Two dimensional Zn-stilbenedicarboxylic acid (SDC) metal-organic frameworks for cyclic carbonate synthesis from CO<Subscript>2</Subscript> and epoxides

A two-dimensional Zn-based metal-organic framework has been synthesized by using Zn(II) ions and H₂SDC (4,4′-stilbenedicarboxylic acid) under solvothermal conditions. The framework having a trinuclear Zn₃-(RCO₂)₆ SBUs connected by the 4,4′-stilbenedicarboxylic acid to form a hexagonal network, shows a two-dimensional structure and displays high thermal stability up to approximately 330 °C. The role of Zn²⁺ (from Zn-SDC) for epoxide activation and Br-ion (from TBABr) for ring opening of epoxide was studied for the cycloaddition reaction of CO₂ and propylene oxide (PO) under ambient conditions. Zn-SDC was found catalytically efficient towards CO₂-epoxide coupling under ambient reaction conditions with high selectivity towards the desired cyclic carbonates under solvent-free conditions. The effects of various reaction parameters such as catalyst loading, temperature, CO₂ pressure, and time were evaluated. Zn-SDC was easily separable and reusable at least five times without any considerable loss in the initial activity. A plausible reaction mechanism for the cycloaddition reaction was also proposed based on literature and experimental inferences.     

Syntheses and characterizations of two new pillared-layer coordination polymers constructed from lanthanides and mixed O-donor ligands

Two new pillared-layer frameworks have been obtained through self-assembly of 4,4′-azobenzene dicarboxylatic acid (4,4′-H₂ABDC), oxalate, hydroxyl and LnCl₃(Ln = Sm, Eu) under hydrothermal environment and characterized by TGA, IR spectroscopy, element analyses, and X-ray single crystal diffraction. The X-ray structure analyses reveal that the oxalates link the Ln(III) to form metal layers, and 4,4′-ABDC ligands work as pillars to connect adjacent layers to further extend into 3D frameworks. Their magnetic studies show that the two compounds have typical anti-ferromagnetic behaviors.     

Synthesis of MIL-101@g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> nanocomposite for enhanced adsorption capacity towards CO<Subscript>2</Subscript>

MIL-101@g-C₃N₄ nanocomposite was prepared by solvothermal synthesis and used for CO₂ adsorption. The parent materials (MIL-101 and g-C₃N₄) and the MIL-101@g-C₃N₄ were characterized by X-ray diffraction, argon adsorption/desorption, Fourier transform infrared spectroscopy, thermal analysis (TG/DTA), transmission electronic microscopy, and Energy-dispersive X-ray spectroscopy. The results confirmed the formation of well-defined MIL-101@g-C₃N₄ with interesting surface area and pore volume. Furthermore, both MIL-101 and MIL-101@g-C₃N₄ were accomplished in carbon dioxide capture at different temperatures (280, 288, 273 and 298 K) at lower pressure. The adsorption isotherms show that the nanocomposite has a good CO₂ adsorption affinity compared to MIL-101. The best adsorption capacity is about 1.6 mmol g^?1 obtained for the nanocomposite material which is two times higher than that of MIL-101, indicating strong interactions between CO₂ and MIL-101@g-C₃N₄. This difference in efficacy is mainly due to the presence of the amine groups dispersed in the nanocomposite. Finally, we have developed a simple route for the preparation of an effective and new adsorbent for the removal of CO₂, which can be used as an excellent candidate for gas storage, catalysis, and adsorption.     

Fabrication of MIL-100(Fe)@SiO<Subscript>2</Subscript>@Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> core-shell microspheres as a magnetically recyclable solid acidic catalyst for the acetalization of benzaldehyde and glycol

Heterogeneous catalysts with convenient recyclability and reusability are vitally important to reduce the cost of catalysts as well as to avoid complex separation and recovery operations. In this regard, magnetic MIL-100 (Fe)@SiO₂@Fe₃O₄ microspheres with a novel core-shell structure were fabricated by the in-situ self-assembly of a metal-organic MIL-100(Fe) framework around pre-synthesized magnetic SiO₂@Fe₃O₄ particles under relatively mild and environmentally benign conditions. The catalytic activity of the MIL-100(Fe)@SiO2@Fe3O4 catalyst was tested for the liquid-phase acetalization of benzaldehyde and glycol. The MIL-100(Fe)@SiO₂@Fe₃O₄ catalyst has a significant amount of accessible Lewis acid sites and therefore exhibited good acetalization catalytic activity. Moreover, due to its superparamagnetism properties, the heterogeneous MIL-100(Fe)@SiO₂@Fe₃O₄ catalyst can be easily isolated from the reaction system within a few seconds by simply using an external magnet. The catalyst could then be reused at least eight times without significant loss in catalytic efficiency.

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Sorption studies of CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript>, N<Subscript>2</Subscript>, CO,O<Subscript>2</Subscript> and Ar on nanoporous aluminum terephthalate [MIL-53(Al)]

Aluminum terephthalate, MIL-53(Al), metal–organic framework synthesized hydrothermally and purified by solvent extraction method was used as an adsorbent for gas adsorption studies. The synthesized MIL-53(Al) was characterized by powder X-Ray diffraction analysis, surface area measurement using N₂ adsorption–desorption at 77 K, FTIR spectroscopy and thermo gravimetric analysis. Adsorption isotherms of CO₂, CH₄, CO, N₂, O₂ and Ar were measured at 288 and 303 K. The absolute adsorption capacity was found in the order CO₂>CH₄>CO>N₂>Ar>O₂. Henry’s constants, heat of adsorption in the low pressure region and adsorption selectivities for the adsorbate gases were calculated from their adsorption isotherms. The high selectivity and low heat of adsorption for CO₂ suggests that MIL-53(Al) is a potential adsorbent material for the separation of CO₂ from gas mixtures. The high selectivity for CH₄ over O₂ and its low heat of adsorption suggests that MIL-53(Al) could also be a compatible adsorbent for the separation of methane from methane–oxygen gas mixtures.     

Influence of operating temperature on CO<Subscript>2</Subscript>-NH<Subscript>3</Subscript> reaction in an aqueous solution

Although aqueous ammonia solution has been focused on the removal of CO₂ from flue gas, there have been very few reports regarding the underlying analysis of the reaction between CO₂ and NH₃. In this work, we explored the reaction of CO₂-NH₃-H₂O system at various operating temperatures: 40 °C, 20 °C, and 5 °C. The CO₂ removal efficiency and the loss of ammonia were influenced by the operating temperatures. Also, infrared spectroscopy measurement was used in order to understand the formation mechanism of ion species in absorbent, such as NH₂COO⁻, HCO₃⁻, CO₃²⁻, and NH₄⁺, during CO₂, NH₃, and H₂O reaction. The reactions of CO₂-NH₃-H₂O system at 20 °C and 40 °C have similar reaction routes. However, a different reaction route was observed at 5 °C compared to the other operating temperatures, showing the solid products of ammonium bicarbonates, relatively. The CO₂ removal efficiency and the formation of carbamate and bicarbonate were strongly influenced by the operating temperatures. In particular, the analysis of the formation carbamate and bicarbonate by infrared spectroscopy measurement provides useful information on the reaction mechanism of CO₂ in an aqueous ammonia solution.     

Synthesis,structure and properties of (4,4′-H2bipy)[HgBr4] · H2O with strong fluorescence

(4,4′-H₂bipy)[HgBr₄] · H₂O (1), has been synthesized via hydrothermal reaction. The title compound features an isolated structure, based on discrete 4,4′-H₂bipy moieties, lattice water molecules and tetrahedral mercury atoms terminally coordinated by four bromine atoms. The 4,4′-H₂bipy moieties, lattice water molecules and tetrabromo-mercury dianions are linked via hydrogen bonds. Optical absorption spectrum reveals that the presence of an optical gap of 2.53 eV, indicating that compound 1 exhibits a semiconductor property. Photoluminescent investigation reveals that the title compound displays a strong blue-light emission, which maybe originates from π → π¹ charge-transfer interaction of 4,4′-H₂bipy. IR, SEM/EDS and thermogravimetry-differential thermal analyses (TG-DTA) are also presented.     

Incorporation of Metal Ions into Silica-Grafted Imidazolium-Based Ionic Liquids to Efficiently Catalyze Cycloaddition Reactions of CO<Subscript>2</Subscript> and Epoxides

Abstract  

A variety of imidazolium-based ionic liquids (ILs) have been widely developed to effectively catalyze the cycloaddition reactions of CO₂ and epoxides. To further improve the catalytic performance of those IL catalysts, we incorporated various metal chlorides (CoCl₂, NiCl₂, CuCl₂, ZnCl₂, and MnCl₂) into silica-grafted 1-methyl-3-[(triethoxysilyl)propyl] imidazolium chloride to produce a series of heterogeneous catalysts. Catalytic reaction tests demonstrated that the incorporation of such metal ions can significantly enhance the catalytic reactivity of the silica-grafted ILs towards cycloaddition reactions of CO₂ and epoxides that produce cyclic carbonates in solvent-free conditions. In addition, the effects on the catalytic reactivity of reaction parameters including reaction time, reaction temperature and CO₂ pressure were investigated.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript>@TiO<Subscript>2</Subscript>-OSO<Subscript>3</Subscript>H: an efficient hierarchical nanocatalyst for the organic quinazolines syntheses

A sulfonic acid functionalized titanium dioxide quasi-superparamagnetic nanocatalyst Fe₃O₄@SiO₂@TiO₂-OSO₃H with average size of 61 nm and semispherical shape with surface area about 97 m² g^?1 with saturation magnetization 17.7 emu g^?1 and the coercivity 9.84 Oe was successfully synthesized. The structure and morphology of the nanocatalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray spectroscopy, X-ray diffraction pattern, transmission electron microscopy, field-emission scanning electron microscopy, vibrating sample magnetometer and Brunauer–Emmett–Teller surface area analysis. The catalytic usage of the nanocatalyst was exemplified in synthesis of 2,3-dihydroquinazolin-4(1H)-one and spiroquinazolin-4(3H)-one derivatives in deep eutectic solvents (DESs) based on choline chloride and urea. We suggest that the synergistic effects in catalytic activities of titanium dioxide, organic acid and the CO₂ capture property of DES are the main reasons for the improvement of catalytic activity. The synthesized spiroquinazolinones and dihydroquinazolinones derivatives were characterized by FT-IR, ¹H and ¹³C nuclear magnetic resonance spectroscopy. The magnetic nanocatalyst exhibit high catalytic activity and can be simply separated from reaction media by an external magnet in a few seconds and could be reused for six cycles without significant loos in activity, which indicates the good immobilization of sulfonic acid on the magnetic titanium dioxide support. Furthermore, the solvent which has been used in this work can be readily isolated and reused for several times.     

Reduction of CO<Subscript>2</Subscript> to CO via reverse water-gas shift reaction over CeO<Subscript>2</Subscript> catalyst

CeO₂ catalysts with different structure were prepared by hard-template (Ce-HT), complex (Ce-CA), and precipitation methods (Ce-PC), and their performance in CO₂ reverse water gas shift (RWGS) reaction was investigated. The catalysts were characterized using XRD, TEM, BET, H₂-TPR, and in-situ XPS. The results indicated that the structure of CeO₂ catalysts was significantly affected by the preparation method. The porous structure and large specific surface area enhanced the catalytic activity of the studied CeO₂ catalysts. Oxygen vacancies as active sites were formed in the CeO₂ catalysts by H₂ reduction at 400 °C. The Ce-HT, Ce-CA, and Ce-PC catalysts have a 100% CO selectivity and CO₂ conversion at 580 °C was 15.9%, 9.3%, and 12.7%, respectively. The highest CO₂ RWGS reaction catalytic activity for the Ce-HT catalyst was related to the porous structure, large specific surface area (144.9 m²?g^?1) and formed abundant oxygen vacancies.     

TiO<Subscript>2</Subscript>/Ni Inverse-Catalysts Prepared by Atomic Layer Deposition (ALD)

Abstract  

Atomic layer deposition (ALD) was used to deposit TiO₂ on Ni particles, and the catalytic activity of Ni for CO₂ reforming of methane (CRM) was evaluated. In the presence of TiO₂ islands on Ni surfaces, the onset temperature of the CRM reaction was lower than that of bare Ni. During the CRM reaction, carbon was deposited on the surface of bare Ni, which reduced the catalytic activity of the surface with time, and TiO₂ islands were able to remove carbon deposits from the surface. When the Ni surface was completely covered with TiO₂, the catalytic activity disappeared, demonstrating that tuning of the TiO₂ coverage on Ni is important to maximize the activity of the CRM reaction.     

Biodiesel Production from Soybean Oil Catalyzed by Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>

In the present study, we synthesized biodiesel from soybean oil through a transesterification reaction catalyzed by lithium carbonate. Under the optimal reaction conditions of methanol/oil molar ratio 32:1, 12 % (wt/wt oil) catalyst amount, and a reaction temperature of 65 °C for 2 h, there was a 97.2 % conversion to biodiesel from soybean oil. The present study also evaluated the effects of methanol/oil ratio, catalyst amount, and reaction time on conversion. The catalytic activity of solid base catalysts was insensitive to exposure to air prior to use in the transesterification reaction. Results from ICP-OES exhibited non-significant leaching of the Li₂CO₃ active species into the reaction medium, and reusability of the catalyst was tested successfully in ten subsequent cycles. Free fatty acid in the feedstock for biodiesel production should not be higher than 0.12 % to afford a product that passes the EN biodiesel standard. Product quality, ester content, free glycerol, total glycerol, density, flash point, sulfur content, kinematic viscosity, copper corrosion, cetane number, iodine value, and acid value fulfilled ASTM and EN standards. Commercially available Li₂CO₃ is suitable for direct use in biodiesel production without further drying or thermal pretreatment, avoiding the usual solid catalyst need for activation at high temperature.     

Low-temperature CO oxidation of Pt/Al<Subscript>0.1</Subscript>Ce<Subscript>0.9</Subscript>O<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> catalysts: Effects of supports prepared with different precipitants

We prepared 0.1Al-0.9Ce supports using various precipitants such as NH₄OH, KOH, NaOH, K₂CO₃, and Na₂CO₃ to prepare Pt-based CO oxidation catalysts. Of the studied catalysts, the Pt/0.1Al-0.9Ce_NH₄OH catalyst showed the optimum activity for CO oxidation. Catalysts prepared with carbonate-form precipitants revealed relatively lower activity than carbonate-free precipitants. A temperature at 50% CO conversion of all samples was observed in the low-temperature region in the presence of water vapor because of the promotional effect of the water-gas shift reaction. Several characterization results revealed that catalytic activity was related to oxygen capacity and Pt dispersion was attributable to precipitant nature.     

Ni-Co bimetallic catalyst for CH<Subscript>4</Subscript> reforming with CO<Subscript>2</Subscript>

A co-precipitation method was employed to prepare Ni/Al₂O₃-ZrO₂, Co/Al₂ O₃-ZrO₂ and Ni-Co/Al₂O₃-ZrO₂ catalysts. Their properties were characterized by N₂ adsorption (BET), thermogravimetric analysis (TGA), temperature-programmed reduction (TPR), temperature-programmed desorption (CO₂-TPD), and temperature-programmed surface reaction (CH₄-TPSR and CO₂-TPSR). Ni-Co/Al₂O₃-ZrO₂ bimetallic catalyst has good performance in the reduction of active components Ni, Co and CO₂ adsorption. Compared with mono-metallic catalyst, bimetallic catalyst could provide more active sites and CO₂ adsorption sites (C + CO₂ = 2CO) for the methane-reforming reaction, and a more appropriate force formed between active components and composite support (SMSI) for the catalytic reaction. According to the CH₄-CO₂-TPSR, there were 80.9% and 81.5% higher CH₄ and CO₂ conversion over Ni-Co/Al₂O₃-ZrO₂ catalyst, and its better resistance to carbon deposition, less than 0.5% of coke after 4 h reaction, was found by TGA. The high activity and excellent anti-coking of the Ni-Co/Al₂O₃-ZrO₂ catalyst were closely related to the synergy between Ni and Co active metal, the strong metal-support interaction and the use of composite support.     

Two new luminescent Cd(II)/Zn(II) metal–organic frameworks for exceptionally selective detection of picric acid explosives

Two new coordination polymers, {[Cd(BIDPT)(oba)]·0.5H₂O}_n (1) and {[Zn(BIDPT)(4,4′-sdb)]·2.25H₂O}_n (2) (BIDPT = 4,4′-bis(imidazol-l-yl)diphenyl thioether, H₂oba = 4,4′-oxydibenzoic acid, 4,4′-H₂sdb = 4,4′-sulfonyldibenzoic acid), have been solvothermally synthesized and characterized. Both 1 and 2 show 2-fold interpenetrating 3D frameworks with {6⁵ ∙ 8} cds and {6⁶} dia topology, respectively. These two coordination polymers show strong luminescence and their luminescence could be quenched by a series of nitro explosives. Importantly, they exhibit very highly sensitive and selective detection of picric acid compared to other nitro explosives.     

Simultaneous MS-IR Studies of Surface Formate Reactivity Under Methanol Synthesis Conditions on Cu/SiO<Subscript>2</Subscript>

The coverages and surface lifetimes of copper-bound formates on Cu/SiO₂ catalysts, and the steady-state rates of reverse water-gas shift and methanol synthesis have been measured simultaneously by mass (MS) and infrared (IR) spectroscopies under a variety of elevated pressure conditions at temperatures between 140 and 160 °C. DCOO lifetimes under steady state catalytic conditions in CO₂:D₂ atmospheres were measured by ¹²C–¹³C isotope transients (SSITKA). The values range from 220 s at 160 °C to 660 s at 140 °C. The catalytic rates of both reverse water gas shift (RWGS) and methanol synthesis are ~100-fold slower than this formate removal rate back to CO₂ + 1/2 H₂, and thus they do not significantly influence the formate lifetime or coverage at steady state. The formate coverage is instead determined by formate’s rapid production/decomposition equilibrium with gas phase CO₂ + H₂. The results are consistent with formate being an intermediate in methanol synthesis, but with the rate-controlling step being after formate production (for example, its further hydrogenation to methoxy). A 2–3 fold shorter life time (faster decomposition rate) was observed for formate under reactions conditions, with both D₂ and CO₂ present, than in pure Ar or D₂ + Ar alone. This effect, due in part to the effects of the coadsorbates produced under reaction conditions, illustrates the importance of using in situ techniques in the study of catalytic mechanisms. The carbon which appears in the methanol product spends a longer time on the surface than the formate species, 1.8 times as long at 140 °C. The additional delay on the surface is attributed in part to readsorption of methanol on the catalyst, thus obscuring the mechanistic link between formate and methanol.     

CO and CO<Subscript>2</Subscript> Methanation Over Ni/SiC and Ni/SiO<Subscript>2</Subscript> Catalysts

Ni/SiC and Ni/SiO₂ catalysts prepared by both wet impregnation (WI) and deposition–precipitation (DP) methods were compared for CO and CO₂ methanation. The prepared catalysts were characterized using N₂ physisorption, temperature-programmed reduction with H₂ (H₂-TPR), H₂ chemisorption, pulsed CO₂ chemisorption, temperature-programmed desorption of CO₂ (CO₂-TPD), transmission electron microscopy, and X-ray diffraction. H₂-TPR analysis revealed that the catalysts prepared by DP exhibit stronger interaction between the nickel oxides and support than those prepared by WI. The former catalysts exhibit higher Ni dispersions than the latter. The catalytic activities for both reactions over Ni/SiC and Ni/SiO₂ catalysts prepared by WI increase on increasing the Ni content from 10 to 20 wt%. The Ni/SiC catalyst prepared by DP shows higher catalytic activity for CO and CO₂ methanation than that of the Ni/SiC catalyst prepared by WI. Furthermore, it exhibits the highest catalytic activity for CO methanation among the tested catalysts. The high Ni dispersion achieved by the DP method and the high thermal conductivity enabled by SiC are beneficial for both CO and CO₂ methanation.     

A couple of Co(II) enantiomers constructed from semirigid lactic acid derivatives

Enantiopure organic linkers (R)-H₂CBA and (S)-H₂CBA have been synthesized from nature lactic acid and rigid 4-hydroxybenzoate. With the help of auxiliary ligand 4,4′-BIP, (R)-H₂CBA and (S)-H₂CBA afford two enantiomeric coordination polymers, namely [Co₂((R)-CBA)₂(4,4′-BIP)₂]⋅ xH₂O (1-D) and [Co₂((S)-CBA)₂ (4,4′-BIP)₂]⋅ xH₂O (1-L). In complexes 1-D and 1-L, the CBA^2 − ligands and dinuclear Co units form 4-connected Co-CBA layers, which are further linked to a pillared-layer framework with 2-fold interpenetration pcu structure by 4,4′-BIP ligands. Moreover, complex 1-D displays antiferromagnetic interactions.     

The catalytic effect of both oxygen-bearing functional group and ash in carbonaceous catalyst on CH<Subscript>4</Subscript>-CO<Subscript>2</Subscript> reforming

A kind of new catalyst—carbonaceous catalyst—for CH₄-CO₂ reformation has been developed in our laboratory. The effect of both oxygen-bearing functional group such as phenolic hydroxyl, carbonyl, carboxyl, and lactonic, and ash such as Fe₂O₃, Na₂CO₃, and K₂CO₃ in the carbonaceous catalyst on the CH₄-CO₂ reforming has been investigated with a fixed-bed reactor. It has been found that the carbonaceous catalyst is an efficient catalyst on CO₂-CH₄ reforming. With the decrease of oxygen-bearing functional group, the catalytic activity of carbonaceous catalyst decreases quickly. The oxygen-bearing functional groups play a significant role in the carbonaceous-catalyzed CO₂-CH₄ reforming; the ash components in carbonaceous catalyst also have an important influence on the CO₂-CH₄ reforming. Fe₂O₃, Na₂CO₃, and K₂CO₃ in the ash can catalyze the CO₂-CH₄ reforming reaction; CaO has little effect on CO₂-CH₄ reforming reaction. CaO can catalyze the gasification between carbonaceous catalyst and CO₂; Al₂O₃ and MgO inhibit the CO₂-CH₄ reforming.     

Facile synthesis of amine-functionalized MIL-53(Al) by ultrasound microwave method and application for CO<Subscript>2</Subscript> capture

An amine functional MIL-53(Al) material was prepared through a clean, rapid, energy-efficient method of microwave and ultrasound irradiation. The pure phase NH₂-MIL-53(Al) can be formed in 25 min, utilizing the synergistic effect of microwave and ultrasound irradiation. The dramatic acceleration in reaction rates suggested that the removal of a passivation coating on the substrate particles and the resultant enhancement in mass and heat transfer. The porous MOFs exhibited a high thermal and chemical stability, decomposing at temperatures above 410 °C in air. The NH₂-MIL-53(Al) performed an excellent adsorption for CO₂. The CO₂ capacities up to 33.86 cm³ g^?1 at 298 K at low pressures, which suggests chemisorption between CO₂ and pendan amine groups. Measurement of CO₂ adsorption cycles proved that the functionalized materials show good regenerability and stability.