CATALYTIC REDUCTION OF HEMOGLOBIN AT THIONINE CHEMICALLY MODIFIED ELECTRODE AND FIA APPLICATIONS

Thionine-containing chemically modified electrode (cme) was constructed with glassy carbon substrate by potential sweep oxidation, electrodeposition and adsorption procedures, and electrocatalytic reduction of hemoglobin was carried out and characterized at the cme under batch and flow conditions. Comparison of the catalytic response toward hemoglobir obtained at the cme was made mainly in terms of the potential dependence, the detectability and long-term stability. When used in flow injection analysis (FIA) experiments with the detector monitored at a constant potential applied at -0.35 V vs sce, detection limit of 0.15-1.5 pmol level of hemoglobin injected was achieved at the cme, with linear response range over 2 orders of magnitude. All the cme s retained more than 70% of their initial hemoglobin response level over 8 h of continuous service in the flow-through system.

ELECTRODEPOSITION OF PLATINUM PARTICLES ON GLASSY-CARBON MODIFIED WITH COBALT PORPHYRIN AND NAFION FILM AND THEIR ELECTROCATALYTIC REDUCTION OF DIOXYGEN

In this paper, five types of chemically modified electrode (CMEs) prepared with the deposition of platinum particles on various surfaces of glassy carbon (GC) modified with cobalt porphyrin and Nafion(R) solution are characterized using the electron scanning microscope (SEM). Their activities in the four-electron reduction of dioxygen to water on the basis of their electrochemical data from cyclic voltammetric and rotating ring-disk electrode (RRDE) experiments are examined and compared. Platinum particles dispersed on the GC surface adsorbed with the cobalt porphyrin exhibit the highest activity for the electrocatalytic reduction of dioxygen. However it is interesting that the cobalt ion is lost from the center of the porphyrin ring during the preparation of the cobalt porphyrin + Nafion mixture solution, while the porphyrin ring still remains in the Nafion film, as shown by EDX analysis. The incorporation of the porphyrin may change the structure of the Nafion film into a looser form, since the platinum particles dispersed in the film are more readily exposed, resulting in more favourable mass transfer and higher activity for the electrocatalytic reduction of dioxygen.

ROLE OF H2S IN THE REDUCTION OF MOO3/AL2O3

MoO3/Al2O3 is reduced at least partly by sulfur which is formed from H2S in sulfidation with H2S/N2 mixture. SO2 formation during TPD of MoO3/Al2O3 with presorbed H2S provides evidence for the explanation.

STUDY ON THE COMPLEXATION OF ACENAPHTHENE AND FLUORANTHENE WITH CYCLODEXTRINS BY MEANS OF TIME-RESOLVED FLUORESCENCE TECHNIQUE

The complexation of acenaphthene and fluoranthene with beta-cyclodextrin (CD) in aqueous solutions in the presence and absence of ethanol was investigated by means of the time-resolved fluorescence technique. The appearance of a longer lifetime component and the increase of its fraction relative to that of the shorter lifetime component with increasing CD concentration demonstrate the formation of inclusion complex between the guest molecule and CD. The formation constants for complexation were derived from the pre-exponential factor A(i) of fluorescence decay curves. The presence of ethanol in the reaction systems enhanced the inclusion to a large extent.

Microwave effects on the selective reduction of NO by CH4 over an In-Fe2O3/HZSM-5 catalyst

Microwave effects have been shown to promote the activation of NOx molecules in the process of selective reduction of NO by CH4 over an In-Fe2O3/HZSM-5 catalyst and to enhance the water tolerance of this catalyst for NO reduction.

Catalytic reduction of NO over in situ synthesized Ir/ZSM-5 monoliths

The catalytic performance of Ir-based catalysts was investigated for the reduction of NO under lean-burn conditions over binderless Ir/ZSM-5 monoliths, which were prepared by a vapor phase transport (VPT) technique. The catalytic activity was found to be dependent not only on the Ir content, but also on the ZSM-5 loading of the monolith. With the decreasing of the Ir content or the increasing of the ZSM-5 loading of the monolith, NO conversion increased. When the ZSM-5 loading on the cordierite monolith was raised up to ca. 11% and the metal Ir content was about 5 g/l, the NO conversion reached its maximum value of 73% at 533 K and SV of 20 000 h(-1). Furthermore, both the presence of 10% water vapor in the feed gas and the variation of space velocity of the reaction gases have little effect on the NO conversion. A comparative test between Ir/ZSM-5 and Cu/ZSM-5, as well as the variation of the feed gas compositions, revealed that Ir/ZSM-5 is very active for the reduction of NO by CO under lean conditions, although it is a poor catalyst for the C3H8-SCR process. This unique property of Ir/ZSM-5 makes it superior to the traditional three-way catalyst (TWC) for NO reduction under lean conditions. (C) 2001 Elsevier Science B.V. All rights reserved.

On the selectively catalytic reduction of NOx with methane over Ag-ZSM-5 catalysts

The catalytic performance of silver-modified ZSM-5 catalysts in the selectively catalytic reduction (SCR) of NOx with methane was investigated. NO was selectively reduced by CH4 to N-2 in the presence of excess O-2, and the catalytic activity depended on both the activation of CH4 and the adsorption properties of NOx. Silver incorporated in ZSM-5 zeolite activated CH4 at low temperatures and lowered the "light-off" temperature for the CH4-SCR of NOx. Temperature-programmed (TP) spectroscopy studies depicted that surface nitrosyl species directly decomposed to N-2 in the absence of O-2. CH4 could not effectively reduce surface nitrosyl species, but might facilitate the direct decomposition of NO through the removal of surface oxygen. Surface nitrates were formed in NO and O-2 coexisting system and could be effectively reduced by CR4 to nitrogen. The priority of surface nitrates to O-2 in the reaction with CH4 clearly demonstrated that CH4 selectively and preferentially reduced the surface nitrate species to N-2 in the excess of oxygen. (C) 2002 Elsevier Science B.V. All rights reserved.

Kinetics of the selective reduction of NO with CH4 over an In-Fe2O3/HZSM-5 catalyst

A kinetic model presented for the selective reduction of NO with CH4 over an InFe2O3/HZSM-5 catalyst by considering the process as a combination of two simultaneous reactions: NO+O2CH4 (reaction 1) and O-2+CH4 (reaction 2). Linear regression calculation was employed to find the kinetic parameters. It was found that although the activation energies of the two reactions were almost identical, the reaction rate constants were dramatically different, namely, k(1)much greater than k(2), indicating that the NO+O-2+CH4 reaction was more preferable to take place on the In-Fe2O3/HZSM-5 catalyst as compared with the O-2+CH4 reaction.