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Layered double hydroxides (LDHs) of various compositions, i.e. Mg–Al, Mg–Mn–Al, are applied as the precursors of metal oxides for the preparation of N-doped carbon materials via chemical vapour deposition (CVD) with acetonitrile (as carbon and nitrogen source) at 600 and 700 °C. The use of Mn-containing LDHs for the preparation of the carbon materials is a novelty. The impact of transition metal species, i.e. MnxOy, in a blend of metal oxides derived from LDHs on the amount of carbon deposit and its composition, morphology, textural and capacitive properties is investigated. Mn-containing species occurring in a mixture of metal oxides enhance the quantity of carbonaceous product compared to those derived from Mg–Al LDHs. Thermally heated Mg–Mn–Al LDHs contain structural defects due to manganese oxides, which promote the formation of carbon deposit, especially higher production of amorphous carbons. The addition of Mn into Mg–Al LDHs matrix leads to carbon particles with increased N-doping and enhanced volume of mesopores. Furthermore, graphitic domains occurring in the carbon materials obtained with Mg–Mn–Al LDHs are thicker than those in the corresponding samples obtained with Mg–Al LDHs as Mn-containing species influence the concentration and location of N-containing groups in graphitic array. The specific capacitance of the carbon materials produced by CVD with the compounds derived from Mg–Al LDHs or Mg–Mn–Al LDHs is comparable (20–25 μF cm−2). The formation of electrical double layer at electrode/electrolyte interface is easier for the carbon materials prepared at 700 °C than for the carbon materials prepared at 600 °C. The maximum charge is stored either in the shallow parts of carbon particles for the former, as they contain bottleneck mesopores, or in the deep parts of carbon particles for the latter, as they contain slit-shaped mesopores. [ABSTRACT FROM AUTHOR]

Cross-linking of poly(hydromethylsiloxane) (PHMS) with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D4Vi) in water-in-oil high internal phase emulsion (HIPE) whose aqueous phase comprises PdCl2 is developed as a new, one-step route for the fabrication of polysiloxane-based, porous HIPE-templated materials (polyHIPEs) containing palladium. It is shown that the microstructure of the systems depends on the amount of D4Vi with respect to PHMS and is also significantly influenced by the presence of PdCl2 in HIPE. PolyHIPEs thus obtained contain metallic Pd nanoparticles (~ 4–10 nm in size) that strongly interact with the polysiloxane matrix they are dispersed in. The materials catalyse phenylacetylene hydrogenation to styrene yielding this product with fair selectivity. Incorporation of Pd into the pre-formed PHMS-based polyHIPE (the two-step procedure) conducted for comparison results in the material containing nanoclusters of Pd and displaying highly selective hydrogenation of phenylacetylene to styrene, but at a relatively low rate. [ABSTRACT FROM AUTHOR]

Carbon (Vulcan XC-72)-supported bimetallic Pd–Ir catalysts with different Pd/Ir proportions (5–50 mol% Ir, 2 wt% Pd) were prepared by "water-in-oil" microemulsion method (w/o) using solutions of low (0.02 M, L series) and high concentration (0.2 M, H series) of the metals precursors (PdCl2 and IrCl3). The bimetallic particles were examined in terms of nanoscale phase properties (extent of Pd–Ir alloying, phase separation), surface composition (Pd and Ir fractions) and electrocatalytic performance for the formic acid oxidation reaction. Structural characterization was performed using XRD, SEM and HRTEM techniques. Electrochemical characterization allowed estimating the PdH formation ability and the surface composition of Pd–Ir particles what was confirmed by XPS data. The Pd–Ir nanoparticles of similar average size (ca. 4 nm), close to that of Ir (3.8 nm) and below that of Pd (6.2 nm) were formed regardless of the Pd/Ir proportion and the concentration of the metals precursors in the w/o. In contrast to the largely alloyed PdIr nanoparticles with the Pd-rich surface formed at low concentration of the metals precursors (0.02 M), the particles of almost closed surface and bulk Pd/Ir ratios composed mostly of randomly distributed single-phase domains were formed at high concentration (0.2 M). At the lowest bulk Ir content, 5 mol%, the particles have Ir-rich surface regardless of the preparation method. The catalytic studies involving formic acid electrooxidation reaction showed the activity enhancement for the L series catalysts with respect to monometallic Pd/C (twofold TOF increase) and H series counterparts. The Pd85Ir15/C catalyst of the Pd–Ir alloyed and the surface composition expressed by the Pd/Ir atomic ratio near to 6 displayed the highest activity which was 2.9-times higher relative to that of Pd. [ABSTRACT FROM AUTHOR]

Two series of nanostructured carbon replicas were synthesized through a hard-templating method using ordered SBA-15 or disordered mesoporous spherical silica gel as the templates and furfuryl alcohol or sucrose as the carbon source. They were explored to synthesize the Pd catalysts (ca. 1.5 wt% Pd loading) by the colloid-based microemulsion procedure which allowed preparing the catalysts of monodispersed Pd particles of similar size (4–5 nm). The palladium phase in the catalysts (e.g. the Pd particles distribution and extent of agglomeration) varied depending on the textural and surface characteristics of the carbon replicas. In the furfural hydrogenation studied as a probe reaction (2-propanol, 35 °C, 6 bar H2), furfuryl alcohol and tetrahydrofurfuryl alcohol were the major products formed. The catalytic reactivity has been related to the properties of the Pd phase including the surface Pd concentration and the extent of the Pd particles aggregation accompanied by the nearest palladium environment expressed by the surface O/Pd atomic ratio. At high O/Pd ratio the reaction slowed down because of a facilitated furfuryl alcohol adsorption resulting most probably in a blockage of the active sites. The SiO2 sucrose system provided the catalyst which was characterized by relatively low O/Pd ratio with well-dispersed Pd particles and the highest and stable activity for the furfural hydrogenation. The SBA-series catalysts, with lower O/Pd and more aggregated Pd particles, exhibited lower activity but somewhat higher tendency to the tetrahydrofurfuryl alcohol formation. [ABSTRACT FROM AUTHOR]

Supported Pd/Ir bimetallic catalysts were synthesized by the "water-in-oil" microemulsion method at different precursor concentrations and characterized by XRD, XPS, SEM, TEM, and cyclic voltammetry. Depending on the preparation conditions, formation of bimetallic catalysts with different metal segregation and surface composition can be easily obtained, thus tuning the bimetallic structure of catalysts as well as their relative catalytic properties. Bimetallic Pd/Ir systems were efficiently tested in the hydrogenation of cinnamaldehyde showing a better performance than analogous monometallic catalysts. [ABSTRACT FROM AUTHOR]

The hydrogenation of furfural (FU) under mild conditions (isopropyl alcohol, 35 °C, 6 bar) was studied over 2 wt% Pd supported on non-treated (Pd/C) and SO3H-modified carbon supports. The catalysts of similar metal particles size (5-6 nm) were prepared by the colloid-based microemulsion method. The products of the Pd-catalyzed FU hydrogenation as well as the acid-sites catalyzed reactions of FU acetalization and etherification were formed. The SO3H groups in the carbon supports influence reactivity of the Pd-sites due to the Pd-electron deficient species formation manifested by the enhanced promotion of furan ring hydrogenation producing tetrahydrofurfuryl alcohol and 2-methyltetrahydrofuran. Furfural diisopropyl acetal was formed even over the Pd/C catalyst of very low acid capacity and acetalization reaction was enhanced over the catalysts with SO3H groups. The furfural diisopropyl acetal content slowly decreased with furfural conversion, assisted by the growth of furfuryl isopropyl ether content. The capacity of acid sites did not strongly affect the process of ether formation evidenced by similar selectivity (10-15%) over all studied catalysts. [ABSTRACT FROM AUTHOR]

A series of novel iodinated NO2-substituted aza-BODIPYs have been synthesized and characterized. Highly desirable photophysical and photochemical properties were induced in NO2-substituted aza-BODIPYs by iodination of the pyrrole rings. In particular, high values of singlet oxygen quantum yields ( ΦΔ) ranging from 0.79 to 0.85 were measured. The photooxygenation process proceeds via a Type II mechanism under the experimental conditions applied. The compounds studied exhibited an absorption band within the so-called 'therapeutic window', with λmax located between 645 nm to 672 nm. They were non-fluorescent at room temperature with excited singlet-state lifetimes within the picosecond range as measured by femtosecond transient absorption. Nanosecond laser flash photolysis experiments revealed T1→T n absorption spanning from ca. 400 nm to ca. 500 nm and allowed determination of the triplet-state lifetimes. The estimated triplet lifetimes ( τT) in deaerated acetonitrile ranged between 2.74 μs and 3.50 μs. As estimated by CV/DPV measurements, all iodinated aza-BODIPYs studied exhibited one irreversible oxidation and two quasi-reversible reductions processes. Estimation of the EHOMO gave the value of −6.06 to −6.26 eV while the ELUMO was found to be located at ca. −4.6 eV. Thermogravimetric (TGA) analysis revealed that iodinated aza-BODIPYs were stable up to approximately 300 °C. All compounds studied exhibit high photostability in toluene solution. [ABSTRACT FROM AUTHOR]

A microcalorimetric method has been combined with a potentiostatic method to measure simultaneously the rate of heat evolution and the electrical current in a powdered sample of palladium during thermokinetic oscillations accompanying the sorption of deuterium in the metal. Deterministic chaos has been confirmed in the temporal variations in current (of ca. 1–4 mA) on the onset of both the sorption and the desorption of deuterium from Pd. It has been found that the first derivative of the current in time, dI/dt, turns out to be correlated precisely with the periodicity of thermokinetic oscillations. The dI/dt curves consist of regularly timed outbursts of aperiodic, high frequency (HF) fluctuations, interlinked by calm periods. The calm periods correlate with the descending slopes of thermokinetic oscillations (i.e., with decrease in the rate of heat evolution) and their lengths depend on the frequency of thermokinetic oscillations. In turn, the outbursts of aperiodic HF fluctuations in the dI/dt derivatives correlate with the ascending slopes of thermokinetic oscillations (i.e., with increasing rate of heat production), but their length is practically constant, irrespective of the thermokinetic frequency. We propose a periodic mechanism of sorption including a collective action of adsorbed deuterium taking place on the Pd surface. The periodicity of this mechanism arises from the temporal separation of its two sub-processes. The sub-process (1) involves only the adsorption of molecular D2 on the Pd surface and proceeds with little heat evolution until a critical coverage of D2 is achieved. The sub-process (2) initiates the dissociation of the adsorbed D2 and the penetration of the dissociated atomic D species into the Pd lattice. It is the more energetic of the two, but it only begins after a threshold coverage of D2 on the Pd surface has been achieved. We suggest that these sub-processes occurring alternatingly may provide a kernel for the oscillatory behavior observed in Pd/H(D) systems. [ABSTRACT FROM AUTHOR]

Present studies concentrated on the preparation, characterization, and electroactivity of palladium-polypyrrole (Pd/PPY) catalysts for oxygen reduction reaction. In particular, the effect of Nafion ionomer on their electroactivity was evaluated. In all catalysts prepared by 'water-in-oil' microemulsion method, the Pd nanoparticles of ca. 7 nm in size appeared regardless of the Pd content (ranging from 2 to 20 wt.%). For comparison, carbon black-supported (Vulcan XC-72) catalyst (20 wt.% Pd) was also synthesized. Coating of the Pd/PPY samples with Nafion ionomer reduced their surface area and porosity. Chemical interaction due to Nafion acid functionalities affected the N-state of pyrrole as well as electron state of Pd in the Pd/PPY catalysts. As a result, the contribution of more oxidized palladium (Pd) increased. These interactions played an essential role in the electroactivity of Pd/PPY for oxygen reduction reaction. The increased amount of Nafion relative to that of PPY reduced limiting current density whereas the half-wave potential shifted to a more positive value and the fraction of hydrogen peroxide remarkably decreased. [ABSTRACT FROM AUTHOR]

Application of a catalyst preparation method known as 'water-in-oil' microemulsion allowed to obtain a series of palladium/polypyrrole (Pd/PPY) electrocatalysts with various Pd contents (2-20 wt%) and Pd particle size within a narrow and similar range of 6-8 nm. The textural features of the samples (surface area, porosity) as well as the palladium phase (metal particle size, shape) were characterized by a number of techniques. Electrocatalytic activity of the prepared materials towards oxygen reduction reaction (ORR) was studied in 0.5 M HSO using rotating ring disc electrode voltammetry (RRDE) and cyclic voltammetry techniques. All prepared Pd/PPY samples exhibited electrocatalytic activity towards ORR. At a constant palladium loading on the electrode, the polymer to Pd weight ratio was found to play a decisive role in the electrocatalytic performance of the samples. Their catalytic performance in terms of the increased reduction current and positively shifted half-wave potential (RRDE measurements) was improved when Pd content in polymer was grown from 2 to 12 wt% Pd. At the optimum Pd content, 10-12 wt%, the analysis of the RRDE data confirmed that molecular oxygen underwent mainly a desired four-electron reduction. By further increasing the Pd content and thus decreasing the PPY to Pd ratio, the selectivity to water continuously decreased while the fraction of undesired HO product significantly increased. Therefore, a role of PPY to Pd weight ratio in the electrocatalytic performance of the investigated catalysts is discussed here. [ABSTRACT FROM AUTHOR]

Two polyaniline (PANI) samples of various molecular masses were used for the preparation of palladium catalysts (with 2 mass % of Pd). The physicochemical features of starting polyanilines were found to substantially affect the size and extent of palladium nanoparticles aggregation. Strongly aggregated large palladium particles appeared in the PANI sample of more compact morphology (PANI-H), higher crystallinity and lower specific surface area. Pd nanoparticles of a definitively smaller size were formed in the more amorphous PANI sample of looser morphology (PANI-L) and the extent of particles aggregation was markedly lower. The catalytic properties of Pd/PANI samples were studied in a liquid phase hydrogenation of unsaturated triple bond (C≡C) in alkynes reactants, phenylacetylene, and cyclohexylacetylene. The 2 mass % Pd/PANI-L catalyst prepared using polymer of less compact texture exhibited much higher activity in both reactions. In the presence of the 2 mass % Pd/PANI-L catalyst, alkene products were formed with a high selectivity (approximately 90 %) attained at the almost complete conversion of alkynes. This highly selective hydrogenation of the C≡C to the C=C bond was related to the presence of an electroactive polymer, PANI, in close proximity with Pd active sites. Polyaniline could have a role in a steric effect as well as in a modification of adsorptive properties of Pd centres. [ABSTRACT FROM AUTHOR]

Liquid phase hydrogenation of acetophenone (ACT) is studied over ruthenium catalysts (1-4 wt% Ru) supported on gel-type methacrylate-styrene resin (FCN) functionalized with C=O, -NH, and -NH groups. Microscopic studies (SEM, STEM) show that the nature of Ru particles depends on the level of Ru doping. At low Ru content (1-2 wt%) ruthenium nano-clusters are formed, while at 4 wt% Ru, metal crystallites of few nanometers in size are observed. Catalytic reactions are performed at mild conditions (atmospheric pressure of hydrogen, 40 °C) in biphasic isooctane-water (IO/HO) solvent system, and, for comparison, in a single component solvent (isooctane or ethanol). The use of biphasic IO/HO solvent system results in a dramatic improvement of selectivity. The hydrogenation of C=O in acetophenone dominates over the hydrogenation of aromatic ring, yielding 1-phenylethanol with ca. 80% selectivity. Ru/FCN catalysts exhibit higher selectivity than the reference Ru/AlO. This is tentatively assigned to the steric effects induced by the polymer network on migrating reactant molecules. Advantageous influence of biphasic IO/HO solvent system has been attributed to the solvation of phenyl ring of acetophenone by non-polar isooctane, which facilitates the interaction with the catalyst surface via carbonyl group and leads to the preferential reduction to 1-phnenylethanol. Graphical Abstract: Liquid phase hydrogenation of acetophenone was studied over ruthenium catalysts (1-4 wt% Ru) supported on diamine group functionalized gel-type polymer (FCN).[MediaObject not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Present research concentrates on the process of anthraquinone degradation in the course of hydrogenation carried out in the presence of palladium catalyst. Hydrogenation experiments were carried out using agitated glass laboratory batch type reactor at atmospheric pressure of hydrogen and temperature of 55 °C. Catalytic tests were performed using solutions composed of 2-ethyl-9,10-anthraquinone (eAQ) and a mixture of eAQ and 2-ethyloxanthrone (OXO) with various proportions. Degradation of anthraquinone was studied and in particular, the role of reduced forms of quinone namely hydroquinone and its tautomer OXO is discussed. A difference in the course of reactions pathways: hydrogenation of aromatic rings to give 2-ethyl-5,6,7,8-tetrahydro-9,10-anthraquinone (active quinone) and hydrogenolysis reactions yielding degradation products was observed. Graphical Abstract: Present research concentrates on the process of 2-ethyl-9,10-anthraquinone degradation on palladium catalyst. The role of reduced forms, hydroquinone-enol form and its keto-tautomer is discussed. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

The cesium salts Cs xH3− xPW12O40 of Cs content x = 2 up to x = 3 were tested as the catalysts in the gas and liquid phase reactions. Dehydration of ethanol and transesterification of triglycerides with methanol were selected as the catalytic reactions. Apart from the standard preparation, the catalysts were prepared by two-stage procedure with methanol or water as a solvent. The Cs-salts were characterized by FT-IR, XRD, scanning electron microscopy and energy dispersive X-ray techniques. In turn, the influence of Cs-salts composition on the pH and conductivity of their aqueous colloidal solutions was investigated. The results obtained by the latter techniques were also characteristic for acidity of surface layer of colloidal particles because of surface layer-solution equilibrium. It has been shown that the secondary structure of acidic cesium salts existing in crystalline samples (solid solution of H3PW12O40 in Cs3PW12O40) changes after contacting with polar medium to the system consisting most probably of Cs3PW12O40 core with epitaxial layer of heteropolyacid. This is result of the protons migration from bulk to surface layer of primary particles enhanced by polar medium. It strongly influences the surface acidity of primary particles as well as the activity of Cs-salts in transesterification of triglycerides with methanol. In such polar medium, Cs2HPW12O40 salt becomes the most active catalyst, more active than Cs2.5H0.5PW12O40. An accumulation of partial glycerides and in particular glycerol on the surface of primary particles of Cs-salts resulted in relatively low maximum conversion of triglycerides, most probably due to partial blockage of the catalytic centers. This effect and the almost constant activity of Cs-salts under recycling use in the transesterification experiments are considered to be experimental evidences that methanolysis over Cs-salts was accomplished with the participation of surface protons. [ABSTRACT FROM AUTHOR]

Methanolysis of castor oil to methyl esters, a key step in Biodiesel production, was studied with the use of KOH, H2SO4 and 12-tungstophosphoric acid (H3PW12O40, HPW) as the homogeneous catalysts. Reaction was also performed in the presence of solid salts of HPW, namely M x H3− x PW12O40, where M = K or Cs and x = 2, 2.5 and 3 (abbreviated as K2, K2.5, K3 and Cs2, Cs2.5, Cs3, respectively). The HPW salts were precipitated by K2CO3 and Cs2CO3 or CsCl. Their properties were characterized by BET, electron microscopy (SEM, EDS) and colloidal particles size distribution (laser diffraction technique). The potassium doped HPW samples, K2 and K2.5, prove to be much more active catalysts (ca. 3 times) than their Cs-containing analogues. Among the K, Cs salts, K2 salt was the most active catalyst. The activity of catalysts was found to depend on preparation stages such as the temperature of drying or annealing and aging of the samples. Microscopic studies evidenced colloidal form of Cs and K salts particles under the catalytic reaction. The size of colloidal particles was found to depend upon the type of cation, Cs+ or K+, as well as the “history” of catalysts preparation (temperature of drying). Based on the results obtained in this work, we concluded that activity was determined by the accessibility of the reactants to acid sites which is facilitated by the high surface area and open structure of the colloidal form. This may lead to better utilization of acid sites and higher activity of samples with lower content of K+ or Cs+ cations in the HPW. [ABSTRACT FROM AUTHOR]

Functional gel type resins of various crosslinking degrees (3–20%) with C=O and carboxylic groups were used as the supports for Pd catalysts (0.5–2 wt% Pd). The role of polymer properties was studied in the hydrogenation of 2-Butyne-1,4-diol (B3-D) to alkene (B2-D) and alkane (B1-D). Hydrogenation was studied at atmospheric pressure of hydrogen using THF, H2O and THF + H2O mixtures as the solvents. Systematic studies were carried out to determine the role of the type of solvent, crosslinking degree of polymer, the content of Pd in catalysts, initial B3-D concentration and the procedure of catalyst reduction in activity/selectivity behaviour of catalysts. Swelling degree of polymer matrix under the catalytic run exhibits crucial role in the activity and selectivity to alkene, B2-D. In the presence of highly expanded catalyst (THF solvent, 3% crosslinking degree, 1 wt% Pd) the alkyne, B3-D, is hydrogenated to alkene, B2-D, with selectivity ca. 85% up to high B3-D conversion (90%). The suppression of alkene to alkane hydrogenation in the stage of B3-D is ascribed to high ability of Pd centres in the Pd/OFP catalysts to strong adsorption of alkyne substrate. It may also be related to steric hindrances of polymer in the vicinity of active Pd centres. At small content of added water (5% by vol.) to THF the catalysts offer very attractive performance in terms of activity and 98% selectivity to alkene. Water facilitates interactions of B3-D with functional groups of polymer that leads to better expansion of polymer matrix and more effective suppression of alkene hydrogenation in the alkyne stage. [ABSTRACT FROM AUTHOR]

The effects of the type of support and Pd concentration profile in alumina and silica supported egg-shell catalysts and their performance in the hydrogenation of 2-ethylanthraquinone (eAQ) were studied in ‘Anthra’ (AQ) and ‘All-Tetra’ systems. The activity and deactivation of catalysts were determined in the fixed-bed reactor. Solution saturated with hydrogen, (concentration of active quinones 60g/dm3, eAQ in the AQ system, 30% of eAQ and 70% of H4eAQ–2-ethlytetrahydroanthraquinone, in the All-Tetra system) was circulated through the catalyst bed at temperature 50°C and pressure 5bar. The contents of eAQ, active quinones, H4eAQ and degradation products were determined in the course of hydrogenation by GC method. The egg-shell palladium catalysts (1–2wt% Pd) prepared by the precipitation of palladium hydroxide onto alumina and silica supports pre-impregnated with various alkaline (NaHCO3, NaH2PO4, Na2SiO3) solutions were used in the hydrogenation experiments. Pd concentration profile inside the grains of catalysts was characterized by scanning electron microscopy. A difference between alumina and silica carriers with respect to the course of side reactions producing degradation products was found. Degradation of quinones in the hydrogenolytic reactions predominated on alumina supported catalysts, while the catalysts with silica favoured the hydrogenation of aromatic rings resulting in H4eAQ-active quinone. As a crucial factor for the decrease in the activity during the hydrogenation run, the reactivity of catalyst in the hydrogenolytic reactions was established. Alumina supported catalysts exhibited much higher deactivation than those of silica supported ones. Silica carrier as well as silica species introduced onto alumina under pre-impregnation with Na2SiO3 exhibited an advantageous role in the catalyst performance, in terms of activity and deactivation. [ABSTRACT FROM AUTHOR]

By doping of polyaniline (PANI) in PdCl2 aqueous and ethanol solutions the catalysts containing crystalline and colloidal Pd particles of different sizes were prepared. The size of palladium particles present in Pd/PANI catalysts (characterised by SEM and XRD methods) influenced the course of 2 ethylanthraquinone (eAQ) hydrogenation, a key step in the industrial production of H2O2. The presence of large palladium particles promotes reactions leading to the formation of the so termed “degradation products” not capable of hydrogen peroxide formation. [ABSTRACT FROM AUTHOR]