Catalysts

11 pages, 3978 KiB

Open AccessArticle

Montmorillonite K10-Catalyzed Solvent-Free Conversion of Furfural into Cyclopentenones

by Sonia Bonacci, Monica Nardi, Paola Costanzo, Antonio De Nino, Maria Luisa Di Gioia, Manuela Oliverio and Antonio Procopio

Catalysts 2019, 9(3), 301; https://doi.org/10.3390/catal9030301 - 26 Mar 2019

Cited by 28 | Viewed by 6571

Abstract

A simple and eco-friendly montmorillonite K10 (MK10)-catalyzed method for the synthesis of cyclopentenone derivatives from biomass-produced furfural has been developed. The versatility of this protocol is that the reactions were performed under solvent-free conditions and in a short reaction time under heterogeneous catalysis. [...] Read more.

A simple and eco-friendly montmorillonite K10 (MK10)-catalyzed method for the synthesis of cyclopentenone derivatives from biomass-produced furfural has been developed. The versatility of this protocol is that the reactions were performed under solvent-free conditions and in a short reaction time under heterogeneous catalysis. Montmorillonite K10 is mostly explored as a heterogeneous catalyst since it is inexpensive and environmentally friendly. Full article

(This article belongs to the Special Issue Green Synthesis and Catalysis)

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24 pages, 12799 KiB

Open AccessArticle

Suzuki–Miyaura Coupling Using Monolithic Pd Reactors and Scaling-Up by Series Connection of the Reactors

by Aiichiro Nagaki, Katsuyuki Hirose, Yuya Moriwaki, Masahiro Takumi, Yusuke Takahashi, Koji Mitamura, Kimihiro Matsukawa, Norio Ishizuka and Jun-ichi Yoshida

Catalysts 2019, 9(3), 300; https://doi.org/10.3390/catal9030300 - 25 Mar 2019

Cited by 18 | Viewed by 4869

Abstract

The space integration of the lithiation of aryl halides, the borylation of aryllithiums, and Suzuki–Miyaura coupling using a Pd catalyst supported by a polymer monolith flow reactor without using an intentionally added base was achieved. To scale up the process, a series connection [...] Read more.

The space integration of the lithiation of aryl halides, the borylation of aryllithiums, and Suzuki–Miyaura coupling using a Pd catalyst supported by a polymer monolith flow reactor without using an intentionally added base was achieved. To scale up the process, a series connection of the monolith Pd reactor was examined. To suppress the increase in the pressure drop caused by the series connection, a monolith reactor having larger pore sizes was developed by varying the temperature of the monolith preparation. The monolithic Pd reactor having larger pore sizes enabled Suzuki–Miyaura coupling at a higher flow rate because of a lower pressure drop and, therefore, an increase in productivity. The present study indicates that series connection of the reactors with a higher flow rate serves as a good method for increasing the productivity without decreasing the yields. Full article

(This article belongs to the Special Issue Catalysts for Suzuki–Miyaura Coupling Reaction)

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9 pages, 6528 KiB

Open AccessArticle

One-Step Synthesis of MoS₂/TiSi₂ via an In Situ Photo-Assisted Reduction Method for Enhanced Photocatalytic H₂ Evolution under Simulated Sunlight Illumination

by Chunyong Zhang, Aijuan Liu, Kezhen Li, Yukou Du and Ping Yang

Catalysts 2019, 9(3), 299; https://doi.org/10.3390/catal9030299 - 25 Mar 2019

Cited by 3 | Viewed by 3553

Abstract

A new MoS₂/TiSi₂ complex catalyst was designed and synthesized by a simple one-step in situ photo-assisted reduction procedure. The structural and morphological properties of the composites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), [...] Read more.

A new MoS₂/TiSi₂ complex catalyst was designed and synthesized by a simple one-step in situ photo-assisted reduction procedure. The structural and morphological properties of the composites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and ultraviolet-visible diffused reflectance spectroscopy (UV-vis DRS), which proved the formation of MoS₂/TiSi₂. MoS₂/TiSi₂ with optimized composition showed obviously enhanced photocatalytic activity and superior durability for water reduction to produce H₂. The H₂ generation rate over the MoS₂/TiSi₂ photocatalyst containing 3 wt % MoS₂ reached 214.1 μmol·h⁻¹·g⁻¹ under visible light irradiation, which was ca. 5.6 times that of the pristine TiSi₂. The improved photocatalytic activity of MoS₂/TiSi₂ could be related to the broad response spectrum, large visible light absorption, and synergies among MoS₂ and TiSi₂ that enhance photoexcited charge transfer and separation. Full article

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19 pages, 3132 KiB

Open AccessArticle

Synthesis and Evaluation of Copper-Supported Titanium Oxide Nanotubes as Electrocatalyst for the Electrochemical Reduction of Carbon Oxide to Organics

by SK Safdar Hossain, Junaid Saleem, SleemUr Rahman, Syed Mohammed Javaid Zaidi, Gordon McKay and Chin Kui Cheng

Catalysts 2019, 9(3), 298; https://doi.org/10.3390/catal9030298 - 25 Mar 2019

Cited by 27 | Viewed by 5540

Abstract

Carbon dioxide (CO₂) is considered as the prime reason for the global warming effect and one of the useful ways to transform it into an array of valuable products is through electrochemical reduction of CO₂ (ERC). This process requires an [...] Read more.

Carbon dioxide (CO₂) is considered as the prime reason for the global warming effect and one of the useful ways to transform it into an array of valuable products is through electrochemical reduction of CO₂ (ERC). This process requires an efficient electrocatalyst with high faradaic efficiency at low overpotential and enhanced reaction rate. Herein, we report an innovative way of reducing CO₂ using copper-metal supported on titanium oxide nanotubes (TNT) electrocatalysts. The TNT support material was synthesized using alkaline hydrothermal process with Degussa (P-25) as a starting material. Copper nanoparticles were anchored on the TNT by homogeneous deposition-precipitation method (HDP) with urea as precipitating agent. The prepared catalysts were tested in a home-made H-cell with 0.5 M NaHCO₃ aqueous solution in order to examine their activity for ERC and the optimum copper loading. Continuous gas-phase ERC was carried out in a solid polymer electrolyte (SPE) reactor. The 10% Cu/TNT catalysts were employed in the gas diffusion layer (GDL) on the cathode side with Pt-Ru/C on the anode side. Faradaic efficiencies for the three major products namely methanol, methane, and CO were found to be 4%, 3%, and 10%, respectively at −2.5 V with an overall current density of 120 mA/cm². The addition of TNT significantly increased the catalytic activity of electrocatalyst for ERC. It is mainly attributed to their better stability towards oxidation, increased CO₂ adsorption capacity and stabilization of the reaction intermediate, layered titanates, and larger surface area (400 m²/g) as compared with other support materials. Considering the low cost of TNT, it is anticipated that TNT support electrocatalyst for ECR will gain popularity. Full article

(This article belongs to the Special Issue Sustainable Applications in Surface Chemistry and Catalysis)

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19 pages, 3783 KiB

Open AccessArticle

Zirconia-Supported Silver Nanoparticles for the Catalytic Combustion of Pollutants Originating from Mobile Sources

by Maia Montaña, María S. Leguizamón Aparicio, Marco A. Ocsachoque, Marisa B. Navas, Ivoneide de C. L. Barros, Enrique Rodriguez-Castellón, Mónica L. Casella and Ileana D. Lick

Catalysts 2019, 9(3), 297; https://doi.org/10.3390/catal9030297 - 25 Mar 2019

Cited by 19 | Viewed by 3961

Abstract

This work presents the physicochemical characterization and activity of zirconia-supported silver catalysts for the oxidation of pollutants present in diesel engine exhaust (propane, propene, naphthalene and soot). A series of silver-supported catalysts AgxZ (x = 1, 5 and 10 wt.%, Z = zirconia) [...] Read more.

This work presents the physicochemical characterization and activity of zirconia-supported silver catalysts for the oxidation of pollutants present in diesel engine exhaust (propane, propene, naphthalene and soot). A series of silver-supported catalysts AgxZ (x = 1, 5 and 10 wt.%, Z = zirconia) were prepared, which were studied by various characterization techniques. The results show that silver is mainly found under the form of small metal nanoparticles (<10 nm) dispersed over the support. The metallic phase coexists with the AgO_x oxidic phases. Silver is introduced onto the zirconia, generating Ag–ZrO₂ catalysts with high activity for the oxidation of propene and naphthalene. These catalysts also show some activity for soot combustion. Silver species can contribute with zirconia in the catalytic redox cycle, through a synergistic effect, providing sites that facilitate the migration and availability of oxygen, which is favored by the presence of structural defects. This is a novel application of the AgO_x–Ag/ZrO₂ system in the combustion reaction of propene and naphthalene. The results are highly promising, given that the T50 values found for both model molecules are quite low. Full article

(This article belongs to the Special Issue Catalysis for Global Development. Contributions around the Iberoamerican Federation of Catalysis)

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15 pages, 2732 KiB

Open AccessArticle

Biodiesel Production (FAEEs) by Heterogeneous Combi-Lipase Biocatalysts Using Wet Extracted Lipids from Microalgae

by Alejandra Sánchez-Bayo, Victoria Morales, Rosalía Rodríguez, Gemma Vicente and Luis Fernando Bautista

Catalysts 2019, 9(3), 296; https://doi.org/10.3390/catal9030296 - 25 Mar 2019

Cited by 37 | Viewed by 4769

Abstract

The production of fatty acids ethyl esters (FAEEs) to be used as biodiesel from oleaginous microalgae shows great opportunities as an attractive source for the production of renewable fuels without competing with human food. To ensure the economic viability and environmental sustainability of [...] Read more.

The production of fatty acids ethyl esters (FAEEs) to be used as biodiesel from oleaginous microalgae shows great opportunities as an attractive source for the production of renewable fuels without competing with human food. To ensure the economic viability and environmental sustainability of the microbial biomass as a raw material, the integration of its production and transformation into the biorefinery concept is required. In the present work, lipids from wet Isochrysis galbana microalga were extracted with ethyl acetate with and without drying the microalgal biomass (dry and wet extraction method, respectively). Then, FAEEs were produced by lipase-catalyzed transesterification and esterification of the extracted lipids with ethanol using lipase B from Candida antarctica (CALB) and Pseudomonas cepacia (PC) lipase supported on SBA-15 mesoporous silica functionalized with amino groups. The conversion to FAEEs with CALB (97 and 85.5 mol% for dry and wet extraction, respectively) and PC (91 and 87 mol%) biocatalysts reached higher values than those obtained with commercial Novozym 435 (75 and 69.5 mol%). Due to the heterogeneous nature of the composition of microalgae lipids, mixtures with different CALB:PC biocatalyst ratio were used to improve conversion of wet-extracted lipids. The results showed that a 25:75 combi-lipase produced a significantly higher conversion to FAEEs (97.2 mol%) than those produced by each biocatalyst independently from wet-extracted lipids and similar ones than those obtained by each lipase from the dry extraction method. Therefore, that optimized combi-lipase biocatalyst, along with achieving the highest conversion to FAEEs, would allow improving viability of a biorefinery since biodiesel production could be performed without the energy-intensive step of biomass drying. Full article

(This article belongs to the Special Issue Catalysis for Global Development. Contributions around the Iberoamerican Federation of Catalysis)

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14 pages, 5161 KiB

Open AccessArticle

Defect-Rich Nickel Nanoparticles Supported on SiC Derived from Silica Fume with Enhanced Catalytic Performance for CO Methanation

by Qi Song, Xingwu Zhai, Feng Yu, Jiangbing Li, Xin Ren, Haiyang Zhang, Mingyuan Zhu, Bin Dai, Guixian Ge and Jinli Zhang

Catalysts 2019, 9(3), 295; https://doi.org/10.3390/catal9030295 - 24 Mar 2019

Cited by 7 | Viewed by 4312

Abstract

With the increased demands of environmental protection, recycling/utilization of industrial byproducts has attracted much attention from both industry and academic communities. In this work, silicon carbide (SiC) was successfully synthesized from industrial waste silica fume (SF) during metallic silicon production. Following this, Ni [...] Read more.

With the increased demands of environmental protection, recycling/utilization of industrial byproducts has attracted much attention from both industry and academic communities. In this work, silicon carbide (SiC) was successfully synthesized from industrial waste silica fume (SF) during metallic silicon production. Following this, Ni nanoparticles with many defects were supported on the as-obtained SiC by conventional impregnation method. The results showed that defect-rich Ni nanoparticles were dispersed onto the surface of SiC. The as-obtained Ni/SF-SiC exhibited an enhanced metal-support interaction between Ni and SiC. Furthermore, the density functional theory (DFT) calculations showed that the H₂ and CO adsorption energy on Ni vacancy (V_Ni) sites of Ni/SF-SiC were 1.84 and 4.88 eV, respectively. Finally, the Ni/SF-SiC performed high catalytic activity with CO conversion of 99.1% and CH₄ selectivity of 85.7% at 350 °C, 0.1 MPa and a gas hourly space velocity (GHSV) of 18,000 mL·g⁻¹·h⁻¹. Moreover, Ni/SF-SiC processed good catalytic stability in the 50 h continuous reaction. Full article

(This article belongs to the Special Issue Catalysts for Stable Molecules (CO₂, CO, CH₄, NH₃) Conversion)

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12 pages, 1659 KiB

Open AccessArticle

Photocatalytic Degradation of Profenofos and Triazophos Residues in the Chinese Cabbage, Brassica chinensis, Using Ce-Doped TiO₂

by Xiangying Liu, You Zhan, Zhongqin Zhang, Lang Pan, Lifeng Hu, Kailin Liu, Xuguo Zhou and Lianyang Bai

Catalysts 2019, 9(3), 294; https://doi.org/10.3390/catal9030294 - 22 Mar 2019

Cited by 25 | Viewed by 4205

Abstract

Pesticides have revolutionized the modern day of agriculture and substantially reduced crop losses. Synthetic pesticides pose a potential risk to the ecosystem and to the non-target organisms due to their persistency and bioaccumulation in the environment. In recent years, a light-mediated advanced oxidation [...] Read more.

Pesticides have revolutionized the modern day of agriculture and substantially reduced crop losses. Synthetic pesticides pose a potential risk to the ecosystem and to the non-target organisms due to their persistency and bioaccumulation in the environment. In recent years, a light-mediated advanced oxidation processes (AOPs) has been adopted to resolve pesticide residue issues in the field. Among the current available semiconductors, titanium dioxide (TiO₂) is one of the most promising photocatalysts. In this study, we investigated the photocatalytic degradation of profenofos and triazophos residues in Chinese cabbage, Brassica chinensis, using a Cerium-doped nano semiconductor TiO₂ (TiO₂/Ce) under the field conditions. The results showed that the degradation efficiency of these organophosphate pesticides in B. chinensis was significantly enhanced in the presence of TiO₂/Ce. Specifically, the reactive oxygen species (ROS) contents were significantly increased in B. chinensis with TiO₂/Ce treatment, accelerating the degradation of profenofos and triazophos. Ultra-performance liquid chromatography–mass spectroscopy (UPLC-MS) analysis detected 4-bromo-2-chlorophenol and 1-phenyl-3-hydroxy-1,2,4-triazole, the major photodegradation byproducts of profenofos and triazophos, respectively. To better understand the relationship between photodegradation and the molecular structure of these organophosphate pesticides, we investigated the spatial configuration, the bond length and Mulliken atomic charge using quantum chemistry. Ab initio analysis suggests that the bonds connected by P atom of profenofos/triazophos are the initiation cleavage site for photocatalytic degradation in B. chinensis. Full article

(This article belongs to the Special Issue State-of-the-Art Photocatalytical Technology in North America)

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27 pages, 2101 KiB

Open AccessEditor’s ChoiceReview

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

by M. Consuelo Alvarez-Galvan, Jose M. Campos-Martin and Jose L. G. Fierro

Catalysts 2019, 9(3), 293; https://doi.org/10.3390/catal9030293 - 22 Mar 2019

Cited by 80 | Viewed by 9019

Abstract

Recently, catalysts based on transition metal phosphides (TMPs) have attracted increasing interest for their use in hydrodeoxygenation (HDO) processes destined to synthesize biofuels (green or renewable diesel) from waste vegetable oils and fats (known as hydrotreated vegetable oils (HVO)), or from bio-oils. This [...] Read more.

Recently, catalysts based on transition metal phosphides (TMPs) have attracted increasing interest for their use in hydrodeoxygenation (HDO) processes destined to synthesize biofuels (green or renewable diesel) from waste vegetable oils and fats (known as hydrotreated vegetable oils (HVO)), or from bio-oils. This fossil-free diesel product is produced completely from renewable raw materials with exceptional quality. These efficient HDO catalysts present electronic properties similar to noble metals, are cost-efficient, and are more stable and resistant to the presence of water than other classical catalytic formulations used for hydrotreatment reactions based on transition metal sulfides, but they do not require the continuous supply of a sulfide source. TMPs develop a bifunctional character (metallic and acidic) and present tunable catalytic properties related to the metal type, phosphorous-metal ratio, support nature, texture properties, and so on. Here, the recent progress in TMP-based catalysts for HDO of waste oils is reviewed. First, the use of TMPs in catalysis is addressed; then, the general aspects of green diesel (from bio-oils or from waste vegetable oils and fats) production by HDO of nonedible oil compounds are presented; and, finally, we attempt to describe the main advances in the development of catalysts based on TMPs for HDO, with an emphasis on the influence of the nature of active phases and effects of phosphorous, promoters, and preparation methods on reactivity. Full article

(This article belongs to the Special Issue Development of Catalysts for Green Diesel Production)

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18 pages, 5310 KiB

Open AccessArticle

CO₂ Microwave Plasma—Catalytic Reactor for Efficient Reforming of Methane to Syngas

by Se Min Chun, Dong Hun Shin, Suk Hwal Ma, Geon Woo Yang and Yong Cheol Hong

Catalysts 2019, 9(3), 292; https://doi.org/10.3390/catal9030292 - 22 Mar 2019

Cited by 36 | Viewed by 9178

Abstract

CO₂ was converted to synthesis gas in a microwave plasma–catalytic reactor by methane reforming at atmospheric pressure. The hybrid system used waste heat from the plasma to heat the catalyst. Conversion degrees were examined as a function of gas temperature, and the [...] Read more.

CO₂ was converted to synthesis gas in a microwave plasma–catalytic reactor by methane reforming at atmospheric pressure. The hybrid system used waste heat from the plasma to heat the catalyst. Conversion degrees were examined as a function of gas temperature, and the reforming efficiency of the plasma-only system was compared with that of the hybrid system. As a result, the hybrid system was shown to be more efficient under catalyst-free conditions. The use of microwave plasma alone resulted in low conversions of CO₂ and CH₄, which were 32.9% and 42.7%, respectively, at 3 kW microwave power. High CO₂ and CH₄ conversions of 87.9% and 92.9%, respectively, were achieved in the presence of catalyst at the same microwave power. At constant microwave power, catalyst addition increased the H₂ and CO mass yield rates to 0.27 kg/h and 2.012 kg/h, respectively. Additionally, the H₂ energy yield were 270 g/h, and 91.2 g/kWh. Thus, the developed hybrid system is well suited for efficient and economically viable CO₂ reduction and synthesis gas production, paving the way for next-generation CO₂ utilization and zero-emission industrial processes. Full article

(This article belongs to the Special Issue Catalytic Reforming of Methane)

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14 pages, 3375 KiB

Open AccessArticle

Catalytic Cracking of Biodiesel Waste Using Metal Supported SBA-15 Mesoporous Catalysts

by Duangkamon Jiraroj, Tunyatorn Tongtooltush, Joongjai Panpranot, Piyasan Praserthdam and Duangamol Nuntasri Tungasmita

Catalysts 2019, 9(3), 291; https://doi.org/10.3390/catal9030291 - 22 Mar 2019

Cited by 4 | Viewed by 3859

Abstract

Palladium (Pd) and aluminium (Al) supported on SBA-15 were prepared as catalysts for cracking biodiesel waste from biodiesel production. Mesoporous silica SBA-15 was first synthesized by a hydrothermal method and then loaded with Al or Pd particles were loaded using postsynthesis or aqueous [...] Read more.

Palladium (Pd) and aluminium (Al) supported on SBA-15 were prepared as catalysts for cracking biodiesel waste from biodiesel production. Mesoporous silica SBA-15 was first synthesized by a hydrothermal method and then loaded with Al or Pd particles were loaded using postsynthesis or aqueous wet impregnation methods, respectively. The physical properties of the catalysts were characterized by X-ray diffraction (XRD), nitrogen (N₂) adsorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analyses. The catalytic cracking performance of biodiesel waste was evaluated at reaction temperatures above 400 °C under a N₂ atmosphere in a batch reactor for 40 min in comparison with that for pure glycerol, where the conversion of biodiesel waste reached 86.8% with 10 wt% Pd-SBA-15 at 650 °C. The product types depended on whether the starting material was pure glycerol or biodiesel waste. The main gaseous products were carbon monoxide as synthesis gas, carbon dioxide, and 1,3-butadiene. Additionally, 2-cyclopenten-1-one and 2-propen-1-ol were major products in the liquid fraction, which can be used in pharmaceuticals and as a flame retardant, respectively. Full article

(This article belongs to the Special Issue Catalytic Transformation of Glycerol)

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13 pages, 3204 KiB

Open AccessArticle

Mechanochemically Synthesized Supported Magnetic Fe-Nanoparticles as Catalysts for Efficient Vanillin Production

by María Dolores Márquez-Medina, Daily Rodríguez-Padrón, Alina M. Balu, Antonio A. Romero, Mario J. Muñoz-Batista and Rafael Luque

Catalysts 2019, 9(3), 290; https://doi.org/10.3390/catal9030290 - 21 Mar 2019

Cited by 10 | Viewed by 3680

Abstract

Magnetically separable nanocatalysts were synthesized by incorporating iron nanoparticles on a mesoporous aluminosilicate (Al-SBA-15) through a mechanochemical grinding pathway in a single step. Noticeably, magnetic features were achieved by employing biomass waste as a carbon source, which additionally may confer high oxygen functionalities [...] Read more.

Magnetically separable nanocatalysts were synthesized by incorporating iron nanoparticles on a mesoporous aluminosilicate (Al-SBA-15) through a mechanochemical grinding pathway in a single step. Noticeably, magnetic features were achieved by employing biomass waste as a carbon source, which additionally may confer high oxygen functionalities to the resulting material. The resulting catalysts were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, porosimetry, and magnetic susceptibility. The magnetic nanocatalysts were tested in the selective oxidative cleavage reaction of isoeugenol and vanillyl alcohol to vanillin. As a result, the magnetic nanocatalysts demonstrated high catalytic activity, chemical stability, and enormous separation/reusability qualities. The origin of catalytic properties and its relationship with the iron oxide precursor were analyzed in terms of the chemical, morphological, and structural properties of the samples. Such analysis allows, thus, to highlight the superficial concentration of the iron entities and the interaction with Al as key factors to obtain a good catalytic response. Full article

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13 pages, 4014 KiB

Open AccessArticle

H₂O and/or SO₂ Tolerance of Cu-Mn/SAPO-34 Catalyst for NO Reduction with NH₃ at Low Temperature

by Guofu Liu, Wenjie Zhang, Pengfei He, Shipian Guan, Bing Yuan, Rui Li, Yu Sun and Dekui Shen

Catalysts 2019, 9(3), 289; https://doi.org/10.3390/catal9030289 - 21 Mar 2019

Cited by 21 | Viewed by 4189

Abstract

A series of molecular sieve catalysts (Cu–Mn/SAPO-34) with different loadings of Cu and Mn components were prepared by the impregnation method. The deNO_x activity of the catalyst was investigated during the selective catalytic reduction (SCR) of NO with NH₃ in the [...] Read more.

A series of molecular sieve catalysts (Cu–Mn/SAPO-34) with different loadings of Cu and Mn components were prepared by the impregnation method. The deNO_x activity of the catalyst was investigated during the selective catalytic reduction (SCR) of NO with NH₃ in the temperature range of 120 °C to 330 °C, including the effects of H₂O vapors and SO₂. In order to understand the poisoning mechanism by the injection of H₂O and/or SO₂ into the feeding gas, the characteristics of the fresh and spent catalyst were identified by means of Brunner−Emmet−Teller (BET), X-ray Diffraction (XRD), Scanning Electronic Microscopy (SEM) and Thermal Gravity- Differential Thermal Gravity (TG-DTG). The conversion of NO by the catalyst can achieve at 72% under the reaction temperature of 120 °C, while the value reached more than 90% under the temperature between 180 °C and 330 °C. The deNO_x activity test shows that the H₂O has a reversible negative effect on NO conversion, which is mainly due to the competitive adsorption of H₂O and NH₃ on Lewis acid sites. When the reaction temperature increases to 300 °C, the poisoning effect of H₂O can be negligible. The poisoning effect of SO₂ on deNO_x activity is dependent on the reaction temperature. At low temperature, the poisoning effect of SO₂ is permanent with no recovery of deNO_x activity after the elimination of SO₂. The formation of (NH4)₂SO₄, which results in the plug of active sites and a decrease of surface area, and the competitive adsorption of SO₂ and NO should be responsible for the loss of deNO_x activity over Cu/SAPO-34. Full article

(This article belongs to the Special Issue Emissions Control Catalysis)

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16 pages, 4393 KiB

Open AccessArticle

Morphology and Crystal-Plane Effects of Fe/W-CeO₂ for Selective Catalytic Reduction of NO with NH₃

by Feihu Liu, Zhong Wang, Da Wang, Dan Chen, Fushan Chen and Xuebing Li

Catalysts 2019, 9(3), 288; https://doi.org/10.3390/catal9030288 - 21 Mar 2019

Cited by 11 | Viewed by 3783

Abstract

The CeO₂ ordinary amorphous, nanopolyhedrons, nanorods, and nanocubes were prefabricated by the hydrothermal method, and employed as carriers of Fe/W–CeO₂ catalysts to selectively catalyze the reduction of NO with ammonia. Characterization results indicated that the morphology of CeO₂ support originated [...] Read more.

The CeO₂ ordinary amorphous, nanopolyhedrons, nanorods, and nanocubes were prefabricated by the hydrothermal method, and employed as carriers of Fe/W–CeO₂ catalysts to selectively catalyze the reduction of NO with ammonia. Characterization results indicated that the morphology of CeO₂ support originated from selectively exposing different crystal surfaces, which has a significant effect on oxygen vacancies, acid sites and the dispersion of Fe₂O₃. The CeO₂ nanopolyhedrons catalyst (Fe/W–CeO₂–P) showed most oxygen vacancies, the largest the quantity of acid sites, the largest BET (Brunauer-Emmett-Teller) surface area and the best dispersion of Fe₂O₃, which was associated with predominately exposing CeO₂ (111) planes. Consequently, the Fe/W–CeO₂–P catalyst has the highest NO conversion rate in the temperature range of 100–325 °C among the ordinary amorphous, nanorods, and nanocubes Fe/W–CeO₂ catalysts. Full article

(This article belongs to the Section Environmental Catalysis)

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23 pages, 4024 KiB

Open AccessFeature PaperArticle

Optimization Parameters, Kinetics, and Mechanism of Naproxen Removal by Catalytic Wet Peroxide Oxidation with a Hybrid Iron-Based Magnetic Catalyst

by Ysabel Huaccallo-Aguilar, Silvia Álvarez-Torrellas, Marcos Larriba, V. Ismael Águeda, José Antonio Delgado, Gabriel Ovejero and Juan García

Catalysts 2019, 9(3), 287; https://doi.org/10.3390/catal9030287 - 20 Mar 2019

Cited by 21 | Viewed by 4643

Abstract

This work presents a study of the assessment of the operating parameters of the catalytic wet peroxide oxidation (CWPO) of naproxen (NAP) using magnetite/multi-walled carbon nanotubes (Fe₃O₄/MWCNTs) as a catalyst. The effect of pH, temperature, and H₂O [...] Read more.

This work presents a study of the assessment of the operating parameters of the catalytic wet peroxide oxidation (CWPO) of naproxen (NAP) using magnetite/multi-walled carbon nanotubes (Fe₃O₄/MWCNTs) as a catalyst. The effect of pH, temperature, and H₂O₂ dosage on CWPO process was evaluated by using the response surface model (RSM), allowing us to obtain an optimum NAP removal of 82% at the following operating conditions: pH = 5, T = 70 °C, [H₂O₂]₀ = 1.5 mM, and [NAP]₀ = 10.0 mg/L. Therefore, NAP degradation kinetics were revealed to follow a pseudo-second-order kinetic model, and an activation energy value of 4.75 kJ/mol was determined. Adsorption and using only H₂O₂ experiments, both considered as blank tests, showed no significant removal of the pollutant. Moreover, Fe₃O₄/MWCNTs material exhibited good recyclability along three consecutive cycles, finding an average NAP removal percentage close to 80% in each cycle of 3 h reaction time. In addition, the scavenging tests confirmed that the degradation of NAP was mainly governed by ^•OH radicals attack. Two reaction sequences were proposed for the degradation mechanism according to the detected byproducts. Finally, the versatility of the catalyst was evidenced in the treatment of different environmentally relevant aqueous matrices (wastewater treatment plant effluent (WWTP), surface water (SW), and a hospital wastewater (HW)) spiked with NAP, obtaining total organic carbon (TOC) removal efficiencies after 8 h in the following order: NAP-SW > NAP-HW > NAP-WWTP. Full article

(This article belongs to the Special Issue Environmental Catalysis for Water Remediation)

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20 pages, 4507 KiB

Open AccessArticle

Aqueous Dehydration, Hydrogenation, and Hydrodeoxygenation Reactions of Bio-Based Mucic Acid over Ni, NiMo, Pt, Rh, and Ru on Neutral or Acidic Catalyst Supports

by Brigita Hočevar, Miha Grilc and Blaž Likozar

Catalysts 2019, 9(3), 286; https://doi.org/10.3390/catal9030286 - 20 Mar 2019

Cited by 29 | Viewed by 6668

Abstract

Hydrotreatment of mucic acid (also known as galactaric acid, an glucaric acid enantiomer), one of the most promising bio-based platform chemicals, was systematically investigated in aqueous media over alumina, silica, or carbon-supported transition (nickel and nickel-molybdenum) or noble (platinum, ruthenium and rhodium) metals. [...] Read more.

Hydrotreatment of mucic acid (also known as galactaric acid, an glucaric acid enantiomer), one of the most promising bio-based platform chemicals, was systematically investigated in aqueous media over alumina, silica, or carbon-supported transition (nickel and nickel-molybdenum) or noble (platinum, ruthenium and rhodium) metals. Mucic acid was only converted into mucic-1,4-lactone under non-catalytic reaction conditions in N₂ atmosphere, while the 5 MPa gaseous H₂ addition triggers hydrogenation in the bulk phase, resulting in formation of galacturonic and galactonic acid. However, dehydroxylation, hydrogenation, decarbonylation, decarboxylation, and cyclization occurred during catalytic hydrotreatment, forming various partially and completely deoxygenated products with a chain length of 3–6 C atoms. Characterization results of tested catalysts were correlated with their activity and selectivity. Insufficient pore diameter of microporous supports completely hindered the mass transfer of reactants to the active sites, resulting in negligible conversion of mucic acid. A comprehensive reaction pathway network was proposed and several industrially interesting compounds were formed, including levulinic acid, furoic acid, and adipic acid. However, selectivity towards adipic acid, a bio-based nylon 6,6 precursor, was low (up to 5 mol%) in aqueous media and elevated temperatures. Full article

(This article belongs to the Special Issue Heterogeneous Catalysis for Valorization of Lignocellulosic Biomass)

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18 pages, 5075 KiB

Open AccessFeature PaperArticle

Photocatalytic Hydrogen Evolution Using Bi-Metallic (Ni/Pt) Na₂Ti₃O₇ Whiskers: Effect of the Deposition Order

by Luis F. Garay-Rodríguez, S. Murcia-López, T. Andreu, Edgar Moctezuma, Leticia M. Torres-Martínez and J. R. Morante

Catalysts 2019, 9(3), 285; https://doi.org/10.3390/catal9030285 - 20 Mar 2019

Cited by 28 | Viewed by 4008

Abstract

Photocatalytic hydrogen production through ethanol photo-reforming using Na₂Ti₃O₇ whiskers increases if the sodium titanate is decorated with well-known metallic catalysts such as Ni and Pt. Whereas wet impregnation with nickel gives only a slight increase in the activity, [...] Read more.

Photocatalytic hydrogen production through ethanol photo-reforming using Na₂Ti₃O₇ whiskers increases if the sodium titanate is decorated with well-known metallic catalysts such as Ni and Pt. Whereas wet impregnation with nickel gives only a slight increase in the activity, photo-deposition of Pt increased the H₂ production by more than one order of magnitude. Through the combination of both co-catalysts (Ni and Pt) a superior performance in terms of H₂ production is further observed. However, hydrogen yield is largely enhanced (almost three-fold), up to 778 μmol·g⁻¹·h⁻¹, if the Pt is photo-deposited on the surface of the catalyst before wet impregnation with Ni species (NTO/Pt/Ni) compared to H₂ yield (283 μmol·g⁻¹·h⁻¹) achieved with the catalyst prepared in the reverse order (NTO/Ni/Pt). Structural, morphological, optical, and chemical characterization was carried out in order to correlate physicochemical properties with their photocatalytic activity. The X-ray photoelectron spectroscopy (XPS) results show a higher concentration of Pt²⁺ species if this metallic layer is under the nickel oxide layer. Moreover, X-ray diffraction patterns (XRD) show that Na₂Ti₃O₇ surface is modified for both metal decoration processes. Full article

(This article belongs to the Section Photocatalysis)

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16 pages, 2285 KiB

Open AccessArticle

Cyanosilylation of Aldehydes Catalyzed by Ag(I)- and Cu(II)-Arylhydrazone Coordination Polymers in Conventional and in Ionic Liquid Media

by Gonçalo A. O. Tiago, Kamran T. Mahmudov, M. Fátima C. Guedes da Silva, Ana P. C. Ribeiro, Luís C. Branco, Fedor I. Zubkov and Armando J. L. Pombeiro

Catalysts 2019, 9(3), 284; https://doi.org/10.3390/catal9030284 - 20 Mar 2019

Cited by 15 | Viewed by 4298

Abstract

The novel Ag(I) and Cu(II) coordination polymers [Ag(μ₃-1κO;2:3κO′;4κN-HL)]_n∙n/2H₂O (1) and [Cu(en)₂(μ-1κO;2κN-L)]_n∙nH₂O (2) [HL⁻ [...] Read more.

The novel Ag(I) and Cu(II) coordination polymers [Ag(μ₃-1κO;2:3κO′;4κN-HL)]_n∙n/2H₂O (1) and [Cu(en)₂(μ-1κO;2κN-L)]_n∙nH₂O (2) [HL⁻ = 2-(2-(1-cyano-2-oxopropylidene)hydrazinyl)benzene sulfonate] were synthesized and characterized by IR and ESI-MS spectroscopies, elemental and single crystal X-ray diffraction analyses. Compounds 1 and 2 as well as the already known complex salt [Cu(H₂O)₂(en)₂](HL)₂ (3) have been tested as homogenous catalysts for the cyanosilylation reaction of different aldehydes with trimethylsilyl cyanide, to provide cyanohydrin trimethylsilyl ethers. Coordination polymer 2 was found to be the most efficient one, with yields ranging from 76 to 88% in methanol, which increases up to 99% by addition of the ionic liquid [DHTMG][L-Lactate]. Full article

(This article belongs to the Special Issue Catalysis in Unconventional Media)

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0 pages, 1545 KiB

Open AccessArticle

RETRACTED: Transient Operation: A Catalytic Chemoselective Hydrogenation of 2-Methyl-3-Butyn-2-ol via a Cooperative Pd and Radiofrequency Heating Directed Kinetic Resolution

by Duaa Raja, Jabbar Gardy, Ali Hassanpour, Chun-Yu Ho and Javier Fernandez Garcia

Catalysts 2019, 9(3), 283; https://doi.org/10.3390/catal9030283 - 20 Mar 2019

Cited by 1 | Viewed by 4229 | Retraction

Abstract

The effect of periodic temperature oscillations has been studied for the hydrogenation of 2-methyl-3-butyn-2-ol over a Pd-based catalyst in a micro-trickle bed reactor. This hydrogenation was investigated using a radiofrequency heated reactor under transient conditions using temperature cycling. The dynamic operation using this [...] Read more.

The effect of periodic temperature oscillations has been studied for the hydrogenation of 2-methyl-3-butyn-2-ol over a Pd-based catalyst in a micro-trickle bed reactor. This hydrogenation was investigated using a radiofrequency heated reactor under transient conditions using temperature cycling. The dynamic operation using this configuration was found to increase both conversion and selectivity towards 2-methyl-3-buten-2-ol compared to the steady-state operation with an improvement of up to 24% for the selectivity being observed. The developments made here also result in a lower activation energy in comparison to previous data, providing a starting point for radiofrequency heating to enhance reaction rate through the exploitation of thermal cycling at production scale. Full article

(This article belongs to the Special Issue Selected Papers from the 2nd Edition of Global Conference on Catalysis, Chemical Engineering and Technology (CAT 2018))

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15 pages, 9692 KiB

Open AccessArticle

Highly Dispersed Ni Nanocatalysts Derived from NiMnAl-Hydrotalcites as High-Performing Catalyst for Low-Temperature Syngas Methanation

by Bin Lu, Jiahao Zhuang, Jinping Du, Fangna Gu, Guangwen Xu, Ziyi Zhong, Qing Liu and Fabing Su

Catalysts 2019, 9(3), 282; https://doi.org/10.3390/catal9030282 - 19 Mar 2019

Cited by 16 | Viewed by 4482

Abstract

Increasing the low-temperature performance of nickel-based catalysts in syngas methanation is critical but very challenging, because at low temperatures there is high concentration of CO on the catalyst surface, causing formation of nickel carbonyl with metallic Ni and further catalyst deactivation. Herein, we [...] Read more.

Increasing the low-temperature performance of nickel-based catalysts in syngas methanation is critical but very challenging, because at low temperatures there is high concentration of CO on the catalyst surface, causing formation of nickel carbonyl with metallic Ni and further catalyst deactivation. Herein, we have prepared highly dispersed Ni nanocatalysts by in situ reduction of NiMnAl-layered double hydroxides (NiMnAl-LDHs) and applied them to syngas methanation. The synthesized Ni nanocatalysts maintained the nanosheet structure of the LDHs, in which Ni particles were decorated with MnO_y species and embedded in the AlO_x nanosheets. It was observed that the Ni nanocatalysts exhibited markedly better low-temperature performance than commercial catalysts in the syngas methanation. At 250 °C, 3.0 MPa and a high weight hourly space velocity (WHSV) of 30,000 mL·g⁻¹·h⁻¹, both the CO conversion and the CH₄ selectivity reached 100% over the former, while those over the commercial catalyst were only 14% and 76%, respectively. Furthermore, this NiMnAl catalyst exhibited strong anti-carbon and anti-sintering properties at high temperatures. The enhanced low-temperature performance and high-temperature stability originated from the promotion effect of MnO_y and the embedding effect of AlO_x in the catalyst. Full article

(This article belongs to the Special Issue Ni-Containing Catalysts)

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25 pages, 3755 KiB

Open AccessReview

Review on the Macro-Transport Processes Theory for Irregular Pores able to Perform Catalytic Reactions

by Iván Santamaría-Holek, Saúl I. Hernández, Consuelo García-Alcántara and Aldo Ledesma-Durán

Catalysts 2019, 9(3), 281; https://doi.org/10.3390/catal9030281 - 19 Mar 2019

Cited by 14 | Viewed by 4035

Abstract

We review and generalize a recent theoretical framework that provides a sound physicochemical basis to describe how volume and surface diffusion are affected by adsorption and desorption processes, as well as by catalytic conversion within the space defined by the irregular geometry of [...] Read more.

We review and generalize a recent theoretical framework that provides a sound physicochemical basis to describe how volume and surface diffusion are affected by adsorption and desorption processes, as well as by catalytic conversion within the space defined by the irregular geometry of the pores in a material. The theory is based on two single-dimensional mass conservation equations for irregular domains deduced for the volumetric (bulk) and surface mass concentrations. It offers a powerful tool for analyzing and modeling mass transport across porous media like zeolites or artificially build materials, since it establishes how the microscopic quantities that refer to the internal details of the geometry, the flow and the interactions within the irregular pore can be translated into macroscopic variables that are currently measured in experiments. The use of the theory in mass uptake experiments is explained in terms of breakthrough curves and effective mass diffusion coefficients which are explicitly related to the internal geometry of the pores. Full article

(This article belongs to the Special Issue Microporous Zeolites and Related Nanoporous Materials: Synthesis, Characterization and Applications in Catalysis)

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15 pages, 2073 KiB

Open AccessArticle

Preparation and Catalytic Performance of Expanded Graphite for Oxidation of Organic Pollutant

by Ruijia Lan, Wenbin Su and Jitai Li

Catalysts 2019, 9(3), 280; https://doi.org/10.3390/catal9030280 - 19 Mar 2019

Cited by 35 | Viewed by 5211

Abstract

A classic carbon material—expanded graphite (EG), was prepared and proposed for a new application as catalysts for activating peroxydisulfate (PDS). EG samples prepared at different expansion temperatures were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and other methods. It was observed [...] Read more.

A classic carbon material—expanded graphite (EG), was prepared and proposed for a new application as catalysts for activating peroxydisulfate (PDS). EG samples prepared at different expansion temperatures were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and other methods. It was observed that there existed a remarkable synergistic effect in the EG/PDS combined system to degrade Acid Red 97 (AR97). Unlike other carbon material catalysts, sp² carbon structure may be the main active site in the catalytic reaction. The EG sample treated at 600 °C demonstrated the best catalytic activity for the activation of PDS. Degradation efficiency of AR97 increased with raising PDS dosage and EG loadings. The pH of aqueous solution played an important role in degradation and adsorption, and near-neutrality was the optimal pH in this research. It was assumed that the radical pathway played a dominant role in AR97 degradation and that oxidation of AR97 occurred in the pores and interface layer on the external surface of EG by SO₄·⁻ and ·OH, generated on or near the surface of EG. The radical oxidation mechanism was further confirmed by electron paramagnetic resonance spectroscopy. The EG sample could be regenerated by annealing, and the catalytic ability was almost fully recovered. Full article

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22 pages, 12840 KiB

Open AccessArticle

Photocatalytic Activity of Nanostructured Titania Films Obtained by Electrochemical, Chemical, and Thermal Oxidation of Ti6Al4V Alloy—Comparative Analysis

by Aleksandra Radtke

Catalysts 2019, 9(3), 279; https://doi.org/10.3390/catal9030279 - 19 Mar 2019

Cited by 3 | Viewed by 3921

Abstract

Three different Ti6Al4V surface oxidation methods have been applied to obtain three types of titania materials of different nanoarchitecture. Electrochemical oxidation of titanium alloy allowed for obtaining titania nanotubes (TNT), chemical oxidation led to obtain titania nanofibers (TNF), and thermal oxidation gave titania [...] Read more.

Three different Ti6Al4V surface oxidation methods have been applied to obtain three types of titania materials of different nanoarchitecture. Electrochemical oxidation of titanium alloy allowed for obtaining titania nanotubes (TNT), chemical oxidation led to obtain titania nanofibers (TNF), and thermal oxidation gave titania nanowires (TNW). My earlier investigations of these nanomaterials were focused mainly on the estimation of their bioactivity and potential application in modern implantology. In this article, the comparative analysis of the photocatalytic activity of produced systems, as well as the impact of their structure and morphology on this activity, are discussed. The activity of studied nanomaterials was estimated basis of UV-induced degradation of methylene blue and also acetone, and it was determined quantitatively according to the Langmuir–Hinshelwood reaction mechanism. The obtained results were compared to the activity of Pilkington Glass Activ^TM (reference sample). Among analyzed systems, titania nanofibers obtained at 140 and 120 °C, possessing anatase and anatase/amorphous structure, as well as titania nanowires obtained at 475 and 500 °C, possessing anatase and anatase/rutile structure, were better photocatalyst than the reference sample. Completely amorphous titania nanotubes, turned out to be an interesting alternative for photocatalytic materials in the form of thin films, however, their photocatalytic activity is lower than for Pilkington Glass Activ^TM. Full article

(This article belongs to the Special Issue Sustainable Applications in Surface Chemistry and Catalysis)

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14 pages, 1209 KiB

Open AccessArticle

Cu(II)-Catalyzed Oxidative Trifluoromethylation of Indoles with KF as the Base

by Xiaolin Shi, Xiaowei Li, Lina Ma and Dayong Shi

Catalysts 2019, 9(3), 278; https://doi.org/10.3390/catal9030278 - 19 Mar 2019

Cited by 21 | Viewed by 4061

Abstract

This paper offers an efficient copper-catalyzed oxidative trifluoromethylation of indoles with low-cost CF₃SO₂Na via C–H activation. Notably, the use of a base is crucial for the trifluoromethylation of indoles. This reaction proceeds efficiently in good to excellent yields and [...] Read more.

This paper offers an efficient copper-catalyzed oxidative trifluoromethylation of indoles with low-cost CF₃SO₂Na via C–H activation. Notably, the use of a base is crucial for the trifluoromethylation of indoles. This reaction proceeds efficiently in good to excellent yields and is tolerance of a broad range of functional groups. Furthermore, melatonin, a medicine for sleep disorders, is converted to its 2-CF₃ analogue in 68% yield. Studies of possible reaction pathways suggest that this reaction proceeds through a radical process. Full article

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16 pages, 3413 KiB

Open AccessArticle

Catalysts of PtSn/C Modified with Ru and Ta for Electrooxidation of Ethanol

by Maria Aparecida Ribeiro Queiroz and Josimar Ribeiro

Catalysts 2019, 9(3), 277; https://doi.org/10.3390/catal9030277 - 18 Mar 2019

Cited by 8 | Viewed by 3583

Abstract

PtSn/C-type catalysts modified with Ta and Ru were prepared by the thermal decomposition of polymeric precursors with the following nominal compositions: Pt₇₀Sn₁₀Ta₂₀/C, Pt₇₀Sn₁₀Ta₁₅Ru₅/C, Pt₇₀Sn₁₀Ta₁₀ [...] Read more.

PtSn/C-type catalysts modified with Ta and Ru were prepared by the thermal decomposition of polymeric precursors with the following nominal compositions: Pt₇₀Sn₁₀Ta₂₀/C, Pt₇₀Sn₁₀Ta₁₅Ru₅/C, Pt₇₀Sn₁₀Ta₁₀Ru₁₀/C and Pt₇₀Sn₁₀Ta₅Ru₁₅/C. The physicochemical characterization was performed by X-ray diffraction (XRD) and energy dispersive X-ray (EDX). The electrochemical characterization was performed using cyclic voltammetry, chronoamperometry and fuel cell testing. PtSnTaRu/C catalysts were characterized in the absence and presence of ethanol in an acidic medium (H₂SO₄ 0.5 mol L⁻¹). All the catalysts showed activity for the oxidation of ethanol. The results indicated that the addition of Ta increased the stability and performance of the catalysts, as the Pt₇₀Sn₁₀Ta₂₀/C catalyst had the maximum power density of 27.3 mW cm⁻² in an acidic medium. The results showed that the PtSn/C-type catalysts modified with Ta and Ru showed good performance against alcohol oxidation, representingan alternative to the use of direct ethanol fuel cells. Full article

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35 pages, 2989 KiB

Open AccessEditor’s ChoiceArticle

Photocatalytic Hydrogen Production: Role of Sacrificial Reagents on the Activity of Oxide, Carbon, and Sulfide Catalysts

by Vignesh Kumaravel, Muhammad Danyal Imam, Ahmed Badreldin, Rama Krishna Chava, Jeong Yeon Do, Misook Kang and Ahmed Abdel-Wahab

Catalysts 2019, 9(3), 276; https://doi.org/10.3390/catal9030276 - 18 Mar 2019

Cited by 252 | Viewed by 21015

Abstract

Photocatalytic water splitting is a sustainable technology for the production of clean fuel in terms of hydrogen (H₂). In the present study, hydrogen (H₂) production efficiency of three promising photocatalysts (titania (TiO₂-P25), graphitic carbon nitride (g [...] Read more.

Photocatalytic water splitting is a sustainable technology for the production of clean fuel in terms of hydrogen (H₂). In the present study, hydrogen (H₂) production efficiency of three promising photocatalysts (titania (TiO₂-P25), graphitic carbon nitride (g-C₃N₄), and cadmium sulfide (CdS)) was evaluated in detail using various sacrificial agents. The effect of most commonly used sacrificial agents in the recent years, such as methanol, ethanol, isopropanol, ethylene glycol, glycerol, lactic acid, glucose, sodium sulfide, sodium sulfite, sodium sulfide/sodium sulfite mixture, and triethanolamine, were evaluated on TiO₂-P25, g-C₃N₄, and CdS. H₂ production experiments were carried out under simulated solar light irradiation in an immersion type photo-reactor. All the experiments were performed without any noble metal co-catalyst. Moreover, photolysis experiments were executed to study the H₂ generation in the absence of a catalyst. The results were discussed specifically in terms of chemical reactions, pH of the reaction medium, hydroxyl groups, alpha hydrogen, and carbon chain length of sacrificial agents. The results revealed that glucose and glycerol are the most suitable sacrificial agents for an oxide photocatalyst. Triethanolamine is the ideal sacrificial agent for carbon and sulfide photocatalyst. A remarkable amount of H₂ was produced from the photolysis of sodium sulfide and sodium sulfide/sodium sulfite mixture without any photocatalyst. The findings of this study would be highly beneficial for the selection of sacrificial agents for a particular photocatalyst. Full article

(This article belongs to the Special Issue Photocatalytic Hydrogen Evolution)

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37 pages, 9821 KiB

Open AccessReview

Hydrogenation of Carbon Dioxide to Value-Added Chemicals by Heterogeneous Catalysis and Plasma Catalysis

by Miao Liu, Yanhui Yi, Li Wang, Hongchen Guo and Annemie Bogaerts

Catalysts 2019, 9(3), 275; https://doi.org/10.3390/catal9030275 - 18 Mar 2019

Cited by 141 | Viewed by 13239

Abstract

Due to the increasing emission of carbon dioxide (CO₂), greenhouse effects are becoming more and more severe, causing global climate change. The conversion and utilization of CO₂ is one of the possible solutions to reduce CO₂ concentrations. This can [...] Read more.

Due to the increasing emission of carbon dioxide (CO₂), greenhouse effects are becoming more and more severe, causing global climate change. The conversion and utilization of CO₂ is one of the possible solutions to reduce CO₂ concentrations. This can be accomplished, among other methods, by direct hydrogenation of CO₂, producing value-added products. In this review, the progress of mainly the last five years in direct hydrogenation of CO₂ to value-added chemicals (e.g., CO, CH₄, CH₃OH, DME, olefins, and higher hydrocarbons) by heterogeneous catalysis and plasma catalysis is summarized, and research priorities for CO₂ hydrogenation are proposed. Full article

(This article belongs to the Special Issue Emissions Control Catalysis)

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18 pages, 1087 KiB

Open AccessReview

Advances in the Green Synthesis of Microporous and Hierarchical Zeolites: A Short Review

by Tao Pan, Zhijie Wu and Alex C. K. Yip

Catalysts 2019, 9(3), 274; https://doi.org/10.3390/catal9030274 - 17 Mar 2019

Cited by 54 | Viewed by 7733

Abstract

Hierarchical zeolites have been extensively studied due to their enhancement of intra-crystalline diffusion, which leads to the improved catalytic activity and resistance to coking-deactivation. Traditional synthesis strategies of hierarchical zeolites via post-treatment or directing synthesis with the aid of mesoporous template are often [...] Read more.

Hierarchical zeolites have been extensively studied due to their enhancement of intra-crystalline diffusion, which leads to the improved catalytic activity and resistance to coking-deactivation. Traditional synthesis strategies of hierarchical zeolites via post-treatment or directing synthesis with the aid of mesoporous template are often characterized by high energy consumption and substantial use of expensive and environmentally unfriendly organic templates. In the recent decade, new green synthesis protocols have been developed for the effective synthesis of conventional and hierarchical zeolites. In this review, the latest advancements on the green synthesis of hierarchical zeolites are summarized and discussed in detail. Full article

(This article belongs to the Special Issue Synthesis and Application of Zeolite Catalysts)

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11 pages, 4805 KiB

Open AccessArticle

Efficient Dye-Sensitized Solar Cells Composed of Nanostructural ZnO Doped with Ti

by Mati Ur Rahman, Mingdeng Wei, Fengyan Xie and Matiullah Khan

Catalysts 2019, 9(3), 273; https://doi.org/10.3390/catal9030273 - 17 Mar 2019

Cited by 46 | Viewed by 4010

Abstract

Photoanode materials with optimized particle sizes, excellent surface area and dye loading capability are preferred in good-performance dye sensitized solar cells. Herein, we report on an efficient dye-sensitized mesoporous photoanode of Ti doped zinc oxide (Ti-ZnO) through a facile hydrothermal method. The crystallinity, [...] Read more.

Photoanode materials with optimized particle sizes, excellent surface area and dye loading capability are preferred in good-performance dye sensitized solar cells. Herein, we report on an efficient dye-sensitized mesoporous photoanode of Ti doped zinc oxide (Ti-ZnO) through a facile hydrothermal method. The crystallinity, morphology, surface area, optical and electrochemical properties of the Ti-ZnO were investigated using X-ray photoelectron spectroscopy, transmission electron microscopy and X-ray diffraction. It was observed that Ti-ZnO nanoparticles with a high surface area of 131.85 m² g⁻¹ and a controlled band gap, exhibited considerably increased light harvesting efficiency, dye loading capability, and achieved comparable solar cell performance at a typical nanocrystalline ZnO photoanode. Full article

(This article belongs to the Special Issue Photocatalytic Organic Synthesis)

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10 pages, 1487 KiB

Open AccessArticle

Microwave-Assisted Homogeneous Acid Catalysis and Chemoenzymatic Synthesis of Dialkyl Succinate in a Flow Reactor

by Laura Daviot, Thomas Len, Carol Sze Ki Lin and Christophe Len

Catalysts 2019, 9(3), 272; https://doi.org/10.3390/catal9030272 - 16 Mar 2019

Cited by 15 | Viewed by 4372

Abstract

Two new continuous flow systems for the production of dialkyl succinates were developed via the esterification of succinic acid, and via the trans-esterification of dimethyl succinate. The first microwave-assisted continuous esterification of succinic acid with H₂SO₄ as a chemical homogeneous [...] Read more.

Two new continuous flow systems for the production of dialkyl succinates were developed via the esterification of succinic acid, and via the trans-esterification of dimethyl succinate. The first microwave-assisted continuous esterification of succinic acid with H₂SO₄ as a chemical homogeneous catalyst was successfully achieved via a single pass (ca 320 s) at 65–115 °C using a MiniFlow 200ss Sairem Technology. The first continuous trans-esterification of dimethyl succinate with lipase Cal B as an enzymatic catalyst was developed using a Syrris Asia Technology, with an optimal reaction condition of 14 min at 40 °C. Dialkyl succinates were produced with the two technologies, but higher productivity was observed for the microwave-assisted continuous esterification using chemical catalysts. The continuous flow trans-esterification demonstrated a number of advantages, but it resulted in lower yield of the target esters. Full article

(This article belongs to the Special Issue Catalytic Methods in Flow Chemistry)

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