{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,8]],"date-time":"2026-01-08T23:46:22Z","timestamp":1767915982228,"version":"3.49.0"},"reference-count":48,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2020,8,29]],"date-time":"2020-08-29T00:00:00Z","timestamp":1598659200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UIDB\/50011\/2020 & UIDP\/50011\/2020"],"award-info":[{"award-number":["UIDB\/50011\/2020 & UIDP\/50011\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["SFRH\/BD\/140230\/2018"],"award-info":[{"award-number":["SFRH\/BD\/140230\/2018"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["CEECIND\/00263\/2018"],"award-info":[{"award-number":["CEECIND\/00263\/2018"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["SAICTPAC\/0032\/2015, POCI-01-0145-FEDER-016422"],"award-info":[{"award-number":["SAICTPAC\/0032\/2015, POCI-01-0145-FEDER-016422"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Nanomaterials"],"abstract":"<jats:p>The utilization of biobased materials for the fabrication of naturally derived ion-exchange membranes is breezing a path to sustainable separators for polymer electrolyte fuel cells (PEFCs). In this investigation, bacterial nanocellulose (BNC, a bacterial polysaccharide) and lignosulfonates (LS, a by-product of the sulfite pulping process), were blended by diffusion of an aqueous solution of the lignin derivative and of the natural-based cross-linker tannic acid into the wet BNC nanofibrous three-dimensional structure, to produce fully biobased ion-exchange membranes. These freestanding separators exhibited good thermal-oxidative stability of up to about 200 \u00b0C, in both inert and oxidative atmospheres (N2 and O2, respectively), high mechanical properties with a maximum Young\u2019s modulus of around 8.2 GPa, as well as good moisture-uptake capacity with a maximum value of ca. 78% after 48 h for the membrane with the higher LS content. Moreover, the combination of the conducting LS with the mechanically robust BNC conveyed ionic conductivity to the membranes, namely a maximum of 23 mS cm\u22121 at 94 \u00b0C and 98% relative humidity (RH) (in-plane configuration), that increased with increasing RH. Hence, these robust water-mediated ion conductors represent an environmentally friendly alternative to the conventional ion-exchange membranes for application in PEFCs.<\/jats:p>","DOI":"10.3390\/nano10091713","type":"journal-article","created":{"date-parts":[[2020,8,30]],"date-time":"2020-08-30T06:06:22Z","timestamp":1598767582000},"page":"1713","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":32,"title":["Flexible Nanocellulose\/Lignosulfonates Ion-Conducting Separators for Polymer Electrolyte Fuel Cells"],"prefix":"10.3390","volume":"10","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9212-2704","authenticated-orcid":false,"given":"Carla","family":"Vilela","sequence":"first","affiliation":[{"name":"Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"given":"Jo\u00e3o D.","family":"Morais","sequence":"additional","affiliation":[{"name":"Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8015-5904","authenticated-orcid":false,"given":"Ana Cristina Q.","family":"Silva","sequence":"additional","affiliation":[{"name":"Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"given":"Daniel","family":"Mu\u00f1oz-Gil","sequence":"additional","affiliation":[{"name":"Department of Materials and Ceramic Engineering, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7799-2608","authenticated-orcid":false,"given":"Filipe M. L.","family":"Figueiredo","sequence":"additional","affiliation":[{"name":"Department of Materials and Ceramic Engineering, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5403-8416","authenticated-orcid":false,"given":"Armando J. D.","family":"Silvestre","sequence":"additional","affiliation":[{"name":"Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"given":"Carmen S. R.","family":"Freire","sequence":"additional","affiliation":[{"name":"Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2020,8,29]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"5836","DOI":"10.1039\/C5CS00302D","article-title":"A concise guide to sustainable PEMFCs: Recent advances in improving both oxygen reduction catalysts and proton exchange membranes","volume":"44","author":"Scofield","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"20045","DOI":"10.1039\/C9TA07466J","article-title":"Nanocellulose-based materials as components of polymer electrolyte fuel cells","volume":"7","author":"Vilela","year":"2019","journal-title":"J. Mater. Chem. A"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"63","DOI":"10.1016\/j.carbpol.2019.05.008","article-title":"Bacterial cellulose production, properties and applications with different culture methods\u2014A review","volume":"219","author":"Wang","year":"2019","journal-title":"Carbohydr. Polym."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"633","DOI":"10.1111\/1751-7915.13386","article-title":"Molecular aspects of bacterial nanocellulose biosynthesis","volume":"12","author":"Jacek","year":"2019","journal-title":"Microb. Biotechnol."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"52","DOI":"10.1016\/j.electacta.2017.02.145","article-title":"Protonic conductivity and fuel cell tests of nanocomposite membranes based on bacterial cellulose","volume":"233","author":"Gadim","year":"2017","journal-title":"Electrochim. Acta"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"115604","DOI":"10.1016\/j.carbpol.2019.115604","article-title":"Conductive polysaccharides-based proton-exchange membranes for fuel cell applications: The case of bacterial cellulose and fucoidan","volume":"230","author":"Vilela","year":"2019","journal-title":"Carbohydr. Polym."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"122","DOI":"10.1016\/j.compscitech.2017.04.002","article-title":"Sulfonated bacterial cellulose\/polyaniline composite membrane for use as gel polymer electrolyte","volume":"145","author":"Yue","year":"2017","journal-title":"Compos. Sci. Technol."},{"key":"ref_8","doi-asserted-by":"crossref","unstructured":"Vilela, C., Martins, A.P.C., Sousa, N., Silvestre, A., Figueiredo, F.M.L., and Freire, C. (2018). Poly(bis[2-(methacryloyloxy)ethyl] phosphate)\/Bacterial Cellulose Nanocomposites: Preparation, Characterization and Application as Polymer Electrolyte Membranes. Appl. Sci., 8.","DOI":"10.3390\/app8071145"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"7864","DOI":"10.1021\/am501191t","article-title":"Nanostructured Bacterial Cellulose\u2013Poly(4-styrene sulfonic acid) Composite Membranes with High Storage Modulus and Protonic Conductivity","volume":"6","author":"Gadim","year":"2014","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"100376","DOI":"10.1016\/j.biteb.2019.100376","article-title":"Poly(4-styrene sulfonic acid)\/bacterial cellulose membranes: Electrochemical performance in a single-chamber microbial fuel cell","volume":"9","author":"Vilela","year":"2020","journal-title":"Bioresour. Technol. Rep."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"697","DOI":"10.1016\/j.jpowsour.2014.09.145","article-title":"Bacterial nanocellulose\/Nafion composite membranes for low temperature polymer electrolyte fuel cells","volume":"273","author":"Jiang","year":"2015","journal-title":"J. Power Sources"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"212","DOI":"10.1016\/j.indcrop.2016.01.028","article-title":"Nafion\u00ae and nanocellulose: A partnership for greener polymer electrolyte membranes","volume":"93","author":"Gadim","year":"2016","journal-title":"Ind. Crop. Prod."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"109453","DOI":"10.1016\/j.eurpolymj.2019.109453","article-title":"Proton conducting electrolytes composed of chondroitin sulfate polysaccharide and citric acid","volume":"124","author":"Santos","year":"2020","journal-title":"Eur. Polym. J."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4805","DOI":"10.1021\/acs.chemmater.6b01990","article-title":"High Temperature Proton Conduction in Nanocellulose Membranes: Paper Fuel Cells","volume":"28","author":"Bayer","year":"2016","journal-title":"Chem. Mater."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Holladay, J.E., White, J.F., Bozell, J.J., and Johnson, D. (2007). Top Value-Added Chemicals from Biomass Volume II\u2014Results of Screening for Potential Candidates from Biorefinery Lignin.","DOI":"10.2172\/921839"},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Moreno, A., and Sipponen, M.H. (2020). Lignin-based smart materials: A roadmap to processing and synthesis for current and future applications. Mater. Horiz.","DOI":"10.1039\/D0MH00798F"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1861","DOI":"10.1002\/cssc.201700082","article-title":"Production and Application of Lignosulfonates and Sulfonated Lignin","volume":"10","author":"Aro","year":"2017","journal-title":"ChemSusChem"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"30440","DOI":"10.1016\/j.ijhydene.2019.09.216","article-title":"High temperature proton exchange porous membranes based on polybenzimidazole\/lignosulfonate blends: Preparation, morphology and physical and proton conductivity properties","volume":"44","author":"Barati","year":"2019","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"292","DOI":"10.1016\/j.jpowsour.2005.02.052","article-title":"Lignin-based membranes for electrolyte transference","volume":"145","author":"Zhang","year":"2005","journal-title":"J. Power Sources"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1859","DOI":"10.1002\/adv.21844","article-title":"The influence of nano-silica on properties of sulfonated polystyrene-lignosulfonate membranes as proton exchange membranes for direct methanol fuel cell application","volume":"37","author":"Gonggo","year":"2017","journal-title":"Adv. Polym. Technol."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1016\/j.enzmictec.2006.07.038","article-title":"Physical properties of bacterial cellulose sheets produced in presence of lignosulfonate","volume":"40","author":"Keshk","year":"2006","journal-title":"Enzym. Microb. Technol."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"89","DOI":"10.6028\/jres.081A.011","article-title":"Humidity fixed points of binary saturated aqueous solutions","volume":"81","author":"Greenspan","year":"1977","journal-title":"J. Res. Natl. Bur. Stand. Sect. Phys. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"720","DOI":"10.1016\/j.mattod.2018.02.001","article-title":"Nanocellulose as a natural source for groundbreaking applications in materials science: Today\u2019s state","volume":"21","author":"Klemm","year":"2018","journal-title":"Mater. Today"},{"key":"ref_24","unstructured":"Ghazali, N.A., Naganawa, S., and Masuda, Y. (2018, January 12\u201314). Feasibility Study of Tannin-Lignosulfonate Drilling Fluid System for Drilling Geothermal Prospect. Proceedings of the 43rd Workshop on Geothermal Reservoir Engineering, Standford University, Stanford, CA, USA. SGP-TR-213."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"4476","DOI":"10.1021\/acs.biomac.9b01223","article-title":"Superstrong and Tough Hydrogel through Physical Cross-Linking and Molecular Alignment","volume":"20","author":"Chen","year":"2019","journal-title":"Biomacromolecules"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"3962","DOI":"10.1021\/ma800186q","article-title":"Hydrogen-Bonded Multilayers of a Neutral Polymer and a Polyphenol","volume":"41","author":"Sukhishvili","year":"2008","journal-title":"Macromolecules"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"666","DOI":"10.1021\/acs.macromol.6b02106","article-title":"Supramolecular Hydrogel Formation Based on Tannic Acid","volume":"50","author":"Fan","year":"2017","journal-title":"Macromolecules"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2609","DOI":"10.1039\/C6CS00895J","article-title":"Current characterization methods for cellulose nanomaterials","volume":"47","author":"Foster","year":"2018","journal-title":"Chem. Soc. Rev."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"207","DOI":"10.1016\/j.carbpol.2019.04.046","article-title":"Nanocellulose-based antifungal nanocomposites against the polymorphic fungus Candida albicans","volume":"217","author":"Vilela","year":"2019","journal-title":"Carbohydr. Polym."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"57","DOI":"10.1016\/j.colsurfa.2008.01.012","article-title":"A comparison of the surface properties of lignin and sulfonated lignins by FTIR spectroscopy and wicking technique","volume":"320","author":"Shen","year":"2008","journal-title":"Colloids Surf. Physicochem. Eng. Asp."},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Bellamy, L.J. (1975). The Infrared Spectra of Complex Molecules, Chapman and Hall Ltd.. [3rd ed.].","DOI":"10.1007\/978-94-011-6017-9"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"273","DOI":"10.1007\/s11051-017-3973-9","article-title":"The role of tannic acid and sodium citrate in the synthesis of silver nanoparticles","volume":"19","author":"Tomaszewska","year":"2017","journal-title":"J. Nanoparticle Res."},{"key":"ref_33","doi-asserted-by":"crossref","unstructured":"Mondal, M.I.H., and Ibrahim, M. (2019). Thermal behavior of bacterial cellulose-based hydrogels with other composites and related instrumental analysis. Cellulose-Based Superabsorbent Hydrogels, Springer.","DOI":"10.1007\/978-3-319-77830-3"},{"key":"ref_34","first-page":"1","article-title":"Carbonized lignosulfonate-based porous nanocomposites for adsorption of environmental contaminants","volume":"1","author":"Yao","year":"2020","journal-title":"Funct. Compos. Mater."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"3677","DOI":"10.1007\/s10570-016-1050-7","article-title":"Nanocellulose\/poly(methacryloyloxyethyl phosphate) composites as proton separator materials","volume":"23","author":"Vilela","year":"2016","journal-title":"Cellulose"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"116","DOI":"10.1016\/j.biombioe.2017.03.016","article-title":"Exploiting poly(ionic liquids) and nanocellulose for the development of bio-based anion-exchange membranes","volume":"100","author":"Vilela","year":"2017","journal-title":"Biomass Bioenergy"},{"key":"ref_37","unstructured":"(2020, July 07). DuPontTM Nafion\u00ae N115, N117, N1110\u2014Ion Exchange Materials, Product Bulletin P-12. Available online: http:\/\/fuelcellearth.com\/pdf\/nafion-N115-N117-N1110.pdf."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"813","DOI":"10.1016\/j.progpolymsci.2011.01.003","article-title":"Polymer membranes for high temperature proton exchange membrane fuel cell: Recent advances and challenges","volume":"36","author":"Bose","year":"2011","journal-title":"Prog. Polym. Sci."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"16064","DOI":"10.1021\/jp0482565","article-title":"Mechanisms of Ion and Water Transport in Perfluorosulfonated Ionomer Membranes for Fuel Cells","volume":"108","author":"Saito","year":"2004","journal-title":"J. Phys. Chem. B"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"5996","DOI":"10.1021\/jp810095g","article-title":"Temperature Dependence of Ion Transport: The Compensated Arrhenius Equation","volume":"113","author":"Petrowsky","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"5338","DOI":"10.1016\/j.ijhydene.2013.12.197","article-title":"Protonic conductivity and viscoelastic behaviour of Nafion\u00ae membranes with periodic mesoporous organosilica fillers","volume":"39","author":"Domingues","year":"2014","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"324","DOI":"10.1016\/j.ssi.2013.09.058","article-title":"Meso-structured organosilicas as fillers for Nafion\u00ae membranes","volume":"262","author":"Domingues","year":"2014","journal-title":"Solid State Ion."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"3646","DOI":"10.1021\/jp003182s","article-title":"Mechanisms of Proton Conductance in Polymer Electrolyte Membranes","volume":"105","author":"Eikerling","year":"2001","journal-title":"J. Phys. Chem. B"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"023001","DOI":"10.1088\/0953-8984\/28\/2\/023001","article-title":"Grotthuss mechanisms: From proton transport in proton wires to bioprotonic devices","volume":"28","author":"Miyake","year":"2015","journal-title":"J. Phys. Condens. Matter"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"719","DOI":"10.1002\/mame.200900143","article-title":"Recent Progress on Nafion-Based Nanocomposite Membranes for Fuel Cell Applications","volume":"294","author":"Cele","year":"2009","journal-title":"Macromol. Mater. Eng."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"348","DOI":"10.1016\/j.memsci.2016.12.030","article-title":"Thermo-mechanically stable sustainable polymer based solid electrolyte membranes for direct methanol fuel cell applications","volume":"526","author":"Gaur","year":"2017","journal-title":"J. Membr. Sci."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"641","DOI":"10.1016\/j.ultsonch.2017.10.029","article-title":"Construction of proton exchange membranes under ultrasonic irradiation based on novel fluorine functionalizing sulfonated polybenzimidazole\/cellulose\/silica bionanocomposite","volume":"41","author":"Esmaielzadeh","year":"2018","journal-title":"Ultrason. Sonochem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"1700070","DOI":"10.1002\/adsu.201700070","article-title":"Eco-Friendly Red Seaweed-Derived Electrolytes for Electrochemical Devices","volume":"1","author":"Nunes","year":"2017","journal-title":"Adv. Sustain. 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