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While catalytic sulfur hosts have been extensively investigated to accelerate the sulfur redox reaction (SRR), the effect of host architecture in governing Li\n                    <jats:sup>+<\/jats:sup>\n                    transport and SRR kinetics remains insufficiently understood. Here, 2D Co\n                    <jats:sub>3<\/jats:sub>\n                    S\n                    <jats:sub>4<\/jats:sub>\n                    with tunable architectures is employed as a model electrocatalyst to elucidate this structural influence. Combined experimental analyses and COMSOL simulations reveal an intrinsic trade\u2010off between catalytic material packing and transport\u2010accessible interfacial activity: increasing structural compactness in dense Co\n                    <jats:sub>3<\/jats:sub>\n                    S\n                    <jats:sub>4<\/jats:sub>\n                    concentrates catalytic material but simultaneously increases Li\n                    <jats:sup>+<\/jats:sup>\n                    transport resistance and concentration polarization, whereas porous frameworks facilitate Li\n                    <jats:sup>+<\/jats:sup>\n                    migration and suppress concentration gradients. An optimized porous Co\n                    <jats:sub>3<\/jats:sub>\n                    S\n                    <jats:sub>4<\/jats:sub>\n                    architecture balances accessible catalytic interfaces with efficient Li\n                    <jats:sup>+<\/jats:sup>\n                    transport, thereby accelerating SRR kinetics and regulating Li\n                    <jats:sub>2<\/jats:sub>\n                    S deposition. As a result, Li\u2013S cells incorporating this optimized Co\n                    <jats:sub>3<\/jats:sub>\n                    S\n                    <jats:sub>4<\/jats:sub>\n                    host deliver long\u2010term cycling stability, retaining 657 mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 0.2 C with a low\u2010capacity decay of 0.051% per cycle over 1000 cycles. These findings establish porosity engineering as a critical design principle for catalytic sulfur hosts in high\u2010performance Li\u2013S batteries.\n                  <\/jats:p>","DOI":"10.1002\/smll.202512552","type":"journal-article","created":{"date-parts":[[2026,1,27]],"date-time":"2026-01-27T12:19:13Z","timestamp":1769516353000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Balancing Transport\u2010Accessible Catalytic Interfaces and Li\n                    <sup>+<\/sup>\n                    Transport via Porosity Engineering for High\u2010Performance Li\u2013S Batteries"],"prefix":"10.1002","volume":"22","author":[{"given":"Huimin","family":"Gu","sequence":"first","affiliation":[{"name":"Research School of Chemistry Australian National University  Canberra Australian Capital Territory 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Darlington New South Wales Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tsz Lok","family":"Wan","sequence":"additional","affiliation":[{"name":"Institute For Catalysis Hokkaido University  Sapporo Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Takashi","family":"Toyao","sequence":"additional","affiliation":[{"name":"Institute For Catalysis Hokkaido University  Sapporo Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zongyou","family":"Yin","sequence":"additional","affiliation":[{"name":"Research School of Chemistry Australian National University  Canberra Australian Capital Territory Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4964-2111","authenticated-orcid":false,"given":"Antonio","family":"Tricoli","sequence":"additional","affiliation":[{"name":"Nanotechnology Research Laboratory Faculty of Engineering University of Sydney  Darlington New South 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