{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T15:56:35Z","timestamp":1792598195225,"version":"4.5.0"},"reference-count":33,"publisher":"American Chemical Society (ACS)","issue":"41","license":[{"start":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T00:00:00Z","timestamp":1791158400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T00:00:00Z","timestamp":1791158400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T00:00:00Z","timestamp":1791158400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/100023581","name":"National Science Foundation Graduate Research Fellowship Program","doi-asserted-by":"publisher","award":["1745302"],"award-info":[{"award-number":["1745302"]}],"id":[{"id":"10.13039\/100023581","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100023581","name":"National Science Foundation Graduate Research Fellowship Program","doi-asserted-by":"publisher","award":["2141064"],"award-info":[{"award-number":["2141064"]}],"id":[{"id":"10.13039\/100023581","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006151","name":"Basic Energy Sciences","doi-asserted-by":"publisher","award":["DE-SC0016214"],"award-info":[{"award-number":["DE-SC0016214"]}],"id":[{"id":"10.13039\/100006151","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006151","name":"Basic Energy Sciences","doi-asserted-by":"publisher","award":["DE-SC0020973"],"award-info":[{"award-number":["DE-SC0020973"]}],"id":[{"id":"10.13039\/100006151","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006151","name":"Basic Energy Sciences","doi-asserted-by":"publisher","award":["DE-SC0023464"],"award-info":[{"award-number":["DE-SC0023464"]}],"id":[{"id":"10.13039\/100006151","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006919","name":"Massachusetts Institute of Technology","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100006919","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,21]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Electrostatic polarization of catalyst-solution interfaces can modulate the rate of liquid-phase heterogeneous Br\u00f8nsted acid catalysis by up to 5 orders of magnitude. Previous studies in acetonitrile establish that maximal rate-potential scaling emerges only at high ionic strength, indicating that rate promotion is sensitive to the interfacial electrostatic potential profile. Herein, we examine the role of the solvent on the electrolyte strength sensitivity of polarization-induced promotion of Br\u00f8nsted acid catalysis. Using carbon paper with Br\u00f8nsted acid functionalities, we measured 1-methylcyclopentanol dehydration rates in dimethyl carbonate, acetonitrile, and propylene carbonate, with electrolyte concentrations ranging from 1 to 600 mM. In acetonitrile and dimethyl carbonate, the alcohol dehydration rate-potential scaling is a function of ionic strength, implying that the proton traverses only a fraction of the electrostatic potential drop to form a surface-bound oxonium intermediate prior to the rate-limiting C\u2013O bond cleavage. In contrast, in more polar propylene carbonate, the rate-potential scaling aligns well with the maximum dependence predicted for a single-charge process and is insensitive to electrolyte concentration down to 1 mM. This behavior is consistent with the proton traversing the entire electrostatic potential drop to form a freely solvated oxonium intermediate outside the electrochemical double layer. These findings highlight that enhanced solvation of protonated intermediates is essential for maximizing electrostatic promotion in Br\u00f8nsted acid catalysis. Together, the kinetic data show that solvent selection modulates both the intrinsic reaction rate and sensitivity to catalyst potential, emphasizing the importance of understanding interfacial electrostatic effects in thermochemical reaction systems.<\/jats:p>","DOI":"10.1021\/jacs.6c13986","type":"journal-article","created":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T17:02:23Z","timestamp":1791219743000},"page":"44669-44678","source":"Crossref","is-referenced-by-count":0,"title":["The Key Role of Solvation\nin Enhancing Electrochemical\nPromotion of Br\u00f8nsted Acid Catalysis"],"prefix":"10.1021","volume":"148","author":[{"given":"Katelyn","family":"Groenhout","sequence":"first","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7611-101X","authenticated-orcid":true,"given":"Bhavish","family":"Dinakar","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Karl S.","family":"Westendorff","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mostapha","family":"Dakhchoune","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3721-6131","authenticated-orcid":true,"given":"Melissa T.","family":"Manetsch","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9342-0191","authenticated-orcid":true,"given":"Heather J.","family":"Kulik","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]},{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1016-3420","authenticated-orcid":true,"given":"Yogesh","family":"Surendranath","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]},{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0025-4233","authenticated-orcid":true,"given":"Yuriy","family":"Roma\u0301n-Leshkov","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]},{"name":"Massachusetts Institute of Technology , , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,5]]},"reference":[{"issue":"1","key":"2026102111084505900_cit1","doi-asserted-by":"publisher","first-page":"372","DOI":"10.1021\/acscatal.7b03369","article-title":"Hydrophobic\nSolid Acids and Their Catalytic Applications in Green and Sustainable\nChemistry","volume":"8","author":"Liu","year":"2018","journal-title":"ACS Catal."},{"issue":"5","key":"2026102111084505900_cit2","doi-asserted-by":"publisher","first-page":"303","DOI":"10.1039\/cs9962500303","article-title":"Environmentally\nFriendly Catalytic Methods","volume":"25","author":"Clark","year":"1996","journal-title":"Chem. Soc. Rev."},{"issue":"1","key":"2026102111084505900_cit3","doi-asserted-by":"publisher","first-page":"171","DOI":"10.1021\/cr960400y","article-title":"Catalysis\nby Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase\nReactions","volume":"98","author":"Kozhevnikov","year":"1998","journal-title":"Chem. Rev."},{"issue":"2","key":"2026102111084505900_cit4","doi-asserted-by":"publisher","first-page":"381","DOI":"10.1016\/j.jcat.2006.10.027","article-title":"Transesterification of triacetin\nwith methanol on Nafion\u00ae acid resins","volume":"245","author":"Lopez","year":"2007","journal-title":"J.\nCatal."},{"issue":"9","key":"2026102111084505900_cit5","doi-asserted-by":"publisher","first-page":"3790","DOI":"10.1021\/cr050994h","article-title":"Advances in the Synthesis\nand Catalytic\nApplications of Organosulfonic-Functionalized Mesostructured Materials","volume":"106","author":"Melero","year":"2006","journal-title":"Chem. Rev."},{"key":"2026102111084505900_cit6","doi-asserted-by":"publisher","first-page":"178","DOI":"10.1038\/438178a","article-title":"Biodiesel\nmade with sugar catalyst","volume":"438","author":"Toda","year":"2005","journal-title":"Nature"},{"issue":"3","key":"2026102111084505900_cit7","doi-asserted-by":"publisher","first-page":"559","DOI":"10.1021\/cr00035a006","article-title":"Inorganic\nSolid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions","volume":"95","author":"Corma","year":"1995","journal-title":"Chem.Rev."},{"issue":"22","key":"2026102111084505900_cit8","doi-asserted-by":"publisher","first-page":"7548","DOI":"10.1039\/C3CS60394F","article-title":"Zeolites as catalysts in oil refining","volume":"43","author":"Primo","year":"2014","journal-title":"Chem. Soc. 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Chem.\nRes."},{"issue":"5","key":"2026102111084505900_cit10","doi-asserted-by":"publisher","first-page":"2879","DOI":"10.1021\/acscatal.0c05674","article-title":"Differences in Mechanism\nand Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and\nAqueous Phase","volume":"11","author":"Chen","year":"2021","journal-title":"ACS Catal."},{"issue":"22","key":"2026102111084505900_cit11","doi-asserted-by":"publisher","first-page":"19040","DOI":"10.1021\/acscatal.5c04772","article-title":"Rationalizing\nSolvent Effect in Bro\u0337nsted Acid-Catalyzed\nC\u2013O Scission: A Thermodynamically Consistent Framework with\nAssessable Descriptors","volume":"15","author":"Guo","year":"2025","journal-title":"ACS Catal."},{"issue":"41","key":"2026102111084505900_cit12","doi-asserted-by":"publisher","first-page":"13586","DOI":"10.1021\/jacs.6b06083","article-title":"Single Molecule Nanospectroscopy Visualizes Proton-Transfer\nProcesses within a Zeolite Crystal","volume":"138","author":"Ristanovic","year":"2016","journal-title":"J. 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Am. Chem. Soc."},{"issue":"24","key":"2026102111084505900_cit18","doi-asserted-by":"publisher","first-page":"13317","DOI":"10.1002\/anie.202017057","article-title":"Electrochemical\nCharacterization of Single Layer Graphene\/Electrolyte\nInterface: Effect of Solvent on the Interfacial Capacitance","volume":"60","author":"Wu","year":"2021","journal-title":"Angew. Chem., Int. Ed."},{"issue":"22","key":"2026102111084505900_cit19","doi-asserted-by":"publisher","first-page":"6632","DOI":"10.1016\/j.electacta.2010.06.011","article-title":"Effects of electrolytic\ncomposition on the electric double-layer capacitance at smooth-surface\ncarbon electrodes in organic media","volume":"55","author":"Kim","year":"2010","journal-title":"Electrochim.\nActa"},{"issue":"22","key":"2026102111084505900_cit20","doi-asserted-by":"publisher","first-page":"12391","DOI":"10.1021\/acs.chemrev.3c00806","article-title":"How to\nAssess and Predict Electrical Double Layer Properties. Implications\nfor Electrocatalysis","volume":"124","author":"Schott","year":"2024","journal-title":"Chem. Rev."},{"issue":"19","key":"2026102111084505900_cit21","doi-asserted-by":"publisher","first-page":"10153","DOI":"10.1021\/jp5018289","article-title":"Solvent Variables Controlling\nElectric Double Layer Capacitance at the Metal\u2013Solution Interface","volume":"118","author":"Hou","year":"2014","journal-title":"J. Phys. Chem. C"},{"issue":"7","key":"2026102111084505900_cit22","doi-asserted-by":"publisher","first-page":"3360","DOI":"10.1021\/acs.jctc.6b00446","article-title":"Computing\npKa Values in Different\nSolvents by Electrostatic Transformation","volume":"12","author":"Rossini","year":"2016","journal-title":"J.\nChem. Theory Comput."},{"issue":"1","key":"2026102111084505900_cit23","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.27517","article-title":"H., pKa prediction\nin non-aqueous solvents","volume":"46","author":"Zheng","year":"2025","journal-title":"J. Comput. 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Thermodyn."},{"issue":"3","key":"2026102111084505900_cit26","doi-asserted-by":"publisher","first-page":"1103","DOI":"10.1021\/je700055p","article-title":"Static Dielectric\nConstants of Acetonitrile\/Water Mixtures at Different Temperatures\nand Debye-Huckel A and a0B Parameters for Activity Coefficients","volume":"52","author":"Gagliardi","year":"2007","journal-title":"J. Chem. Eng. Data"},{"issue":"4","key":"2026102111084505900_cit27","doi-asserted-by":"publisher","first-page":"1102","DOI":"10.1021\/je0498863","article-title":"Electrolytic\nConductivity and Glass Transition Temperatures as Functions of Salt\nContent, Solvent Composition, or Temperature for LiBF4 in Propylene\nCarbonate + Diethyl Carbonate","volume":"49","author":"Ding","year":"2004","journal-title":"J. Chem. Eng.\nData"},{"key":"2026102111084505900_cit28","volume-title":"Electrochemical Methods","author":"Bard","year":"1980"},{"issue":"2","key":"2026102111084505900_cit29","doi-asserted-by":"publisher","first-page":"245","DOI":"10.1515\/pac-2014-5026","article-title":"Defining the transfer coefficient\nin electrochemistry: An assessment (IUPAC Technical Report)","volume":"86","author":"Guidelli","year":"2014","journal-title":"Pure Appl. Chem."},{"issue":"5","key":"2026102111084505900_cit30","doi-asserted-by":"publisher","first-page":"831","DOI":"10.1021\/acscentsci.9b00114","article-title":"Graphite-Conjugated\nAcids Reveal\na Molecular Framework for Proton-Coupled Electron Transfer at Electrode\nSurfaces","volume":"5","author":"Jackson","year":"2019","journal-title":"ACS Cent. Sci."},{"key":"2026102111084505900_cit31","volume-title":"Electrochemical Engineering","author":"Fuller","year":"2018"},{"issue":"4","key":"2026102111084505900_cit32","doi-asserted-by":"publisher","first-page":"479","DOI":"10.1346\/CCMN.1996.0440405","article-title":"Potential-distance\nrelationships of clay-water systems\nconsidering the Stern theory","volume":"44","author":"Sridharan","year":"1996","journal-title":"Clay Clay Miner."},{"issue":"9","key":"2026102111084505900_cit33","first-page":"1","article-title":"Investigations on the Activity of\nIons","volume":"7","author":"Bjerrum","year":"1926","journal-title":"Mater. Fys. Medd"}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c13986","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/41\/44669\/68746950\/jacs.6c13986.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/41\/44669\/68746950\/jacs.6c13986.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T15:30:17Z","timestamp":1792596617000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/41\/44669\/5444646\/The-Key-Role-of-Solvation-in-Enhancing"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,5]]},"references-count":33,"journal-issue":{"issue":"41","published-online":{"date-parts":[[2026,10,5]]},"published-print":{"date-parts":[[2026,10,21]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c13986","relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.15005640\/v1","asserted-by":"object"}]},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,5]]}}}