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Here we show that hydroxide transport in rigid microporous ionomers can be accelerated through topological ionic nodes that regulate local transport energetics. Incorporation of hexaphenylbenzene (HPB) into an ether-free poly(aryl piperidinium) framework simultaneously generates interconnected microporosity and spatially correlates multiple cationic sites within pore walls. Density functional theory and free-energy analysis show that HPB weakens hydroxide binding and lowers intersite hopping barriers by smoothing the local energetic landscape under confinement. The optimized membrane reaches 168.6 mS cm\u20131 at 90 \u00b0C, exhibits an apparent activation energy of 12.7 kJ mol\u20131, and swells by only 12.1% despite 75.6% water uptake. It retains 97.4% of its conductivity after 2000 h in 2 M KOH at 90 \u00b0C. These advantages translate into a peak fuel cell power density of 2.50 W cm\u20132 and an electrolyzer current density of 8.05 A cm\u20132 at 2.0 V, with stable operation over 2500 h. Spatially correlated ionic nodes therefore provide a molecular strategy to regulate hydroxide transport energetics in rigid microporous ionomers.<\/jats:p>","DOI":"10.1021\/jacs.6c07266","type":"journal-article","created":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T04:02:18Z","timestamp":1785902538000},"page":"34268-34277","source":"Crossref","is-referenced-by-count":0,"title":["Hexaphenylbenzene Nodes\nReshape Hydroxide Transport\nEnergetics in Rigid Microporous Membranes"],"prefix":"10.1021","volume":"148","author":[{"given":"Wenfeng","family":"Li","sequence":"first","affiliation":[{"name":"University of Science and Technology of China , , ,","place":["Hefei, China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wentao","family":"Jin","sequence":"additional","affiliation":[{"name":"Hefei University of Technology , , ,","place":["Hefei, China, 230009"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weisheng","family":"Yu","sequence":"additional","affiliation":[{"name":"University of Science and Technology of China , , ,","place":["Hefei, China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xian","family":"Liang","sequence":"additional","affiliation":[{"name":"University of Science and Technology of China , , ,","place":["Hefei, China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhiru","family":"Liu","sequence":"additional","affiliation":[{"name":"University of Science and Technology of China , , ,","place":["Hefei, China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yan","family":"Xu","sequence":"additional","affiliation":[{"name":"University of Science and Technology of China , , ,","place":["Hefei, China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Luxin","family":"Xiong","sequence":"additional","affiliation":[{"name":"University of Science and Technology of China , , ,","place":["Hefei, China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0930-1091","authenticated-orcid":true,"given":"Cenfeng","family":"Fu","sequence":"additional","affiliation":[{"name":"Hefei University of Technology , , ,","place":["Hefei, China, 230009"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4651-9820","authenticated-orcid":true,"given":"Jin","family":"Ran","sequence":"additional","affiliation":[{"name":"Hefei University of Technology , , ,","place":["Hefei, China, 230009"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8377-5834","authenticated-orcid":true,"given":"Liang","family":"Wu","sequence":"additional","affiliation":[{"name":"University of Science and Technology of China , , ,","place":["Hefei, China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9221-5126","authenticated-orcid":true,"given":"Tongwen","family":"Xu","sequence":"additional","affiliation":[{"name":"University of Science and Technology of China , , ,","place":["Hefei, China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,4]]},"reference":[{"key":"2026081910241857500_cit1","doi-asserted-by":"publisher","first-page":"4583","DOI":"10.1039\/D0CS01079K","article-title":"Water electrolysis: From textbook knowledge\nto the latest scientific strategies and industrial developments","volume":"51","author":"Chatenet","year":"2022","journal-title":"Chem. 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