ABSTRACT
CAT-ACT-the hard X-ray beamline for CATalysis and ACTinide/radionuclide research at the KIT synchrotron radiation facility ANKA-is dedicated to X-ray spectroscopy, including "flux hungry" photon-in/photon-out and correlative techniques and combines state-of-the-art optics with a unique infrastructure for radionuclide and catalysis research. Measurements can be performed at photon energies varying between 3.4 keV and 55 keV, thus encompassing the actinide M- and L-edge or potassium K-edge up to the K-edges of the lanthanide series such as cerium. Well-established X-ray absorption fine structure spectroscopy in transmission and fluorescence detection modes is available in combination with high energy-resolution X-ray emission spectroscopy or X-ray diffraction techniques. The modular beamline design with two alternately operated in-line experimental stations enables sufficient flexibility to adapt sample environments and detection systems to many scientific challenges. The ACT experimental station focuses on various aspects of nuclear waste disposal within the mission of the Helmholtz association to contribute to the solution of one of the greatest scientific and social challenges of our time-the safe disposal of heat producing, highly radioactive waste forms from nuclear energy production. It augments present capabilities at the INE-Beamline by increasing the flux and extending the energy range into the hard X-ray regime. The CAT experimental station focuses on catalytic materials, e.g., for energy-related and exhaust gas catalysis. Characterization of catalytically active materials under realistic reaction conditions and the development of in situ and operando cells for sample environments close to industrial reactors are essential aspects at CAT.
ABSTRACT
We report on a new modular setup on a silicon-based microreactor designed for correlative spectroscopic, scattering, and analytic on-line gas investigations for in situ studies of heterogeneous catalysts. The silicon microreactor allows a combination of synchrotron radiation based techniques (e.g., X-ray diffraction and X-ray absorption spectroscopy) as well as infrared thermography and Raman spectroscopy. Catalytic performance can be determined simultaneously by on-line product analysis using mass spectrometry. We present the design of the reactor, the experimental setup, and as a first example for an in situ study, the catalytic partial oxidation of methane showing the applicability of this reactor for in situ studies.
ABSTRACT
Flame spray pyrolysis (FSP) of Bi(III)- and Mo(VI)-2-ethylhexanoate dissolved in xylene resulted in various nanocrystalline bismuth molybdate phases depending on the Bi/Mo ratio. Besides α-Bi2Mo3O12 and γ-Bi2MoO6, FSP gave direct access to the metastable ß-Bi2Mo2O9 phase with high surface area (19 m(2) g(-1)). This phase is normally only obtained at high calcination temperatures (>560 °C) resulting in lower surface areas. The ß-phase was stable up to 400 °C and showed superior catalytic performance compared to α- and γ-phases in selective oxidation of propylene to acrolein at temperatures relevant for industrial applications (360 °C).
Subject(s)
Acrolein/chemistry , Alkenes/chemistry , Bismuth/chemistry , Molybdenum/chemistry , Catalysis , Hot Temperature , Oxidation-Reduction , Powder Diffraction , Surface Properties , X-Ray DiffractionABSTRACT
The fluorescence EXAFS (FLEXAFS) technique has been combined with an in situ cell and on-line gas analysis. For this purpose a seven-element silicon drift detector has been used, which has high count rate capabilities and can be operated at room temperature. The potential of this technique is shown by the study of the state of copper promoter atoms in Fe-Cr based high temperature shift (HTS) catalysts. The FLEXAFS measurements revealed that Cu (0.17-1.5 wt%) is present in the metallic state under working conditions of the catalysts but easily re-oxidizes upon air exposure. The reduction behaviour of copper depends strongly on the copper concentration and the pre-treatment, i.e. if the catalysts have been calcined or used in the HTS reaction. For used catalysts, a Cu(I) phase was detected as intermediate during reduction. Its stability was especially high at low copper concentration.
ABSTRACT
Twelve novel 2,4-diamino-5-(4'-benzylamino)- and 2,4-diamino-5[4'-(N-methylbenzylamino)-3'-nitrophenyl]-6-ethylp yrimidines bearing 4-substituents on the benzylamino or N-methylbenzylamino aryl ring were synthesized and evaluated as nonclassical inhibitors of Pneumocystis carinii and Toxoplasma gondii dihydrofolate reductase (DHFR). Compounds were prepared by reaction of 2,4-diamino-5-(4'-chloro-3'-nitrophenyl)- (8) or 2,4-diamino-5-(4'-fluoro-3'-nitrophenyl)-6-ethylpyrimidine (15) with the appropriate 4-substituted (CO2H, CO2Me, SO2NH2, dioxolan-2-yl, CHO, dimethyloxazolin-2-yl) benzylamine or N-methylbenzylamine derivative. Compounds 25-29 were synthesized from 2,4-diamino-5-{4'-[N-(4"-carboxybenzyl)amino]-3'-nitrophenyl}-6- ethylpyrimidine (10) and the corresponding amine (NH3, MeNH2, Me2NH, piperidine, diethyl L-glutamate) via isobutyl mixed anhydride coupling; hydrolysis of the diethyl L-glutamate 29 afforded the L-glutamate analogue 30. The compounds exhibited potent inhibitory activity against T. gondii (IC50 values 0.0018-0.14 microM) and rat liver (IC50 values 0.0029-0.27 microM) DHFR, with a 4-substituent invariably enhancing binding to both enzymes relative to the unsubstituted benzoprim (5) or methylbenzoprim (6). Modest selectivity for T. gondii enzyme was observed with several analogues, whereas all of the compounds were relatively weak inhibitors of P. carinii DHFR and exhibited no selectivity. Selected analogues were evaluated for in vivo antitumor activity against the methotrexate-resistant M5076 murine reticulosarcoma, with 2,4-diamino-5-{4'-[N-[4"-(N"-methylcarbamoyl)benzyl]-N- methylamino]-3'-nitrophenyl}-6-ethylpyrimidine (14) (Ki for rat liver DHFR = 0.00035 +/- 0.00029 nM) combining significant antitumor activity with minimal toxicity.
