Hydrogen Production from Methanol Steam Reforming over Fe-Modified Cu/CeO2 Catalysts.

Fe-modified Cu catalysts with CeO2 support, prepared by the impregnation method, were subjected to physicochemical analysis and catalytic tests in the steam reforming of methanol (SRM). Physicochemical studies of the catalysts were carried out using the XRF, TEM, STEM-EDS, XRD, TPR and nitrogen adsorption/desorption methods. XRD, TEM studies and catalytic tests of the catalysts were carried out at two reduction temperatures, 260 °C and 400 °C, to determine the relationship between the form and oxidation state of the active phase of the catalysts and the catalytic properties of these systems in the SRM. Additionally, the catalysts after the reaction were analysed for the changes in the structure and morphology using TEM methods. The presented results show that the composition of the catalysts, morphology, structure, form and oxidation state of the Cu and Fe active metals in the catalysts and the reaction temperature significantly impact their activity, selectivity and stability in the SRM process. The gradual deactivation of the studied catalysts under SRM conditions could result from the forming of carbon deposits and/or the gradual oxidation of the copper and iron phases under the reaction conditions.

Unraveling the NH3-SCR-DeNOx Mechanism of Cu-SSZ-13 Variants by Spectroscopic and Transient Techniques.

Commercial SSZ-13 zeolite with different n(Si)/n(Al) ratios and from different suppliers were subjected to a post-synthetic treatment in order to create mesopores of up to 15 nm. Furthermore, the materials were modified with copper ions and thoroughly physico-chemically characterized. The modified textural properties varied the nature of copper species, and thus, activity in the selective catalytic reduction of NOx with ammonia (NH3-SCR-DeNOx). Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) studies with hexane as probe liquid revealed improved intracrystalline diffusion for some Cu-containing SSZ-13 materials. The NH3-SCR-DeNOx pathways are verified via in situ DR UV-Vis, in situ FT-IR and EPR, temperature-programmed studies as well as SSITKA studies that provide a mechanistic understanding of the reaction. Kinetic modelling results demonstrate the highest NH3-SCR-DeNOx reaction rates and up to 20 % lower energy barriers with n(Si)/n(Al) ratio of 6.5 for all modified forms (i. e., (NH4)Cu-SSZ-13_6.5 and Cu-SSZ-13_6.5_NaOH/0.1) and cause only negligible parasitic ammonia oxidation. The modelling of the stop-flow experiments further demonstrates that the SCR pathway via the HONO surface intermediate is present but barely contributes to the overall NO conversion compared to the dominant path between adsorbed NH3 and NO from the gas phase.

Effect of Potassium Doping on the Structural and Catalytic Properties of Co/MnOx Catalyst in the Steam Reforming of Ethanol.

The promotional effect of potassium (~1.25 wt%) on a Co/MnOx catalyst was studied for samples prepared by the impregnation method in the steam reforming of ethanol (SRE) process at 420 °C for a H2O/EtOH molar ratio of 12/1. The catalysts were characterized using physicochemical methods to study their textural, structural, and redox properties. The XRD studies revealed that, during the treatment of both cobalt-based catalysts under a hydrogen atmosphere at 500 °C, Co0 and MnO phases were formed by the reduction in Co3O4 and Mn2O3/Mn3O4 phases, respectively. Potassium doping significantly improved stability and ability for the C-C bond cleavage of the Co/MnOx catalyst. The enhancement of activity (at ~25%) and selectivity to hydrogen (at ca. 10%) and the C1 product, mainly carbon dioxide (at ~20%), of the Co/MnOx catalyst upon potassium doping was clarified by the alkali promoter's impact on the reducibility of the cobalt and manganese oxides. The microscopic observations revealed that fibrous carbon deposits are present on the surface of Co/MnOx and KCo/MnOx catalysts after the SRE reaction and their formation is the main reason these catalysts deactivate under SRE conditions. However, carbon accumulation on the surface of the potassium-promoted catalyst was ca. 12% lower after 18 h of SRE reaction compared to the unpromoted sample.

Electrochemically Pretreated Sensor Based on Screen-Printed Carbon Modified with Pb Nanoparticles for Determination of Testosterone.

Testosterone (TST), despite its good properties, may be harmful to the human organism and the environment. Therefore, monitoring biological fluids and environmental samples is important. An electrochemically pretreated screen-printed carbon sensor modified with Pb nanoparticles (pSPCE/PbNPs) was successfully prepared and used for the determination of TST. The surface morphology and electrochemical properties of unmodified and modified sensors were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning and transmission electron microscopy (SEM and TEM), and energy-dispersive X-ray spectroscopy (EDS). Selective determinations of TST at the pSPCE/PbNPs were carried out by differential pulse adsorptive stripping voltammetry (DPAdSV, EPb dep.and TST acc. of -1.1 V, t Pb dep.and TST acc. of 120 s, ΔEA of 50 mV, ν of 175 mV s-1, and tm of 5 ms) in a solution containing 0.075 mol L-1 acetate buffer of pH = 4.6 ± 0.1, and 7.5 × 10-5 mol L-1 Pb(NO3)2. The analytical signal obtained at the potential around -1.42 V (vs. silver pseudo-reference electrode) is related to the reduction process of TST adsorbed onto the electrode surface. The use of pSPCE/PbNPs allows obtaining a very low limit of TST detection (2.2 × 10-12 mol L-1) and wide linear ranges of the calibration graph (1.0 × 10-11-1.0 × 10-10, 1.0 × 10-10-2.0 × 10-9, and 2.0 × 10-9-2.0 × 10-8 mol L-1). The pSPCE/PbNPs were successfully applied for the determination of TST in reference material of human urine and wastewater purified in a sewage treatment plant without preliminary preparation.

First Screen-Printed Sensor (Electrochemically Activated Screen-Printed Boron-Doped Diamond Electrode) for Quantitative Determination of Rifampicin by Adsorptive Stripping Voltammetry.

In this paper, a screen-printed boron-doped electrode (aSPBDDE) was subjected to electrochemical activation by cyclic voltammetry (CV) in 0.1 M NaOH and the response to rifampicin (RIF) oxidation was used as a testing probe. Changes in surface morphology and electrochemical behaviour of RIF before and after the electrochemical activation of SPBDDE were studied by scanning electron microscopy (SEM), CV and electrochemical impedance spectroscopy (EIS). The increase in number and size of pores in the modifier layer and reduction of charge transfer residence were likely responsible for electrochemical improvement of the analytical signal from RIF at the SPBDDE. Quantitative analysis of RIF by using differential pulse adsorptive stripping voltammetry in 0.1 mol L-1 solution of PBS of pH 3.0 ± 0.1 at the aSPBDDE was carried out. Using optimized conditions (Eacc of -0.45 V, tacc of 120 s, ΔEA of 150 mV, ν of 100 mV s-1 and tm of 5 ms), the RIF peak current increased linearly with the concentration in the four ranges: 0.002-0.02, 0.02-0.2, 0.2-2.0, and 2.0-20.0 nM. The limits of detection and quantification were calculated at 0.22 and 0.73 pM. The aSPBDDE showed satisfactory repeatability, reproducibility, and selectivity towards potential interferences. The applicability of the aSPBDDE for control analysis of RIF was demonstrated using river water samples and certified reference material of bovine urine.

Direct Conversion of Carbon Dioxide to Methane over Ceria- and Alumina-Supported Nickel Catalysts for Biogas Valorization.

Direct methanation of CO2 over ceria- and alumina-supported nickel catalysts in the feed stream containing methane and traces of H2 S is reported. Stability tests for 20 h at 350 and 600 °C with a packed-bed reactor showed high resistance of the catalysts to sintering processes. Higher conversion at 350 °C was observed for ceria supported nickel catalyst. Thermodynamic analysis indicated that CO2 contained in biogas can be converted to methane without carbon formation under specific reaction conditions. An introduction of CH4 to CO2 -H2 feed stream led to the decrease in CO2 conversion and CH4 selectivity. An introduction of the trace amounts of H2 S into the feed stream led to the fast drop of CO2 conversion and CH4 selectivity; higher durability (20 %) was observed for Al2 O3 than CeO2 supported catalysts. An improved performance of catalysts coated onto high-pressure microchannel microreactors for the direct CO2 methanation reaction applying model biogas mixture was demonstrated.

Development simple and sensitive voltammetric procedure for ultra-trace determination of U(VI).

A simple and sensitive adsorptive stripping voltammetric procedure for the determination of trace concentration of U(VI) in natural water samples was developed. In order to remove surface active compounds from water sample solutions, a TiO2/Al2O3 photocatalysis system was applied. The linear calibration graph of U(VI) in the simultaneous presence of 2mgL-1 anionic, cationic and nonionic surfactants, in the range from 5×10-10 to 2×10-8molL-1 (180s) was achieved. The detection limit obtained in the solution after the use of UV-irradiation (10min) with TiO2/Al2O3 photocatalyst (0.9g) is equal to 2.3×10-10mol L-1. The presented procedure was successfully applied to uranium determination in SLEW-3 certified reference material, and to river water samples. In addition, a very low detection limit (2.9×10-11molL-1) for accumulation time of 180s was achieved due to application of a reversible deposited mediator (Zn) in the step of lead film electrode preparation.

Voltammetric determination of platinum at a lead film electrode in environmental water samples.

The paper presents the first report on the application of a lead film electrode for the determination of ultratrace concentrations of platinum. The procedure is based on preconcentration of the Pt(IV)-formaldehyde complexes at an in situ plated lead film electrode held at -0.9 V (vs. Ag/AgCl), followed by a negatively sweeping differential pulse voltammetric scan. The composition of the supporting electrolyte, the influence of accumulation potential and time on the sensitivity of platinum responses are discussed. The detection limit of Pt(IV) with the accumulation time of 60 was equal to 9.2 × 10(-12) mol L(-1). The application of this method was tested by recovery of Pt(IV) from spiked environmental water samples.