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dc.contributor.authorGani, Terry Zhi Hao
dc.contributor.authorIoannidis, Efthymios Ioannis
dc.contributor.authorKulik, Heather Janine
dc.date.accessioned2017-08-17T17:34:48Z
dc.date.available2017-08-17T17:34:48Z
dc.date.issued2016-09
dc.date.submitted2016-06
dc.identifier.issn0897-4756
dc.identifier.issn1520-5002
dc.identifier.urihttp://hdl.handle.net/1721.1/110968
dc.description.abstractSelective ion separation is a major challenge with far-ranging impact from water desalination to product separation in catalysis. Recently introduced ferrocene (Fc)/ferrocenium (Fc⁺) polymer electrode materials have been demonstrated experimentally and theoretically to selectively bind carboxylates over perchlorate through weak C–H···O hydrogen bond (HB) interactions that favor carboxylates, despite the comparable size and charge of the two species. However, practical application of this technology in aqueous environments requires further selectivity enhancement. Using a first-principles discovery approach, we investigate the effect of Fc/Fc⁺ functional groups (FGs) on the selectivity and reversibility of formate–Fc⁺ adsorption with respect to perchlorate in aqueous solution. Our wide design space of 44 FGs enables identification of FGs with higher selectivity and rationalization of trends through electronic energy decomposition analysis or geometric hydrogen bonding analysis. Overall, we observe weaker, longer HBs for perchlorate as compared to formate with Fc⁺. We further identify Fc⁺ functionalizations that simultaneously increase selectivity for formate in aqueous environments but permit rapid release from neutral Fc. We introduce the materiaphore, a 3D abstraction of these design rules, to help guide next-generation material optimization for selective ion sorption. This approach is expected to have broad relevance in computational discovery for molecular recognition, sensing, separations, and catalysis.en_US
dc.description.sponsorshipNational Science Foundation (U.S.) (ECCS-1449291)en_US
dc.language.isoen_US
dc.publisherAmerican Chemical Society (ACS)en_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/acs.chemmater.6b02378en_US
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.en_US
dc.sourceProf. Kuliken_US
dc.titleComputational Discovery of Hydrogen Bond Design Rules for Electrochemical Ion Separationen_US
dc.typeArticleen_US
dc.identifier.citationGani, Terry Z. H. et al. “Computational Discovery of Hydrogen Bond Design Rules for Electrochemical Ion Separation.” Chemistry of Materials 28, 17 (September 2016): 6207–6218 © 2016 American Chemical Societyen_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemical Engineeringen_US
dc.contributor.approverKulik, Heather Jen_US
dc.contributor.mitauthorGani, Terry Zhi Hao
dc.contributor.mitauthorIoannidis, Efthymios Ioannis
dc.contributor.mitauthorKulik, Heather Janine
dc.relation.journalChemistry of Materialsen_US
dc.eprint.versionAuthor's final manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dspace.orderedauthorsGani, Terry Z. H.; Ioannidis, Efthymios I.; Kulik, Heather J.en_US
dspace.embargo.termsNen_US
dc.identifier.orcidhttps://orcid.org/0000-0003-0357-6390
dc.identifier.orcidhttps://orcid.org/0000-0001-9342-0191
mit.licensePUBLISHER_POLICYen_US


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