scholarly journals Vapour-Phase Selective O-Methylation of Catechol with Methanol over Metal Phosphate Catalysts

Catalysts ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 531
Author(s):  
Haifang Mao ◽  
Xiaolei Li ◽  
Fen Xu ◽  
Zuobing Xiao ◽  
Wenxiang Zhang ◽  
...  
Keyword(s):  
Heterogeneous Catalysts ◽  
Vapour Phase ◽  
Catalytic Performance ◽  
Industrial Applications ◽  
Metal Phosphate ◽  
Aluminium Phosphate ◽  
Cerium Phosphate ◽  
Metal Phosphates ◽  
Temperature Programmed ◽  
Methylating Agents

Guaiacol (2-methoxyphenol), an important fine chemical intermediate, is conventionally synthesized by liquid-phase processes with expensive, corrosive and toxic methylating agents such as dimethyl sulphate and dimethyl iodide. Recently, vapour-phase alkylation of catechol (1, 2-dihydroxybenzene) with methanol for the synthesis of guaiacol in the presence of heterogeneous catalysts has received more attention, as the route is economical and environmentally friendly. However, most of the investigated catalysts exhibited unsatisfactory catalytic performance for industrial applications. In this study, five metal phosphates M-P-O (M = La, Ce, Mg, Al, Zn) catalysts were synthesized and tested in the selective O-methylation of catechol with methanol. Among these catalysts, cerium phosphate (CP) showed the highest catalytic activity and guaiacol yield. Lanthanum phosphate (LP) was the second most active, which was still obviously better than magnesium phosphate (MP) and aluminium phosphate (ALP). Zinc phosphate (ZP) was not active in the reaction. Relevant samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), N2 adsorption-desorption, temperature programmed desorption of NH3 or CO2 (NH3-TPD, CO2-TPD). The suitable acid-base properties contribute to the superior catalytic performance of CP. Long-term stability and regeneration tests were also studied.

scholarly journals Catalytic Performance of CPM-200-In/Mg in the Cycloaddition of CO2 and Epoxides

Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 430
Author(s):  
Yunjang Gu ◽  
Youngson Choe ◽  
Dae-Won Park
Keyword(s):  
Density Functional ◽  
Heterogeneous Catalysts ◽  
Cycloaddition Reaction ◽  
Catalytic Performance ◽  
X Ray Diffraction ◽  
Solvent Free Conditions ◽  
Simple Filtration ◽  
Acidic Sites ◽  
Metal Organic ◽  
Temperature Programmed

Crystalline porous materials (CPM)-200-In and CPM-200-In/Mg metal-organic frameworks (MOFs) were synthesized by a solvothermal method and were characterized by using powder X-ray diffraction (PXRD), FT-IR, Brunauer–Emmett–Teller (BET), temperature programmed desorption (TPD), TGA, XPS, and SEM-EDS. They were used as heterogeneous catalysts for the cycloaddition of CO2 with epoxides and found to be highly efficient toward the cycloaddition reaction at moderate reaction conditions under solvent-free conditions. The catalyst was easily separated by a simple filtration and can be reused up to five consecutive times without any considerable decrease of its initial activity. CPM-200-In/Mg showed excellent catalytic performance in the cycloaddition reaction due to the synergistic role of the acidic sites and basic sites. A plausible reaction mechanism for the CPM-200-In/Mg MOF catalyzed cycloaddition reaction is proposed based on the experimental results and our previously reported DFT (Density Functional Theory) studies.

Metal Phosphates: Preparation, Characterization and Catalytic Evolution for Vapour Phase Dehydration of Glycerol to Acrolein

2020 ◽  
Vol 12 (3) ◽  
pp. 356-363
Author(s):  
Ginjupalli Srinivasa Rao ◽  
Balla Putra Kumar ◽  
Shaik Hussain ◽  
Ponnala Bhanuchander
Keyword(s):  
Vapour Phase ◽  
Ex Situ ◽  
Metal Phosphate ◽  
Metal Component ◽  
Life Activity ◽  
Glycerol Conversion ◽  
Metal Phosphates ◽  
Physico Chemical ◽  
Glycerol Dehydration ◽  
Ft Ir

Metal phosphate (MP; M = Al, Ti, Zr and Nb) catalysts have been examined for the continuous dehydration of glycerol to acrolein and hydroxyacetone. These catalysts are prepared by hydrothermal procedure and the physico-chemical characteristics were probe by XRD, N2 sorption, FT-IR, UV-DRS, ex-situ Py-FT-IR and TPD-NH3 to gain the insight effect of the samples structural and superficial acidity with changing the metal component. The glycerol dehydration activity will be interpreted with respected to the acidity and skeletal behavior of the MP catalysts. The outcomes indicated that the NbP was the best catalyst, achieving 100% glycerol conversion, followed by TiP, ZrP and AlP. However, due to its expanded porosity, TiP catalyst proved its long life activity during vapor phase glycerol dehydration.

Substituent Effects on the Thermal Decomposition of Phosphate Esters on Ferrous Surfaces

2019 ◽  
Author(s):  
James Ewen ◽  
Carlos Ayestaran Latorre ◽  
Arash Khajeh ◽  
Joshua Moore ◽  
Joseph Remias ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Film Formation ◽  
Substituent Effects ◽  
Vapour Phase ◽  
Industrial Applications ◽  
Phosphate Esters ◽  
Antiwear Additives ◽  
Formation Mechanisms ◽  
Phosphate Ester ◽  
Wide Range

<p>Phosphate esters have a wide range of industrial applications, for example in tribology where they are used as vapour phase lubricants and antiwear additives. To rationally design phosphate esters with improved tribological performance, an atomic-level understanding of their film formation mechanisms is required. One important aspect is the thermal decomposition of phosphate esters on steel surfaces, since this initiates film formation. In this study, ReaxFF molecular dynamics simulations are used to study the thermal decomposition of phosphate esters with different substituents on several ferrous surfaces. On Fe<sub>3</sub>O<sub>4</sub>(001) and α-Fe(110), chemisorption interactions between the phosphate esters and the surfaces occur even at room temperature, and the number of molecule-surface bonds increases as the temperature is increased from 300 to 1000 K. Conversely, on hydroxylated, amorphous Fe<sub>3</sub>O<sub>4</sub>, most of the molecules are physisorbed, even at high temperature. Thermal decomposition rates were much higher on Fe<sub>3</sub>O<sub>4</sub>(001) and particularly α-Fe(110) compared to hydroxylated, amorphous Fe<sub>3</sub>O<sub>4</sub>. This suggests that water passivates ferrous surfaces and inhibits phosphate ester chemisorption, decomposition, and ultimately film formation. On Fe<sub>3</sub>O<sub>4</sub>(001), thermal decomposition proceeds mainly through C-O cleavage (to form surface alkyl and aryl groups) and C-H cleavage (to form surface hydroxyls). The onset temperature for C-O cleavage on Fe<sub>3</sub>O<sub>4</sub>(001) increases in the order: tertiary alkyl < secondary alkyl < primary linear alkyl ≈ primary branched alkyl < aryl. This order is in agreement with experimental observations for the thermal stability of antiwear additives with similar substituents. The results highlight surface and substituent effects on the thermal decomposition of phosphate esters which should be helpful for the design of new molecules with improved performance.</p>

scholarly journals Novel Nickel- and Magnesium-Modified Cenospheres as Catalysts for Dry Reforming of Methane at Moderate Temperatures

Catalysts ◽  
2019 ◽  
Vol 9 (12) ◽  
pp. 1066 ◽  
Author(s):  
Bogdan Samojeden ◽  
Marta Kamienowska ◽  
Armando Izquierdo Colorado ◽  
Maria Elena Galvez ◽  
Ilona Kolebuk ◽  
...  
Keyword(s):  
Supported Catalysts ◽  
Temperature Programmed Desorption ◽  
Catalytic Performance ◽  
Dry Reforming ◽  
Dry Reforming Of Methane ◽  
Temperature Programmed Reduction ◽  
Fly Ashes ◽  
Coal Fly Ashes ◽  
Temperature Programmed ◽  
Mg Content

Cenospheres from coal fly ashes were used as support in the preparation of Ni–Mg catalysts for dry reforming of methane. These materials were characterized by means of XRD, H2-temperature-programmed reduction (H2-TPR), CO2-temperature-programmed desorption (CO2-TPD), and low-temperature nitrogen sorption techniques. The cenosphere-supported catalysts showed relatively high activity and good stability in the dry reforming of methane (DRM) at 700 °C. The catalytic performance of modified cenospheres was found to depend on both Ni and Mg content. The highest activity at 750 °C and 1 atm was observed for the catalyst containing 30 wt % Mg and 10, 20, and 30 wt % Ni, yielding to CO2 and CH4 conversions of around 95%.

scholarly journals The Effect of Mg and Zn Dopants on Pt/Al2O3 for the Dehydrogenation of Perhydrodibenzyltoluene

Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 490
Author(s):  
Rudaviro Garidzirai ◽  
Phillimon Modisha ◽  
Innocent Shuro ◽  
Jacobus Visagie ◽  
Pieter van Helden ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Inductively Coupled Plasma ◽  
Flow Reactor ◽  
Plug Flow ◽  
Optical Emission ◽  
Catalytic Performance ◽  
Emission Spectrometry ◽  
Hydrogen Yield ◽  
X Ray ◽  
Temperature Programmed

The effects of Mg and Zn dopants on the catalytic performance of Pt/Al2O3 catalyst were investigated for dehydrogenation of perhydrodibenzyltoluene (H18-DBT) as a liquid organic hydrogen carrier. Al2O3 supports were modified with Mg and Zn to produce Mg-Al2O3 and Zn-Al2O3 with a target loading of 3.8 wt.% for dopants. The modified supports were impregnated with chloroplatinic acid solution to produce the catalysts Pt/Al2O3, Pt/Mg-Al2O3 and Pt/Zn-Al2O3 of 0.5 wt.% Pt loading. Thereafter, the catalysts were characterised using inductively coupled plasma- optical emission spectrometry, scanning electron microscopy-energy dispersive X-ray spectroscopy, hydrogen temperature-programmed reduction, carbon-monoxide pulse chemisorption, ammonia temperature-programmed desorption, X-ray diffraction and transmission electron microscopy. The dehydrogenation experiments were performed using a horizontal plug flow reactor system and the catalyst time-on-stream was 22 h. Pt/Mg-Al2O3 showed the highest average hydrogen flowrate of 29 nL/h, while an average of 27 nL/h was obtained for both Pt/Al2O3 and Pt/Zn-Al2O3. This has resulted in a hydrogen yield of 80% for Pt/Mg-Al2O3, 71% for Pt/Zn-Al2O3 and 73% for Pt/Al2O3. In addition, the conversion of H18-DBT ranges from 99% to 92%, Pt 97–90% and 96–90% for Pt/Mg-Al2O3, Pt/Zn-Al2O3 and Pt/Al2O3, respectively. Following the latter catalyst order, the selectivity to dibenzyltoluene (H0-DBT) ranges from 78% to 57%, 75–51% and 71–45%. Therefore, Pt/Mg-Al2O3 showed improved catalytic performance towards dehydrogenation of H18-DBT.

scholarly journals Ambient base-free glycerol oxidation over bimetallic PdFe/SiO2 by in situ generated active oxygen species

2021 ◽  
Author(s):  
Ricci Underhill ◽  
Mark Douthwaite ◽  
Richard J. Lewis ◽  
Peter J. Miedziak ◽  
Robert D. Armstrong ◽  
...  
Keyword(s):  
Heterogeneous Catalysts ◽  
Bimetallic Catalyst ◽  
Electron Paramagnetic Resonance Spectroscopy ◽  
Active Oxygen Species ◽  
Catalytic Performance ◽  
Resonance Spectroscopy ◽  
Oxygen Species ◽  
Paramagnetic Resonance ◽  
Temperature Oxidation

AbstractLow temperature oxidation of alcohols over heterogeneous catalysts is exceptionally challenging, particularly under neutral conditions. Herein, we report on an efficient, base-free method to oxidise glycerol over a 0.5%Pd-0.5%Fe/SiO2 catalyst at ambient temperature in the presence of gaseous H2 and O2. The exceptional catalytic performance was attributed to the in situ formation of highly reactive surface-bound oxygenated species, which promote the dehydrogenation on the alcohol. The PdFe bimetallic catalyst was determined to be significantly more active than corresponding monometallic analogues, highlighting the important role both metals have in this oxidative transformation. Fe leaching was confirmed to occur over the course of the reaction but sequestering experiments, involving the addition of bare carbon to the reactions, confirmed that the reaction was predominantly heterogeneous in nature. Investigations with electron paramagnetic resonance spectroscopy suggested that the reactivity in the early stages was mediated by surface-bound reactive oxygen species; no homogeneous radical species were observed in solution. This theory was further evidenced by a direct H2O2 synthesis study, which confirmed that the presence of Fe in the bimetallic catalyst neither improved the synthesis of H2O2 nor promoted its decomposition over the PdFe/SiO2 catalyst.

scholarly journals Exploiting the Potential of Biosilica from Rice Husk as Porous Support for Catalytically Active Iron Oxide Nanoparticles

Nanomaterials ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 1259
Author(s):  
Ana Franco ◽  
Rafael Luque ◽  
Carolina Carrillo-Carrión
Keyword(s):  
Iron Oxide ◽  
Iron Oxide Nanoparticles ◽  
Rice Husk ◽  
Heterogeneous Catalysts ◽  
Catalytic Performance ◽  
Added Value ◽  
Oxide Nanoparticles ◽  
Porous Support ◽  
Green Materials ◽  
Catalytically Active

Biomass-derived materials are put forward as eco-friendly alternatives to design heterogeneous catalysts. To contribute in this field, we explored the potential of mesoporous biogenic silica (RH-Silica) obtained from lignocellulosic waste, in particular from rice husk, as an inorganic support to prepare heterogenized iron oxide-based catalysts. Mechanochemistry, considered as a green and sustainable technique, was employed to synthetize iron oxide nanoparticles in pure hematite phase onto the biosilica (α-Fe2O3/RH-Silica), making this material a good candidate to perform catalyzed organic reactions. The obtained material was characterized by different techniques, and its catalytic activity was tested in the selective oxidation of styrene under microwave irradiation. α-Fe2O3/RH-Silica displayed a good catalytic performance, achieving a conversion of 45% under optimized conditions, and more importantly, with a total selectivity to benzaldehyde. Furthermore, a good reusability was achieved without decreasing its activity after multiple catalytic cycles. This work represents a good example of using sustainable approaches and green materials as alternatives to conventional methods in the production of high-added value products.

scholarly journals Novel Preparation of Cu and Fe Zirconia Supported Catalysts for Selective Catalytic Reduction of NO with NH3

Catalysts ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 55
Author(s):  
Katarzyna Świrk ◽  
Ye Wang ◽  
Changwei Hu ◽  
Li Li ◽  
Patrick Da Costa ◽  
...  
Keyword(s):  
Selective Catalytic Reduction ◽  
Catalytic Reduction ◽  
Supported Catalysts ◽  
Catalytic Performance ◽  
Experimental Conditions ◽  
One Pot ◽  
Nh3 Scr ◽  
Scr Of No ◽  
Temperature Programmed ◽  
Stationary Sources

Copper and iron promoted ZrO2 catalysts were prepared by one-pot synthesis using urea. The studied catalysts were characterized by XRD, N2 physisorption, XPS, temperature-programmed desorption of NH3 (NH3-TPD), and tested by the selective catalytic reduction by ammonia (NH3-SCR) of NO in the absence and presence of water vapor, under the experimental conditions representative of exhaust gases from stationary sources. The influence of SO2 on catalytic performance was also investigated. Among the studied catalysts, the Fe-Zr sample showed the most promising results in NH3-SCR, being active and highly selective to N2. The addition of SO2 markedly improved NO and NH3 conversions during NH3-SCR in the presence of H2O. The improvement in acidic surface properties is believed to be the cause.

scholarly journals Influence of Sulfur-Containing Sodium Salt Poisoned V2O5–WO3/TiO2 Catalysts on SO2–SO3 Conversion and NO Removal

Catalysts ◽  
2018 ◽  
Vol 8 (11) ◽  
pp. 541 ◽  
Author(s):  
Haiping Xiao ◽  
Chaozong Dou ◽  
Hao Shi ◽  
Jinlin Ge ◽  
Li Cai
Keyword(s):  
Photoelectron Spectroscopy ◽  
No Reduction ◽  
Catalytic Performance ◽  
Acid Sites ◽  
Impregnation Method ◽  
So2 Oxidation ◽  
Sodium Salts ◽  
X Ray ◽  
Temperature Programmed ◽  
Physical Features

A series of poisoned catalysts with various forms and contents of sodium salts (Na2SO4 and Na2S2O7) were prepared using the wet impregnation method. The influence of sodium salts poisoned catalysts on SO2 oxidation and NO reduction was investigated. The chemical and physical features of the catalysts were characterized via NH3-temperature programmed desorption (NH3-TPD), H2-temperature programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FT-IR). The results showed that sodium salts poisoned catalysts led to a decrease in the denitration efficiency. The 3.6% Na2SO4 poisoned catalyst was the most severely deactivated with denitration efficiency of only 50.97% at 350 °C. The introduction of SO42− and S2O72− created new Brønsted acid sites, which facilitated the adsorption of NH3 and NO reduction. The sodium salts poisoned catalysts significantly increased the conversion of SO2–SO3. 3.6%Na2S2O7 poisoned catalyst had the strongest effect on SO2 oxidation and the catalyst achieved a maximum SO2–SO3-conversion of 1.44% at 410 °C. Characterization results showed sodium salts poisoned catalysts consumed the active ingredient and lowered the V4+/V5+ ratio, which suppressed catalytic performance. However, they increased the content of chemically adsorbed oxygen and the strength of V5+=O bonds, which promoted SO2 oxidation.

scholarly journals Chemocatalytic Production of Lactates from Biomass-Derived Sugars

2018 ◽  
Vol 2018 ◽  
pp. 1-18 ◽  
Author(s):  
Heng Zhang ◽  
Yulin Hu ◽  
Liying Qi ◽  
Jian He ◽  
Hu Li ◽  
...  
Keyword(s):  
Lactic Acid ◽  
Heterogeneous Catalysts ◽  
Catalytic Performance ◽  
Green Solvents ◽  
Separation And Purification ◽  
Sustainable Resources ◽  
Base Catalysts ◽  
Heterogeneous Catalytic ◽  
Acid And Base ◽  
Relative Separation

In recent decades, a great deal of attention has been paid to the exploration of alternative and sustainable resources to produce biofuels and valuable chemicals, with aims of reducing the reliance on depleting confined fossil resources and alleviating serious economic and environmental issues. In line with this, lignocellulosic biomass-derived lactic acid (LA, 2-hydroxypropanoic acid), to be identified as an important biomass-derived commodity chemical, has found wide applications in food, pharmaceuticals, and cosmetics. In spite of the current fermentation of saccharides to produce lactic acid, sustainability issues such as environmental impact and high cost derived from the relative separation and purification process will be growing with the increasing demands of necessary orders. Alternatively, chemocatalytic approaches to manufacture LA from biomass (i.e., inedible cellulose) have attracted extensive attention, which may give rise to higher productivity and lower costs related to product work-up. This work presents a review of the state-of-the-art for the production of LA using homogeneous, heterogeneous acid, and base catalysts, from sugars and real biomass like rice straw, respectively. Furthermore, the corresponding bio-based esters lactate which could serve as green solvents, produced from biomass with chemocatalysis, is also discussed. Advantages of heterogeneous catalytic reaction systems are emphasized. Guidance is suggested to improve the catalytic performance of heterogeneous catalysts for the production of LA.

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