Understanding catalytic reactions over zeolites: A density functional theory study of selective catalytic reduction of NOX by NH3 over Cu-SAPO-34

Metal exchanged CHA-type (SAPO-34 and SSZ-13) zeolites are promising catalysts for selective catalytic reduction (SCR) of NOx by NH3. However, the understanding of the process at the molecular level is still limited, which hinders the identification of its mechanism and the design of more efficient zeolite catalysts. In this work, modelling the reaction over Cu-SAPO-34, a periodic density functional theory (DFT) study of NH3-SCR was performed using hybrid functional with the consideration of van der Waals (vdW) interactions. A mechanism with a low N–N coupling barrier is proposed to account for the activation of NO. The redox cycle of Cu2+ and Cu+, which is crucial for the SCR process, is identified with detailed analyses. Besides, the decomposition of NH2NO is shown to readily occur on the Brønsted acid site by a hydrogen push-pull mechanism, confirming the collective efforts of Brønsted acid and Lewis acid (Cu2+) sites. The special electronic and structural properties of Cu-SAPO-34 are demonstrated to play an essential role the reaction, which may have a general implication on the understanding of zeolite catalysis.

XFEL resonant photo-pumping of dense plasmas and dynamic evolution of autoionizing core hole states

Similarly to the case of LIF (Laser-Induced Fluorescence), an equally revolutionary impact to science is expected from resonant X-ray photo-pumping. It will particularly contribute to a progress in high energy density science: pumped core hole states create X-ray transitions that can escape dense matter on a 10 fs-time scale without essential photoabsorption, thus providing a unique possibility to study matter under extreme conditions. In the first proof of principle experiment at the X-ray Free Electron Laser LCLS at SCLAC [Seely, J., Rosmej, F.B., Shepherd, R., Riley, D., Lee, R.W. Proposal to Perform the 1^st High Energy Density Plasma Spectroscopic Pump/Probe Experiment", approved LCLS proposal L332 (2010)] we have successfully pumped inner-shell X-ray transitions in dense plasmas. The plasma was generated with a YAG laser irradiating solid Al and Mg targets attached to a rotating cylinder. In parallel to the optical laser beam, the XFEL was focused into the plasma plume at different delay times and pump energies. Pumped X-ray transitions have been observed with a spherically bent crystal spectrometer coupled to a Princeton CCD. By using this experimental configuration, we have simultaneously achieved extremely high spectral (λ/δλ ≈ 5000) and spatial resolution (δx≈70 μm) while maintaining high luminosity and a large spectral range covered (6.90 - 8.35 Å). By precisely measuring the variations in spectra emitted from plasma under action of XFEL radiation, we have successfully demonstrated transient X- ray pumping in a dense plasma.