Co-Fe Clusters Supported on N-Doped Graphitic Carbon as Highly Selective Catalysts for Reverse Water Gas Shift Reaction

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acssuschemeng.1c01401[EN] Graphitic carbons are suitable supports of metal nanoparticles with catalytic activity. In the present study, the preparation of N-doped graphitic carbon supporting clusters of Fe-Co alloys starting from biomass waste is reported. These sub-nanometric Co-Fe clusters supported on N-doped graphitic carbon at a metal loading below 0.2 wt % exhibit high activity for the selective hydrogenation of CO2 to CO. Operating at 500 degrees C and 10 bar with an H-2/CO2 molar ratio of 7 and a space velocity of 600 h(-1), a conversion of 56% with a selectivity of over 98% to CO, and remarkable stability over 30 h operation was obtained. Interestingly, analogous catalysts based on N-doped graphitic carbon with much higher Co-Fe loadings and an average particle size range of 1-5 nm exhibit only half of this activity, with similar CO selectivity. This contrasting behavior reveals the dramatic effect of the particle size on the catalytic activity. In comparison, SiO2 as support under similar conditions affords CH4 as the main product.Financial support by the Spanish Ministry of Science, Innovation, and University (Severo Ochoa and RTI2018.98237-B-CO1) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. L.P. thanks the Generalitat Valenciana for a Santiago Grisolia scholarship. BASF is thanked for financial support.Peng, L.; Jurca, B.; Primo Arnau, AM.; Gordillo, A.; Parvulescu, VI.; García Gómez, H. (2021). Co-Fe Clusters Supported on N-Doped Graphitic Carbon as Highly Selective Catalysts for Reverse Water Gas Shift Reaction. ACS Sustainable Chemistry & Engineering. 9(28):9264-9272. https://doi.org/10.1021/acssuschemeng.1c014019264927292

Co-Fe Nanoparticles Wrapped on N-Doped Graphitic Carbons as Highly Selective CO2 Methanation Catalysts

[EN] Pyrolysis of chitosan containing various loadings of Co and Fe renders Co-Fe alloy nanoparticles supported on N-doped graphitic carbon. Transmission electron microscopy (TEM) images show that the surface of Co-Fe NPs is partially covered by three or four graphene layers. These Co-Fe@(N)C samples catalyze the Sabatier CO2 hydrogenation, increasing the activity and CH4 selectivity with the reaction temperature in the range of 300-500 degrees C. Under optimal conditions, a CH4 selectivity of 91% at an 87% CO2 conversion was reached at 500 degrees C and a space velocity of 75 h(-1) under 10 bar. The Co-Fe alloy nanoparticles supported on N-doped graphitic carbon are remarkably stable and behave differently as an analogous Co-Fe catalyst supported on TiO2.Financial support by the Spanish Ministry of Science, Innovation and University (Severo Ochoa and RTI2018.98237-B-CO1) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. L.P. thanks the Generalitat Valenciana for a Santiago Grisolia scholarship, and A.P. thanks the Spanish Ministry of Science and Education for a Ramon y Cajal research associate contract. V.I.P. thanks the UEFISCDI for continued funding through the projects PN-IIIP1-1.2-PCCDI-2017-0541 1/2018, PN-III-P4-ID-PCCF-20160088 17/2021, and PN-III-P4-ID-PCE-2020-1532. BASF is thanked for the financial support.Jurca, B.; Peng, L.; Primo Arnau, AM.; Gordillo, A.; Parvulescu, VI.; García Gómez, H. (2021). Co-Fe Nanoparticles Wrapped on N-Doped Graphitic Carbons as Highly Selective CO2 Methanation Catalysts. ACS Applied Materials & Interfaces. 13(31):36976-36981. https://doi.org/10.1021/acsami.1c055423697636981133

N-Doped Defective Graphene from Biomass as Catalyst for CO2 Hydrogenation to Methane

This is the peer reviewed version of the following article: B. Jurca, C. Bucur, A. Primo, P. Concepción, V. I. Parvulescu, H. García, ChemCatChem 2019, 11, 985, which has been published in final form at https://doi.org/10.1002/cctc.201801984. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] N-doped, defective graphene obtained by pyrolysis of chitosan at 900 degrees C under Ar exhibits catalytic activity for the Sabatier hydrogenation of CO2 to CH4 at temperatures about 500 degrees C with estimated turnover frequencies and activation energy values of 73.17s(-1) and 24.3 kcal x mol(-1), respectively. It has been found that this enhanced catalytic activity compared to other related doped defective graphenes derives from the presence of pyridinic N atoms that adsorbs CO2 forming carbamate-type adsorbates.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, Grapas and CTQ2015-69153-CO2-R1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged. A.P. thanks the Spanish Ministry for a Ramon y Cajal research associate contract. V.I.P. kindly acknowledges UEFISCDI for financial support (projects PN-III-P4-ID-PCE-2016-0146, Nr. 121/2017, PN-III-P4-ID-PCCF-2016-0088 and PN-III-P1-1.2-PCCDI-2017-0541). Cristina Bucur thanks IFTM for the financial support.Jurca, B.; Bucur, C.; Primo Arnau, AM.; Concepción Heydorn, P.; Parvulescu, VI.; García Gómez, H. (2019). N-Doped Defective Graphene from Biomass as Catalyst for CO2 Hydrogenation to Methane. ChemCatChem. 11(3):985-990. https://doi.org/10.1002/cctc.201801984S98599011

Promotional Effects on the Catalytic Activity of Co-Fe Alloy Supported on Graphitic Carbon for CO2 Hydrogenation

[EN] Starting from the reported activity of Co-Fe nanoparticles wrapped onto graphitic carbon (Co-Fe@C) as CO2 hydrogenation catalysts, the present article studies the influence of a series of metallic (Pd, Ce, Ca, Ca, and Ce) and non-metallic (S in various percentages and S and alkali metals) elements as Co-Fe@C promoters. Pd at 0.5 wt % somewhat enhances CO2 conversion and CH4 selectivity, probably due to H-2 activation and spillover on Co-Fe. At similar concentrations, Ce does not influence CO2 conversion but does diminish CO selectivity. A 25 wt % Fe excess increases the Fe-Co particle size and has a detrimental effect due to this large particle size. The presence of 25 wt % of Ca increases the CO2 conversion and CH4 selectivity remarkably, the effect being attributable to the CO2 adsorption capacity and basicity of Ca. Sulfur at a concentration of 2.1% or higher acts as a strong poison, decreasing CO2 conversion and shifting selectivity to CO. The combination of S and alkali metals as promoters maintain the CO selectivity of S but notably increase the CO2 conversion. Overall, this study shows how promoters and poisons can alter the catalytic activity of Co/Fe@C catalysts, changing from CH4 to CO. It is expected that further modulation of the activity of Co/Fe@C catalysts can serve to drive the activity and selectivity of these materials to any CO2 hydrogenation products that are wanted.This research was funded by the Spanish Ministry of Science and Innovation and the University (Severo Ochoa SEV2021 and RTI2018.98237-B-CO1) and Generalitat Valenciana (Prometeo 2017/083). A.P. is the recipient of a Ramon y Cajal research associate contract awarded by the Spanish Ministry of Science and Innovation. L.P. thanks the Generalitat Valenciana for a Santiago Grisolia scholarship. BASF is thanked for financial support.Jurca, B.; Peng, L.; Primo Arnau, AM.; Gordillo, A.; Dhakshinamoorthy, A.; Parvulescu, VI.; García Gómez, H. (2022). Promotional Effects on the Catalytic Activity of Co-Fe Alloy Supported on Graphitic Carbon for CO2 Hydrogenation. Nanomaterials. 12(18):1-13. https://doi.org/10.3390/nano12183220113121

CO2 methanation catalyzed by oriented MoS2 nanoplatelets supported on few layers graphene

[EN] Powders of molybdenum disulfide platelets strongly grafted on graphene have been prepared by pyrolysis of ammonium alginate containing adsorbed various proportions of (NH4)(2)MoS4. After pyrolysis, formation of MoS2 supported on graphene was determined by XRD and electron microscopy and spectroscopic techniques. MoS2/G exhibits catalytic activity for the methanation of CO2, the performance being optimal at intermediate loadings. The catalytic activity of sharply contrasts with that of bulk MoS2 that promotes the reverse water gas shift, affording CO as the main product. Characterization of the spent MoS2/G catalyst shows the partial conversion of external MoS2 into MoO3. Comparison of the catalytic activity of MoS2/G with that of MoO3/G shows that the latter is less efficient, but more selective for CO2 methanation.Vasile I. Parvulescu kindly acknowledges UEFISCDI for financial support (project PN-III-P4-ID-PCE-2016-0146, Nr. 121/2017 and project PN-III-P1-1.2-PCCDI-2017-0541). Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2015-69653-CO2-R1) and Generalitat Valencia (Prometeo 2017-083) is gratefully acknowledged. A.P. also thanks the Spanish Ministry for a Ramon y Cajal research associate contract.Primo Arnau, AM.; He, J.; Jurca, B.; Cojocaru, B.; Bucur, C.; Parvulescu, VI.; García Gómez, H. (2019). CO2 methanation catalyzed by oriented MoS2 nanoplatelets supported on few layers graphene. Applied Catalysis B Environmental. 245:351-359. https://doi.org/10.1016/j.apcatb.2018.12.034S35135924

Rezultati dela Ambulante za bolezni dojk pri Splošni bolnišnici Trbovlje

V članku avtorji prikazujejo rezultate dela Ambulante za bolezni dojk pri ginekološko-porodniškem oddelku Splošne bolnišnice Trbovlje. V devetih letih dela ambulante za bolezni dojk so opravili več kot 10.000 pregledov. Na dodatne preglede so napotili 171 pregledanih žensk. Pri 78 (47 %) napotenih ženskah je bil potrjen rak dojke. Pri 15 (19,2 %) je bil rak dojke v začetnem, neinvazivnem stadiju, pri 63 (80,7 %) pa v invazivnem stadiju bolezni. Pri 24 (30,7 %) so bile metastaze že v regionalnih bezgavkah, pri 48 (61,54 %) bolnicah pa takih metastaz niso ugotovili. Za 5 (6,4 %) bolnic ni podatkov, ugotovili so en primer vnetnega raka. Ugotavljajo 9 intervalnih rakov, kar je 0,09 % od vseh pregledanih žensk oz. 11,3 % ugotovljenih rakov. Ugotavljajo, da je v prikazanem vzorcu rak dojke zelo pogost že pred 50. letom starosti28,2 % primerov je bilo v starostni skupini 30–49 let, v skupini 50–69 let pa 47,4 % vseh za rakom na dojki obolelih žensk. To pomeni, da je v starostni skupini 30–69 let za rakom dojke zbolelo 75,6 % vseh obolelih. Ugotavljajo tudi pomanjkljivo povezavo med družinskimi zdravniki, Onkološkim inštitutom in ambulanto za bolezni dojk

Risk Measurement of Perinatal and Neonatal Morbidity Characteristics and Applicability of GAIA Case Definitions: Results and Lessons Learnt of a Hospital-Based Prospective Cohort Study in the Valencia Region (2019–2020)

Post-marketing safety surveillance of new vaccines aimed to be administered during pregnancy is crucial to orchestrate efficient adverse events evaluation. This is of special relevance in the current landscape of new vaccines being introduced in the pregnant women population, and particularly due to the recent administration of COVID-19 vaccines in pregnant women. This multicenter prospective cohort study, nested within the WHO-Global Vaccine Safety-MCC study, involved two hospitals in the Valencia region. Hereby, the incidence rates of seven perinatal and neonatal outcomes in the Valencia region are presented. The pooled data analysis of the two Valencian hospitals allowed the estimation of incidence rates in the Valencia Region (per 1000 live births): 86.7 for low birth weight, 78.2 for preterm birth, 58.8 for small for gestational age, 13 for congenital microcephaly, 0.4 for stillbirth, 1.2 for neonatal death and 6.5 for neonatal infection. These figures are in line with what is expected from a high-income country and the previously reported rates for Spain and Europe, except for the significantly increased rate for congenital microcephaly. Regarding the data for maternal immunization, the vaccination status was collected for 94.4% of the screened pregnant women, highlighting the high quality of the Valencian Vaccine Registry. The study also assessed the Valencian hospitals’ capacity for identifying and collecting data on maternal immunization status, as well as the applicability of the GAIA definitions to the identified outcomes.Medicin