{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,15]],"date-time":"2026-01-15T00:48:02Z","timestamp":1768438082246,"version":"3.49.0"},"reference-count":51,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2021,7,9]],"date-time":"2021-07-09T00:00:00Z","timestamp":1625788800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Membranes"],"abstract":"<jats:p>The external surface of a commercial porous stainless steel (PSS) was modified by either oxidation in air at varying temperatures (600, 700, and 800 \u00b0C) or coating with different oxides (SiO2, Al2O3, and ZrO2). Among them, PSS-ZrO2 appears as the most suitable carrier for the synthesis of the Pd membrane. A composite Pd membrane supported on the PSS-ZrO2 substrate was prepared by the electroless plating deposition method. Supported Ru catalysts were first evaluated for the low-temperature methane dry reforming (DRM) reaction in a continuous flow reactor (CR). Ru\/ZrO2-La2O3 catalyst was found to be active and stable, so it was used in a membrane reactor (MR), which enhances the methane conversions above the equilibrium values. The influence of adding H2O to the feed of DRM was investigated over a Ru\/ZrO2-La2O3 catalyst in the MR. Activity results are compared with those measured in a CR. The addition of H2O into the feed favors other reactions such as Water-Gas Shift (RWGS) and Steam Reforming (SR), which occur together with DRM, resulting in a dramatic decrease of CO2 conversion and CO production, but a marked increase of H2 yield.<\/jats:p>","DOI":"10.3390\/membranes11070518","type":"journal-article","created":{"date-parts":[[2021,7,9]],"date-time":"2021-07-09T10:50:38Z","timestamp":1625827838000},"page":"518","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Preparation, Characterization, and Activity of Pd\/PSS-Modified Membranes in the Low Temperature Dry Reforming of Methane with and without Addition of Extra Steam"],"prefix":"10.3390","volume":"11","author":[{"given":"Cecilia","family":"Mateos-Pedrero","sequence":"first","affiliation":[{"name":"Instituto de Cat\u00e1lisis y Petroleoqu\u00edmica, CSIC, Calle Marie Curie 2, 28049 Madrid, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4694-3680","authenticated-orcid":false,"given":"Miguel A.","family":"Soria","sequence":"additional","affiliation":[{"name":"Instituto de Cat\u00e1lisis y Petroleoqu\u00edmica, CSIC, Calle Marie Curie 2, 28049 Madrid, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1848-5985","authenticated-orcid":false,"given":"Antonio","family":"Guerrero-Ru\u00edz","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica y Qu\u00edmica T\u00e9cnica, Facultad de Ciencias UNED, Senda del Rey 9, 28040 Madrid, Spain"},{"name":"UA UNED-ICP (CSIC), Grupo de Dise\u00f1o y Aplicaci\u00f3n de Catalizadores Heterog\u00e9neos, 28049 Madrid, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4622-6008","authenticated-orcid":false,"given":"Inmaculada","family":"Rodr\u00edguez-Ramos","sequence":"additional","affiliation":[{"name":"Instituto de Cat\u00e1lisis y Petroleoqu\u00edmica, CSIC, Calle Marie Curie 2, 28049 Madrid, Spain"},{"name":"UA UNED-ICP (CSIC), Grupo de Dise\u00f1o y Aplicaci\u00f3n de Catalizadores Heterog\u00e9neos, 28049 Madrid, Spain"}]}],"member":"1968","published-online":{"date-parts":[[2021,7,9]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"343","DOI":"10.1016\/j.memsci.2016.09.029","article-title":"Natural gas steam reforming reaction at low temperature and pressure conditions for hydrogen production via Pd\/PSS membrane reactor","volume":"522","author":"Anzelmo","year":"2017","journal-title":"J. Membr. Sci."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"5558","DOI":"10.1021\/acs.energyfuels.0c04352","article-title":"Palladium-Alloy Membrane Reactors for Fuel Reforming and Hydrogen Production: A Review","volume":"35","author":"Habib","year":"2021","journal-title":"Energy Fuels"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"211","DOI":"10.1016\/S0376-7388(98)00256-7","article-title":"Model of hydrogen permeation behavior in palladium membranes","volume":"153","author":"Ward","year":"1999","journal-title":"J. Membr. Sci."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"206","DOI":"10.1016\/j.jiec.2019.09.010","article-title":"Preparation of Pd\/SAPO-34\/PSS composite membranes for hydrogen separation: Effect of crystallization time on the zeolite growth on PSS support","volume":"81","author":"Kiadehi","year":"2020","journal-title":"J. Ind. Eng. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"92","DOI":"10.1016\/j.memsci.2005.08.003","article-title":"Different oxides used as diffusion barriers in composite hydrogen permeable membranes","volume":"274","author":"Yepes","year":"2006","journal-title":"J. Membr. Sci."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"779","DOI":"10.1016\/S0167-2991(10)75159-4","article-title":"Modifications of porous stainless steel previous to the synthesis of Pd membranes","volume":"175","author":"Soria","year":"2010","journal-title":"Stud. Surf. Sci. Catal."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"72","DOI":"10.1016\/S0040-6090(96)08544-6","article-title":"Structurally stable composite Pd-Ag alloy membranes: Introduction of a diffusion barrier","volume":"286","author":"Shu","year":"1996","journal-title":"Thin Solid Film."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"213","DOI":"10.1016\/j.memsci.2012.05.001","article-title":"Durability of PSS-supported Pd-membranes under mixed gas and water\u2013gas shift conditions","volume":"415-416","author":"Augustine","year":"2012","journal-title":"J. Membr. Sci."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1274","DOI":"10.1016\/j.fuel.2009.12.006","article-title":"Hydrogen separation through palladium\u2013copper membranes on porous stainless steel with sol\u2013gel derived ceria as diffusion barrier","volume":"89","author":"Qiao","year":"2010","journal-title":"Fuel"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"267","DOI":"10.1016\/j.memsci.2010.12.006","article-title":"Surface characterization of Pd-Ag composite membranes after annealing at various temperatures","volume":"369","author":"Bosko","year":"2011","journal-title":"J. Membr. Sci."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"84","DOI":"10.1016\/j.memsci.2005.03.039","article-title":"Preparation of a pinhole-free Pd-Ag membrane on a porous metal support for pure hydrogen separation","volume":"260","author":"Tong","year":"2005","journal-title":"J. Membr. Sci."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.memsci.2012.10.029","article-title":"PdAu membranes supported on top of vacuum-assisted ZrO2-modified porous stainless steel substrates","volume":"428","author":"Tarditi","year":"2013","journal-title":"J. Membr. Sci."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"160","DOI":"10.1016\/j.memsci.2007.06.040","article-title":"Preparation of thin palladium membranes on a porous support with rough surface","volume":"302","author":"Huang","year":"2007","journal-title":"J. Membr. Sci."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"13007","DOI":"10.1016\/j.ijhydene.2012.05.064","article-title":"Fabrication of H2-permeable palladium membranes based on pencil-coated porous stainless steel substrate","volume":"37","author":"Wei","year":"2012","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"6030","DOI":"10.1016\/j.ijhydene.2011.12.164","article-title":"Influence of the type of siliceous material used as intermediate layer in the preparation of hydrogen selective palladium composite membranes over a porous stainless steel support","volume":"37","author":"Calles","year":"2012","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"54","DOI":"10.1016\/j.jechem.2019.12.017","article-title":"Tuning combined steam and dry reforming of methane for \u201cmetgas\u201d production: A thermodynamic approach and state-of-the-art catalysts","volume":"48","author":"Jabbour","year":"2020","journal-title":"J. Energy Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1254","DOI":"10.1016\/j.renene.2020.05.023","article-title":"Hydrogen and\/or syngas production through combined dry and steam reforming of biogas in a membrane reactor: A thermodynamic study","volume":"157","author":"Parente","year":"2020","journal-title":"Renew. Energy"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"239","DOI":"10.1016\/S0926-860X(02)00337-X","article-title":"On the applicability of membrane technology to the catalysed dry reforming of methane","volume":"237","year":"2002","journal-title":"Appl. Catal. A Gen."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"10444","DOI":"10.1016\/j.ijhydene.2011.09.149","article-title":"Dry reforming of methane has no future for hydrogen production: Comparison with steam reforming at high pressure in standard and membrane reactors","volume":"37","author":"Oyama","year":"2012","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"122","DOI":"10.1016\/j.micromeso.2017.11.028","article-title":"Combined steam and CO2 reforming of methane for syngas production over carbon-resistant boron-promoted Ni\/SBA-15 catalysts","volume":"262","author":"Siang","year":"2018","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"15212","DOI":"10.1016\/j.ijhydene.2011.08.117","article-title":"Thermodynamic and experimental study of combined dry and steam reforming of methane on Ru\/ ZrO2-La2O3 catalyst at low temperature","volume":"36","author":"Soria","year":"2011","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"8","DOI":"10.1016\/j.coche.2015.07.003","article-title":"Catalytic bi-reforming of methane: From greenhouse gases to syngas","volume":"9","author":"Kumar","year":"2015","journal-title":"Curr. Opin. Chem. Eng."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"527","DOI":"10.1016\/j.apcatb.2016.08.009","article-title":"Ordered mesoporous \u201cone-pot\u201d synthesized Ni-Mg(Ca)-Al2O3 as effective and remarkably stable catalysts for combined steam and dry reforming of methane (CSDRM)","volume":"201","author":"Jabbour","year":"2017","journal-title":"Appl. Catal. B Environ."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"126","DOI":"10.1016\/j.cattod.2011.02.020","article-title":"Catalytic steam reforming of methane under conditions of applicability with Pd membranes over supported Ru catalysts","volume":"171","author":"Soria","year":"2011","journal-title":"Catal. Today"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"177","DOI":"10.1016\/S0926-860X(98)00048-9","article-title":"Comparative study at low and medium reaction temperatures of syngas production by methane reforming with carbon dioxide over silica and alumina supported catalysts","volume":"170","year":"1998","journal-title":"Appl. Catal. A Gen."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"80","DOI":"10.1016\/j.apenergy.2016.04.006","article-title":"Combined steam and carbon dioxide reforming of methane and side reactions: Thermodynamic equilibrium analysis and experimental application","volume":"173","author":"Jang","year":"2016","journal-title":"Appl. Energy"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"2950","DOI":"10.1016\/j.ijhydene.2010.11.080","article-title":"CO2 reforming of methane over Pt-Ni\/Al2O3 catalysts: Effects of catalyst composition, and water and oxygen addition to the feed","volume":"36","author":"Aksoylu","year":"2011","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"135","DOI":"10.1016\/j.cattod.2013.02.024","article-title":"Comparison of Ru\/La2O2CO3 performance in two different membrane reactors for hydrogen production","volume":"213","author":"Faroldi","year":"2013","journal-title":"Catal. Today"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"194","DOI":"10.3390\/fuels2020012","article-title":"Biogas Dry Reforming for Hydrogen through Membrane Reactor Utilizing Negative Pressure","volume":"2","author":"Nishimura","year":"2021","journal-title":"Fuels"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"218","DOI":"10.1016\/j.memsci.2013.02.029","article-title":"Dry reforming of methane using Pd-based membrane reactors fabricated from different substrates","volume":"435","author":"Soria","year":"2013","journal-title":"J. Membr. Sci."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1016\/j.memsci.2010.07.039","article-title":"Dry reforming of methane in membrane reactors using Pd and Pd\u2013Ag composite membranes on a NaA zeolite modified porous stainless steel support","volume":"364","author":"Bosko","year":"2010","journal-title":"J. Membr. Sci."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Caravella, A., Brunetti, A., Grandinetti, M., and Barbieri, G. (2018). Dry Reforming of Methane in a Pd-Ag Membrane Reactor: Thermodynamic and Experimental Analysis. ChemEngineering, 2.","DOI":"10.3390\/chemengineering2040048"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"772","DOI":"10.1016\/j.cej.2019.03.199","article-title":"Pure hydrogen from biogas: Intensified methane dry reforming in a two-zone fluidized bed reactor using permselective membranes","volume":"370","author":"Soler","year":"2019","journal-title":"Chem. Eng. J."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"185","DOI":"10.1016\/j.apcata.2011.04.030","article-title":"Pd based membrane reactor for ultra pure hydrogen production through the dry reforming of methane. Experimental and modeling studies","volume":"400","author":"Coronel","year":"2011","journal-title":"Appl. Catal. A Gen."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1051","DOI":"10.1002\/aic.690480514","article-title":"Analyzing enhancement of CO2, reforming of CH4, in Pd membrane reactors","volume":"48","author":"Raybold","year":"2002","journal-title":"AIChE J."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"928","DOI":"10.1021\/ie030485a","article-title":"Experimental Study of the Methane Steam Reforming Reaction in a Dense Pd\/Ag Membrane Reactor","volume":"43","author":"Gallucci","year":"2004","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Iulianelli, A., Alavi, M., Bagnato, G., Liguori, S., Wilcox, J., Rahimpour, M.R., Eslamlouyan, R., Anzelmo, B., and Basile, A. (2016). Supported Pd-Au Membrane Reactor for Hydrogen Production: Membrane Preparation, Characterization and Testing. Molecules, 21.","DOI":"10.3390\/molecules21050581"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"25","DOI":"10.1016\/j.jpowsour.2014.09.058","article-title":"Model biogas steam reforming in a thin Pd-supported membrane reactor to generate clean hydrogen for fuel cells","volume":"273","author":"Iulianelli","year":"2015","journal-title":"J. Power Sources"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"451","DOI":"10.1016\/j.ces.2009.04.013","article-title":"Steam reforming of biogas mixtures with a palladium membrane reactor system","volume":"65","author":"Sato","year":"2010","journal-title":"Chem. Eng. Sci."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"131","DOI":"10.1016\/j.cep.2018.04.023","article-title":"Potentiality of a biogas membrane reformer for decentralized hydrogen production","volume":"129","author":"Foresti","year":"2018","journal-title":"Chem. Eng. Process. Process Intensif."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"10","DOI":"10.1016\/j.memsci.2005.03.016","article-title":"A novel method for the preparation of thin dense Pd membrane on macroporous stainless steel tube filter","volume":"260","author":"Tong","year":"2005","journal-title":"J. Membr. Sci."},{"key":"ref_42","unstructured":"Ma, Y.H., Mardilovich, P.P., and She, Y. (2000). Hydrogen Gas-Extraction Module and Method of Fabrication. (6,152,987), U.S. Patent."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"366","DOI":"10.1016\/j.apcata.2011.11.030","article-title":"Kinetic analysis of the Ru\/SiO2-catalyzed low temperature methane steam reforming","volume":"413\u2013414","author":"Soria","year":"2012","journal-title":"Appl. Catal. A Gen."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"3821","DOI":"10.1016\/S0009-2509(98)00189-4","article-title":"Ethylene epoxidation in a catalytic packed-bed membrane reactor","volume":"53","author":"Carr","year":"1998","journal-title":"Chem. Eng. Sci."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"57","DOI":"10.1016\/j.memsci.2009.01.005","article-title":"NaA zeolite as an effective diffusion barrier in composite Pd\/PSS membranes","volume":"331","author":"Bosko","year":"2009","journal-title":"J. Membr. Sci."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"893","DOI":"10.1002\/cber.191004301152","article-title":"Solubility of gases in metals and alloys","volume":"43","author":"Sieverts","year":"1910","journal-title":"Ber. Deut. Chem. Ges."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"15783","DOI":"10.1016\/j.ijhydene.2011.08.102","article-title":"Preparation, testing and modelling of a hydrogen selective Pd\/YSZ\/SS composite membrane","volume":"36","author":"Sanz","year":"2011","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"87","DOI":"10.1016\/j.cattod.2020.09.014","article-title":"Combined steam and dry reforming of methane for syngas production from biogas using bimodal pore catalysts","volume":"366","author":"Dan","year":"2021","journal-title":"Catal. Today"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"199","DOI":"10.1007\/s11814-016-0227-y","article-title":"Parametric studies for CO2 reforming of methane in a membrane reactor as a new CO2 utilization process","volume":"34","author":"Lee","year":"2017","journal-title":"Korean J. Chem. Eng."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1016\/j.apcata.2005.03.018","article-title":"A stable, novel catalyst improves hydrogen production in a membrane reactor","volume":"287","author":"Irusta","year":"2005","journal-title":"Appl. Catal. A Gen."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"114","DOI":"10.1016\/j.apcata.2013.09.018","article-title":"Supported Rh nanoparticles on CaO\u2013SiO2 binary systems for the reforming of methane by carbon dioxide in membrane reactors","volume":"474","author":"Faroldi","year":"2014","journal-title":"Appl. Catal. A Gen."}],"container-title":["Membranes"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2077-0375\/11\/7\/518\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:28:25Z","timestamp":1760164105000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2077-0375\/11\/7\/518"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,7,9]]},"references-count":51,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2021,7]]}},"alternative-id":["membranes11070518"],"URL":"https:\/\/doi.org\/10.3390\/membranes11070518","relation":{},"ISSN":["2077-0375"],"issn-type":[{"value":"2077-0375","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,7,9]]}}}