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Here, we report a precisely engineered core\u2013shell Co@Co3O4 catalyst that utilizes a reversible solid-state redox equilibrium (Co0(s) + 2Co3+(s) \u2194 3Co2+(s)) during toluene oxidation, a benchmark transformation for the activation of inert C(sp3)\u2013H bonds. Operando XAFS and XPS results reveal that the dynamically generated Co2+ species correlate directly with catalytic activity. Systematically integrated operando characterizations, DFT calculations, and control experiments establish Co2+ as a multifunctional center that activates toluene via electronic donation and concurrently facilitates O2 activation at surface oxygen vacancies, initiating a reactive oxygen species cascade (O2(g) \u2192 \u2022O2\u2013(ads) \u2192 \u2022OH(ads)) that drives a dual-channel oxidation mechanism through low-energy-barrier routes. The catalyst achieves a turnover frequency of 33.8 h\u20131 (surpassing reported catalysts by 4- to 360-fold) with 90% selectivity in batch operation. We further establish a continuous-flow toluene oxidation system, which delivers a turnover number of 45425 and a space-time yield of 362.3 g\u00b7gcat\u20131\u00b7h\u20131 over 260 h of stable operation, producing ca. 3.25 kg of benzoic acid. The dynamic active site paradigm demonstrates broad utility, as evidenced by the successful oxidation of 42 aromatic alkanes and its application in the synthesis of a cholesteric liquid crystal intermediate.<\/jats:p>","DOI":"10.1021\/jacs.6c09906","type":"journal-article","created":{"date-parts":[[2026,8,10]],"date-time":"2026-08-10T08:01:54Z","timestamp":1786348914000},"page":"34806-34820","source":"Crossref","is-referenced-by-count":0,"title":["Engineered Dynamic\nCo2+ Sites Resolve the\nComplete Reaction Network for C(sp3)\u2013H Oxidation"],"prefix":"10.1021","volume":"148","author":[{"given":"Xin","family":"Zhao","sequence":"first","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510640"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yueshuai","family":"Wang","sequence":"additional","affiliation":[{"name":"Beijing University of Technology , , ,","place":["Beijing, China, 100124"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chenying","family":"Gong","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510640"]},{"name":"Yueyang Xingchang Petro-Chemical Co., Ltd. , ,","place":["Yueyang, China, 414000"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jie","family":"Wen","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510640"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jie","family":"Kang","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510640"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lifang","family":"Huang","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510640"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9934-4983","authenticated-orcid":true,"given":"Ruiqi","family":"Fang","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510640"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1527-551X","authenticated-orcid":true,"given":"Yingwei","family":"Li","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510640"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,10]]},"reference":[{"key":"2026081910245615000_cit1","doi-asserted-by":"publisher","first-page":"195","DOI":"10.1126\/science.1198458","article-title":"Solvent-free oxidation\nof primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles","volume":"331","author":"Kesavan","year":"2011","journal-title":"Science"},{"key":"2026081910245615000_cit2","doi-asserted-by":"publisher","first-page":"391","DOI":"10.1038\/446391a","article-title":"C\u2013H\nactivation","volume":"446","author":"Bergman","year":"2007","journal-title":"Nature"},{"key":"2026081910245615000_cit3","doi-asserted-by":"publisher","first-page":"854","DOI":"10.1038\/s44160-026-00998-6","article-title":"Hydrated\nCO2-mediated redox chemistry for biophotoelectrocatalytic\noxyfunctionalization of C\u2013H bonds","volume":"5","author":"Kim","year":"2026","journal-title":"Nat.\nSynth."},{"key":"2026081910245615000_cit4","doi-asserted-by":"publisher","first-page":"4651","DOI":"10.1038\/s41467-025-58997-8","article-title":"Three distinct\nstrategies lead to programmable aliphatic C\u2013H oxidation in\nbicyclomycin biosynthesis","volume":"16","author":"Wu","year":"2025","journal-title":"Nat. Commun."},{"key":"2026081910245615000_cit5","doi-asserted-by":"publisher","first-page":"1453","DOI":"10.1038\/s44160-025-00866-9","article-title":"Photobiocatalytic benzylic\nC\u2013H\nacylation enabled by the synergy of a thiamine-dependent enzyme, an\norganophotocatalyst and hydrogen-atom transfer","volume":"4","author":"Peng","year":"2025","journal-title":"Nat. Synth."},{"key":"2026081910245615000_cit6","doi-asserted-by":"publisher","first-page":"704","DOI":"10.1038\/s41929-018-0128-z","article-title":"A photochromic\ncomposite with enhanced carrier separation\nfor the photocatalytic activation of benzylic C\u2013H bonds in\ntoluene","volume":"1","author":"Cao","year":"2018","journal-title":"Nat. Catal."},{"key":"2026081910245615000_cit7","doi-asserted-by":"publisher","first-page":"3811","DOI":"10.1021\/cr010364p","article-title":"Photocatalysis with\norganized systems\nfor the oxofunctionalization of hydrocarbons by O2","volume":"102","author":"Maldotti","year":"2002","journal-title":"Chem. Rev."},{"key":"2026081910245615000_cit8","doi-asserted-by":"publisher","first-page":"16852","DOI":"10.1021\/jacs.3c05237","article-title":"Achieving high selectivity in photocatalytic oxidation\nof toluene on amorphous BiOCl nanosheets coupled with TiO2","volume":"145","author":"Wang","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026081910245615000_cit9","doi-asserted-by":"publisher","first-page":"7946","DOI":"10.1002\/anie.201804946","article-title":"Catalytic\naerobic oxidation of C\n(sp3)\u2013H bonds","volume":"58","author":"Sterckx","year":"2019","journal-title":"Angew. Chem.,\nInt. 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Catal."},{"key":"2026081910245615000_cit14","doi-asserted-by":"publisher","first-page":"151","DOI":"10.1016\/j.jcat.2023.01.012","article-title":"Regulating CeO2 morphologies\non the catalytic oxidation\nof toluene at lower temperature: a study of the structure\u2013activity\nrelationship","volume":"418","author":"Zhu","year":"2023","journal-title":"J. Catal."},{"key":"2026081910245615000_cit15","doi-asserted-by":"publisher","first-page":"115654","DOI":"10.1016\/j.ces.2020.115654","article-title":"Mesoporous\nCo3O4 derived from Co-MOFs with different morphologies\nand ligands for\ntoluene catalytic oxidation","volume":"220","author":"Lei","year":"2020","journal-title":"Chem. Eng. Sci."},{"key":"2026081910245615000_cit16","doi-asserted-by":"publisher","first-page":"196","DOI":"10.1021\/jacs.0c08640","article-title":"Operando investigation\nof toluene oxidation over 1D Pt@CeO2 derived from Pt cluster-containing\nMOF","volume":"143","author":"Wang","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"2026081910245615000_cit17","doi-asserted-by":"publisher","first-page":"1314","DOI":"10.1038\/s41929-025-01449-9","article-title":"Local solid-state processes adjust\nthe selectivity\nin catalytic oxidation reactions on cobalt oxides","volume":"8","author":"Go\u0308tsch","year":"2025","journal-title":"Nat. Catal."},{"key":"2026081910245615000_cit18","doi-asserted-by":"publisher","first-page":"3465","DOI":"10.1002\/anie.201410738","article-title":"Heterogeneous\ncatalysis","volume":"54","author":"Schlo\u0308gl","year":"2015","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026081910245615000_cit19","doi-asserted-by":"publisher","first-page":"11825","DOI":"10.1021\/jacs.7b05004","article-title":"Ethylene epoxidation at the phase\ntransition of copper\noxides","volume":"139","author":"Greiner","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"2026081910245615000_cit20","doi-asserted-by":"publisher","first-page":"3554","DOI":"10.1038\/s41467-020-17346-7","article-title":"In situ\nobservation of oscillatory redox dynamics of\ncopper","volume":"11","author":"Cao","year":"2020","journal-title":"Nat. Commun."},{"key":"2026081910245615000_cit21","doi-asserted-by":"publisher","first-page":"13422","DOI":"10.1002\/anie.201606776","article-title":"Formation of CoS2 nanobubble\nhollow prisms for highly reversible lithium storage","volume":"55","author":"Yu","year":"2016","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026081910245615000_cit22","doi-asserted-by":"publisher","first-page":"2675","DOI":"10.1002\/anie.201812387","article-title":"Synthesis of cobalt sulfide multi-shelled nanoboxes\nwith precisely controlled two to five shells for sodium-ion batteries","volume":"58","author":"Wang","year":"2019","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026081910245615000_cit23","doi-asserted-by":"publisher","first-page":"1605051","DOI":"10.1002\/adma.201605051","article-title":"Formation of onion-like\nNiCo2S4 particles via sequential ion-exchange for hybrid supercapacitors","volume":"29","author":"Guan","year":"2017","journal-title":"Adv. Mater."},{"key":"2026081910245615000_cit24","doi-asserted-by":"publisher","first-page":"949","DOI":"10.1002\/anie.201106826","article-title":"Serial ionic exchange\nfor the synthesis of multishelled\ncopper sulfide hollow spheres","volume":"51","author":"Xiong","year":"2012","journal-title":"Angew. Chem.,\nInt. Ed."},{"key":"2026081910245615000_cit25","doi-asserted-by":"publisher","first-page":"3711","DOI":"10.1002\/anie.201400226","article-title":"Formation of NixCo3-xS4 hollow nanoprisms with\nenhanced pseudocapacitive properties","volume":"53","author":"Yu","year":"2014","journal-title":"Angew.\nChem., Int. 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Chem., Int.\nEd."},{"key":"2026081910245615000_cit29","doi-asserted-by":"publisher","first-page":"23138","DOI":"10.1021\/jacs.4c05044","article-title":"Pore-specific anisotropic etching\nof zeolitic imidazolate frameworks by carboxylic acid vapors","volume":"146","author":"Chen","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026081910245615000_cit30","doi-asserted-by":"publisher","first-page":"5780","DOI":"10.1021\/acsnano.0c00712","article-title":"Self-templating synthesis of hollow\nCo3O4 nanoparticles embedded in N,S-dual-doped\nreduced graphene oxide for lithium ion batteries","volume":"14","author":"Zhu","year":"2020","journal-title":"ACS Nano"},{"key":"2026081910245615000_cit31","doi-asserted-by":"publisher","first-page":"1501835","DOI":"10.1002\/aenm.201501835","article-title":"Atomic layer-by-layer Co3O4\/graphene\ncomposite for high performance lithium-ion batteries","volume":"6","author":"Dou","year":"2016","journal-title":"Adv. Energy Mater."},{"key":"2026081910245615000_cit32","doi-asserted-by":"publisher","first-page":"811","DOI":"10.1021\/jacs.6b10710","article-title":"Activating cobalt\nnanoparticles via the Mott\u2013Schottky effect in nitrogen-rich\ncarbon shells for base-free aerobic oxidation of alcohols to esters","volume":"139","author":"Su","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"2026081910245615000_cit33","doi-asserted-by":"publisher","first-page":"10882","DOI":"10.1021\/ja505777v","article-title":"Phenylenediamine-Based\nFeNx\/C catalyst with high activity for oxygen reduction\nin acid medium and its active-site probing","volume":"136","author":"Wang","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"2026081910245615000_cit34","doi-asserted-by":"publisher","first-page":"414","DOI":"10.1039\/C6QM00273K","article-title":"Multi-shelled\nhollow micro-\/nanostructures: promising platforms for lithium-ion\nbatteries","volume":"1","author":"Wang","year":"2017","journal-title":"Mater. Chem. Front."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c09906","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/32\/34806\/66469523\/jacs.6c09906.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/32\/34806\/66469523\/jacs.6c09906.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,19]],"date-time":"2026-08-19T14:48:52Z","timestamp":1787150932000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/32\/34806\/5250990\/Engineered-Dynamic-Co2-Sites-Resolve-the-Complete"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,10]]},"references-count":34,"journal-issue":{"issue":"32","published-online":{"date-parts":[[2026,8,10]]},"published-print":{"date-parts":[[2026,8,19]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c09906","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,10]]}}}