Pd[tBuNH(S)NHP(O)(OiPr)2-S]2Cl2 Complex as Air- and Moisture-Stable Catalyst for Palladium Catalyzed Suzuki Cross-Coupling Reaction

A highly efficient Suzuki cross-coupling reaction between phenyl bromide and phenylboronic acid catalyzed by the palladium complex Pd[tBuNH(S)NHP(O)(OiPr)₂-S]₂Cl₂ in acetonitrile, toluene, THF or DMF has been investigated. The bases we have employed for this reaction were Na₂CO₃, K₂CO₃ or Cs₂CO₃. It was established that using DMF and K₂CO₃ at 100 °C shows excellent yields of the product at the catalyst amount of 0.1 mmol. The cross-coupling reactions of iodo- and chloro-benzene with phenylboronic acid were also investigated. The influence of the halide nature was as expected.     

Production of Monoacylglycerols from Fully Hydrogenated Palm Oil Catalyzed by Hydrotalcite Loaded with K2CO3

This study reports a new method of producing high-purity monoacylglycerols (MAGs) by glycerolysis of fully hydrogenated palm oil (FHPO) catalyzed by hydrotalcite loaded with K₂CO₃ (K₂CO₃/HT). The effects of reaction temperature, reaction time, catalyst (K₂CO₃/HT) loading, and mass ratio of FHPO to glycerol on glycerolysis were investigated. The selected conditions included a reaction temperature of 200°C, K₂CO₃/HT loading at 0.8 wt.% (FHPO mass), a 5:2 mass ratio of FHPO to glycerol, and a reaction time of 2 h. Under these selected conditions, the yield of MAGs in the acylglycerol phase reached 46.8 wt.%. A two-stage molecular distillation was introduced to purify MAGs, and the final MAG product was obtained with a purity of 96.6 wt.% and a recovery of 96.8%. Furthermore, the recycled K₂CO₃/HT was reactivated with restored catalytic efficiency through impregnation, carbonation, and recalcination.     

Low-Temperature Sintering of (K0.5Na0.5)NbO3 Piezoelectric Ceramics

(K_0.5Na_0.5)NbO₃ piezoelectric ceramics can be sintered at a temperature as low as 750 °C for 5 h by incorporating Li₂CO₃ + Bi₂O₃ + ZnO as the sintering aid, whereas the conventional sintering temperature is around 1,100 °C. The optimal “soft” piezoelectric properties are obtained for ceramics sintered at 850 °C for 5 h. The dielectric permittivity (ε), piezoelectric coefficient (d ₃₃), electromechanical coupling (k _p) and mechanical quality factors (Q _m) of (K, Na)NbO₃ modified with 5.5 wt% sintering aids are 1,436, 90 pC/N, 0.3 and 10, respectively. These values are similar to the values obtained for (K_0.5Na_0.5)NbO₃ ceramics sintered above 1,100 °C. The underlying mechanism for abrupt change of dielectric permittivity is explained.     

A Novel Process for Renewable Methane Production: Combining Direct Air Capture by K<Subscript>2</Subscript>CO<Subscript>3</Subscript>/Alumina Sorbent with CO<Subscript>2</Subscript> Methanation over Ru/Alumina Catalyst

CO₂ methanation over supported ruthenium catalysts is considered to be a promising process for carbon capture and utilization and power-to-gas technologies. In this work 4% Ru/Al₂O₃ catalyst was synthesized by impregnation of the support with an aqueous solution of Ru(OH)Cl₃, followed by liquid phase reduction using NaBH₄ and gas phase activation using the stoichiometric mixture of CO₂ and H₂ (1:4). Kinetics of CO₂ methanation reaction over the Ru/Al₂O₃ catalyst was studied in a perfectly mixed reactor at temperatures from 200 to 300 °C. The results showed that dependence of the specific activity of the catalyst on temperature followed the Arrhenius law. CO₂ conversion to methane was shown to depend on temperature, water vapor pressure and CO₂:H₂ ratio in the gas mixture. The Ru/Al₂O₃ catalyst was later tested together with the K₂CO₃/Al₂O₃ composite sorbent in the novel direct air capture/methanation process, which combined in one reactor consecutive steps of CO₂ adsorption from the air at room temperature and CO₂ desorption/methanation in H₂ flow at 300 or 350 °C. It was demonstrated that the amount of desorbed CO₂ was practically the same for both temperatures used, while the total conversion of carbon dioxide to methane was 94.2–94.6% at 300 °C and 96.1–96.5% at 350 °C.     

Pincer Type Ditertiary Aminomethylphosphine–Pd(II) Complexes Supported on Multi-Walled Carbon Nanotube: Catalytic Properties in Heck C–C Coupling Reactions

Pincer type aminomethylphosphine–Pd(II) complexes supported on multi-walled carbon nanotube (MWCNT) have been synthesized and characterized using X-Ray diffraction spectrometry, scanning electron microscopy, thermal analysis, energy dispersive X-Ray, Fourier transform infrared spectrometry, transmission electron microscopy (TEM) and ultraviolet–visible spectrometry techniques. The novel complexes were tried as catalysts in Heck C–C coupling reactions. The crystallite size and lattice strain of the MWCNT based compounds were calculated by the Scherrer’s equation. The optical parameters of the MWCNT based structures were analyzed and the band gap enhanced from 4.42 to 4.98 eV. Different solvents (toluene, 1,4-diooxane, DMF and NMP) and bases (Et₃N, Na₂CO₃, NaOAc and K₂CO₃) were tried at different temperatures (80, 100 and 110 °C) in the cross-coupling of bromobenzene with styrene. The optimum yield was found in the presence of K₂CO₃, 110 °C in 1,4-dioxane solvent system.     

One step preparation of ZnFe2O4/Zn5(OH)6(CO3)2 nanocomposite with improved As(V) removal capacity

Novel adsorbents consisting of ZnFe₂O₄/Zn₅(OH)₆(CO₃)₂ (hydrozincite) nanocomposite materials were studied for efficient As(V) removal from water. Nanocomposites were synthesized by the co-precipitation of Zn and Fe salts in alkaline conditions. Depending on the Zn/Fe molar ratio, a variety of materials was produced with different ZnFe₂O₄/Zn₅(OH)₆(CO₃)₂ contents. The adsorbent’s efficiency for As(V) removal was enhanced proportionally to the percentage of Zn₅(OH)₆(CO₃)₂ content. The nanocomposite with 74 ± 7 wt% of Zn₅(OH)₆(CO₃)₂ provided a capacity of 18.4 μg As(V)/mg for residual concentration of 10 μg/L (pH 7) which is over twice that of an iron oxy-hydroxide prepared under similar conditions.     

Synthesis and characterizations of a layered antimony (III) phosphonate: [NH2CH2CH2NH2][Sb2(O3PCH(OH)CO2)2]

In the presence of ethylenediamine template agents, a layered antimony (III) phosphonate, [NH₂CH₂CH₂NH₂][Sb₂{O₃PCH(OH)CO₂}₂] (1) has been synthesized by hydrothermal reaction at 140 °C and characterized by single-crystal X-ray diffraction as well as by infrared spectroscopy, elemental and thermogravimetric analysis. The structure of compound 1 comprises [SbO₄E] trigonal bipyramids (E is the lone pair electrons occupying an axial position) and [O₃PC] tetrahedra connected by [O₃PCH(OH)CO₂]³⁻ to form a 2D layered structure with a one-dimensional channel system, and the ethylenediamine template agent is located inside the channels.     

Catalytic conversion of 1,1,1,2-tetrafluoroethane (HFC-134a)

We examined the conversion of HFC-134a over five catalysts, Na₂CO₃, CaO, CaCO₃, and two types of γ-Al₂O₃ with different surface areas, between 300 and 600 °C. HFC-134a was barely converted via the non-catalytic reaction, even at the highest temperature (600 °C). The operating temperatures for the catalytic conversion of HFC-134a were reduced dramatically and its efficiency increased with increasing temperature. Among the catalysts used, γ-Al₂O₃ with the larger surface area showed the highest conversion rate of HFC-134a, which was followed, in order, by γ-Al₂O₃ with the smaller surface area, CaCO₃, CaO, and Na₂CO₃. The conversion rate of γ-Al₂O₃ decreased rapidly due to catalyst deactivation. The catalytic efficiency of γ-Al₂O₃ was maintained for a longer period by water addition. Water acted as a hydrogen donor for the dehydrofluorination reaction.     

Catalytic activity of potassium halides in water vapour gasification of graphite

The catalytic activity of potassium halides in water vapour gasification of graphite was studied at 900 ° C and pressures up to 2 MPa. The initial step is the hydrolysis of the potassium halide which controls the catalytic activity: KF >KCl >KBr. Main steps of the catalysed gasification reaction are in good agreement with an oxygen transfer mechanism. The following general reaction scheme is proposed not only for the potassium halides, but also for K₂CO₃ and KNO₃. Initial reactions: K₂CO₃ + H₂O → 2KOH + CO₂; KNO₃ + H₂O → KOH + NO_x; KX + H₂O → KOH + HX. Intermediate step: KOH + C, H₂ → K + CO, H₂O. K-catalysed gasification reactions: K + H₂O → K(O) + H₂; K(O) + C → K + CO; K(O) + CO → K + CO₂.     

Catalytic Removal of Toluene over Co3O4–CeO2 Mixed Oxide Catalysts: Comparison with Pt/Al2O3

The catalytic oxidation of toluene, chosen as VOC probe molecule, was investigated over Co₃O₄, CeO₂ and over Co₃O₄–CeO₂ mixed oxides and compared with the catalytic behavior of a conventional Pt(1 wt%)/Al₂O₃ catalyst. Complete toluene oxidation to carbon dioxide and water was achieved over all the investigated systems at temperatures below 500 °C. The most efficient catalyst, Co₃O₄(30 wt%)–CeO₂(70 wt%), showed full toluene conversion at 275 °C, comparing favorably with Pt/Al₂O₃ (100% toluene conversion at 225 °C).     

Effect of Regeneration Temperature on the Composition and Carbon Dioxide Sorption Ability of a K2CO3/Al2O3 Solid Sorbent in a Bubbling Fluidized Bed Reactor

The effect of the regeneration temperature (150°, 250°, and 350°C) during multiple CO₂ cyclic sorption-regeneration cycles of a K₂CO₃/Al₂O₃ solid sorbent in a bubbling fluidized bed reactor was evaluated in terms of the CO₂ capture capacity and chemical composition of the solid sorbent. The CO₂ capture capacity after regeneration at 150° and 250°C decreased with increasing cycle numbers, reaching approximately 57 and 78%, respectively, and 19.0 and 39.3%, respectively, of the original capacity after one and five regeneration cycles. This decline in the CO₂ capture capacity was due to the accumulation of KHCO₃ (at 150°C) and KAl(CO₃)₂(OH)₂ (150° and 250°C) from their incomplete degradation back to the K₂CO₃/Al₂O₃ solid sorbent. When regenerated at 350°C, the CO₂ capture capacity remained essentially constant in each cycle number because of complete desorption (no residual KHCO₃ and KAl(CO₃)₂(OH)₂). The formation mechanism of complex structure occurred similar to the one in a fixed bed reactor/thermogravimetric analyzer with lower regeneration temperature. The general operation conditions for K₂CO₃/Al₂O₃ solid sorbents are summarized.     

Supramolecular Chemistry of Organoplatinum(IV) Complexes Bearing Ligands with Remote Carboxylic Acid Substituents

The oxidative addition of compounds RBr to [PtMe₂(bpox)], 1, bpox = 2,5-bis(2-pyridyl)-1,3,4-oxadiazole gave the corresponding organoplatinum(IV) complexes [PtBrMe₂(R)(bpox)], 2, R = CH₂CO₂H; 3, R = CH₂-4-C₆H₄CO₂H; 4, R = CH₂-4-C₆H₄CH₂CO₂H, whereas the reaction with BrCH₂CH₂CO₂H gave only the platinum(II) complex [PtBrMe(bpox)], 5. The organoplatinum(IV) complexes with carboxylic acid substituents form unusual supramolecular structures in the solid state through hydrogen bonding interactions, some of which are supramolecular polymers.     

Sintering behaviour and microwave dielectric properties of BaAl2−2x(ZnSi)xSi2O8 ceramics

BaAl_2?2x(ZnSi)_xSi₂O₈ (x = 0.2–1.0) ceramics were prepared using the conventional solid-state reaction method. The sintering behaviour, phase composition and microwave dielectric properties of the prepared compositions were then investigated. All compositions showed a single phase except for x = 0.8. By substituting (Zn_0.5Si_0.5)³⁺ for Al³⁺ ions, the optimal sintering temperatures of the compositions decreased from 1475 °C (x = 0) to 1000 °C (x = 0.8), which then slightly increased to 1100 °C (x = 1.0). Moreover, the phase stability of BaAl₂Si₂O₈ was improved. A novel BaZnSi₃O₈ microwave dielectric ceramic was obtained at the sintering temperature of 1100 °C. This ceramic possesses good microwave dielectric properties with ε_r = 6.60, Q × f = 52401 GHz (at 15.4 GHz) and τ_f = ?24.5 ppm/°C.     

Oxygen Reduction Electrode Properties of Manganese Oxide Nanosheet-Based Materials

Two types of oxide nanosheet-based materials, H₃O⁺-form regularly stacked manganese oxide nanosheets (H₃O⁺-RG(Mn)) and H₃O⁺-form randomly restacked manganese oxide nanosheets (H₃O⁺-RE(Mn)) were synthesized by soft chemical methods, and their oxygen reduction reaction (ORR) activities were examined by cyclic voltammetry (CV) and semi-steady-state voltammetry (SSV) with a rotating ring-disc electrode at 70 °C in 0.1 M KOH. Both samples showed high onset potentials (E _on) of the ORR current and high efficiencies (Eff ₄) of the 4-electron reduction of oxygen, and E _on and Eff ₄ values were improved by electrochemical oxidation up to 1.2 V (vs. reversible hydrogen electrode) in the CV measurement prior to the SSV measurement. As a result, the nanosheet-based samples exhibited higher ORR activities than the starting materials, K⁺-form layered manganese oxide K_0.5MnO₂ (K⁺-RG(Mn)) and Mn₂O₃, and a well-known ORR catalyst, MnO₂. The H₃O⁺-RE(Mn) sample electrochemically oxidized up to 1.2 V showed the highest ORR activity, E _on = 0.97 V and Eff ₄ = 99%, which were comparable to those of a conventional 20 mass% Pt/C catalyst. The comparison of their ORR activities, BET surface areas and X-ray photoelectron spectra suggests that the enhancement of the ORR activity is attributed to an increase in the numbers of the ORR active sites and a large amount of H₂O in the interlayers and on the surface of the nanosheets because of rapid of H₂O-supply enough for ORR in alkaline solution.     

Synthesis and characterization of poly(benzimidazolium) membranes for anion exchange membrane fuel cells

Poly(dimethyl benzimidazolium) iodides were synthesized from polybenzimidazole derivatives by permethylation. They were easily changed to OH^?, CO₃ ^2? and HCO₃ ^? ion conducting electrolytes by immersing in 1 M of KOH, K₂CO₃ and KHCO₃. Properties of polymers were changed by the ion exchange process. The anion conducting membranes showed tough and flexible properties. The water uptake, ion exchange capacity and conductivity varied depending on the counter anions. One of the poly(dimethyl benzimidazolium) carbonate membranes, Me-DAB-OBBA-carbonate showed the highest water uptake (59 %) as well as ion conductivity (33.74 mS/cm at 80 °C), and could be a good candidate for an anion exchange membrane for anion exchange membrane fuel cells.     

Tuning the Activity and Selectivity of CuCl2/γ-Al2O3 Ethene Oxychlorination Catalyst by Selective Promotion

CuCl₂/γ-Al₂O₃ catalysts with and without promoter metal chlorides (Cu5.0, K3.1Cu5.0, La10.9Cu5.0, Li0.5Cu5.0, Cs10.4Cu5.0, Mg1.9Cu5.0, Ce5.5La5.45Cu5.0, and K1.55La5.45Cu5.0) were studied for the ethene oxychlorination reaction in a fixed-bed reactor at 503 and 573 K, with C₂H₄:HCl:O₂:He = 1.0:1.1:0.38:14.4 (mole ratio), P(tot) = 1 atm and weight hourly space velocity (WHSV) = 1.5 g g^?1 h^?1 (based on ethene). It was found that all promoter metals enhanced the activity of the catalyst, as well as its selectivity towards the target product 1,2-dichloroethane (1,2-EDC). Co-promoted catalysts (K1.55La5.45Cu5.0 and Ce5.5La5.45Cu5.0) gave even higher activity and product selectivity than the single metal promoted catalysts. The activity of the CuCl₂/γ-Al₂O₃ catalyst, as well as the γ-Al₂O₃ support, both with and without metal chloride promoter(s), were further tested for 1,2-EDC conversion to byproducts in a fixed-bed reactor at 503 K, under a feed stream of 1,2-EDC:Ar = 1:11.5 (mole ratio), at P(tot) = 1 atm and WHSV = 1.5 g g^?1 h^?1 (based on 1,2-EDC). Prior to testing, the catalysts were pretreated in flowing ethene, HCl and/or O₂. It was observed that Lewis and Brønsted acid sites on the alumina surface were main reaction sites for conversion of 1,2-EDC to chlorinated byproducts: vinyl chloride monomer (VCM), 1,1-EDC, 1,2-dichloroethene (1,2-DCE) and ethyl chloride (EC) as well as dimerisation (butadiene) and aromatisation reactions (toluene), both with and without the presence of the Cu phase. The Cu phase was shown to contribute mainly to CO₂ and trichloroethane formation from 1,2-EDC via VCM. Co-promotion (K1.55La5.45Cu5.0) was found to enhance the activity of the Cu phase, and to mask acid sites on the alumina surface, thereby promoting ethene oxychlorination while at the same time hindering undesired conversion of the target product 1,2-EDC.     

Low-temperature catalytic conversion of lignite: 2. Recovery and reuse of potassium carbonate supported on perovskite oxide in steam gasification

Catalytic recovery after repeated uses of unsupported K₂CO₃ or K₂CO₃ supported on 3 kinds of perovskites (LaMn_0.8Cu_0.2O₃, LaMn_0.8Cu_0.2O₃/γ-alumina, and La_0.9K_0.1MnO₃) was investigated during steam gasification of an Indonesian lignite (Adaro) at 700 °C. Perovskite supports effectively retained K₂CO₃ and maintained higher catalytic activity than K₂CO₃ alone. The supported catalysts were recovered from the ash after gasification based on their size and ferromagnetism. Quartz and alumina accumulation on the catalyst poisoned the ash due to reactivity with potassium. Catalytic activity as high as 90% carbon conversion was maintained up to seven cycles, and separation from the ash after gasification regenerated the activity.     

SOLID BASE CATALYZED TRANSESTERIFICATION OF CANOLA OIL

Catalytic activities of synthesized solid base catalysts (alumina loaded with solution of different potassium compounds such as KI, KF, K₂CO₃, and KNO₃ with the loading amount of 35 wt.%) were tested for the transesterification reaction of canola oil with methanol and ethanol in a batch reactor in a temperature range of 25–60°C and different feed ratios of methanol/oil between 6:1 and 18:1. Synthesized KF/Al₂O₃ solid base catalyst showed the highest activity in the transesterification of canola oil with methanol and gave much stabler methyl ester content during the reaction with the highest yield of 99.6% at the end of the eight-hour reaction time at 60°C, with a methanol/oil ratio of 15:1 and a catalyst amount of 3 wt.%. Formation of K₂O phase and the formation of the surface Al-O-K groups by salt-support interactions were observed during the synthesis of the catalysts. Methanol was found to be much more reactive than ethanol in the transesterification reaction.     

Preferential CO oxidation over Pt–SnO2/Al2O3 in hydrogen rich streams containing CO2 and H2O (CO removal from H2 with PROX)

The effects of reaction gases including CO₂ and H₂O and temperature on the selective low-temperature oxidation of CO were studied in hydrogen rich streams using a flow micro-reactor packed with a Pt–SnO₂/Al₂O₃ sol–gel catalyst that was initially designed and optimized for operation in the absence of CO₂ and H₂O. 100% CO conversion was achieved over the 1 wt% Pt–3 wt% SnO₂/Al₂O₃ catalyst at 110 °C using a feed composition of 1.0% CO, 1.5% O₂, 25% CO₂, 10% H₂O, 58% H₂ and He as balance at a space velocity of 24,000 cm³/(g h). CO₂ in the feed was found to decrease CO conversion significantly while the presence of H₂O in the feed increased CO conversion, balancing the effect of CO₂.     

The Synergy of the Support Acid Function and the Metal Function in the Catalytic Hydrodeoxygenation of m-Cresol

The hydrodeoxygenation (HDO) of m-cresol is investigated as a model for the HDO of phenolic compounds from lignin pyrolysis. Pt catalysts supported on ??-Al₂O₃ and SiO₂ are effective for the conversion of m-cresol to toluene and methylcyclohexane at 533?K and 0.5?atm H₂. Experiments using Pt/??-Al₂O₃ show that the reaction proceeds by a combination of Pt-catalyzed hydrogenation and acid-catalyzed dehydration reactions. Dehydration of a partially hydrogenated oxygenate intermediate is most likely the dominant reaction pathway to toluene. The acidity of the ??-Al₂O₃ support was modified by base (K₂CO₃) and acid (NH₄F) treatments, and increasing the number and strength of acid sites was found to increase the rate of HDO. Pt/SiO₂ was more active for m-cresol HDO than Pt/Al₂O₃. The reaction rate on Pt/Al₂O₃ and Pt/SiO₂ decreased after 5?h on stream, but Pt/Al₂O₃ regained initial reactivity after reductive treatment in H₂.