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Here we report a hollow porous CuO\/Cu2O nanoreactor that integrates spatial confinement with interfacial electronic modulation via scalable spray pyrolysis. The hollow cavity creates a confined microenvironment that extends *CO diffusion pathways and enriches *CO intermediates, while the mixed-valence CuO\/Cu2O interface acts as an electronic buffer to stabilize Cu+-rich active species under reduction conditions. This synergy delivers a C2+ Faradaic efficiency of 82.4 \u00b1 1.8% at 900 mA cm\u20132 and a partial current density of 741.3 mA cm\u20132. Operando spectroscopy reveals that the confined structure promotes *CO retention and C\u2013C coupling, while the dynamic Cu+\/Cu2+ interface sustains Cu+ activity. This work establishes a generalizable confinement electronic codesign strategy for efficient CO2 to C2+ conversion under industrially relevant conditions.<\/jats:p>","DOI":"10.1021\/acs.jpclett.6c01873","type":"journal-article","created":{"date-parts":[[2026,7,20]],"date-time":"2026-07-20T05:03:53Z","timestamp":1784523833000},"page":"8707-8715","source":"Crossref","is-referenced-by-count":0,"title":["Confined Mixed-Valence\nCuO\/Cu2O Hollow\nNanoreactors for Synergistic CO2 Electroreduction to C2+ Products"],"prefix":"10.1021","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0009-0004-5786-9003","authenticated-orcid":true,"given":"Changjiang","family":"Liu","sequence":"first","affiliation":[{"name":"Anhui Normal University , , Jiuhua Road 189 , ,","place":["Wuhu, P. R. China, 241002"]},{"name":"Central South University , , ,","place":["Changsha, P. R. China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yingjie","family":"He","sequence":"additional","affiliation":[{"name":"Central South University , , ,","place":["Changsha, P. R. China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hao","family":"Fan","sequence":"additional","affiliation":[{"name":"Anhui Normal University , , Jiuhua Road 189 , ,","place":["Wuhu, P. R. China, 241002"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hu","family":"Zang","sequence":"additional","affiliation":[{"name":"Anhui Normal University , , Jiuhua Road 189 , ,","place":["Wuhu, P. R. China, 241002"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nan","family":"Yu","sequence":"additional","affiliation":[{"name":"Anhui Normal University , , Jiuhua Road 189 , ,","place":["Wuhu, P. R. China, 241002"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongmei","family":"Li","sequence":"additional","affiliation":[{"name":"Central South University , , ,","place":["Changsha, P. R. China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5446-3217","authenticated-orcid":true,"given":"Haiying","family":"Wang","sequence":"additional","affiliation":[{"name":"Central South University , , ,","place":["Changsha, P. R. China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9007-4817","authenticated-orcid":true,"given":"Min","family":"Liu","sequence":"additional","affiliation":[{"name":"Central South University , , ,","place":["Changsha, P. R. China, 410083"]},{"name":"Central South University , , ,","place":["Changsha, P. R. China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3657-0510","authenticated-orcid":true,"given":"Baoyou","family":"Geng","sequence":"additional","affiliation":[{"name":"Anhui Normal University , , Jiuhua Road 189 , ,","place":["Wuhu, P. R. China, 241002"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,20]]},"reference":[{"issue":"9","key":"2026073009072633800_cit1","doi-asserted-by":"publisher","first-page":"732","DOI":"10.1038\/s41560-019-0450-y","article-title":"Advances and challenges in understanding\nthe electrocatalytic conversion of carbon dioxide to fuels","volume":"4","author":"Birdja","year":"2019","journal-title":"Nat. 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