Storage Material Effects on the Performance of Ru-Based CO2 Capture and Methanation Dual Functioning Materials

In this study, a systematic investigation on Dual Functioning Materials (DFMs) for the capture and methanation of CO₂ is carried out. The attention is focused on the nature of the CO₂ adsorbent component (storage material, SM) varying between alkaline (Li, Na, K) and alkaline-earth (Mg, Ca, Ba) metal oxides in combination with Ru, both supported on an Al₂O₃ support. Combining gas phase reactivity analysis and FT-IR characterization, the samples are characterized in terms of CO₂ storage capacity. It is found that all the SM-containing samples adsorb significant amounts of CO₂ as carbonate species, with the higher amounts being adsorbed when the more thermally stable species are formed, i.e., when Ca, Ba, or K are employed as SMs. In all cases, the hydrogenation of the adsorbed carbonates to CH₄ occurs at lower temperature, if compared to their thermal desorption. However, in the case of Ca- and Ba-based DFMs, resilient carbonates are present on the material surface. It was found that the SMs able to form the more thermally stable carbonates upon CO₂ adsorption also showed the best performances in capture/methanation cycles at 350 °C, even if some residual carbonates were left on the DFM after the hydrogenation step. In particular, the following order of reactivity has in fact been observed in terms of CH₄ production: Ru–K ≥ Ru–Ba > Ru–Ca > Ru–Na ≫ Ru–Mg ≅ Ru–Li ≅ Ru. The presence of steam and O₂ during the capture step has a detrimental effect on the CO₂ adsorption for all samples and, as a result, on CH₄ production due to the competition of CO₂ and water for the same adsorption sites. Thus, only SMs able to form strongly bound carbonates species upon CO₂ exposure can retain significant CO₂ storage capacity also in the presence of water in the adsorption feed

Ceria-based catalysts for NOx removal in NSR processes: A fundamental study of the catalyst modifications explored by in situ techniques

In this work, a fundamental and systematic study was conducted, leading to a better understanding of the phenomena occurring on the catalyst’s surface during the NOx reduction process in NSR systems. For this purpose, ceria-based catalysts, with Cu in substitution of noble metal, have been synthesized and deeply characterized by means of XRF, XPS, in situ (XRD, Raman spectroscopy and DRIFTS), temperature-programmed reduction under H2 (H2-TPR) and under NO reaction (NO isothermal reaction + NO-TPR). The whole results show the key role of copper to promote the reducibility and the creation of oxygen vacancies, allowing a high NO consumption and fast kinetics of N2O and N2 formation, until the oxygen vacancies consumption takes place. The study of the surface reactions taking place in the formation of adsorbed NOx species and the oxygen vacancies consumption with NO uptake is complex; however, a hydroxyl consumption route is found to be involved. The reduction of NO provided higher levels of N2 at higher temperatures; also, a very high efficiency of the previously created oxygen vacancies was found for this process.The authors gratefully acknowledge the financial support of Generalitat Valenciana (PROMETEO/2018/076 project) and the Spanish Ministry of Science and Innovation (PID2019-105542RB-I00 project) and the UE-FEDER funding. Martínez-Munuera also acknowledges Spanish Ministry of Science, Innovation and Universities for the financial support through a FPU grant (FPU17/00603)

Silver-based catalytic materials for the simultaneous removal of soot and NOx

The potential of silver-based catalysts in the simultaneous removal of particulate matter (soot) and NOxis investigated in this work and compared with that of a model Pt-Ba/Al2O3catalyst. The Ag (5 wt%) - Ba (10 wt%)/MO (MO = CeO2, ZrO2, Al2O3) and Ag (5 wt%) - Sr (10 wt%)/CeO2catalysts have been prepared by incipient wetness impregnation and characterized by BET, XRD, HRTEM, XPS and temperature-programmed reduction (TPR) experiments. The behavior of the catalyst in the soot combustion (under loose conditions) and NOxremoval has been separately analyzed by means of temperature programmed oxidation (TPO) and isothermal concentration step change (ICSC) experiments, respectively. The results show that all the catalysts are active in soot combustion with a significant decrease of oxidation onset temperature compared to uncatalyzed soot oxidation. The removal of NOxin the absence and in the presence of soot was investigated under cycling conditions, i.e. alternating lean-rich phases according to the LNT strategy. It has been found that the Ag-based samples are able to simultaneously remove soot and NOx. In particular, comparing the behavior of the prepared catalysts, the Ba-containing systems showed higher NOxstorage capacity than Sr-catalyst; also, the nitrogen selectivity increased even if resulted lower than the traditional LNT Pt-based catalyst. A detrimental effect of soot on the NOxstorage activity has been also observed.Postprint (author's final draft

Study of N2O formation over Rh- and Pt-based LNT catalysts

In this paper, mechanistic aspects involved in the formation of N2O over Pt-BaO/Al2O3 and Rh-BaO/Al2O3 model NOx Storage-Reduction (NSR) catalysts are discussed. The reactivity of both gas-phase NO and stored nitrates was investigated by using H2 and NH3 as reductants. It was found that N2O formation involves the presence of gas-phase NO, since no N2O is observed upon the reduction of nitrates stored over both Pt- and Rh-BaO/Al2O3 catalyst samples. In particular, N2O formation involves the coupling of undissociated NO molecules with N-adspecies formed upon NO dissociation onto reduced Platinum-Group-Metal (PGM) sites. Accordingly, N2O formation is observed at low temperatures, when PGM sites start to be reduced, and disappears at high temperatures where PGM sites are fully reduced and complete NO dissociation takes place. Besides, N2O formation is observed at lower temperatures with H2 than with NH3 in view of the higher reactivity of hydrogen in the reduction of the PGM sites and onto Pt-containing catalyst due to the higher reducibility of Pt vs. Rh

Real World Estimate of Vaccination Protection in Individuals Hospitalized for COVID-19

Whether vaccination confers a protective effect against progression after hospital admission for COVID-19 remains to be elucidated. Observational study including all the patients admitted to San Paolo Hospital in Milan for COVID-19 in 2021. Previous vaccination was categorized as: none, one dose, full vaccination (two or three doses >14 days before symptoms onset). Data were collected at hospital admission, including demographic and clinical variables, age-unadjusted Charlson Comorbidity index (CCI). The highest intensity of ventilation during hospitalization was registered. The endpoints were in-hospital death (primary) and mechanical ventilation/death (secondary). Survival analysis was conducted by means of Kaplan-Meier curves and Cox regression models. Effect measure modification by age was formally tested. We included 956 patients: 151 (16%) fully vaccinated (18 also third dose), 62 (7%) one dose vaccinated, 743 (78%) unvaccinated. People fully vaccinated were older and suffering from more comorbidities than unvaccinated. By 28 days, the risk of death was of 35.9% (95%CI: 30.1–41.7) in unvaccinated, 41.5% (24.5–58.5) in one dose and 28.4% (18.2–38.5) in fully vaccinated (p = 0.63). After controlling for age, ethnicity, CCI and month of admission, fully vaccinated participants showed a risk reduction of 50% for both in-hospital death, AHR 0.50 (95%CI: 0.30–0.84) and for mechanical ventilation or death, AHR 0.49 (95%CI: 0.35–0.69) compared to unvaccinated, regardless of age (interaction p > 0.56). Fully vaccinated individuals in whom vaccine failed to keep them out of hospital, appeared to be protected against critical disease or death when compared to non-vaccinated. These data support universal COVID-19 vaccination

An Overview on the Catalytic Materials Proposed for the Simultaneous Removal of NOx and Soot

Vehicular pollution has become a major problem in urban areas due to the exponential increase in the number of automobiles. Typical exhaust emissions, which include nitrogen oxides (NOx), hydrocarbons (HC), carbon monoxide (CO), soot, and particulate matter (PM), doubtless have important negative effects on the environment and human health, including cardiovascular effects such as cardiac arrhythmias and heart attacks, and respiratory effects such as asthma attacks and bronchitis. The mitigation measures comprise either the use of clean alternative fuels or the use of innovative technologies. Several existing emission control technologies have proven effective at controlling emissions individually, such as selective catalytic reduction (SCR) and lean NOx trap (LNT) to reduce NOx and diesel particulate filter (DPF) specifically for PM abatement. These after-treatment devices are the most profitable means to reduce exhaust emissions to acceptable limits (EURO VI norms) with very little or no impact on the engine performances. Additionally, the relative lack of physical space in which to install emissions-control equipment is a key challenge for cars, especially those of small size. For this reason, to reduce both volume and cost of the after-treatment devices integrated catalytic systems (e.g., a sort of a "single brick") have been proposed, reducing both NOx and PM simultaneously. This review will summarize the currently reported materials for the simultaneous removal of NOx and soot, with particular attention to their nature, properties, and performances

Removal of NOx and soot over Ce/Zr/K/Me (Me = Fe, Pt, Ru, Au) oxide catalysts

The potentiality of ceria/zirconia based catalysts in the simultaneous removal of particulate matter (soot) and NOx is investigated in this work, and compared with that of a model LNT Pt-K/Al2O3 sample. Ceria-zirconia (molar ratio 75/25) catalysts doped with Pt, Au, Ru or Fe (2% by weight) and containing K (7% by weight) were prepared by a modified citrate method and characterized by X-ray diffraction, surface area and pore volume measurements. The behavior of the catalysts in the soot combustion and NOx removal was separately analyzed by means of temperature programmed oxidation (TPO), isothermal combustion and isothermal NOx adsorption experiments. The results showed that all the ceria/zirconia based catalysts are more active than Pt-K/Al2O3 in soot combustion; the Ru-containing system also showed NOx storage performances comparable to Pt-K/Al2O3. Accordingly the capability of the Ru-based catalyst to accomplish the removal of NOx in the absence and in the presence of soot was further investigated by reactivity experiments and FT-IR spectroscopy to analyze both the gas phase and the catalyst surface species. The data indicate that the Ru-based system is able to simultaneously remove soot and adsorb NOx pointing out higher performances in the soot combustion as compared to the Pt-K/Al2O3 catalyst, and similar behavior in the NOx storage capacity. However the NOx reduction activity results lower than the traditional LNT Pt-based catalyst. Conversely, when the Ru-based catalyst is mixed with the LNT sample (physical mixture) a NOx reduction efficiency similar to Pt-K/Al2O3 is found