Unexpected Promotion Effect of H2O on the Selective Catalytic Reduction of NOx with NH3 over Cu-SSZ-39 Catalysts.

Water molecules commonly inhibit the selective catalytic reduction (SCR) of NOx with NH3 on most catalysts, and water resistance is a long-standing challenge for SCR technology. Herein, by combining experimental measurements and density functional theory (DFT) calculations, we found that water molecules do not inhibit and even promote the NOx conversion to some extent over the Cu-SSZ-39 zeolites, a promising SCR catalyst. Water acting as a ligand on active Cu sites and as a reactant in the SCR reaction significantly improves the O2 activation performance and reduces the overall energy barrier of the catalytic cycle. This work unveils the mechanism of the unexpected promotion effect of water on the NH3-SCR reaction over Cu-SSZ-39 and provides fundamental insight into the development of zeolite-based SCR catalysts with excellent activity and water resistance.

Hydrogenation of CO2 to Light Olefins over ZnZrOx /SSZ-13.

Converting CO2 to olefins is an ideal route to achieve carbon neutrality. However, selective hydrogenation to light olefins, especially single-component olefin, while reducing CH4 formation remains a great challenge. Herein, we developed ZnZrOx /SSZ-13 tandem catalyst for the highly selective hydrogenation of CO2 to light olefins. This catalyst shows C2 = -C4 = and propylene selectivity up to 89.4 % and 52 %, respectively, while CH4 is suppressed down to 2 %, and there is no obvious deactivation. It is demonstrated that the isolated moderate Brønsted acid sites (BAS) of SSZ-13 promotes the rapid conversion of intermediate species derived from ZnZrOx , thereby enhancing the kinetic coupling of the reactions and inhibit the formation of alkanes and improve the light olefins selectivity. Besides, the weaker BAS of SSZ-13 promote the conversion of intermediates into aromatics with 4-6 methyl groups, which is conducive to the aromatics cycle. Accordingly, more propene can be obtained by elevating the Si/Al ratio of SSZ-13. This provides an efficient strategy for CO2 hydrogenation to light olefins with high selectivity.

Economical and Sustainable Synthesis of Small-Pore Chabazite Catalysts for NOx Abatement by Recycling Organic Structure-Directing Agents.

The application of small-pore chabazite-type SSZ-13 zeolites, key materials for the reduction of nitrogen oxides (NOx) in automotive exhausts and the selective conversion of methane, is limited by the use of expensive N,N,N-trimethyl-1-ammonium adamantine hydroxide (TMAdaOH) as an organic structure-directing agent (OSDA) during hydrothermal synthesis. Here, we report an economical and sustainable route for SSZ-13 synthesis by recycling and reusing the OSDA-containing waste liquids. The TMAdaOH concentration in waste liquids, determined by a bromocresol green colorimetric method, was found to be a key factor for SSZ-13 crystallization. The SSZ-13 zeolite synthesized under optimized conditions demonstrates similar physicochemical properties (surface area, porosity, crystallinity, Si/Al ratio, etc.) as that of the conventional synthetic approach. We then used the waste liquid-derived SSZ-13 as the parent zeolite to synthesize Cu ion-exchanged SSZ-13 (i.e., Cu-SSZ-13) for ammonia-mediated selective catalytic reduction of NOx (NH3-SCR) and observed a higher activity as well as better hydrothermal stability than Cu-SSZ-13 by conventional synthesis. In situ infrared and ultraviolet-visible spectroscopy investigations revealed that the superior NH3-SCR performance of waste liquid-derived Cu-SSZ-13 results from a higher density of Cu2+ sites coordinated to paired Al centers on the zeolite framework. The technoeconomic analysis highlights that recycling OSDA-containing waste liquids could reduce the raw material cost of SSZ-13 synthesis by 49.4% (mainly because of the higher utilization efficiency of TMAdaOH) and, meanwhile, the discharging of wastewater by 45.7%.

Hydrothermal Aging Alleviates the Phosphorus Poisoning of Cu-SSZ-39 Catalysts for NH3-SCR Reaction.

As a new type of catalyst with the potential for commercial application in NOx removal from diesel engine exhausts, Cu-SSZ-39 catalysts must have excellent resistance to complex and harsh conditions. In this paper, the effects of phosphorus on Cu-SSZ-39 catalysts before and after hydrothermal aging treatment were investigated. Compared with fresh Cu-SSZ-39 catalysts, phosphorus poisoning significantly decreased the low-temperature NH3-SCR catalytic activity. However, such activity loss was alleviated by further hydrothermal aging treatment. To reveal the reason for this interesting result, a variety of characterization techniques including NMR, H2-TPR, X-ray photoelectron spectroscopy, NH3-TPD, and in situ DRIFTS measurements were employed. It was found that Cu-P species produced by phosphorus poisoning decreased the redox ability of active copper species, resulting in the observed low-temperature deactivation. After hydrothermal aging treatment, however, Cu-P species partly decomposed with the formation of active CuOx species and a release of active copper species. As a result, the low-temperature NH3-SCR catalytic activity of Cu-SSZ-39 catalysts was recovered.

Na Cocations and Hydrothermal Aging Cooperatively Boost the Regeneration of Phosphorus-Poisoned Pd/SSZ-13 for Passive NOx Adsorption.

Pd/SSZ-13 has been proposed as a passive NOx adsorber (PNA) for low-temperature NOx adsorption. However, it remains challenging for Pd/SSZ-13 to work efficiently when suffering from phosphorus poisoning. Herein, we report a simple and efficient strategy to regenerate the phosphorus-poisoned Pd/SSZ-13 based on the cooperation between hydrothermal aging treatment and Na cocations. It was found that hydrothermal aging treatment enabled the redispersion of Pd and P-containing species in phosphorus-poisoned Pd/SSZ-13. Meanwhile, the presence of Na cocations significantly reduced the formation of AlPO4 and retained more paired Al sites for highly dispersed Pd2+ ions, which was of great importance for the recovery of adsorption performance. To our satisfaction, the restoration ratio of the adsorption capacity of poisoned Pd/SSZ-13 was >90% after regeneration. Strikingly, the NOx adsorption activities of phosphorus-poisoned Pd/SSZ-13 with phosphorus loadings of 0.2 and 0.4 mmol g-1 almost completely recovered upon regeneration. This study demonstrates the promoting effect of Na cocations on the regeneration of phosphorus-poisoned Pd/SSZ-13 by hydrothermal aging treatment, which provides useful guidance for the design of PNA materials with excellent durability for cold-start application.

The impact of a csDMARD in combination with a TNF inhibitor on drug retention and clinical remission in axial spondyloarthritis.

OBJECTIVES: Many axial spondylarthritis (axSpA) patients receive a conventional synthetic DMARD (csDMARD) in combination with a TNF inhibitor (TNFi). However, the value of this co-therapy remains unclear. The objectives were to describe the characteristics of axSpA patients initiating a first TNFi as monotherapy compared with co-therapy with csDMARD, to compare one-year TNFi retention and remission rates, and to explore the impact of peripheral arthritis. METHODS: Data was collected from 13 European registries. One-year outcomes included TNFi retention and hazard ratios (HR) for discontinuation with 95% CIs. Logistic regression was performed with adjusted odds ratios (OR) of achieving remission (Ankylosing Spondylitis Disease Activity Score (ASDAS)-CRP < 1.3 and/or BASDAI < 2) and stratified by treatment. Inter-registry heterogeneity was assessed using random-effect meta-analyses, combined results were presented when heterogeneity was not significant. Peripheral arthritis was defined as ≥1 swollen joint at baseline (=TNFi start). RESULTS: Amongst 24 171 axSpA patients, 32% received csDMARD co-therapy (range across countries: 13.5% to 71.2%). The co-therapy group had more baseline peripheral arthritis and higher CRP than the monotherapy group. One-year TNFi-retention rates (95% CI): 79% (78, 79%) for TNFi monotherapy vs 82% (81, 83%) with co-therapy (P < 0.001). Remission was obtained in 20% on monotherapy and 22% on co-therapy (P < 0.001); adjusted OR of 1.16 (1.07, 1.25). Remission rates at 12 months were similar in patients with/without peripheral arthritis. CONCLUSION: This large European study of axial SpA patients showed similar one-year treatment outcomes for TNFi monotherapy and csDMARD co-therapy, although considerable heterogeneity across countries limited the identification of certain subgroups (e.g. peripheral arthritis) that may benefit from co-therapy.

Revealing the Synergistic Deactivation Mechanism of Hydrothermal Aging and SO2 Poisoning on Cu/SSZ-13 under SCR Condition.

In real-world application, Cu/SSZ-13 simultaneously suffers severe deactivation from hydrothermal aging and SO2 poisoning during the periodic regeneration of diesel particulate filter (DPF). Herein, we first investigated the synergistic deactivation mechanism of hydrothermal aging and SO2 poisoning on Cu/SSZ-13 under SCR condition. Hydrothermal aging alone induces more severe degradation of selective catalytic reduction (SCR) performance than SO2 poisoning alone, while the presence of SO2 during hydrothermal aging causes further worse SCR performance compared with hydrothermal aging alone. Hydrothermal aging not only damages Si-OH-Al sites, particularly in four-membered ring (4MR) of the CHA cage, but also brings the conversion of ZCuOH, leading to the formation of inactive CuO/CuAlOx species. By contrast, SO2 poisoning alone is more prone to promote the transformation of ZCuOH to Z2Cu. Synergistic deactivation of hydrothermal aging and SO2 poisoning would exacerbate the damage of Si-OH-Al sites and then the formation of CuO/CuAlOx species. These results are expected to assist the knowledge-based catalyst design for diesel aftertreatment applications.

Si/Al Ratio Determines the SCR Performance of Cu-SSZ-13 Catalysts in the Presence of NO2.

A comparative study was performed to investigate the NH3-selective catalytic reduction (SCR) reaction activity of Cu-SSZ-13 zeolites having Si/Al ratios (SARs) of 5, 18, and 30. Remarkably, the Cu-SSZ-13 zeolite catalysts exhibited completely opposite behaviors as a function of SAR under standard SCR (SSCR) and fast SCR (FSCR) reaction atmospheres. Under SSCR conditions, the NOx conversion increased as expected with the decreasing SAR. Under FSCR conditions, however, the NOx conversion decreased as the SAR decreased, contrary to expectations. In this study, based on characterization of the catalysts by X-ray diffraction, transmission electron microscopy, electron paramagnetic resonance, H2-temperature-programmed reduction, temperature-programmed desorption, and diffuse reflectance infrared Fourier transform spectroscopy, together with theoretical calculations, the authors found that the amount of Brønsted acid sites goes up while the SAR goes down, leading to an increase in the accumulation of NH4NO3 under FSCR reaction conditions. Moreover, the accumulated NH4NO3 is of greater stability for those low SAR Cu-SSZ-13 catalysts. These two reasons cause the FSCR performance of Cu-SSZ-13 to decrease with a decrease in SAR. As a result, the NO2 effect on SCR activity changes from promotion to inhibition as the SAR decreases.

First-line csDMARD monotherapy drug retention in psoriatic arthritis: methotrexate outperforms sulfasalazine.

OBJECTIVES: Conventional synthetic DMARDs (csDMARDs) are the first-line treatment for PsA, but there is conflicting data regarding their efficacy and scarce reports describing the duration of use (drug retention) of csDMARD in this population. Their position in treatment recommendations is a matter of growing debate due to the availability of alternative treatment options with higher levels of evidence. We aimed to study drug retention and predictors for drug retention among PsA patients receiving first-line csDMARD monotherapy. METHODS: Retrospective cohort study in DMARD-naïve adult PsA patients in whom a first csDMARD was prescribed as monotherapy primarily to treat PsA-related symptoms. The main outcome was time to failure of the csDMARD (i.e. stopping the csDMARD or adding another DMARD). RESULTS: A total of 187 patients were included, who were mainly prescribed MTX (n = 163) or SSZ (n = 21). The pooled median drug retention time was 31.8 months (interquartile range 9.04-110). Drug retention was significantly higher in MTX (median 34.5 months; interquartile range 9.60-123) as compared with SSZ-treated patients (median 12.0 months; interquartile range 4.80- 55.7) (P =0.016, log-rank test). In multivariable Cox regression, the use of MTX and older age were associated with increased retention. The main reasons for treatment failure were inefficacy (52%) and side effects (28%). Upon failure, MTX treated patients were more commonly, subsequently treated with a biologic DMARD compared with SSZ (P < 0.05). CONCLUSION: MTX outperforms SSZ as a first-line csDMARD in DMARD-naïve PsA patients with respect to monotherapy drug retention in daily clinical practice.

Reaction Pathways of Standard and Fast Selective Catalytic Reduction over Cu-SSZ-39.

Cu-SSZ-39 exhibits excellent hydrothermal stability and is expected to be used for NOx purification in diesel vehicles. In this work, the selective catalytic reduction (SCR) activities in the presence or absence of NO2 were tested over Cu-SSZ-39 catalysts with different Cu contents. The results showed that the NOx conversion of Cu-SSZ-39 was improved by NO2 when NO2/NOx = 0.5, especially for the catalysts with low Cu loadings. The kinetic studies showed two kinetic regimes for fast SCR from 150 to 220 °C due to a change in the rate-controlling mechanism. The activity test and diffuse reflectance infrared Fourier transform spectra demonstrated that the reduction of NO mainly occurred on the Cu species in the absence of feed NO2, and when NO2/NO = 1, NO could react with NH4NO3 on the Brønsted acid sites in addition to undergoing reduction on Cu species. Thus, NO2 can promote the SCR reaction over Cu-SSZ-39 by facilitating the formation of surface nitrate species.

Relationship between different anti-rheumatic drug therapies and complementary and alternative medicine in patients with rheumatoid arthritis: an interview based cross-sectional study.

OBJECTIVES: The use of complementary and alternative medicine (CAM) by patients with rheumatoid arthritis (RA) is highly prevalent. The relationship of these remedies with disease therapy are not fully studied. We aimed to explore the relationship between different anti-rheumatic drug therapy and CAM use in RA patients. METHODS: The study used an interview-based cross-sectional survey in two major referral centres in Riyadh, Saudi Arabia. Patients were adults with confirmed RA that attended rheumatology clinics. Information on the utilization of CAM, RA duration, drug therapy, and laboratory parameters were obtained. Descriptive statistics as well as adjusted odds ratio using bivariate logistic regression were used to explore the different factors related to CAM use, including drug therapy. RESULTS: A total of 438 adult patients with RA were included. The mean (±SD) age of the patients was 49 (±15.0) years. The majority were women 393 (89.7%). Two hundred and ninety-two patients (66.7%) had used CAM. The CAM users who had a longer disease duration (AOR 1.041 [95% CI: 1.011, 1.073]; p = 0.008) were more likely to be female (AOR 2.068 [95% CI: 1.098, 3.896]; p = 0.024), and use methotrexate (AOR 1.918 [95% CI: 1.249, 2.946]; p = 0.003) as opposed to celecoxib (AOR 0.509 [95% CI: 0.307, 0.844]; p = 0.009) and biologic monotherapy (AOR 0.443 [95% CI: 0.224, 0.876]; p = 0.019). Other factors related to CAM were meloxicam use (AOR 2.342 [95% CI: 1.341, 4.089]; p = 0.003) and traditional therapy (AOR 2.989 [95% CI: 1.647, 5.425]; p = 0.000). The remaining factors were not significant. CONCLUSION: CAM use is prevalent in patients with RA. Understanding patients and disease related factors associated with higher use of CAM is warranted to improve RA management and provide more rational use of these remedies.

One-pot synthesis of Fe/Cu-SSZ-13 catalyst and its highly efficient performance for the selective catalytic reduction of nitrogen oxide with ammonia.

Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy. The obtained catalysts were subjected to selective catalytic reduction (SCR) of NOx with NH3 and were characterized by various techniques. The results show that Fe0.63/Cu1.50-SSZ-13 catalyst with proper Fe content exhibits excellent catalytic activity with widest operation temperature window from 160 to 580°C, excellent hydrothermal stability as well as good resistance to sulfur poisoning when compared with Cu-SSZ-13, signifying its great potential for practical applications. Further characterizations reveal that the synthesized Fe/Cu-SSZ-13 catalysts present typical chabazite (CHA) structure with good crystallinity, while isolated Cu2+ and monomeric Fe3+ are revealed as the predominant copper and iron species. At low temperatures, isolated Cu2+ species act as primary active sites for SCR reaction, while monomeric Fe3+ species provide sufficient active sites for sustain the SCR activity at high temperature. Moreover, Fe over doping would lead to the damage of zeolite structure, destruction of isolated Cu2+ site, as well as the formation of highly oxidizing Fe2O3, thus causing deterioration of catalytic performances.

Effect of preparation methods on the performance of CuFe-SSZ-13 catalysts for selective catalytic reduction of NOx with NH3.

CuFe-SSZ-13 catalyst showed excellent performance in the selective catalytic reduction of NOx with NH3 (NH3-SCR) for diesel engine exhaust purification. To investigate the effect of preparation methods on NH3-SCR performance, Fe was loaded into one-pot synthesized Cu-SSZ-13 catalysts through solid-state ion-exchange (SSIE), homogeneous deposition precipitation (HDP) and liquid ion-exchange (IE), respectively. Three CuFe-SSZ-13 catalysts showed similar SO2 resistance, which was better than that of Cu-SSZ-13. The improvement was attributed to the protection of Fe species. Hydrothermal stability of three CuFe-SSZ-13 catalysts was significantly different, which was attributed to the state of active species caused by different preparation methods. Compared with the other two catalysts, more active species existed inside the zeolite pores of CuFe-SSZ-13SSIE. During hydrothermal aging, the aggregation of these active species in the pores caused the collapse of catalyst structure, ultimately leading to the deactivation of CuFe-SSZ-13SSIE. In contrast, Fe species was dispersed better on the surface over CuFe-SSZ-13IE, enhancing the hydrothermal stability of catalysts. Consequently, Fe loading effectively improved the resistance of SO2 and H2O over Cu-SSZ-13. For CuFe-SSZ-13, large amounts of active species located inside the zeolite pores are not beneficial for the hydrothermal stability.

SSZ-27: A Small-Pore Zeolite with Large Heart-Shaped Cavities Determined by Using Multi-crystal Electron Diffraction.

The high-silica zeolite SSZ-27 was synthesized using one of the isomers of the organic structure-directing agent that is known to produce the large-pore zeolite SSZ-26 (CON). The structure of the as-synthesized form was solved using multi-crystal electron diffraction data. Data were collected on eighteen crystals, and to obtain a high-quality and complete data set for structure refinement, hierarchical cluster analysis was employed to select the data sets most suitable for merging. The framework structure of SSZ-27 can be described as a combination of two types of cavities, one of which is shaped like a heart. The cavities are connected through shared 8-ring windows to create straight channels that are linked together in pairs to form a one-dimensional channel system. Once the framework structure was known, molecular modelling was used to find the best fitting isomer, and this, in turn, was isolated to improve the synthesis conditions for SSZ-27.

Template-Free Synthesis of Hierarchical SSZ-13 Microspheres with High MTO Catalytic Activity.

Hierarchical SSZ-13 microspheres, with abundant mesoporous channels, have been successfully synthesized by addition of calcined SSZ-13 crystals in the starting gel in the absence of any organic templates. This strategy not only remarkably reduces the production cost and environmental pollution, but also significantly decreases the crystallization time as well as evidently reducing the zeolite crystal sizes in many cases. The synthesized sample was characterized by XRD, BET, ICP, SEM, TEM, TG, and NH3 -TPD, which indicates that the organic template free synthesized SSZ-13 exhibits high crystallinity, textural properties, and acidity. Moreover, the synthesized hierarchical SSZ-13 catalyst shows outstanding performance in the methanol-to-olefin (MTO) reaction, with slightly higher ethylene plus propylene selectivity and prolonged catalyst lifetime as compared to the templated SSZ-13 catalyst.

Can Dynamics Be Responsible for the Complex Multipeak Infrared Spectra of NO Adsorbed to Copper(II) Sites in Zeolites?

Copper-exchanged SSZ-13 is a very efficient material in the selective catalytic reduction of NO(x) using ammonia (deNO(x)-SCR) and characterizing the underlying distribution of copper sites in the material is of prime importance to understand its activity. The IR spectrum of NO adsorbed to divalent copper sites are modeled using ab initio molecular dynamics simulations. For most sites, complex multi-peak spectra induced by the thermal motion of the cation as well as the adsorbate are found. A finite temperature spectrum for a specific catalyst was constructed, which shows excellent agreement with previously reported data. Additionally these findings allow active and inactive species in deNO(x)-SCR to be identified. To the best of our knowledge, this is the first time such complex spectra for single molecules adsorbed to single active centers have been reported in heterogeneous catalysis, and we expect similar effects to be important in a large number of systems with mobile active centers.

Unraveling the NH3-SCR-DeNOx Mechanism of Cu-SSZ-13 Variants by Spectroscopic and Transient Techniques.

Commercial SSZ-13 zeolite with different n(Si)/n(Al) ratios and from different suppliers were subjected to a post-synthetic treatment in order to create mesopores of up to 10 nm. Furthermore, the materials were modified with copper ions and thoroughly physico-chemically characterized. The modified textural properties varied the nature of copper species, and thus, activity in the selective catalytic reduction of NOx with ammonia (NH3-SCR-DeNOx). Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) studies with hexane as probe liquid revealed improved intracrystalline diffusion for some Cu-containing SSZ-13 materials. The NH3-SCR-DeNOx pathway is verified viain situ DR UV-Vis, in situ FT-IR and EPR, temperature-programmed studies as well as SSITKA studies that provide a mechanistic understanding of the reaction. Kinetic modelling results demonstrate the highest NH3-SCR-DeNOx reaction rates and up to 20 % lower energy barriers with n(Si)/n(Al) ratio of 6.5 for all modified forms (i.e., (NH4)Cu-SSZ-13_6.5 and Cu-SSZ-13_6.5_NaOH/0.1) and cause only negligible parasitic ammonia oxidation. The modelling of the stop-flow experiments further demonstrates that the SCR pathway via the HONO surface intermediate is present but barely contributes to the overall NO conversion compared to the dominant path between adsorbed NH3 and NO from the gas phase.

Synthesis and Neurobehavioral Evaluation of a Potent Multitargeted Inhibitor for the Treatment of Alzheimer's Disease.

Alzheimer's disease (AD) poses a significant health challenge worldwide, affecting millions of individuals, and projected to increase further as the global population ages. Current pharmacological interventions primarily target acetylcholine deficiency and amyloid plaque formation, but offer limited efficacy and are often associated with adverse effects. Given the multifactorial nature of AD, there is a critical need for novel therapeutic approaches that simultaneously target multiple pathological pathways. Targeting key enzymes involved in AD pathophysiology, such as acetylcholinesterase, butyrylcholinesterase, beta-site APP cleaving enzyme 1 (BACE1), and gamma-secretase, is a potential strategy to mitigate disease progression. To this end, our research group has conducted comprehensive in silico screening to identify some lead compounds, including IQ6 (SSZ), capable of simultaneously inhibiting the enzymes mentioned above. Building upon this foundation, we synthesized SSZ, a novel multitargeted ligand/inhibitor to address various pathological mechanisms underlying AD. Chemically, SSZ exhibits pharmacological properties conducive to AD treatment, featuring pyrrolopyridine and N-cyclohexyl groups. Preclinical experimental evaluation of SSZ in AD rat model showed promising results, with notable improvements in behavioral and cognitive parameters. Specifically, SSZ treatment enhanced locomotor activity, ameliorated gait abnormalities, and improved cognitive function compared to untreated AD rats. Furthermore, brain morphological analysis demonstrated the neuroprotective effects of SSZ, attenuating Aß-induced neuronal damage and preserving brain morphology. Combined treatment of SSZ and conventional drugs (DON and MEM) showed synergistic effects, suggesting a potential therapeutic strategy for AD management. Overall, our study highlights the efficacy of multitargeted ligands like SSZ in combating AD by addressing the complex etiology of the disease. Further research is needed to elucidate the full therapeutic potential of SSZ and the exploration of similar compounds in clinical settings, offering hope for an effective AD treatment in the future.

Improving Copper Active Site Speciation on Cu-Ce/SSZ-13 for Ammonia Oxidation via Si/Al Ratio Modulation.

Catalytic oxidation is a promising purification technique for ammonia (NH3) emission. However, high ignition temperatures and NOx peroxide generation limit its effectiveness due to a lack of active sites. Herein, the effects of Si/Al ratio (SAR) modulation on the speciation of copper active sites and the reaction mechanism at different acidic sites were investigated by loading CuO-CeO2 onto SSZ-13 with different SARs (Cu-Ce/SAR15, 20, and 30). Among them, Cu-Ce/SAR20 exhibits the lowest induction temperature (T20 = 180 °C) and the highest nitrogen selectivity (above 95%), attributing to a higher number of Cu2+ exchange sites. In situ IR spectroscopy and isotopic (18O2) transient response experiments indicate that more active Cu2+ in Cu-Ce/SAR20 provides sufficient Lewis acidic sites for NH3 adsorption and favors the stability of Si-OH-Al structures (Brønsted acid sites). NH3 adsorbed at Lewis acidic sites tends to form peroxide byproducts (NOx), while the NH4+ adsorbed at Brønsted acidic sites generates the key intermediate NH4NO2, which decomposes to N2 at high temperatures, thus enhancing nitrogen selectivity. The whole process mainly follows the Mars-van Krevelen (M-K) mechanism, with the Langmuir-Hinshelwood (L-H) mechanism playing a supporting role. Z2Cu2+ coordinates with adjacent Al atoms within the six-membered ring (6MR) and undergoes a slight deformation at high temperatures, facilitating the migration of the lattice oxygen. SAR plays a crucial role in local environmental speciation of reactive Cu2+, where the sufficient isolated Al provided in SAR20 pulls Cu2+ into the eight-membered ring (8MR), allowing it to come into contact with NH3 more readily.

Novel insights on the Pd speciation in Pd/SSZ-13 and on the role of H2O in the Pd reduction by CO.

Pd speciation induced by the combined effect of CO and water on Pd/SSZ-13 samples prepared by both impregnation and ion exchange was examined by FT-IR spectroscopy of CO adsorbed at room temperature and at liquid nitrogen temperature on anhydrous and hydrated samples. Starting from the literature findings related to the CO reducing effect on Pd cations, the present work gives precise spectroscopic evidences on how water is necessary in this process not only for compensating with H+ the zeolite exchange sites set free by Pd reduction, but also for mobilizing isolated Pd2+/Pd+ cations and making possible the reduction reactions. The aggregation of some Pd+ sites, just formed by the reduction and mobilized by the hydration, gives rise to the formation of Pd2O particles. Also, Pd0(100) sites are observed with CO on hydrated sample, formed by the aggregation and reduction of isolated Pd cations. Moreover, Pd0(111) sites are formed on the surface of PdOx particles during CO outgassing. The observation of the combined effect of water and CO allowed to define assignments of IR bands related to carbonyls of Pd in different oxidation states and coordination degrees.