Experimental investigation and CFD analysis of pressure drop in an ORC boiler for a WHRS implementation

Waste heat dissipated in the exhaust system of a combustion engine represents a major source of energy to be recovered and converted into useful work. The Waste Heat Recovery System (WHRS) based in an Organic Rankine Cycle (ORC) is an approach for recovering energy from heat sources, achieving a significant reduction in fuel consumption and, as a result, exhaust emissions. This paper studies pressure drop in an ORC shell-and-tubes boiler for a WHRS implementation experimentally and with computational simulations based on a 1-dimensional heat transfer model coupled with 3D calculations. An experimental database is developed, using ethanol in a pressure range of 10–15 absolute bar as working fluid, with mass fluxes inside the tubes in the range of 349.31 kg/s-m2 and 523.97 kg/s-m2, and inlet temperatures in the range of 60 °C and 80 °C. Thus, the friction factor of different regions of the boiler were estimated using both CFD simulations, experimental data, and bibliographic correlations. Simulations of operating points and the results of the experimental test bench showed good agreement in pressure drop results, with a mean absolute error of 15.47%, without a significant increment in the computational cost

The Influence of the Support Nature and the Metal Precursor in the Activity of Pd-based Catalysts for the Bromate Reduction Reaction

This is the peer reviewed version of the following article: J. L. Cerrillo, C. W. Lopes, F. Rey, A. E. Palomares, ChemCatChem 2021, 13, 1230, which has been published in final form at https://doi.org/10.1002/cctc.202001797. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Palladium catalysts supported on different materials (alumina, activated carbon and mixed oxide derived from hydrotalcite) and prepared with different metal precursors (nitrate, chloride and acetate) have been characterized and tested for the bromate reduction reaction. The catalytic behavior depends on the support nature and on the metallic precursor used for the catalyst preparation. Pd catalyst supported on a mixed oxide has a low activity due to the high affinity of the reconstructed support for the Br- formed, preventing the reactants to approximate the active Pd sites. Pd catalyst supported on activated carbon has a surface negative charge and a microporous structure, making difficult the interaction of the active sites with the reactants. The best results are obtained with the catalyst supported on alumina due to its physical-chemical properties, i. e. mesoporosity, positive surface charge and reversible adsorption of reactants and products. These characteristics make easy bromate and H-2 adsorption on the active sites and subsequent reaction, thus resulting in a better activity. The Pd precursor salt also influences the catalytic activity as it has an effect on the Pd nanocrystal size. The best results are obtained with the metal precursor that produces homogeneous and large Pd metallic crystallites.Authors thank the Spanish Ministry of Economy and Competitiveness through RTI2018-101784-B-I00 (MINECO/FEDER) and SEV2016-0683 projects for the financial support. We gratefully acknowledge ALBA synchrotron for allocating beamtime and CLAESS beamline staff for their technical support during our experiment. C.W. Lopes (Science without Frontiers -Process no. 13191/13-6) thanks CAPES for a predoctoral fellowship. J.L. Cerrillo is grateful to MINECO for the Severo Ochoa contract for PhD formation (SVP-2014-068600).The authors also wish to thank Elena Crespo and Adrian Pla for their collaboration in the experimental part of the paper.Cerrillo, JL.; Lopes, CW.; Rey Garcia, F.; Palomares Gimeno, AE. (2021). The Influence of the Support Nature and the Metal Precursor in the Activity of Pd-based Catalysts for the Bromate Reduction Reaction. ChemCatChem. 13(4):1230-1238. https://doi.org/10.1002/cctc.202001797S1230123813

An in situ XAS study of the activation of precursor-dependent Pd nanoparticles

[EN] The activation of precursor-dependent Pd nanoparticles was comprehensively followed by in situ X-ray absorption spectroscopy on two inorganic supports for rationalizing the final catalytic activity. Two series of Pd-based catalysts (7 wt% Pd) were prepared by impregnation of gamma-Al2O3 and activated carbon supports varying the metal precursor (Pd(NO3)(2), PdCl2 and Pd(OAc)(2)). The most relevant physicochemical properties of the studied catalysts were determined by several techniques including ICP-OES, XRD, N-2 adsorption and XAS. The results indicate that the thermal stability of the metal precursor plays an important role in the size and speciation of the formed Pd nanoparticles after the activation process. The Cl-based precursor, which presents high thermal stability, passes through a PdOxCly mixed phase when submitted to calcination on Pd/Al2O3 and leaves Cl-species after metal reduction on Pd/C (which can be detrimental to catalytic reactions). Differently, Pd(OAc)(2) and Pd(NO3)(2) promote the formation of larger species due to different precursor decomposition pathways. Ordered PdO is observed even before calcination when Pd(NO3)(2) was used as a metallic source, which translates into large nanoparticles after reduction in H-2. By using the average coordination numbers of Pd species obtained from EXAFS data of the as-reduced catalysts, a correlation was observed comparing the three precursors: PdCl2 generates smaller nanoparticles than Pd(OAc)(2), which in turn generates smaller nanoparticles than Pd(NO3)(2), regardless of the support used for catalyst preparation.The authors thank the Spanish Ministry of Economy and Competitiveness through MAT2015-71842-P (MINECO/FEDER) and SEV-2016-0683 projects for the financial support. We gratefully acknowledge ALBA synchrotron for allocating beamtime (proposal 2015091414), Carlo Marini and CLAESS beamline staff for their help and technical support during our experiment. C. W. Lopes (Science without Frontiers - Process no. 13191/13-6) thanks CAPES for a predoctoral fellowship. J.L. Cerrillo wishes to thank MINECO for the Severo Ochoa contract for PhD formation (SVP-2014-068600).Wittee Lopes, C.; Cerrillo, JL.; Palomares Gimeno, AE.; Rey Garcia, F.; Agostini, G. (2018). An in situ XAS study of the activation of precursor-dependent Pd nanoparticles. Physical Chemistry Chemical Physics. 20(18):12700-12709. https://doi.org/10.1039/C8CP00517FS12700127092018Chen, X., Huo, X., Liu, J., Wang, Y., Werth, C. J., & Strathmann, T. J. (2017). Exploring beyond palladium: Catalytic reduction of aqueous oxyanion pollutants with alternative platinum group metals and new mechanistic implications. Chemical Engineering Journal, 313, 745-752. doi:10.1016/j.cej.2016.12.058Lu, C., Wang, M., Feng, Z., Qi, Y., Feng, F., Ma, L., … Li, X. (2017). 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Effect of Pre-Reduction on the Properties and the Catalytic Activity of Pd/Carbon Catalysts: A Comparison with Pd/Al2O3. ACS Catalysis, 4(1), 187-194. doi:10.1021/cs400507mCho, S. J., & Kang, S. K. (2000). Reversible Structural Transformation of Palladium Catalyst Supported on La−Al2O3Probed with X-ray Absorption Fine Structure. The Journal of Physical Chemistry B, 104(34), 8124-8128. doi:10.1021/jp991857pHarada, M., & Inada, Y. (2009). In Situ Time-Resolved XAFS Studies of Metal Particle Formation by Photoreduction in Polymer Solutions. Langmuir, 25(11), 6049-6061. doi:10.1021/la900550tSingh, J., Lamberti, C., & van Bokhoven, J. A. (2010). Advanced X-ray absorption and emission spectroscopy: in situ catalytic studies. Chemical Society Reviews, 39(12), 4754. doi:10.1039/c0cs00054jD. C. Koningsberger and R.Prins , X-Ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES , Wiley , 1988Wang, J., Wang, Q., Jiang, X., Liu, Z., Yang, W., & Frenkel, A. I. (2014). Determination of Nanoparticle Size by Measuring the Metal–Metal Bond Length: The Case of Palladium Hydride. The Journal of Physical Chemistry C, 119(1), 854-861. doi:10.1021/jp510730aAgostini, G., Pellegrini, R., Leofanti, G., Bertinetti, L., Bertarione, S., Groppo, E., … Lamberti, C. (2009). Determination of the Particle Size, Available Surface Area, and Nature of Exposed Sites for Silica−Alumina-Supported Pd Nanoparticles: A Multitechnical Approach. The Journal of Physical Chemistry C, 113(24), 10485-10492. doi:10.1021/jp9023712Frenkel, A. I., Hills, C. W., & Nuzzo, R. G. (2001). A View from the Inside:  Complexity in the Atomic Scale Ordering of Supported Metal Nanoparticles. The Journal of Physical Chemistry B, 105(51), 12689-12703. doi:10.1021/jp012769jFrenkel, A. I. (1999). Solving the structure of nanoparticles by multiple-scattering EXAFS analysis. 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Adsorption by Powders and Porous Solids, 269-302. doi:10.1016/b978-0-08-097035-6.00008-5Simonelli, L., Marini, C., Olszewski, W., ��vila P��rez, M., Ramanan, N., Guilera, G., … Klementiev, K. (2016). CL��SS: The hard X-ray absorption beamline of the ALBA CELLS synchrotron. Cogent Physics, 3(1). doi:10.1080/23311940.2016.1231987Ravel, B., & Newville, M. (2005). ATHENA,ARTEMIS,HEPHAESTUS: data analysis for X-ray absorption spectroscopy usingIFEFFIT. Journal of Synchrotron Radiation, 12(4), 537-541. doi:10.1107/s0909049505012719Yazawa, Y., Yoshida, H., Takagi, N., Komai, S., Satsuma, A., & Hattori, T. (1998). Oxidation state of palladium as a factor controlling catalytic activity of Pd/SiO2–Al2O3 in propane combustion. Applied Catalysis B: Environmental, 19(3-4), 261-266. doi:10.1016/s0926-3373(98)00080-0Lin, C.-M., Hung, T.-L., Huang, Y.-H., Wu, K.-T., Tang, M.-T., Lee, C.-H., … Chen, Y. Y. (2007). Size-dependent lattice structure of palladium studied by x-ray absorption spectroscopy. Physical Review B, 75(12). doi:10.1103/physrevb.75.125426Fernández-García, M. (2002). XANES analysis of catalytic systems under reaction conditions. Catalysis Reviews, 44(1), 59-121. doi:10.1081/cr-120001459Agostini, G., Groppo, E., Piovano, A., Pellegrini, R., Leofanti, G., & Lamberti, C. (2010). Preparation of Supported Pd Catalysts: From the Pd Precursor Solution to the Deposited Pd2+Phase. Langmuir, 26(13), 11204-11211. doi:10.1021/la1005117Kim, S.-J., Lemaux, S., Demazeau, G., Kim, J.-Y., & Choy, J.-H. (2002). X-Ray absorption spectroscopic study on LaPdO3. Journal of Materials Chemistry, 12(4), 995-1000. doi:10.1039/b106795hGroppo, E., Liu, W., Zavorotynska, O., Agostini, G., Spoto, G., Bordiga, S., … Zecchina, A. (2010). Subnanometric Pd Particles Stabilized Inside Highly Cross-Linked Polymeric Supports. Chemistry of Materials, 22(7), 2297-2308. doi:10.1021/cm903176dGóralski, J., Szczepaniak, B., Grams, J., Maniukiewicz, W., & Paryjczak, T. (2007). Characteristic of physicochemical properties of Pd/MgO catalysts used in the hydrodechlorination process with CCI4. Polish Journal of Chemical Technology, 9(3), 77-80. doi:10.2478/v10026-007-0059-yAgostini, G., Groppo, E., Bordiga, S., Zecchina, A., Prestipino, C., D’Acapito, F., … Lamberti, C. (2007). Reactivity of Cr Species Grafted on SiO2/Si(100) Surface:  A Reflection Extended X-ray Absorption Fine Structure Study down to the Submonolayer Regime. The Journal of Physical Chemistry C, 111(44), 16437-16444. doi:10.1021/jp074066tShen, W.-J., Ichihashi, Y., Ando, H., Okumura, M., Haruta, M., & Matsumura, Y. (2001). Influence of palladium precursors on methanol synthesis from CO hydrogenation over Pd/CeO2 catalysts prepared by deposition–precipitation method. Applied Catalysis A: General, 217(1-2), 165-172. doi:10.1016/s0926-860x(01)00606-8Bugaev, A. L., Guda, A. A., Lazzarini, A., Lomachenko, K. A., Groppo, E., Pellegrini, R., … Lamberti, C. (2017). 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Impact of Biological Agents on Postsurgical Complications in Inflammatory Bowel Disease: A Multicentre Study of Geteccu

Enfermedad de Crohn; Cirugía; Complicaciones postoperatoriasMalaltia de Crohn; Cirurgia; Complicacions postoperatòriesCrohn’s disease; Surgery; Postoperative complicationsBackground: The impact of biologics on the risk of postoperative complications (PC) in inflammatory bowel disease (IBD) is still an ongoing debate. This lack of evidence is more relevant for ustekinumab and vedolizumab. Aims: To evaluate the impact of biologics on the risk of PC. Methods: A retrospective study was performed in 37 centres. Patients treated with biologics within 12 weeks before surgery were considered "exposed". The impact of the exposure on the risk of 30-day PC and the risk of infections was assessed by logistic regression and propensity score-matched analysis. Results: A total of 1535 surgeries were performed on 1370 patients. Of them, 711 surgeries were conducted in the exposed cohort (584 anti-TNF, 58 vedolizumab and 69 ustekinumab). In the multivariate analysis, male gender (OR: 1.5; 95% CI: 1.2-2.0), urgent surgery (OR: 1.6; 95% CI: 1.2-2.2), laparotomy approach (OR: 1.5; 95% CI: 1.1-1.9) and severe anaemia (OR: 1.8; 95% CI: 1.3-2.6) had higher risk of PC, while academic hospitals had significantly lower risk. Exposure to biologics (either anti-TNF, vedolizumab or ustekinumab) did not increase the risk of PC (OR: 1.2; 95% CI: 0.97-1.58), although it could be a risk factor for postoperative infections (OR 1.5; 95% CI: 1.03-2.27). Conclusions: Preoperative administration of biologics does not seem to be a risk factor for overall PC, although it may be so for postoperative infections

AgY zeolite as catalyst for the selective catalytic oxidation of NH3

[EN] Ag-exchanged Y zeolites (Si/Al = 2.5; Ag/Al = 0.30-0.95) have been tested in the NH3-SCO reaction, the most promising method for the elimination of ammonia emissions, and deeply characterized before and after reaction by using a variety of techniques (XRD, TEM, UV-Vis, Ag-109 NMR, XAS spectroscopies). The most active centres for the NH3-SCO reaction are Ag-0 nanoparticles (NPs) formed under reduction conditions and both activity and selectivity to N-2 increase with the silver loading. The Ag-0 NPs are dramatically modified under reaction conditions, being most of them dispersed resulting in small clusters and even atomically Ag+ cations, the latter accounting for around half silver atoms. The presence of water into the reaction feed promotes the dispersion and oxidation of silver nanoparticles, but the catalyst performance is only slightly affected. The results are fully consistent with the previously proposed i-SCR mechanism for NH3-SCO reaction on silver catalysts.Financial support by the Ministerio de Ciencia e Innovacion (MICINN) of Spain through the Severo Ochoa (SEV-2016-0683) , RTI2018-101784-B-I00, RTI2018-09639-A-I00 and InnovaXN-26-2019 projects is gratefully acknowledged. The authors also thank the Microscopy Service of the Universitat Politecnica de Valencia for its assistance in microscopy characterization (TEM and FESEM equipment preparation) . C. W. Lopes (Science without Borders Process no. 13191/13-6) thanks CAPES for a predoctoral fellowship and J. Martinez-Ortigosa (SEV-2012-0267-02) is grateful to Severo Ochoa Program for a predoctoral fellowship. The authors also want to thank the ALBA synchrotron and CL AE SS beamline staff for providing beamtime (proposal 2017092477) and for setting the beamline up to perform these studies.Martinez-Ortigosa, J.; Lopes, CW.; Agostini, G.; Palomares Gimeno, AE.; Blasco Lanzuela, T.; Rey Garcia, F. (2021). AgY zeolite as catalyst for the selective catalytic oxidation of NH3. Microporous and Mesoporous Materials. 323:1-14. https://doi.org/10.1016/j.micromeso.2021.111230S11432

Nature and evolution of Pd catalysts supported on activated carbon fibers during the catalytic reduction of bromate in water

[EN] Catalytic hydrogenation of bromate using Pd catalysts supported on activated carbon fibers is a smart solution to treat bromate polluted water. These catalysts have been analyzed by different techniques for an in-deep characterization of the active sites. The in situ X-ray absorption spectroscopy and the CO chemisorption studies showed that Pd-0 nanoparticles with different crystal sizes were generated on the support during hydrogen activation at 200 degrees C and that the PdHx-phase was formed during the cooling to room temperature. As PdHx species formed on Pd-0 nanoparticles are responsible for bromate reduction, the most active catalysts are those having Pd-0 nanoparticles with large crystal sizes, where PdHx species are easily formed. The catalysts are fully stable in succesive reaction runs. It has been also shown that bromate reduction rate depends on the bromate concentration and on the hydrogen partial pressure, with a pseudo-first reaction order towards both reactants.Authors thank the Spanish Ministry of Economy and Competitiveness through RTI2018-101784-B-I00 (MINECO/FEDER) and SEV-2016-0683 projects for the financial support. We gratefully acknowledge ALBA synchrotron for allocating beamtime (proposal 2015091414) and CLAESS beamline staff for their technical support during our experiment. C. W. Lopes (Science without Frontiers -Process no. 13191/13-6) thanks CAPES for a predoctoral fellowship. J. L. Cerrillo is grateful to MINECO for the Severo Ochoa contract for PhD formation (SVP-2014-068600). L. Kiwi-Minsker acknowledges financial support provided by Russian Science Foundation (project 15-19-20023). Authors also thank Kynol Europa GmbH for the supply of the activated carbon fibers.Cerrillo, JL.; Lopes, CW.; Rey Garcia, F.; Agostini, G.; Kiwi-Minsker, L.; Palomares Gimeno, AE. (2020). Nature and evolution of Pd catalysts supported on activated carbon fibers during the catalytic reduction of bromate in water. Catalysis Science & Technology. 10(11):3646-3653. https://doi.org/10.1039/d0cy00606hS364636531011Naushad, M., Khan, M. R., ALOthman, Z. A., AlSohaimi, I., Rodriguez-Reinoso, F., Turki, T. M., & Ali, R. (2015). Removal of BrO3 − from drinking water samples using newly developed agricultural waste-based activated carbon and its determination by ultra-performance liquid chromatography-mass spectrometry. Environmental Science and Pollution Research, 22(20), 15853-15865. doi:10.1007/s11356-015-4786-yBUTLER, R., GODLEY, A., LYTTON, L., & CARTMELL, E. (2005). Bromate Environmental Contamination: Review of Impact and Possible Treatment. Critical Reviews in Environmental Science and Technology, 35(3), 193-217. doi:10.1080/10643380590917888Weinberg, H. S., Delcomyn, C. A., & Unnam, V. (2003). Bromate in Chlorinated Drinking Waters:  Occurrence and Implications for Future Regulation. Environmental Science & Technology, 37(14), 3104-3110. doi:10.1021/es026400zOMS , Bromate in Drinking-water - Guidelines for Drinking-water Quality , WHO , 2005Jabłońska, M., Król, A., Kukulska-Zając, E., Tarach, K., Girman, V., Chmielarz, L., & Góra-Marek, K. (2015). Zeolites Y modified with palladium as effective catalysts for low-temperature methanol incineration. Applied Catalysis B: Environmental, 166-167, 353-365. doi:10.1016/j.apcatb.2014.11.047Pergher, S. B. ., Dallago, R. M., Veses, R. C., Gigola, C. E., & Baibich, I. M. (2004). Pd/NaY-zeolite and Pd-W/NaY-zeolite catalysts: preparation, characterization and NO decomposition activity. Journal of Molecular Catalysis A: Chemical, 209(1-2), 107-115. doi:10.1016/j.molcata.2003.08.005Chaplin, B. P., Reinhard, M., Schneider, W. F., Schüth, C., Shapley, J. R., Strathmann, T. J., & Werth, C. J. (2012). Critical Review of Pd-Based Catalytic Treatment of Priority Contaminants in Water. Environmental Science & Technology, 46(7), 3655-3670. doi:10.1021/es204087qHöller, V., Rådevik, K., Yuranov, I., Kiwi-Minsker, L., & Renken, A. (2001). Reduction of nitrite-ions in water over Pd-supported on structured fibrous materials. Applied Catalysis B: Environmental, 32(3), 143-150. doi:10.1016/s0926-3373(01)00139-4Shen, W.-J., Ichihashi, Y., Ando, H., Okumura, M., Haruta, M., & Matsumura, Y. (2001). Influence of palladium precursors on methanol synthesis from CO hydrogenation over Pd/CeO2 catalysts prepared by deposition–precipitation method. Applied Catalysis A: General, 217(1-2), 165-172. doi:10.1016/s0926-860x(01)00606-8Hirayama, J., & Kamiya, Y. (2018). Tin-palladium supported on alumina as a highly active and selective catalyst for hydrogenation of nitrate in actual groundwater polluted with nitrate. Catalysis Science & Technology, 8(19), 4985-4993. doi:10.1039/c8cy00730fPalomares, A. E., Franch, C., Yuranova, T., Kiwi-Minsker, L., García-Bordeje, E., & Derrouiche, S. (2014). The use of Pd catalysts on carbon-based structured materials for the catalytic hydrogenation of bromates in different types of water. Applied Catalysis B: Environmental, 146, 186-191. doi:10.1016/j.apcatb.2013.02.056Chen, H., Xu, Z., Wan, H., Zheng, J., Yin, D., & Zheng, S. (2010). Aqueous bromate reduction by catalytic hydrogenation over Pd/Al2O3 catalysts. Applied Catalysis B: Environmental, 96(3-4), 307-313. doi:10.1016/j.apcatb.2010.02.021Soares, O. S. G. P., Freitas, C. M. A. S., Fonseca, A. M., Órfão, J. J. M., Pereira, M. F. R., & Neves, I. C. (2016). Bromate reduction in water promoted by metal catalysts prepared over faujasite zeolite. Chemical Engineering Journal, 291, 199-205. doi:10.1016/j.cej.2016.01.093Freitas, C. M. A. S., Soares, O. S. G. P., Órfão, J. J. M., Fonseca, A. M., Pereira, M. F. R., & Neves, I. C. (2015). Highly efficient reduction of bromate to bromide over mono and bimetallic ZSM5 catalysts. Green Chemistry, 17(8), 4247-4254. doi:10.1039/c5gc00777aRestivo, J., Soares, O. S. G. P., Órfão, J. J. M., & Pereira, M. F. R. (2015). Bimetallic activated carbon supported catalysts for the hydrogen reduction of bromate in water. Catalysis Today, 249, 213-219. doi:10.1016/j.cattod.2014.10.048Restivo, J., Soares, O. S. G. P., Órfão, J. J. M., & Pereira, M. F. R. (2017). Catalytic reduction of bromate over monometallic catalysts on different powder and structured supports. Chemical Engineering Journal, 309, 197-205. doi:10.1016/j.cej.2016.10.025Soares, O. S. G. P., Ramalho, P. S. F., Fernandes, A., Órfão, J. J. M., & Pereira, M. F. R. (2019). Catalytic bromate reduction in water: Influence of carbon support. Journal of Environmental Chemical Engineering, 7(3), 103015. doi:10.1016/j.jece.2019.103015Perez-Coronado, A. M., Soares, O. S. G. P., Calvo, L., Rodriguez, J. J., Gilarranz, M. A., & Pereira, M. F. R. (2018). Catalytic reduction of bromate over catalysts based on Pd nanoparticles synthesized via water-in-oil microemulsion. Applied Catalysis B: Environmental, 237, 206-213. doi:10.1016/j.apcatb.2018.05.077Li, M., Zhou, X., Sun, J., Fu, H., Qu, X., Xu, Z., & Zheng, S. (2019). Highly effective bromate reduction by liquid phase catalytic hydrogenation over Pd catalysts supported on core-shell structured magnetites: Impact of shell properties. Science of The Total Environment, 663, 673-685. doi:10.1016/j.scitotenv.2019.01.392Chen, X., Huo, X., Liu, J., Wang, Y., Werth, C. J., & Strathmann, T. J. (2017). Exploring beyond palladium: Catalytic reduction of aqueous oxyanion pollutants with alternative platinum group metals and new mechanistic implications. 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Nanostructured Catalysts for the Continuous Reduction of Nitrates and Bromates in Water. Industrial & Engineering Chemistry Research, 52(39), 13930-13937. doi:10.1021/ie302977hPalomares, A. E., Franch, C., & Corma, A. (2011). A study of different supports for the catalytic reduction of nitrates from natural water with a continuous reactor. Catalysis Today, 172(1), 90-94. doi:10.1016/j.cattod.2011.05.015Yuranova, T., Franch, C., Palomares, A. E., Garcia-Bordejé, E., & Kiwi-Minsker, L. (2012). Structured fibrous carbon-based catalysts for continuous nitrate removal from natural water. Applied Catalysis B: Environmental, 123-124, 221-228. doi:10.1016/j.apcatb.2012.04.007Lan, H., Mao, R., Tong, Y., Liu, Y., Liu, H., An, X., & Liu, R. (2016). Enhanced Electroreductive Removal of Bromate by a Supported Pd–In Bimetallic Catalyst: Kinetics and Mechanism Investigation. Environmental Science & Technology, 50(21), 11872-11878. doi:10.1021/acs.est.6b02822Yao, F., Yang, Q., Yan, M., Li, X., Chen, F., Zhong, Y., … Li, X. (2020). Synergistic adsorption and electrocatalytic reduction of bromate by Pd/N-doped loofah sponge-derived biochar electrode. Journal of Hazardous Materials, 386, 121651. doi:10.1016/j.jhazmat.2019.121651Morais, D. F. S., Boaventura, R. A. R., Moreira, F. C., & Vilar, V. J. P. (2019). Advances in bromate reduction by heterogeneous photocatalysis: The use of a static mixer as photocatalyst support. Applied Catalysis B: Environmental, 249, 322-332. doi:10.1016/j.apcatb.2019.02.070Cunha, G. S., Santos, S. G. S., Souza-Chaves, B. M., Silva, T. F. C. V., Bassin, J. P., Dezotti, M. W. C., … Vilar, V. J. P. (2019). Removal of bromate from drinking water using a heterogeneous photocatalytic mili-reactor: impact of the reactor material and water matrix. Environmental Science and Pollution Research, 26(32), 33281-33293. doi:10.1007/s11356-019-06266-9Matatov-Meytal, Y., & Sheintuch, M. (2002). Catalytic fibers and cloths. Applied Catalysis A: General, 231(1-2), 1-16. doi:10.1016/s0926-860x(01)00963-2Joannet, E., Horny, C., Kiwi-Minsker, L., & Renken, A. (2002). Palladium supported on filamentous active carbon as effective catalyst for liquid-phase hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol. Chemical Engineering Science, 57(16), 3453-3460. doi:10.1016/s0009-2509(02)00215-4Crespo-Quesada, M., Dykeman, R. R., Laurenczy, G., Dyson, P. J., & Kiwi-Minsker, L. (2011). Supported nitrogen-modified Pd nanoparticles for the selective hydrogenation of 1-hexyne. Journal of Catalysis, 279(1), 66-74. doi:10.1016/j.jcat.2011.01.003Fang, W., Yang, S., Wang, X.-L., Yuan, T.-Q., & Sun, R.-C. (2017). Manufacture and application of lignin-based carbon fibers (LCFs) and lignin-based carbon nanofibers (LCNFs). 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ITQ-69: A Germanium-Containing Zeolite and its Synthesis, Structure Determination, and Adsorption Properties

"This is the peer reviewed version of the following article:ITQ-69: A Germanium-Containing Zeolite and its Synthesis, Structure Determination, and Adsorption Properties, which has been published in final form at https://doi.org/10.1002/anie.202100822. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] In this work, a new zeolite named as ITQ-69, has been synthesized, characterized and its application as selective adsorbent for industrially relevant light olefins/paraffins separations has been assessed. This material has been obtained as pure germania as well as silica-germania zeolites with different Si/Ge ratios using a diquaternary ammonium cation as organic structure directing agent. Its structure was determined by single-crystal X-Ray diffraction showing a triclinic unit cell forming a tridirectional small pore channel system (8x8x8R). Also, it has been found that Si preferentially occupies some special T sites of the structure as deduced from Rietveld analysis of the powder X-ray diffraction patterns. In addition, the new zeolite ITQ-69 has been found to be stable upon calcination and thus, its adsorption properties were evaluated, showing a promising kinetic selectivity for light olefin separations in the C3 fraction.The authors acknowledge the Spanish Ministry of Science, Innovation and Universities (MCIU) for their funding via project RTI2018-101784-B-I00 and Program Severo Ochoa SEV-2016-0683. AS and EPB thanks for their grants BES-2016-078684 and FPU15/01602, respectively. The Microscopy Service of the UPV is acknowledged for their help in sample characterization. By last, authors would like to thank the use of RIAIDT-USC analytical facilities, especially to Dr. Antonio L. Llamas for extremely useful comments on SCXRD analyses.Sala-Gascon, A.; Pérez-Botella, E.; Jorda Moret, JL.; Cantin Sanz, A.; Rey Garcia, F.; Valencia Valencia, S. (2021). ITQ-69: A Germanium-Containing Zeolite and its Synthesis, Structure Determination, and Adsorption Properties. Angewandte Chemie International Edition. 60(21):11745-11750. https://doi.org/10.1002/anie.2021008221174511750602

Evaluation of the silver species nature in Ag-ITQ2 zeolites by the CO oxidation reaction

The authors thank the Spanish Ministry of Economy and Competitiveness through RTI2018-101784-B-I00 (MINECO/FEDER) and SEV-2016-0683 projects for the financial support. We gratefully acknowledge ALBA synchrotron for allocating beamtime (proposal 2015091414) and the CLAESS beamline staff for their help and technical support during our experiment. CG and NB thank the TUW Innovative Project GIP165CDGC. CG, SP, VT, NB and GR are thankful for financial support from the Austrian Science Fund (FWF) through projects DK+ Solids4Fun (W1243) and ComCat (I 1041-N28). I. Lopez Hernandez is grateful to Generalitat Valenciana and European Social Fund for the pre doctoral grant ACIF2017.López-Hernández, I.; García Yago, CI.; Truttmann, V.; Pollit, S.; Barrabés, N.; Rupprechter, G.; Rey Garcia, F.... (2020). Evaluation of the silver species nature in Ag-ITQ2 zeolites by the CO oxidation reaction. Catalysis Today. 345:22-26. https://doi.org/10.1016/j.cattod.2019.12.001S2226345Serhan, N., Tsolakis, A., Wahbi, A., Martos, F. J., & Golunski, S. (2019). Modifying catalytically the soot morphology and nanostructure in diesel exhaust: Influence of silver De-NOx catalyst (Ag/Al2O3). Applied Catalysis B: Environmental, 241, 471-482. doi:10.1016/j.apcatb.2018.09.068Góra-Marek, K., Tarach, K. A., Piwowarska, Z., Łaniecki, M., & Chmielarz, L. (2016). Ag-loaded zeolites Y and USY as catalysts for selective ammonia oxidation. Catalysis Science & Technology, 6(6), 1651-1660. doi:10.1039/c5cy01446hHu, X., Bai, J., Hong, H., & Li, C. (2016). Supercritical carbon dioxide anchored highly dispersed silver nanoparticles on 4A-zeolite and selective oxidation of styrene performance. CrystEngComm, 18(14), 2469-2476. doi:10.1039/c5ce02435hCerrillo, J. L., Palomares, A. E., Rey, F., Valencia, S., Pérez-Gago, M. B., Villamón, D., & Palou, L. (2018). Functional Ag-Exchanged Zeolites as Biocide Agents. 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Chemical Reviews, 118(10), 4981-5079. doi:10.1021/acs.chemrev.7b00776Zhao, J., & Jin, R. (2018). Heterogeneous catalysis by gold and gold-based bimetal nanoclusters. Nano Today, 18, 86-102. doi:10.1016/j.nantod.2017.12.009Zhang, B., Kaziz, S., Li, H., Hevia, M. G., Wodka, D., Mazet, C., … Barrabés, N. (2015). Modulation of Active Sites in Supported Au38(SC2H4Ph)24 Cluster Catalysts: Effect of Atmosphere and Support Material. The Journal of Physical Chemistry C, 119(20), 11193-11199. doi:10.1021/jp512022vZhang, B., Sels, A., Salassa, G., Pollitt, S., Truttmann, V., Rameshan, C., … Barrabés, N. (2018). Ligand Migration from Cluster to Support: A Crucial Factor for Catalysis by Thiolate‐protected Gold Clusters. ChemCatChem, 10(23), 5372-5376. doi:10.1002/cctc.201801474Natarajan, G., Mathew, A., Negishi, Y., Whetten, R. L., & Pradeep, T. (2015). A Unified Framework for Understanding the Structure and Modifications of Atomically Precise Monolayer Protected Gold Clusters. The Journal of Physical Chemistry C, 119(49), 27768-27785. doi:10.1021/acs.jpcc.5b08193Tsukuda, T., & Häkkinen, H. (2015). Introduction. Protected Metal Clusters - From Fundamentals to Applications, 1-7. doi:10.1016/b978-0-08-100086-1.00001-4Zhang, X., Qu, Z., Li, X., Wen, M., Quan, X., Ma, D., & Wu, J. (2010). Studies of silver species for low-temperature CO oxidation on Ag/SiO2 catalysts. Separation and Purification Technology, 72(3), 395-400. doi:10.1016/j.seppur.2010.03.012Kolobova, E., Pestryakov, A., Mamontov, G., Kotolevich, Y., Bogdanchikova, N., Farias, M., … Cortes Corberan, V. (2017). Low-temperature CO oxidation on Ag/ZSM-5 catalysts: Influence of Si/Al ratio and redox pretreatments on formation of silver active sites. Fuel, 188, 121-131. doi:10.1016/j.fuel.2016.10.037Ausavasukhi, A., Suwannaran, S., Limtrakul, J., & Sooknoi, T. (2008). Reversible interconversion behavior of Ag species in AgHZSM-5: XRD, 1H MAS NMR, TPR, TPHE, and catalytic studies. 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Functional Ag-Exchanged Zeolites as Biocide Agents

"This is the peer reviewed version of the following article: Cerrillo, José Luis, Antonio Eduardo Palomares, Fernando Rey, Susana Valencia, María Bernardita Pérez-Gago, Diana Villamón, and Lluís Palou. 2018. Functional Ag-Exchanged Zeolites as Biocide Agents. ChemistrySelect 3 (17). Wiley: 4676 82. doi:10.1002/slct.201800432, which has been published in final form at https://doi.org/10.1002/slct.201800432. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] Materials based on silver are used for controlling different pathogenic microorganisms. However, the influence of the silver carrier in the biocidal activity of the material has been scarcely reported. The present research is focused on studying the influence of zeolite properties on the biocidal activity of silver-exchanged zeolites, acting as reservoirs of silver species. The biocidal action of Ag-Faujasite (Ag-FAU) and Ag-Linde Type A (Ag-LTA) zeolites, containing different silver contents, is studied against different types of bacteria and fungi. Importantly, zeolite structure is found to be a significant parameter for controlling the antibacterial activity of Ag-exchanged zeolites. The results show that Ag-FAU presents a higher activity than Ag-LTA, because the topology of FAU combined with its highest Si/Al ratio favors the formation and release of silver species with important biocidal activity. Some insights on the bactericidal mechanism of Ag-zeolites are envisaged by means of high resolution transmission electron microscopy, showing the multi-targeted biocidal action of Ag species released from zeolites. Besides, it is shown that Ag-zeolites are more active against bacteria than fungi. Antifungal activity is highly dependent on the fungi species and the structure of the zeolite is not as determinant as it is for the antibacterial activity.The authors thank the Spanish Ministry of Economy and Competitiveness through MAT-2015-71842-P and SEV-2016-0683 for the financial support and J.L. Cerrillo wish to thank Spanish Ministry of Economy and Competitiveness for the Severo Ochoa PhD fellowship (SVP-2014-068600).Cerrillo, JL.; Palomares Gimeno, AE.; Rey Garcia, F.; Valencia Valencia, S.; Pérez-Gago, MB.; Villamón-Pérez, D.; Palou-Valls, L. (2018). Functional Ag-Exchanged Zeolites as Biocide Agents. ChemistrySelect. 3(17):4676-4682. https://doi.org/10.1002/slct.201800432S46764682317Dai, D., Prussin, A. J., Marr, L. C., Vikesland, P. J., Edwards, M. A., & Pruden, A. (2017). Factors Shaping the Human Exposome in the Built Environment: Opportunities for Engineering Control. Environmental Science & Technology, 51(14), 7759-7774. doi:10.1021/acs.est.7b01097Klevens, R. 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Antibacterial Activity and Mechanism of Action of the Silver Ion in Staphylococcus aureus and Escherichia coli. Applied and Environmental Microbiology, 74(7), 2171-2178. doi:10.1128/aem.02001-07Sánchez, M. J., Mauricio, J. E., Paredes, A. R., Gamero, P., & Cortés, D. (2017). Antimicrobial properties of ZSM-5 type zeolite functionalized with silver. Materials Letters, 191, 65-68. doi:10.1016/j.matlet.2017.01.039Lalueza, P., Monzón, M., Arruebo, M., & Santamaría, J. (2011). Bactericidal effects of different silver-containing materials. Materials Research Bulletin, 46(11), 2070-2076. doi:10.1016/j.materresbull.2011.06.041Haile, T., Nakhla, G., Zhu, J., Zhang, H., & Shugg, J. (2010). Mechanistic study of the bactericidal action of silver-loaded chabasite on Acidithiobacillus thiooxidans. Microporous and Mesoporous Materials, 127(1-2), 32-40. doi:10.1016/j.micromeso.2009.06.030Saint-Cricq, P., Kamimura, Y., Itabashi, K., Sugawara-Narutaki, A., Shimojima, A., & Okubo, T. (2012). 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Unusually Low Heat of Adsorption of CO2 on AlPO and SAPO Molecular Sieves

[EN] The capture of CO2 from post-combustion streams or from other mixtures, such as natural gas, is an effective way of reducing CO2 emissions, which contribute to the greenhouse effect in the atmosphere. One of the developing technologies for this purpose is physisorption on selective solid adsorbents. The ideal adsorbents are selective toward CO2, have a large adsorption capacity at atmospheric pressure and are easily regenerated, resulting in high working capacity. Therefore, adsorbents combining molecular sieving properties and low heats of adsorption of CO2 are of clear interest as they will provide high selectivities and regenerabilities in CO2 separation process. Here we report that some aluminophosphate (AlPO) and silicoaluminophosphate (SAPO) materials with LTA, CHA and AFI structures present lower heats of adsorption of CO2 (13¿25 kJ/mol) than their structurally analogous zeolites at comparable framework charges. In some cases, their heats of adsorption are even lower than those of pure silica composition (20¿25 kJ/mol). This could mean a great improvement in the regeneration process compared to the most frequently used zeolitic adsorbents for this application while maintaining most of their adsorption capacity, if materials with the right stability and pore size and topology are found.We acknowledge the Spanish Ministry of Sciences, Innovation and Universities (MCIU), State Research Agency (AEI), and the European Fund for Regional Development (FEDER) for their funding via projects Multi2HYcat (EU-Horizon 2020 funded project under grant agreement no. 720783), Program Severo Ochoa SEV-2016-0683 and RTI2018-101033-B-I00 and also Fundacion Ramon Areces for funding through a research contract (CIVP18A3908). EP-B thanks the MCIU for his grant (FPU15/01602). NG-C thanks MCIU for her grant (BES-2016-078178).Pérez-Botella, E.; Martínez-Franco, R.; Gonzalez-Camuñas, N.; Cantin Sanz, A.; Palomino Roca, M.; Moliner Marin, M.; Valencia Valencia, S.... (2020). Unusually Low Heat of Adsorption of CO2 on AlPO and SAPO Molecular Sieves. Frontiers in Chemistry. 8:1-10. https://doi.org/10.3389/fchem.2020.588712S1108Bacsik, Z., Cheung, O., Vasiliev, P., & Hedin, N. (2016). Selective separation of CO2 and CH4 for biogas upgrading on zeolite NaKA and SAPO-56. Applied Energy, 162, 613-621. doi:10.1016/j.apenergy.2015.10.109BaerlocherC. H. McCuskerL. B. Database of Zeolite StructuresBoot-Handford, M. E., Abanades, J. C., Anthony, E. J., Blunt, M. J., Brandani, S., Mac Dowell, N., … Fennell, P. S. (2014). Carbon capture and storage update. Energy Environ. Sci., 7(1), 130-189. doi:10.1039/c3ee42350fBourgogneM. GuthJ.-L. WeyR. Process for the Preparation of Synthetic Zeolites, and Zeolites Obtained by Said Process1985Bui, M., Adjiman, C. 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