{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T08:21:38Z","timestamp":1791361298256,"version":"4.3.1"},"reference-count":53,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2023,4,13]],"date-time":"2023-04-13T00:00:00Z","timestamp":1681344000000},"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 appeal of combining polybenzimidazole (PBI) and graphene oxide (GO) for the manufacturing of membranes is increasingly growing, due to their versatility. Nevertheless, GO has always been used only as a filler in the PBI matrix. In such context, this work proposes the design of a simple, safe, and reproducible procedure to prepare self-assembling GO\/PBI composite membranes characterized by GO-to-PBI (X:Y) mass ratios of 1:3, 1:2, 1:1, 2:1, and 3:1. SEM and XRD suggested a homogenous reciprocal dispersion of GO and PBI, which established an alternated stacked structure by mutual \u03c0-\u03c0 interactions among the benzimidazole rings of PBI and the aromatic domains of GO. TGA indicated a remarkable thermal stability of the composites. From mechanical tests, improved tensile strengths but worsened maximum strains were observed with respect to pure PBI. The preliminary evaluation of the suitability of the GO\/PBI X:Y composites as proton exchange membranes was executed via IEC determination and EIS. GO\/PBI 2:1 (IEC: 0.42 meq g\u22121; proton conductivity at 100 \u00b0C: 0.0464 S cm\u22121) and GO\/PBI 3:1 (IEC: 0.80 meq g\u22121; proton conductivity at 100 \u00b0C: 0.0451 S cm\u22121) provided equivalent or superior performances with respect to similar PBI-based state-of-the-art materials.<\/jats:p>","DOI":"10.3390\/membranes13040428","type":"journal-article","created":{"date-parts":[[2023,4,13]],"date-time":"2023-04-13T02:09:21Z","timestamp":1681351761000},"page":"428","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Study of Innovative GO\/PBI Composites as Possible Proton Conducting Membranes for Electrochemical Devices"],"prefix":"10.3390","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7371-6208","authenticated-orcid":false,"given":"Matteo","family":"Di Virgilio","sequence":"first","affiliation":[{"name":"Department of Chemistry, Materials and Chemical Engineering \u201cGiulio Natta\u201d, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2085-0240","authenticated-orcid":false,"given":"Andrea","family":"Basso Peressut","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Materials and Chemical Engineering \u201cGiulio Natta\u201d, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Angelo","family":"Pontoglio","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Materials and Chemical Engineering \u201cGiulio Natta\u201d, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7087-553X","authenticated-orcid":false,"given":"Saverio","family":"Latorrata","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Materials and Chemical Engineering \u201cGiulio Natta\u201d, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1876-9881","authenticated-orcid":false,"given":"Giovanni","family":"Dotelli","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Materials and Chemical Engineering \u201cGiulio Natta\u201d, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,4,13]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Escorihuela, J., Olvera-Mancilla, J., Alexandrova, L., del Castillo, L.F., and Compa\u00f1, V. (2020). Recent Progress in the Development of Composite Membranes Based on Polybenzimidazole for High Temperature Proton Exchange Membrane (PEM) Fuel Cell Applications. Polymers, 12.","DOI":"10.3390\/polym12091861"},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Quartarone, E., Angioni, S., and Mustarelli, P. (2017). Polymer and Composite Membranes for Proton-Conducting, High-Temperature Fuel Cells: A Critical Review. Materials, 10.","DOI":"10.3390\/ma10070687"},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Kamaroddin, M.F.A., Sabli, N., Tuan Abdullah, T.A., Siajam, S.I., Abdullah, L.C., Abdul Jalil, A., and Ahmad, A. (2021). Membrane-Based Electrolysis for Hydrogen Production: A Review. Membranes, 11.","DOI":"10.3390\/membranes11110810"},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Sun, X., Simonsen, S., Norby, T., and Chatzitakis, A. (2019). Composite Membranes for High Temperature PEM Fuel Cells and Electrolysers: A Critical Review. Membranes, 9.","DOI":"10.3390\/membranes9070083"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1199","DOI":"10.1016\/j.carbon.2010.11.036","article-title":"Graphene oxide\/polybenzimidazole composites fabricated by a solvent-exchange method","volume":"49","author":"Wang","year":"2011","journal-title":"Carbon N. Y."},{"key":"ref_6","doi-asserted-by":"crossref","unstructured":"Sulaiman, R.R.R., Walvekar, R., Khalid, M., Wong, W.Y., and Jagadish, P. (2020). Recent Progress in the Development of Aromatic Polymer-Based Proton Exchange Membranes for Fuel Cell Applications. Polymers, 12.","DOI":"10.3390\/polym12051061"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"110","DOI":"10.1016\/j.memsci.2019.04.030","article-title":"Crosslinked polybenzimidazole containing branching structure with no sacrifice of effective N-H sites: Towards high-performance high-temperature proton exchange membranes for fuel cells","volume":"583","author":"Wang","year":"2019","journal-title":"J. Memb. Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"119288","DOI":"10.1016\/j.memsci.2021.119288","article-title":"Achieving high power density and excellent durability for high temperature proton exchange membrane fuel cells based on crosslinked branched polybenzimidazole and metal-organic frameworks","volume":"630","author":"Wu","year":"2021","journal-title":"J. Memb. Sci."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"601","DOI":"10.1039\/C6CP05331A","article-title":"Why do proton conducting polybenzimidazole phosphoric acid membranes perform well in high-temperature PEM fuel cells?","volume":"19","author":"Melchior","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"365","DOI":"10.1016\/j.jpowsour.2017.07.109","article-title":"Investigation of electrolyte leaching in the performance degradation of phosphoric acid-doped polybenzimidazole membrane-based high temperature fuel cells","volume":"363","author":"Jeong","year":"2017","journal-title":"J. Power Sources"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"28615","DOI":"10.1016\/j.ijhydene.2022.06.156","article-title":"Feasibility of using thin polybenzimidazole electrolytes in high-temperature proton exchange membrane fuel cells","volume":"47","author":"Chen","year":"2022","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Wang, X., Jayaweera, P., Alrasheed, R., Aljlil, S., Alyousef, Y., Alsubaei, M., AlRomaih, H., and Jayaweera, I. (2018). Preparation of Polybenzimidazole Hollow-Fiber Membranes for Reverse Osmosis and Nanofiltration by Changing the Spinning Air Gap. Membranes, 8.","DOI":"10.3390\/membranes8040113"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"120977","DOI":"10.1016\/j.memsci.2022.120977","article-title":"Anti-fouling membranes for organic solvent nanofiltration (OSN) and organic solvent ultrafiltration (OSU): Graft modified polybenzimidazole (PBI)","volume":"662","author":"Oxley","year":"2022","journal-title":"J. Memb. Sci."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Kallem, P., Charmette, C., Drobek, M., Julbe, A., Mallada, R., and Pina, M. (2018). Exploring the Gas-Permeation Properties of Proton-Conducting Membranes Based on Protic Imidazolium Ionic Liquids: Application in Natural Gas Processing. Membranes, 8.","DOI":"10.3390\/membranes8030075"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"27331","DOI":"10.1016\/j.ijhydene.2020.07.091","article-title":"Macrovoid-free high performance polybenzimidazole hollow fiber membranes for elevated temperature H2\/CO2 separations","volume":"45","author":"Singh","year":"2020","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"210","DOI":"10.1016\/j.polymer.2019.04.048","article-title":"Polybenzimidazole membranes functionalised with 1-methyl-2-mesitylbenzimidazolium ions via a hexyl linker for use in vanadium flow batteries","volume":"174","author":"Lee","year":"2019","journal-title":"Polymer"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1594","DOI":"10.1039\/D2EE00267A","article-title":"High-performance PBI membranes for flow batteries: From the transport mechanism to the pilot plant","volume":"15","author":"Dai","year":"2022","journal-title":"Energy Environ. Sci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"2636","DOI":"10.1016\/j.ijhydene.2016.07.009","article-title":"Development of polybenzimidazole\/graphene oxide composite membranes for high temperature PEM fuel cells","volume":"42","author":"Devrim","year":"2017","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"118436","DOI":"10.1016\/j.memsci.2020.118436","article-title":"High temperature membranes based on PBI\/sulfonated polyimide and doped-perovskite nanoparticles for PEM fuel cells","volume":"612","author":"Hooshyari","year":"2020","journal-title":"J. Memb. Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"86","DOI":"10.1002\/jccs.202000196","article-title":"Magnetic field-induced alignment of polybenzimidazole microstructures to enhance proton conduction","volume":"68","author":"Sean","year":"2021","journal-title":"J. Chin. Chem. Soc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1002\/polb.23403","article-title":"A comparative study of phosphoric acid-doped m -PBI membranes","volume":"52","author":"Perry","year":"2014","journal-title":"J. Polym. Sci. Part B Polym. Phys."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"22209","DOI":"10.1016\/j.ijhydene.2019.10.030","article-title":"Phosphoric acid doped composite proton exchange membrane for hydrogen production in medium-temperature copper chloride electrolysis","volume":"45","author":"Kamaroddin","year":"2020","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_23","doi-asserted-by":"crossref","unstructured":"Diaz-Abad, S., Fern\u00e1ndez-Mancebo, S., Rodrigo, M.A., and Lobato, J. (2022). Characterization of PBI\/Graphene Oxide Composite Membranes for the SO2 Depolarized Electrolysis at High Temperature. Membranes, 12.","DOI":"10.3390\/membranes12020116"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"138133","DOI":"10.1016\/j.electacta.2021.138133","article-title":"An efficient barrier toward vanadium crossover in redox flow batteries: The bilayer [Nafion\/(WO3)x] hybrid inorganic-organic membrane","volume":"378","author":"Sun","year":"2021","journal-title":"Electrochim. Acta"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"27956","DOI":"10.1016\/j.ijhydene.2021.06.032","article-title":"Nafion degradation mechanisms in proton exchange membrane fuel cell (PEMFC) system: A review","volume":"46","author":"Okonkwo","year":"2021","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_26","first-page":"442","article-title":"Hydrogen production by PEM water electrolysis\u2014A review","volume":"2","author":"Himabindu","year":"2019","journal-title":"Mater. Sci. Energy Technol."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"76","DOI":"10.1016\/j.polymer.2015.03.040","article-title":"Low acid leaching PEM for fuel cell based on polybenzimidazole nanocomposites with protic ionic liquid modified silica","volume":"66","author":"Maity","year":"2015","journal-title":"Polymer"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"65","DOI":"10.1016\/j.memsci.2014.12.051","article-title":"Transmission electron microscopy study of silica reinforced polybenzimidazole membranes","volume":"478","author":"Heinzl","year":"2015","journal-title":"J. Memb. Sci."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"10044","DOI":"10.1016\/j.ijhydene.2016.02.043","article-title":"Polybenzimidazole\/SiO2 hybrid membranes for high temperature proton exchange membrane fuel cells","volume":"41","author":"Devrim","year":"2016","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"4448","DOI":"10.1016\/j.ijhydene.2017.12.128","article-title":"Effects of mesoporous fillers on properties of polybenzimidazole composite membranes for high-temperature polymer fuel cells","volume":"43","author":"Kuo","year":"2018","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"19690","DOI":"10.1016\/j.ijhydene.2021.11.045","article-title":"Preparation of polybenzimidazole\/ZIF-8 and polybenzimidazole\/UiO-66 composite membranes with enhanced proton conductivity","volume":"47","author":"Eren","year":"2022","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"99","DOI":"10.1016\/j.eurpolymj.2017.05.024","article-title":"Grafted polybenzimidazole copolymers bearing polyhedral oligosilsesquioxane pendant moieties","volume":"94","author":"Zhao","year":"2017","journal-title":"Eur. Polym. J."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"27510","DOI":"10.1016\/j.ijhydene.2020.07.026","article-title":"Sulfonated graphene oxide as an inorganic filler in promoting the properties of a polybenzimidazole membrane as a high temperature proton exchange membrane","volume":"45","author":"Yusoff","year":"2020","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"9004","DOI":"10.1016\/j.ijhydene.2021.12.257","article-title":"Composite membrane by incorporating sulfonated graphene oxide in polybenzimidazole for high temperature proton exchange membrane fuel cells","volume":"47","author":"Devrim","year":"2022","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_35","doi-asserted-by":"crossref","unstructured":"Sulaiman, R.R.R., Walvekar, R., Wong, W.Y., Khalid, M., and Pang, M.M. (2022). Proton Conductivity Enhancement at High Temperature on Polybenzimidazole Membrane Electrolyte with Acid-Functionalized Graphene Oxide Fillers. Membranes, 12.","DOI":"10.3390\/membranes12030344"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"238","DOI":"10.1016\/j.jpowsour.2018.11.057","article-title":"Highly durable polybenzimidazole composite membranes with phosphonated graphene oxide for high temperature polymer electrolyte membrane fuel cells","volume":"412","author":"Zakeri","year":"2019","journal-title":"J. Power Sources"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"480","DOI":"10.1007\/s10965-021-02846-x","article-title":"Phosphorylated graphene oxide-reinforced polybenzimidazole composite membrane for high-temperature proton exchange membrane fuel cell","volume":"28","author":"Zhao","year":"2021","journal-title":"J. Polym. Res."},{"key":"ref_38","doi-asserted-by":"crossref","unstructured":"Basso Peressut, A., Di Virgilio, M., Bombino, A., Latorrata, S., Muurinen, E., Keiski, R.L., and Dotelli, G. (2022). Investigation of Sulfonated Graphene Oxide as the Base Material for Novel Proton Exchange Membranes. Molecules, 27.","DOI":"10.3390\/molecules27051507"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"115858","DOI":"10.1016\/j.ssi.2022.115858","article-title":"Graphene oxide-naphthalene sulfonate blends as possible proton exchange membranes","volume":"376","author":"Latorrata","year":"2022","journal-title":"Solid State Ion."},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Yuan, X.-Z., Song, C., Wang, H., and Zhang, J. (2010). Electrochemical Impedance Spectroscopy in PEM Fuel Cells, Springer.","DOI":"10.1007\/978-1-84882-846-9"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"F914","DOI":"10.1149\/2.0051811jes","article-title":"Phosphoric Acid Doped Crosslinked Polybenzimidazole\/Modified Graphene Oxide Composite Membranes for High Temperature Proton Exchange Membrane Applications","volume":"165","author":"Cai","year":"2018","journal-title":"J. Electrochem. Soc."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1701","DOI":"10.1016\/j.cjche.2020.01.009","article-title":"Influence of solvent on ion conductivity of polybenzimidazole proton exchange membranes for vanadium redox flow batteries","volume":"28","author":"Wang","year":"2020","journal-title":"Chinese J. Chem. Eng."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"4034","DOI":"10.1039\/C4GC00613E","article-title":"Towards non-toxic solvents for membrane preparation: A review","volume":"16","author":"Figoli","year":"2014","journal-title":"Green Chem."},{"key":"ref_44","doi-asserted-by":"crossref","unstructured":"Latorrata, S., Cristiani, C., Basso Peressut, A., Brambilla, L., Bellotto, M., Dotelli, G., Finocchio, E., Gallo Stampino, P., and Ramis, G. (2020). Reduced Graphene Oxide Membranes as Potential Self-Assembling Filter for Wastewater Treatment. Minerals, 11.","DOI":"10.3390\/min11010015"},{"key":"ref_45","doi-asserted-by":"crossref","unstructured":"Haynes, W.M. (2014). CRC Handbook of Chemistry and Physics, CRC Press.","DOI":"10.1201\/b17118"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"12254","DOI":"10.1016\/j.ijhydene.2020.02.193","article-title":"Polybenzimidazole composite membranes containing imidazole functionalized graphene oxide showing high proton conductivity and improved physicochemical properties","volume":"46","author":"Kim","year":"2021","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1155\/2019\/6464713","article-title":"Designing Carbon\/Oxygen Ratios of Graphene Oxide Membranes for Proton Exchange Membrane Fuel Cells","volume":"2019","author":"Ahn","year":"2019","journal-title":"J. Nanomater."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"2425","DOI":"10.1016\/j.cjche.2020.05.016","article-title":"Sulfonated polybenzimidazole\/amine functionalized titanium dioxide (sPBI\/AFT) composite electrolyte membranes for high temperature proton exchange membrane fuel cells usage","volume":"28","author":"Imran","year":"2020","journal-title":"Chin. J. Chem. Eng."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"141252","DOI":"10.1016\/j.electacta.2022.141252","article-title":"N-H group-rich dendrimer doped polybenzimidazole composite membrane with consecutive proton transportation channels for HT-PEMFCs","volume":"434","author":"Cheng","year":"2022","journal-title":"Electrochim. Acta"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"3756","DOI":"10.1002\/adfm.201500998","article-title":"Thickness Dependence of the Mechanical Properties of Free-Standing Graphene Oxide Papers","volume":"25","author":"Gong","year":"2015","journal-title":"Adv. Funct. Mater."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"104945","DOI":"10.1016\/j.jece.2020.104945","article-title":"Composite membrane of sulfonated polybenzimidazole and sulfonated graphene oxide for potential application in microbial fuel cell","volume":"9","author":"Mondal","year":"2021","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"11359","DOI":"10.1039\/c1jm11159k","article-title":"A polybenzimidazole\/sulfonated graphite oxide composite membrane for high temperature polymer electrolyte membrane fuel cells","volume":"21","author":"Xu","year":"2011","journal-title":"J. Mater. Chem."},{"key":"ref_53","doi-asserted-by":"crossref","unstructured":"Sun, C., and Zhang, H. (2019). Investigation of Nafion series membranes on the performance of iron-chromium redox flow battery. Int. J. Energy Res., 43.","DOI":"10.1002\/er.4875"}],"container-title":["Membranes"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2077-0375\/13\/4\/428\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T19:15:13Z","timestamp":1760123713000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2077-0375\/13\/4\/428"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,4,13]]},"references-count":53,"journal-issue":{"issue":"4","published-online":{"date-parts":[[2023,4]]}},"alternative-id":["membranes13040428"],"URL":"https:\/\/doi.org\/10.3390\/membranes13040428","relation":{},"ISSN":["2077-0375"],"issn-type":[{"value":"2077-0375","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,4,13]]}}}