Mechanisms of the action of alkali metal admixtures on the properties of copper–zinc–aluminum water–gas shift catalysts

The effect of alkali metal (Cs, Na) admixtures on the catalytic and physicochemical properties of coprecipitated Cu–Zn–Al catalysts for the low-temperature water–gas shift reaction has been investigated. The inhibition of the formation of methanol, an undesired by-product, by alkali metals is accompanied by a decrease in the activity of the catalyst in the main, water–gas shift reaction ion. The alkali metals exert an adverse effect on the thermal stability of the catalyst. Experimental data are explained in a consistent way on the basis of the following conceptions of the mechanism of the action of alkali metals: (1) the alkali metals stimulate sintering of the crystal structure of the main components of the catalyst, diminishing the activity of the catalyst in the water–gas shift reaction and in methanol formation; (2) the alkali metals directly or indirectly accelerate methanol conversion into other chemical products.     

Selective synthesis of carbon monoxide via formates in reverse water–gas shift reaction over alumina-supported gold catalyst

Thermal decomposition of formic acid on SiO_2, CeO_2 and γ-Al_2O_3 was studied as an elementary step of reverse water–gas shit reaction(RWGS) over supported Au catalysts. γ-Al_2O_3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al_2O_3: three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al_2O_3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO_2 and H_2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al_2O_3.     

Highly efficient In–Sn alloy catalysts for electrochemical reduction of CO2 to formate

Gas diffusion electrodes (GDEs), including GDE-In_0.90Sn_0.10, GDE-In_0.47Sn_0.53 and GDE-In_0.22Sn_0.78, were prepared by electrodeposition of In–Sn alloys on carbon fiber paper, and then used to explore the electroreduction of CO₂ to formate in aqueous solution. Compared with commercial indium or Sn foil catalysts, the GDE-In_0.90Sn_0.10 electrode in particular is shown to have excellent catalytic performance towards electroreduction of CO₂ to formate, with a high Faradaic efficiency (~ 92%). More importantly, the catalytic activity of GDE-In_0.90Sn_0.10 remained reasonably stable over a 22-hour period of electrolysis, and a relatively high electrolytic current density (15 mA cm^− 2) was obtained in an aqueous medium, demonstrating its potential for electrochemical reduction of CO₂ to formate.     

Synthesis and study of Ru–Ba–Cs/Sibunit ternary catalysts for ammonia synthesis

Ru–Ba–Cs/Sibunit ternary catalysts were synthesized. Their activity in ammonia synthesis and the thermal stability of the support in a reducing atmosphere at elevated temperature depend on the molar ratio of the promoters. The results of studies using physical methods suggest that cesium predominantly interacts with the support, acting as an electronic promoter, whereas barium is a structural promoter. The synergistic action of the promoters at increased barium content of the catalyst was revealed. The highest activity in ammonia synthesis, 34.5 mL_NH3 g_cat ^–1 h^–1, was reached for the 4% Ru–10.8% Ba–2.6% Cs/Sibunit catalyst.     

Analysis of potassium formate in airport storm water runoff by headspace solid-phase microextraction and gas chromatography–mass spectrometry

Potassium formate was extracted from airport storm water runoff by headspace solid-phase microextraction (HS-SPME) and analyzed by GC–MS. Formate was transformed to formic acid by adding phosphoric acid. Subsequently, formic acid was derivatized to methyl formate by adding methanol. Using sodium [²H]formate (formate-d) as an internal standard, the relative standard deviation of the peak area ratio of formate (m/z 60) and formate-d (m/z 61) was 0.6% at a concentration of 208.5 mg L⁻¹. Calibration was linear in the range of 0.5–208.5 mg L⁻¹. The detection limit calculated considering the blank value was 0.176 mg L⁻¹. The mean concentration of potassium formate in airport storm water runoff collected after surface de-icing operations was 86.9 mg L⁻¹ (n = 11) with concentrations ranging from 15.1 mg L⁻¹ to 228.6 mg L⁻¹.     

In situ synthesis of DNA micro-arrays using typography technique

A novel typography technique was developed to in situ synthesize oligonucleotide arrays on glass slide,which has the celerity,high spatial resolution,lower cost,reliable operation,and high synthetic efficiency.The principle and process of the typography technique for fabricating gene-chips have been described in detail.A suit of poly(terafluoroethylene)devices for synthesizing oligonucleotide arrays were designed and prepared,and the fiber tubes with a number of nano-or micron-channels were em- ployed.The oligonucleotide arrays of 16 and 160 features with four different probes were synthesized using the typography technique.The four specific oligonucleotide probes including the matched and the mismatched by the fluorescent target sequence gave obviously different hybridization fluorescent signals.It was indicated that the gene-chip fabricated by the typography method could be used to rapidly screen single-nucleotide polymorphisms(SNP)and to detect mutations.     

A facile chemical reduction method for synthesis of platinum–iron catalysts on carbon fiber papers for methanol oxidation

To enhance catalytic activity and durability for methanol oxidation reaction (MOR), we have fabricated bimetallic Pt–Fe catalysts on carbon fiber papers (denoted as Pt–Fe@CFP) by a facile chemical reduction method using iron as the precursor, ascorbic acid and sodium hypophosphite as the reductants, respectively. When ascorbic acid is using as the reductant, the Pt–Fe@CFP catalysts are composed of platinum and disordered Pt–Fe phases. The atomic ratio between Pt and Fe can be adjusted by altering deposition conditions. The Pt–Fe@CFP catalysts with Pt/Fe ratio of 1.1, which deposited with surfactant CTAB in bath at room temperature, exhibit excellent catalytic activity and stability in MOR. However, when sodium hypophosphite is employed as the reductant, the co-deposition of phosphorus would lead to a decreased catalytic performance in MOR.     

Car-Parinello molecular dynamics simulations of thionitroxide and S-nitrosothiol in the gas phase, methanol, and water—A theoretical study of S-nitrosylation

A dilemma about whether thionitroxide radical (RSNHO) or S-nitrosothiol (RSNO) is observed in protein S-nitrosylation has arisen recently. To illustrate the effect of chemical environment on these structures, this paper presents quantum mechanical molecular dynamics of thionitroxide, and cis-and trans-S-nitrosothiols in the gas phase, methanol, and water. By using Car-Parrinello molecular dynamics (CPMD), we have observed that there is free rotation about the S-N bond at 300 K in thionitroxide, but no such rotation is observed for S-nitrosothiol. The C-S-N-O torsion angle distribution in thionitroxide is s-ignificantly dependent upon the surrounding environment, leading to either gauche-, cis-, or trans-conformation. In the case of S-nitrosothiol the C-S-N-O plane is twisted slightly by 5°-15° in the cis-isomer, while the periplanar structure is well-retained in the trans-isomer. The calculated results are in agreement with the X-ray crystallographic data of small molecular RSNO species. Interestingly, for both compounds, the CPMD simulations show that solvation can cause a decrease in the S-N bond length. Moreover, the oxygen atom of thionitroxide is found to be a good hydrogen-bond acceptor, forming an oxyanion-hole-like hydrogen bonding network.     

Surface structure–activity relationships of Cu/ZnGaOX catalysts in low temperature water–gas shift (WGS) reaction for production of hydrogen fuel

A new species’ class of Cu-, Ga- and Zn-based rate catalysts was prepared by a systematic co-precipitation technique at the different related pH values (6.5–8.0) along with calcination functional conditions, influencing components’ physical properties, these were characterized, and their application performance for water–gas shift (WGS) reaction was researched. Substances were analysed by various experimental methods, namely chemisorption, temperature-programmed reduction (TPR) characterisation, diffraction, physisorption and microscopy. A homogenous size dispersion of the compounds with smaller granular particles was obtained for catalysis, implemented with high pH-resulting outputs. H₂ TPR profiles revealed a tailored stronger effect of Cu–Zn on Ga for process, operated with low pH-conditioned forms. Over Cu/ZnGaO_X, WGS was sensitive to Cu, which was primarily active. Catalytic chemical reactivity, activity and selectivity were also found to be critically dependent on material lattice structure, copper surface area and metal–support interaction phenomena. The temperature-programmed surface reaction with mass spectrometry (TPSR–MS) measurements showed that formulations, synthesised at the pH of 8.0, enabled reaching >99% of the equilibrium yield CO conversion at 260 °C. An increase in the converted CO, oxidation and H₂ productivity with the integral steam content in gaseous feed flow was achieved. The heterogeneous phase processing at the correlated pH of 7.6 demonstrated the highest formed CO product at the temperature of 200 °C, compared with literature. This is particularly promising for reagent purity hydrogen-fed fuel cells. The kinetics for each co-precipitated solid was evaluated regarding the efficiency for the WGS in a fixed bed reactor.     

In situ electrochemical contact angle study of hemoglobin and hemoglobin–Fe3O4 nanocomposites

The electrochemical redox-induced contact angle changes of hemoglobin droplets in the absence and presence of tetraheptylammonium-capped Fe₃O₄ nanoparticles have been explored by using in situ electrochemical contact angle measurements. The results indicate that the electrochemical redox process may lead to some structure changes of hemoglobin (Hb), which could further induce the hydrophobic-to-hydrophilic changes of the relative droplets. Our observations demonstrate that hemoglobin could self-assemble on the surface of the functionalized Fe₃O₄ nanoparticles as Hb–Fe₃O₄ nanocomposites, which may contribute to much more significant change of the electrochemical redox-induced contact angle values than that with free nano-Fe₃O₄. These results suggest that in situ electrochemical contact angle measurements could be readily applied as a new and convenient method to detect some specific biological process. Figure Schematic drawing of the possible process and contact angle changes for the self-assembly of hemoglobin on the tetraheptylammonium-capped Fe₃O₄ nanoparticles Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Steric effects of bulky tethered arylpiperazines on the reactivity of Co-Schiff base oxidation catalysts—a synthetic and computational study

New C2-symmetric and C2-asymmetric Co-Schiff base catalysts tethered to arylpiperazine units were synthesized and used to oxidize phenolic lignin models to para-benzoquinones. Synthetic approaches to these catalysts were optimized to include fewer steps and broaden the types of catalyst structures available. In contrast to conventional Co-Schiff base catalysts, these systems induce phenolic oxidation in the absence of an external axial base, simplifying the process. Asymmetric catalysts bearing a phenylethylene or diphenylmethyl piperazine substituent display the highest catalytic activity observed to date for the conversion of S-models to 2,6-dimethoxybenzoquinone (DMBQ). Computational analysis shows that more reactive catalysts populate conformations that favor oxidation in preference to non-productive decomposition routes. This balance between catalyst reactivity and catalyst deactivation is optimized by inclusion of sufficient steric bulk around the periphery of the Schiff base ligand, reducing catalyst deactivation and allowing oxidations to proceed in the absence of an added axial ligand.     

A study on sol–gel synthesis and characterization of SiC nano powder

Nano sized β-SiC particles were synthesized from sol–gel process. Mono dispersed β-SiC nano particles with semi spherical morphology were obtained by employing APC as a dispersant agent and adjusting pH in the range of 2.5–4. Phenolic resin and TEOS were employed as precursors and heat treatment was conducted up to 1500 °C. Different techniques such as XRD, DTA, FTIR, PSA, SEM and TEM were used to characterize the formation of β-SiC. The (Si–O-C) bonds were formed by hydrolysis and condensation reactions in the gel while the nucleation of crystalline β-SiC was found to be initiated at 1400 °C. The primary particles in the sol were found to be (< 10 nm) while the size distribution in the final product was recorded in the range of 30–50 nm.     

A comparative study in structure and reactivity of “FeO_x-on-Pt” and “NiO_x-on-Pt” catalysts

Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on-Pt and Ni Ox-on-Pt catalysts and their activity to CO oxidation reactions using both model catalysts and supported nanocatalysts.Although the active Fe O1x structure is stabilized on the Pt surface in a reductive reaction atmosphere,it is prone to change to an Fe O2x structure in oxidative reaction gases and becomes deactivated.In contrast,a Ni O1x surface structure supported on Pt is stable in both reductive and oxidative CO oxidation atmospheres.Consequently,CO oxidation over the Ni O1x-on-Pt catalyst is further enhanced in the CO oxidation atmosphere with an excess of O2.The present results demonstrate that the stability of the active oxide surface phases depends on the stabilization effect of the substrate surface and is also related to whether the oxide exhibits a variable oxidation state.     

In situ infrared investigation of alkylation reaction of dianionic triruthenium ketenylidene cluster on magnesium oxide with methyl iodide

The reaction between [Ru_3(CO)_9(CCO)]~(2-) supported on magnesium oxide and alky-lating agent CH_3I was investigated in an attempt to understand its reactivity and mechanism byusing FT-IR technique. The IR spectra show that [Ru_3(CO)_9(CCO)]~(2-)/MgO reacts with CH_3Ito produce [Ru_3(CO)_9CC(O)CH_3]-/MgO, which exhibits bands at 2960, 2022, 1988, 1638, 1460and 1350 cm~(-1). The absorption at 2960, 1460 and 1350 cm~(-1) are attributed to -CH_3 group, whilebands at 2022, 1988 and 1952 cm~(-1) are assigned to the terminal CO groups attached to ruthenium.The band at 1638 cm~(-1) was assigned to acyl carbonyl. Isotopes labeled compounds CD3I, ~(13)COand [Ru_3(CO)_9(*C*CO)]~(2-) were used in investigation. The results demonstrate that β-carbon ofCCO ligand is attacked by CH_3~+ species and produces [Ru_3(CO)_9CC(O)CH_3]-/MgO.     

In situ surface Raman study of the induced codeposition mechanism of Ni–Mo alloys

The induced codeposition of molybdenum with nickel on a Ni–Cu alloy electrode has been investigated by means of in situ surface Raman spectroscopy to obtain information about the codeposition mechanism during electrodeposition of Ni–Mo alloys. The experimental results show that, in the NiSO₄-free solution, molybdate can only be reduced to a mixture of polyvalent molybdenum oxides and/or hydroxide, while, in the case where NiSO₄ coexisted in the solution, molybdate is first reduced to Mo(IV) oxide, which, as an intermediate, subsequently is reduced to molybdenum in alloy under the catalysis of inducing nickel.     

Proline–cyclodextrin conjugates: synthesis and evaluation as catalysts for aldol reaction in water

The synthesis of six conjugates of l-proline and β-cyclodextrin and their evaluation as catalysts of aldol reaction in water are described. The results indicated that the nature of the linker between proline and β-cyclodextrin is important for catalytic activity; the one with the most flexible linker gave the best results. Inhibition experiments showed that the cavity of β-cyclodextrin plays a role in the catalysis. Permethylation of the cyclodextrin hydroxyl groups led to higher conversion rates.     

Thermodynamic characteristics of the adsorption of 1,3,4-oxadiazoles and 1,2,4,5-tetrazines from methanol and water–methanol solutions onto hypercrosslinked polystyrene

Russian Journal of Physical Chemistry A - The thermodynamic characteristics of the adsorption of several 1,3,4-oxadiazoles and 1,2,4,5- tetrazines from methanol and water-methanol solutions onto...     

Enthalpic interaction coefficients of NaI–alkanediol pairs in methanol and in water

The dissolution enthalpies of NaI in the mixtures of methanol with 1,2-alkanediols (1,2-propanediol, 1,2-butanediol, 1,2-pentanediol) and with ??,??-alkanediols (1,3-propanediol, 1,4-butanediol, 1,5-pentanediol), as well NaI in the mixtures of water with 1,3-propanediol and 1,2-pentanediol, were determined at 298.15?K. The energetic effect of interactions between the investigated alkanediols and NaI in methanol and in water was calculated using the enthalpic pair interaction coefficients (h _xy ) model. These results along with the other data concerning the NaI?Cnon-electrolyte pairs taken from our earlier reports and from the literature were analyzed with respect to the effect of the non-electrolyte properties on the variations of the h _xy values. The group contributions illustrating the interactions of NaI with selected functional groups in non-electrolyte (alkanediol and alkanol) molecules, namely: CH₂ and OH groups were calculated and discussed.