Unraveling the mysterious failure of Cu/SAPO-34 selective catalytic reduction catalysts.

Commercial Cu/SAPO-34 selective catalytic reduction (SCR) catalysts have experienced unexpected and quite perplexing failure. Understanding the causes at an atomic level is vital for the synthesis of more robust Cu/SAPO-34 catalysts. Here we show, via application of model catalysts with homogeneously dispersed isolated Cu ions, that Cu transformations resulting from low-temperature hydrothermal aging and ambient temperature storage can be semi-quantitatively probed with 2-dimensional pulsed electron paramagnetic resonance. Coupled with kinetics, additional material characterizations and DFT simulations, we propose the following catalyst deactivation steps: (1) detachment of Cu(II) ions from cationic positions in the form of Cu(OH)2; (2) irreversible hydrolysis of the SAPO-34 framework forming terminal Al species; and (3) interaction between Cu(OH)2 and terminal Al species forming SCR inactive, Cu-aluminate like species. Especially significant is that these reactions are greatly facilitated by condensed water molecules under wet ambient conditions, causing low temperature failure of the commercial Cu/SAPO-34 catalysts.

Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis.

Active centers in Cu/SSZ-13 selective catalytic reduction (SCR) catalysts have been recently identified as isolated Cu2+ and [CuII(OH)]+ ions. A redox reaction mechanism has also been established, where Cu ions cycle between CuI and CuII oxidation states during SCR reaction. While the mechanism for the reduction half-cycle (CuII → CuI) is reasonably well-understood, that for the oxidation half-cycle (CuI → CuII) remains an unsettled debate. Herein we report detailed reaction kinetics on low-temperature standard NH3-SCR, supplemented by DFT calculations, as strong evidence that the low-temperature oxidation half-cycle occurs with the participation of two isolated CuI ions via formation of a transient [CuI(NH3)2]+-O2-[CuI(NH3)2]+ intermediate. The feasibility of this reaction mechanism is confirmed from DFT calculations, and the simulated energy barrier and rate constants are consistent with experimental findings. Significantly, the low-temperature standard SCR mechanism proposed here provides full consistency with low-temperature SCR kinetics.

Characterization of Fe²âº ions in Fe,H/SSZ-13 zeolites: FTIR spectroscopy of CO and NO probe molecules.

The IR spectra of adsorbed CO and NO probe molecules were used to characterize the coordination chemistry of Fe(2+) ions in solution ion exchanged Fe,H/SSZ-13 zeolites. The effects of Fe ion exchange levels, as well as the sample pre-treatment conditions, on the adsorption of these probe molecules were investigated. The ion exchange levels (in the range of the study) did not affect significantly the IR spectra of either probe molecule, and the IR features and their intensity ratios were very similar. Experiments with both probe molecules substantiated the presence of two distinct types of Fe(2+) ions in cationic positions. We assign these two Fe(2+) ions to two distinct cationic positions: Fe(2+) in 6R and 8R positions. NO initially adsorbs preferentially onto Fe(2+) sites in the 6R position, and then populates sites in the 8R. Fe(2+) ions in the 8R positions require the interaction of more than one NO molecule to move them out from their adsorbate-free cationic positions. As soon as they move from their stable positions, they are able to bind to multiple NO molecules, and form mostly tri-nitrosyls. These tri-nitrosyls, however, are only stable in the presence of gas phase NO; under dynamic vacuum they lose one of the NO molecules from their coordination sphere and form stable di-nitrosyls. The adsorption of CO is much weaker on Fe(2+) sites than that of NO, and requires cryogenic sample temperatures to initiate CO adsorption. Under the conditions applied in this study, only mono-carbonyl formation was observed. Reduction in H2 at 773 K increased the number of Fe(2+) adsorption sites, primarily in the 8R locations. Oxidation by N2O, on the other hand, selectively reduced the adsorption of both CO and NO on the Fe(2+) sites in 8R positions. Adsorbed oxygen left behind from the decomposition of N2O at 573 K readily reacted with CO to produce CO2 even at 150 K.

Sealed rotors for in situ high temperature high pressure MAS NMR.

Here we present the design of reusable and perfectly sealed all-zirconia MAS rotors. The rotors are used to study AlPO4-5 molecular sieve crystallization under hydrothermal conditions, high temperature high pressure cyclohexanol dehydration reaction, and low temperature metabolomics of intact biological tissue.

Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina.

Catalysis by single isolated atoms of precious metals has attracted much recent interest, as it promises the ultimate in atom efficiency. Most previous reports are on reducible oxide supports. Here we show that isolated palladium atoms can be catalytically active on industrially relevant γ-alumina supports. The addition of lanthanum oxide to the alumina, long known for its ability to improve alumina stability, is found to also help in the stabilization of isolated palladium atoms. Aberration-corrected scanning transmission electron microscopy and operando X-ray absorption spectroscopy confirm the presence of intermingled palladium and lanthanum on the γ-alumina surface. Carbon monoxide oxidation reactivity measurements show onset of catalytic activity at 40 °C. The catalyst activity can be regenerated by oxidation at 700 °C in air. The high-temperature stability and regenerability of these ionic palladium species make this catalyst system of potential interest for low-temperature exhaust treatment catalysts.

Stable platinum nanoparticles on specific MgAl2O4 spinel facets at high temperatures in oxidizing atmospheres.

The development of thermally stable, nanometer-sized precious metal-based catalysts remains a daunting challenge. Such materials, especially those based on the use of costly platinum metal, are essential and, to date, non-replaceable for a large number of industrially important catalytic processes. Here we report a well-defined cuboctahedral MgAl2O4 spinel support material that is capable of stabilizing platinum particles in the range of 1-3 nm on its relatively abundant {111} facets during extremely severe aging at 800 °C in air for 1 week. The aged catalysts retain platinum dispersions of 15.9% with catalytic activities for methanol oxidation being ~80% of that of fresh ones, whereas a conventional Pt/γ-Al2O3 catalyst is severely sintered and nearly inactive. We reveal the origin of the markedly superior ability of spinel {111} facets, resulting from strong interactions between spinel surface oxygens and epitaxial platinum {111} facets, inspiring the rational design of anti-sintering supported platinum group catalysts.

A common intermediate for N2 formation in enzymes and zeolites: side-on Cu-nitrosyl complexes.

Side on! Combined FTIR and NMR studies revealed the presence of a side-on nitrosyl species in the zeolite Cu-SSZ-13. This intermediate is very similar to those found in nitrite reductase enzyme systems. The identification of this intermediate led to the proposal of a reaction mechanism that is fully consistent with the results of both kinetic and spectroscopic studies.

Characterization of Cu-SSZ-13 NH3 SCR catalysts: an in situ FTIR study.

The adsorption of CO and NO over Cu-SSZ-13 zeolite catalysts, highly active in the selective catalytic reduction of NO(x) with NH(3), was investigated by FTIR spectroscopy, and the results obtained were compared to those collected from other Cu-ion exchanged zeolites (Y,FAU and ZSM-5). Under low CO pressures and at room temperature (295 K), CO forms monocarbonyls exclusively on the Cu(+) ions, while in the presence of gas phase CO dicarbonyls on Cu(+) and adsorbed CO on Cu(2+) centers form, as well. At low (cryogenic) sample temperatures, tricarbonyl formation on Cu(+) sites was also observed. The adsorption of NO produces IR bands that can be assigned to nitrosyls bound to both Cu(+) and Cu(2+) centers, and NO(+) species located in charge compensating cationic positions of the chabasite framework. On the reduced Cu-SSZ-13 samples the formation of N(2)O was also detected. The assignment of the adsorbed NO(x) species was aided by adsorption experiments with isotopically labeled (15)NO. The movement of Cu ions from the sterically hindered six member ring position to the more accessible cavity positions as a result of their interaction with adsorbates (NO and H(2)O) was clearly evidenced. Comparisons of the spectroscopy data obtained in the static transmission IR system to those collected in the flow-through diffuse reflectance cell points out that care must be taken when general conclusions are drawn about the adsorptive and reactive properties of metal cation centers based on a set of data collected under well defined, specific experimental conditions.

Two different cationic positions in Cu-SSZ-13?

H(2)-TPR and FTIR were used to characterize the nature of the Cu ions present in the Cu-SSZ-13 zeolite at different ion exchange levels. The results obtained are consistent with the presence of Cu ions at two distinct cationic positions in the SSZ-13 framework.