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Here, it is shown that the synthesis of zeolite ZSM\u20105 samples with distinct particle sizes, combined with solid\u2010state NMR and computational studies of trimethylphosphine oxide (TMPO) adsorption, provides insight into the chemical species on the external surface of the zeolite crystals. <jats:sup>1<\/jats:sup>H\u2013<jats:sup>31<\/jats:sup>P HETCOR NMR spectra of TMPO\u2010loaded zeolites exhibit a broad correlation peak at <jats:italic>\u03b4<\/jats:italic><jats:sub>P<\/jats:sub> \u223c35\u201355\u2005ppm and <jats:italic>\u03b4<\/jats:italic><jats:sub>H<\/jats:sub> \u223c5\u201312\u2005ppm assigned to external SiOH species. Pore\u2010mouth Br\u00f8nsted acid sites exhibit <jats:sup>31<\/jats:sup>P and <jats:sup>1<\/jats:sup>H NMR resonances and adsorption energies close to those reported for internal acid sites interacting with TMPO. The presence of an external tricoordinate Al\u2010Lewis site interacting strongly with TMPO is suggested, resulting in <jats:sup>31<\/jats:sup>P resonances that overlap with the peaks usually ascribed to the interaction of TMPO with Br\u00f8nsted sites.<\/jats:p>","DOI":"10.1002\/chem.202201795","type":"journal-article","created":{"date-parts":[[2022,8,9]],"date-time":"2022-08-09T06:58:11Z","timestamp":1660028291000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Elucidating the Nature of the External Acid Sites of ZSM\u20105 Zeolites Using NMR Probe Molecules"],"prefix":"10.1002","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0325-2356","authenticated-orcid":false,"given":"Carlos","family":"Bornes","sequence":"first","affiliation":[{"name":"CICECO, Aveiro Institute of Materials Department of Chemistry University of Aveiro  3810-193 Aveiro Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0337-8511","authenticated-orcid":false,"given":"Dusan","family":"Stosic","sequence":"additional","affiliation":[{"name":"Laboratoire Catalyse &amp; Spectrochimie (LCS) Normandie Univ ENSICAEN, UNICAEN, CNRS  14000 Caen France"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0837-8329","authenticated-orcid":false,"given":"Carlos F. 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