For the first time, the standard and fast selective catalytic reduction (SCR) of NO by NH3 are described in a complete catalytic cycle that is able to produce the correct stoichiometry while allowing adsorption and desorption of stable molecules only. The standard SCR reaction is a coupling of the activation of NO by O2 with the fast SCR reaction, enabled by the release of NO2. According to the scheme, the SCR reaction can be divided into an oxidation of the catalyst by NO + O2 and a reduction by NO + NH3; these steps together constitute a complete catalytic cycle. Furthermore, both NO and NH3 are required in the reduction, and finally, oxidation by NO + O2 or NO2 leads to the same state of the catalyst. These points are shown experimentally for a Cu-CHA catalyst by combining in situ X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and Fourier transform infrared spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The activation energy calculated by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate-determining for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible influence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR while being a poor catalyst for NO oxidation to NO2.
Cu-SSZ-13 has been characterized by different spectroscopic techniques and compared with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios and prepared by the same ion exchange procedure. On vacuum activated samples, low temperature FTIR spectroscopy allowed us to appreciate a high concentration of reduced copper centres, i.e. isolated Cu(+) ions located in different environments, able to form Cu(+)(N2), Cu(+)(CO)n (n = 1, 2, 3), and Cu(+)(NO)n (n = 1, 2) upon interaction with N2, CO and NO probe molecules, respectively. Low temperature FTIR, DRUV-Vis and EPR analysis on O2 activated samples revealed the presence of different Cu(2+) species. New data and discussion are devoted to (i) [Cu-OH](+) species likely balanced by one framework Al atom; (ii) mono(μ-oxo)dicopper [Cu2(μ-O)](2+) dimers observed in Cu-ZSM-5 and Cu-β, but not in Cu-SSZ-13. UV-Vis-NIR spectra of O2 activated samples reveal an intense and finely structured d-d quadruplet, unique to Cu-SSZ-13, which is persistent under SCR conditions. This differs from the 22,700 cm(-1) band of the mono(μ-oxo)dicopper species of the O2 activated Cu-ZSM-5, which disappears under SCR conditions. The EPR signal intensity sets Cu-β apart from the others.
Cu-CHA combines high activity for the selective catalytic reduction (SCR) reaction with better hydrothermal stability and selectivity compared to other copper-substituted zeolites. At the same time Cu-CHA offers an opportunity for unraveling the coordination environment of the copper centers since the zeolite framework is very simple with only one crystallographically independent tetrahedral site (T-site). In this study the results of an X-band electron paramagnetic resonance (EPR) investigation of ion-exchanged Cu-CHA zeolite with a Si/Al ratio of 14 ± 1 is presented. Different dehydration treatments and rehydration experiments are performed in situ while monitoring with EPR. The results are compared with recent literature evidence from temperature-programmed reduction, X-ray methods, IR spectroscopic methods, and UV−visible spectroscopy. On the basis of these findings quantitative information is obtained for the different copper positions in dehydrated Cu-CHA. The well-defined copper sites in the sixmembered ring of the CHA structure are found to be EPR active, to give two distinct sets of signals in an approximate 1:1 ratio, and to add up to 19 ± 2% of the total copper in the material. The long-standing question of the EPR silent monomeric Cu 2+ in copper-substituted zeolites is suggested to be copper species with an approximate trigonal coordination sphere appearing during the dehydration. After complete dehydration at 250 °C the majority of the EPR silent Cu 2+ is suggested to exist as Cu 2+ −OH − coordinated to two framework oxygen atoms located in the microenvironment of an isolated Al T-site.
Sodium exhibits a pronounced minimum of the melting temperature at approximately 118 gigapascals and 300 kelvin. Using single-crystal high-pressure diffraction techniques, we found that the minimum of the sodium melting curve is associated with a concentration of seven different crystalline phases. Slight changes in pressure and/or temperature induce transitions between numerous structural modifications, several of which are highly complex. The complexity of the phase behavior above 100 gigapascals suggests extraordinary liquid and solid states of sodium at extreme conditions and has implications for other seemingly simple metals.
Accurate structural models of reaction centres in zeolite catalysts are a prerequisite for mechanistic studies and further improvements to the catalytic performance. The Rietveld/maximum entropy method is applied to synchrotron powder X-ray diffraction data on fully dehydrated CHA-type zeolites with and without loading of catalytically active Cu2+for the selective catalytic reduction of NOxwith NH3. The method identifies the known Cu2+sites in the six-membered ring and a not previously observed site in the eight-membered ring. The sum of the refined Cu occupancies for these two sites matches the chemical analysis and thus all the Cu is accounted for. It is furthermore shown that approximately 80% of the Cu2+is located in the new 8-ring site for an industrially relevant CHA zeolite with Si/Al = 15.5 and Cu/Al = 0.45. Density functional theory calculations are used to corroborate the positions and identity of the two Cu sites, leading to the most complete structural description of dehydrated silicoaluminate CHA loaded with catalytically active Cu2+cations.
Of the simple diatomic molecules, oxygen is the only one to carry a magnetic moment. This makes solid oxygen particularly interesting: it is considered a 'spin-controlled' crystal that displays unusual magnetic order. At very high pressures, solid oxygen changes from an insulating to a metallic state; at very low temperatures, it even transforms to a superconducting state. Structural investigations of solid oxygen began in the 1920s and at present, six distinct crystallographic phases are established unambiguously. Of these, the epsilon phase of solid oxygen is particularly intriguing: it exhibits a dark-red colour, very strong infrared absorption, and a magnetic collapse. It is also stable over a very large pressure domain and has been the subject of numerous X-ray diffraction, spectroscopic and theoretical studies. But although epsilon-oxygen has been shown to have a monoclinic C2/m symmetry and its infrared absorption behaviour attributed to the association of oxygen molecules into larger units, its exact structure remains unknown. Here we use single-crystal X-ray diffraction data collected between 13 and 18 GPa to determine the structure of epsilon-oxygen. We find that epsilon-oxygen is characterized by the association of four O2 molecules into a rhombohedral molecular unit, held together by what are probably weak chemical bonds. This structure is consistent with existing spectroscopic data, and further validated by the observation of a newly predicted Raman stretching mode.
Zeolite ZSM-5 is one of the most widely used zeolites, in particular in heterogeneous catalysis. This work investigates the incorporation of Al in the silica framework of monoclinic ZSM-5 and the Al speciation during steam treatment for four ZSM-5 samples with different Si/Al ratios, using ultrahigh field 27 Al NMR (22.3 T), 29 Si NMR, X-ray diffraction, and IR spectroscopy. 27 Al MQMAS NMR at 22.3 T allows identification and quantification of 10 distinct tetrahedral framework resonances which are assigned to the crystallographic sites by their average T−O−T angles, determined from powder XRD patterns for the same samples. A clear Al site preference is observed and found to be dependent on the Si/Al ratio of the parent zeolite. The framework sites facing the intersections in ZSM-5 are found to be most prone to dealumination, whereas Al in the straight and sinusoidal-shaped channels are more stable toward steam treatment at high temperatures. Extra-framework Al species with 5-and 6-fold coordination and two distorted tetrahedral AlO 4 sites have also been identified. The spectroscopic data are supported by catalytic activities from α-test cracking experiments which are in accordance with a reinsertion of Al in the framework at mild steaming and the onset of dealumination at higher temperatures.
The effect of the gas phase during solid-state ion-exchange of copper into zeolites was studied by exposing physical mixtures of copper oxides (Cu I 2 O and Cu II O) and zeolites (MFI, *BEA, and CHA) to various combinations of NO, NH 3 , O 2 , and H 2 O. It is shown that heating these mixtures to 250 °C results in active catalysts for the selective catalytic reduction of NO with NH 3 (NH 3 -SCR), indicating that the Cu has become mobile at that temperature. Such treatment allows for a fast (<5−10 h) preparation of copper-exchanged zeolites. Scanning transmission electron microscopy analysis of Cu-CHA prepared using this method shows homogeneous distribution of the Cu in the primary particles of the zeolite. In situ XRD reveals that the Cu ion-exchange is related to the formation of Cu I 2 O. When the zeolite is mixed with Cu II O, addition of NO to the NH 3 -containing gas phase enhances the formation of Cu I 2 O and the Cu ion-exchange. The mobility of Cu at low temperatures is proposed to be related to the formation of [Cu I (NH 3 ) x ] + (x ≥ 2) complexes.
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