{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,14]],"date-time":"2026-01-14T15:36:03Z","timestamp":1768404963867,"version":"3.49.0"},"reference-count":41,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2023,8,10]],"date-time":"2023-08-10T00:00:00Z","timestamp":1691625600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["52270058"],"award-info":[{"award-number":["52270058"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["2022YFC3203402"],"award-info":[{"award-number":["2022YFC3203402"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["CX2021121"],"award-info":[{"award-number":["CX2021121"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012166","name":"National Key Research and Development Program of China","doi-asserted-by":"publisher","award":["52270058"],"award-info":[{"award-number":["52270058"]}],"id":[{"id":"10.13039\/501100012166","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012166","name":"National Key Research and Development Program of China","doi-asserted-by":"publisher","award":["2022YFC3203402"],"award-info":[{"award-number":["2022YFC3203402"]}],"id":[{"id":"10.13039\/501100012166","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012166","name":"National Key Research and Development Program of China","doi-asserted-by":"publisher","award":["CX2021121"],"award-info":[{"award-number":["CX2021121"]}],"id":[{"id":"10.13039\/501100012166","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Venture &amp; Innovation Support Program for Chongqing Overseas Returnees","award":["52270058"],"award-info":[{"award-number":["52270058"]}]},{"name":"Venture &amp; Innovation Support Program for Chongqing Overseas Returnees","award":["2022YFC3203402"],"award-info":[{"award-number":["2022YFC3203402"]}]},{"name":"Venture &amp; Innovation Support Program for Chongqing Overseas Returnees","award":["CX2021121"],"award-info":[{"award-number":["CX2021121"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Membranes"],"abstract":"<jats:p>Competition for the migration of interfering cations limits the scale-up and implementation of the Donnan dialysis process for the recovery of ammonia nitrogen (NH4+-N) from wastewater in practice. Highly efficient selective permeation of NH4+ through a cation exchange membrane (CEM) is expected to be modulated via tuning the surface charge and structure of CEM. In this work, a novel CEM was designed to form a graphene oxide (GO)-polyethyleneimine (PEI) cross-linked layer by introducing self-assembling layers of GO and PEI on the surface of a commercial CEM, which rationally regulates the surface charge and structure of the membrane. The resulting positively charged membrane surface exhibits stronger repulsion for divalent cations compared to monovalent cations according to Coulomb\u2019s law, while, simultaneously, GO forms \u03c0\u2013metal cation conjugates between metal cations (e.g., Mg2+ and Ca2+), thus limiting metal cation transport across the membrane. During the DD process, higher NH4+ concentrations resulted in a longer time to reach Donnan equilibrium and higher NH4+ flux, while increased Mg2+ concentrations resulted in lower NH4+ flux (from 0.414 to 0.213 mol\u00b7m\u22122\u00b7h\u22121). Using the synergistic effect of electrostatic interaction and non-covalent cross-linking, the designed membrane, referred to as GO-PEI (20) and prepared by a 20 min impregnation in the GO-PEI mixture, exhibited an NH4+ transport rate of 0.429 mol\u00b7m\u22122\u00b7h\u22121 and a Mg2+ transport rate of 0.003 mol\u00b7m\u22122\u00b7h\u22121 in single-salt solution tests and an NH4+\/Mg2+ selectivity of 15.46, outperforming those of the unmodified and PEI membranes (1.30 and 5.74, respectively). In mixed salt solution tests, the GO-PEI (20) membrane showed a selectivity of 15.46 (~1.36, the unmodified membrane) for NH4+\/Mg2+ and a good structural stability after 72 h of continuous operation. Therefore, this facile surface charge modulation approach provides a promising avenue for achieving efficient NH4+-selective separation by modified CEMs.<\/jats:p>","DOI":"10.3390\/membranes13080726","type":"journal-article","created":{"date-parts":[[2023,8,10]],"date-time":"2023-08-10T10:52:40Z","timestamp":1691664760000},"page":"726","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Graphene Oxide\/Polyethyleneimine-Modified Cation Exchange Membrane for Efficient Selective Recovery of Ammonia Nitrogen from Wastewater"],"prefix":"10.3390","volume":"13","author":[{"given":"Yuanyuan","family":"Yu","sequence":"first","affiliation":[{"name":"Key Laboratory of the Three Gorges Reservoir Region\u2019s Eco-Environment, Ministry of Education, College of Environment and Ecology, Chongqing University, Chongqing 400045, China"}]},{"given":"Qin","family":"Zeng","sequence":"additional","affiliation":[{"name":"Key Laboratory of the Three Gorges Reservoir Region\u2019s Eco-Environment, Ministry of Education, College of Environment and Ecology, Chongqing University, Chongqing 400045, China"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4089-5307","authenticated-orcid":false,"given":"Haoquan","family":"Zhang","sequence":"additional","affiliation":[{"name":"Key Laboratory of the Three Gorges Reservoir Region\u2019s Eco-Environment, Ministry of Education, College of Environment and Ecology, Chongqing University, Chongqing 400045, China"}]},{"given":"Maoqin","family":"Ao","sequence":"additional","affiliation":[{"name":"Key Laboratory of the Three Gorges Reservoir Region\u2019s Eco-Environment, Ministry of Education, College of Environment and Ecology, Chongqing University, Chongqing 400045, China"}]},{"given":"Jingmei","family":"Yao","sequence":"additional","affiliation":[{"name":"Key Laboratory of the Three Gorges Reservoir Region\u2019s Eco-Environment, Ministry of Education, College of Environment and Ecology, Chongqing University, Chongqing 400045, China"}]},{"given":"Chun","family":"Yang","sequence":"additional","affiliation":[{"name":"Key Laboratory of the Three Gorges Reservoir Region\u2019s Eco-Environment, Ministry of Education, College of Environment and Ecology, Chongqing University, Chongqing 400045, China"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9446-0897","authenticated-orcid":false,"given":"Svetlozar","family":"Velizarov","sequence":"additional","affiliation":[{"name":"LAQV\/REQUIMTE, Department of Chemistry, NOVA School of Science and Technology, FCT NOVA, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8695-1995","authenticated-orcid":false,"given":"Le","family":"Han","sequence":"additional","affiliation":[{"name":"Key Laboratory of the Three Gorges Reservoir Region\u2019s Eco-Environment, Ministry of Education, College of Environment and Ecology, Chongqing University, Chongqing 400045, China"}]}],"member":"1968","published-online":{"date-parts":[[2023,8,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"10313","DOI":"10.1021\/acs.est.0c01496","article-title":"Utilization of Bidirectional Cation Transport in Thin Film Composite Membrane: Selective Removal and Reclamation of Ammonium from Synthetic Digested Sludge Centrate via Osmosis-Distillation Hybrid Membrane Process","volume":"54","author":"Wang","year":"2020","journal-title":"Environ. Sci. Technol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"11066","DOI":"10.1021\/acs.est.9b00603","article-title":"Mainstream Ammonium Recovery to Advance Sustainable Urban Wastewater Management","volume":"53","author":"Cruz","year":"2019","journal-title":"Environ. Sci. Technol."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"114616","DOI":"10.1016\/j.apenergy.2020.114616","article-title":"From removal to recovery: An evaluation of nitrogen recovery techniques from wastewater","volume":"263","author":"Beckinghausen","year":"2020","journal-title":"Appl. Energy"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"126662","DOI":"10.1016\/j.cej.2020.126662","article-title":"Ammonia harvesting via membrane gas extraction at moderately alkaline pH: A step toward net-profitable nitrogen recovery from domestic wastewater","volume":"405","author":"Lee","year":"2021","journal-title":"Chem. Eng. J."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"696","DOI":"10.1016\/j.cej.2016.08.134","article-title":"Investigation on the simultaneous removal of fluoride, ammonia nitrogen and phosphate from semiconductor wastewater using chemical precipitation","volume":"307","author":"Huang","year":"2017","journal-title":"Chem. Eng. J."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"123","DOI":"10.1016\/j.rser.2015.07.086","article-title":"Challenges and opportunities in application of microalgae (Chlorophyta) for wastewater treatment: A review","volume":"52","author":"Abinandan","year":"2015","journal-title":"Renew. Sustain. Energy Rev."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"38","DOI":"10.1016\/j.desal.2015.06.023","article-title":"Ion hydration number and electro-osmosis during electrodialysis of mixed salt solution","volume":"373","author":"Han","year":"2015","journal-title":"Desalination"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"115036","DOI":"10.1016\/j.desal.2021.115036","article-title":"Fouling dynamics of anion polyacrylamide on anion exchange membrane in electrodialysis","volume":"507","author":"Xiang","year":"2021","journal-title":"Desalination"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"120986","DOI":"10.1016\/j.memsci.2022.120986","article-title":"Unravelling the fouling behavior of anion-exchange membrane (AEM) by organic solute of varying characteristics","volume":"662","author":"Xiang","year":"2022","journal-title":"J. Membr. Sci."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"16134","DOI":"10.1021\/acs.est.2c03771","article-title":"Electrified Ion Exchange Enabled by Water Dissociation in Bipolar Membranes for Nitrogen Recovery from Source-Separated Urine","volume":"56","author":"Dong","year":"2022","journal-title":"Environ. Sci. Technol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"121838","DOI":"10.1016\/j.jclepro.2020.121838","article-title":"Ammonium recovery from wastewater by Donnan Dialysis: A feasibility study","volume":"265","author":"Chen","year":"2020","journal-title":"J. Clean. Prod."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"213","DOI":"10.1016\/S0011-9164(02)00314-4","article-title":"Recovery of metals by Donnan dialysis with ion exchange textiles","volume":"144","author":"Berdous","year":"2002","journal-title":"Desalination"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1603","DOI":"10.1039\/an9840901603","article-title":"Selection of the receiver electrolyte for the Donnan dialysis enrichment of cations","volume":"109","author":"Cox","year":"1984","journal-title":"Analyst"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"119453","DOI":"10.1016\/j.watres.2022.119453","article-title":"Fouling-free membrane stripping for ammonia recovery from real biogas slurry","volume":"229","author":"Chen","year":"2023","journal-title":"Water Res."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"7015","DOI":"10.1021\/acs.est.0c08772","article-title":"Donnan Dialysis-Osmotic Distillation (DD-OD) Hybrid Process for Selective Ammonium Recovery Driven by Waste Alkali","volume":"55","author":"Chen","year":"2021","journal-title":"Environ. Sci. Technol."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"402","DOI":"10.1038\/s41893-020-00674-3","article-title":"Graphene oxide nanofiltration membranes for desalination under realistic conditions","volume":"4","author":"Wang","year":"2021","journal-title":"Nat. Sustain."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"25","DOI":"10.1016\/j.desal.2019.02.004","article-title":"Cation exchange membrane integrated with cationic and anionic layers for selective ion separation via electrodialysis","volume":"458","author":"Afsar","year":"2019","journal-title":"Desalination"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1606","DOI":"10.1016\/j.cjche.2017.06.002","article-title":"Monovalent cation perm-selective membranes (MCPMs): New developments and perspectives","volume":"25","author":"Ge","year":"2017","journal-title":"Chin. J. Chem. Eng."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"4429","DOI":"10.1021\/acssuschemeng.8b06426","article-title":"Hydrophobic Side Chains Impart Anion Exchange Membranes with High Monovalent-Divalent Anion Selectivity in Electrodialysis","volume":"7","author":"Irfan","year":"2019","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"117544","DOI":"10.1016\/j.memsci.2019.117544","article-title":"Enhanced monovalent selectivity of cation exchange membranes via adjustable charge density on functional layers","volume":"595","author":"Pang","year":"2020","journal-title":"J. Membr. Sci."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"153","DOI":"10.1016\/j.memsci.2019.01.052","article-title":"Amphoteric ion-exchange membranes with superior mono-\/bi-valent anion separation performance for electrodialysis applications","volume":"577","author":"Liao","year":"2019","journal-title":"J. Membr. Sci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"263","DOI":"10.1016\/j.memsci.2017.06.017","article-title":"Preparation of a monovalent selective anion exchange membrane through constructing a covalently crosslinked interface by electro-deposition of polyethyleneimine","volume":"539","author":"Pan","year":"2017","journal-title":"J. Membr. Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"43","DOI":"10.1016\/j.watres.2018.09.040","article-title":"Applications of carbon quantum dots (CQDs) in membrane technologies: A review","volume":"147","author":"Zhao","year":"2018","journal-title":"Water Res"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"118078","DOI":"10.1016\/j.memsci.2020.118078","article-title":"Carbon nanotube based Janus composite membrane of oil fouling resistance for direct contact membrane distillation","volume":"607","author":"Han","year":"2020","journal-title":"J. Membr. Sci."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"20942","DOI":"10.1021\/acsami.0c03577","article-title":"Beneficial CNT Intermediate Layer for Membrane Fluorination toward Robust Superhydrophobicity and Wetting Resistance in Membrane Distillation","volume":"12","author":"Wang","year":"2020","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"7586","DOI":"10.1021\/acsnano.1c01105","article-title":"2D Heterostructured Nanofluidic Channels for Enhanced Desalination Performance of Graphene Oxide Membranes","volume":"15","author":"Wu","year":"2021","journal-title":"ACS Nano"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1039\/C3CS60303B","article-title":"Chemical reduction of graphene oxide: A synthetic chemistry viewpoint","volume":"43","author":"Chua","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1253","DOI":"10.1038\/s41467-019-09286-8","article-title":"Controllable ion transport by surface-charged graphene oxide membrane","volume":"10","author":"Zhang","year":"2019","journal-title":"Nat. Commun."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"311","DOI":"10.1016\/j.memsci.2018.09.026","article-title":"Facilitated water-selective permeation via PEGylation of graphene oxide membrane","volume":"567","author":"Zhao","year":"2018","journal-title":"J. Membr. Sci."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"227","DOI":"10.1016\/j.ces.2015.08.019","article-title":"Graphene oxide-embedded nanocomposite membrane for solvent resistant nanofiltration with enhanced rejection ability","volume":"138","author":"Ding","year":"2015","journal-title":"Chem. Eng. Sci."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2623","DOI":"10.1007\/s10008-015-2829-4","article-title":"Influence of conditions of polyaniline synthesis in perfluorinated membrane on electrotransport properties and surface morphology of composites","volume":"19","author":"Kononenko","year":"2015","journal-title":"J. Solid State Electrochem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"120938","DOI":"10.1016\/j.seppur.2022.120938","article-title":"Graphene oxide membrane regulated by surface charges and interlayer channels for selective transport of monovalent ions over divalent ions","volume":"291","author":"Zhang","year":"2022","journal-title":"Sep. Purif. Technol."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"5809","DOI":"10.1002\/adfm.201502205","article-title":"High-Efficiency Water-Transport Channels using the Synergistic Effect of a Hydrophilic Polymer and Graphene Oxide Laminates","volume":"25","author":"Huang","year":"2015","journal-title":"Adv. Funct. Mater."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"e17215","DOI":"10.1002\/aic.17215","article-title":"Exclusive and fast water channels in zwitterionic graphene oxide membrane for efficient water\u2013ethanol separation","volume":"67","author":"Liang","year":"2021","journal-title":"AIChE J."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1349","DOI":"10.1016\/j.jece.2017.02.016","article-title":"Hollow fibre membrane contactors for ammonia recovery: Current status and future developments","volume":"5","author":"Darestani","year":"2017","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"21060","DOI":"10.1039\/D0NR04931J","article-title":"Swelling properties of graphite oxides and graphene oxide multilayered materials","volume":"12","author":"Iakunkov","year":"2020","journal-title":"Nanoscale"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"79","DOI":"10.1016\/S0011-9164(03)00241-8","article-title":"Modification of cation-exchange membrane properties by electro-adsorption of polyethyleneimine","volume":"155","author":"Amara","year":"2003","journal-title":"Desalination"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"185","DOI":"10.1016\/j.desal.2005.04.032","article-title":"The effect of feed ionic strength on salt passage through reverse osmosis membranes","volume":"184","author":"Bartels","year":"2005","journal-title":"Desalination"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"6981","DOI":"10.1021\/acs.jpcc.3c00723","article-title":"Insights into High Li+\/Mg2+ Separation Performance Using a PEI-Grafted Graphene Oxide Membrane","volume":"127","author":"Wang","year":"2023","journal-title":"J. Phys. Chem. C"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"114521","DOI":"10.1016\/j.desal.2020.114521","article-title":"On the permselectivity of di- and mono-valent cations: Influence of applied current density and ionic species concentration","volume":"488","author":"Dong","year":"2020","journal-title":"Desalination"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"11066","DOI":"10.1021\/acs.est.6b04235","article-title":"Aggregation, Adsorption, and Morphological Transformation of Graphene Oxide in Aqueous Solutions Containing Different Metal Cations","volume":"50","author":"Yang","year":"2016","journal-title":"Environ. Sci. Technol."}],"container-title":["Membranes"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2077-0375\/13\/8\/726\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T20:30:45Z","timestamp":1760128245000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2077-0375\/13\/8\/726"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,8,10]]},"references-count":41,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2023,8]]}},"alternative-id":["membranes13080726"],"URL":"https:\/\/doi.org\/10.3390\/membranes13080726","relation":{},"ISSN":["2077-0375"],"issn-type":[{"value":"2077-0375","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,8,10]]}}}