with an external electron donor must be considered to drive hydrogen production with these dye-catalyst assemblies. Full article
(This article belongs to the Special Issue Photo-Induced Electron Transfer Kinetics in Catalysis)
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27 pages, 3809 KiB  
Review
Recent Advances in the Synthesis of Sulfides, Sulfoxides and Sulfones via C-S Bond Construction from Non-Halide Substrates
by Rui Zhang, Huaiwei Ding, Xiangling Pu, Zhiping Qian and Yan Xiao
Catalysts 2020, 10(11), 1339; https://doi.org/10.3390/catal10111339 - 17 Nov 2020
Cited by 46 | Viewed by 5563
Abstract
The construction of a C-S bond is a powerful strategy for the synthesis of sulfur containing compounds including sulfides, sulfoxides, and sulfones. Recent methodological developments have revealed lots of novel protocols for C-S bond formation, providing easy access to sulfur containing compounds. Unlike [...] Read more.
The construction of a C-S bond is a powerful strategy for the synthesis of sulfur containing compounds including sulfides, sulfoxides, and sulfones. Recent methodological developments have revealed lots of novel protocols for C-S bond formation, providing easy access to sulfur containing compounds. Unlike traditional Ullmann typed C-S coupling reaction, the recently developed reactions frequently use non-halide compounds, such as diazo compounds and simple arenes/alkanes instead of aryl halides as substrates. On the other hand, novel C-S coupling reaction pathways involving thiyl radicals have emerged as an important strategy to construct C-S bonds. In this review, we focus on the recent advances on the synthesis of sulfides, sulfoxides, and sulfones from non-halide substrates involving C-S bond construction. Full article
(This article belongs to the Section Catalysis in Organic and Polymer Chemistry)
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38 pages, 4628 KiB  
Review
Nanostructured Anodic Copper Oxides as Catalysts in Electrochemical and Photoelectrochemical Reactions
by Damian Giziński, Anna Brudzisz, Janaina S. Santos, Francisco Trivinho-Strixino, Wojciech J. Stępniowski and Tomasz Czujko
Catalysts 2020, 10(11), 1338; https://doi.org/10.3390/catal10111338 - 17 Nov 2020
Cited by 34 | Viewed by 6654
Abstract
Recently, nanostructured copper oxides formed via anodizing have been intensively researched due to their potential catalytic applications in emerging issues. The anodic Cu2O and CuO nanowires or nanoneedles are attractive photo- and electrocatalysts since they show wide array of desired electronic [...] Read more.
Recently, nanostructured copper oxides formed via anodizing have been intensively researched due to their potential catalytic applications in emerging issues. The anodic Cu2O and CuO nanowires or nanoneedles are attractive photo- and electrocatalysts since they show wide array of desired electronic and morphological features, such as highly-developed surface area. In CO2 electrochemical reduction reaction (CO2RR) copper and copper-based nanostructures indicate unique adsorption properties to crucial reaction intermediates. Furthermore, anodized copper-based materials enable formation of C2+ hydrocarbons and alcohols with enhanced selectivity. Moreover, anodic copper oxides provide outstanding turnover frequencies in electrochemical methanol oxidation at lowered overpotentials. Therefore, they can be considered as precious metals electrodes substituents in direct methanol fuel cells. Additionally, due to the presence of Cu(III)/Cu(II) redox couple, these materials find application as electrodes for non-enzymatic glucose sensors. In photoelectrochemistry, Cu2O-CuO heterostructures of anodic copper oxides with highly-developed surface area are attractive for water splitting. All the above-mentioned aspects of anodic copper oxides derived catalysts with state-of-the-art background have been reviewed within this paper. Full article
(This article belongs to the Special Issue Porous Materials for Photocatalysis and Energy)
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26 pages, 6334 KiB  
Review
Some Critical Insights into the Synthesis and Applications of Hydrophobic Solid Catalysts
by Denise Cavuoto, Federica Zaccheria and Nicoletta Ravasio
Catalysts 2020, 10(11), 1337; https://doi.org/10.3390/catal10111337 - 17 Nov 2020
Cited by 26 | Viewed by 4656
Abstract
The preparation methods of hydrophobic materials such as zeolites, modified silicas and polymers has been reviewed. Particular attention has been paid to the characterization methods classified according to the surface and bulk composition, on one hand, and to the measure of interactions with [...] Read more.
The preparation methods of hydrophobic materials such as zeolites, modified silicas and polymers has been reviewed. Particular attention has been paid to the characterization methods classified according to the surface and bulk composition, on one hand, and to the measure of interactions with water or organic solvents, on the other. Some selected applications are analyzed in order to understand the relevance of the reactants/products adsorption to address activity and selectivity of the reaction. Thus, absorption of a non-polar reactant or desorption of a hydrophilic product are much easier on a hydrophobic surface and can effectively boost the catalytic activity. Full article
(This article belongs to the Section Catalytic Materials)
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14 pages, 8379 KiB  
Article
Application of Supported TiO2 in Carbonated Binding Material and Its Photocatalytic Performance
by Heyang Si, Yongle Fang and Lu Yang
Catalysts 2020, 10(11), 1336; https://doi.org/10.3390/catal10111336 - 17 Nov 2020
Cited by 7 | Viewed by 2333
Abstract
Although photocatalytic concrete can significantly contribute to the degradation of air pollutants and improving the sustainability levels, the complexity of ordinary cement system often caused the uncertain performance of mixed photocatalysts, which limited the real application of photocatalysts. Since the rapid carbonization hardening [...] Read more.
Although photocatalytic concrete can significantly contribute to the degradation of air pollutants and improving the sustainability levels, the complexity of ordinary cement system often caused the uncertain performance of mixed photocatalysts, which limited the real application of photocatalysts. Since the rapid carbonization hardening and relatively simple composition, γ-C2S carbonated binding material has gained considerable attention for its application in construction material. In this work, quartz sand-supported TiO2-C2S(γ) composites (TQSC) were prepared by mixing photocatalytic quartz sand with γ-C2S and mounting in γ-C2S matrix surface methods. The TiO2-coated quartz sand (TQS) was characterized by X-ray diffraction (XRD), quantitative X-ray fluorescence (XRF) and scanning electron microscopy (SEM). The photocatalytic performance and durability (washing resistance) of TQSC were also investigated by the degradation ability of NOx and rhodamine B (RhB). The results show that a uniform TiO2 layer on quartz sand was prepared, and the photocatalytic De-NOx (degradation of NOx) performance increased with increasing the mounted amounts of TiO2/quartz sand in γ-C2S carbonated matrix surface, but would decrease the photocatalytic durability. After water-washing, the De-NOx efficiencies of TQSC specimens decreased quickly at the beginning, which were adhering to the mounted amounts of TiO2/quartz sand, but would become stable after water-washing for 3600 s for all samples. The relatively high De-NOx stability and good self-cleaning effect of the water-washed TQSC-60% specimen can be considered a promising photocatalytic product for real applications. Full article
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22 pages, 8923 KiB  
Article
Preparation and Characterization of Ni/ZrTiAlOx Catalyst via Sol-Gel and Impregnation Methods for Low Temperature Dry Reforming of Methane
by Seol A Shin, Ali Alizadeh Eslami, Young Su Noh, Hyun-tae Song, Hyun Dong Kim, Nasim Ghaffari Saeidabad and Dong Ju Moon
Catalysts 2020, 10(11), 1335; https://doi.org/10.3390/catal10111335 - 17 Nov 2020
Cited by 5 | Viewed by 3745
Abstract
Recently, the dry reforming of methane (DRM) has received much attention as a conversion technology of greenhouse gases. Ni-based catalysts supported on ternary metal oxide composite (ZrTiAlOx) were prepared to improve the coke resistance properties in the DRM (CH4:CO [...] Read more.
Recently, the dry reforming of methane (DRM) has received much attention as a conversion technology of greenhouse gases. Ni-based catalysts supported on ternary metal oxide composite (ZrTiAlOx) were prepared to improve the coke resistance properties in the DRM (CH4:CO2 = 1) at low temperature. The ZrTiAlOx supports with different ratios of Zr/Ti were prepared through the modified Pechini sol-gel method, and then the Ni was impregnated on the synthesized support via the incipient wetness impregnation method. Considering the Zr/Ti ratios, different catalytic activity and durability in the DRM were identified. The Ni/ZrTiAlOx catalyst with Zr/Ti of 2 exhibited enhanced coke inhibition property compared to the others at low temperature DRM for 50 h. The catalysts with a high Zr/Ti ratio under the same condition were rapidly deactivated, while the catalyst with a low Zr/Ti ratio showed deficient activity. It was found from temperature-programmed surface reactions (TPSR) and DRIFTS (Diffuse Reflectance Infrared Fourier Transform Spectroscopy) analysis that the addition of Ti has led in to higher catalytic stability at Zr/Ti = 2, which could be as a result of oxygen vacancies generated by the ternary metal oxides. Ni/ZrTiAlOx catalyst with ratio of Zr/Ti = 2 showed high stability and good catalytic activity towards DRM for the production of syngas. Full article
(This article belongs to the Special Issue Catalytic Steam Reforming)
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