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The multistep 16\u2010electron SRR requires not only strong polysulfides conversion capability but also sustained interfacial electron supply. Herein, we report a MOF\u2010derived catalytic site and Schottky barrier dual\u2010engineered semiconductor\u2010metal heterostructure, denoted DSMH@C, to couple polysulfides catalysis with low\u2010barrier\u2010potential electron injection. In DSMH@C, oxygen\u2010deficient semiconducting In\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3\u2010x<\/jats:sub>\n                    provides vacancy\u2010associated catalytic sites that strengthen LiPSs chemisorption and\n                    <jats:italic>d\u2010p<\/jats:italic>\n                    orbital hybridization with sulfur species, while metallic In serves as an electronically coupled transport domain. More importantly, the defect states in In\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3\u2010x<\/jats:sub>\n                    regulate the energy band and depletion region at the In\/In\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3\u2010x<\/jats:sub>\n                    heterointerface, lowering the electron\u2010injection barrier potential from metallic In to the semiconducting catalytic domain. This dual engineering enables efficient polysulfides conversion with timely electron supply, accelerating SRR kinetics and suppressing LiPSs shuttling. Consequently, DSMH@C delivers 998 mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 1 C, a low capacity decay rate of 0.038% per cycle over 500 cycles, an areal capacity of 11.1 mAh cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    at 10\u00a0mg cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    sulfur loading, and a pouch\u2010cell energy density of 507.5\u00a0Wh kg\n                    <jats:sup>\u22121<\/jats:sup>\n                    .\n                  <\/jats:p>","DOI":"10.1002\/smll.76105","type":"journal-article","created":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T11:26:52Z","timestamp":1791286012000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Schottky Barrier and Interfacial Oxygen Vacancies Engineering Enable Low\u2010Barrier\u2010Potential Electron Injection and Polysulfide Catalysis"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-6003-2420","authenticated-orcid":false,"given":"Haibin","family":"Lu","sequence":"first","affiliation":[{"name":"Guangzhou Key Laboratory of Low\u2010Dimensional Materials and Energy Storage Devices School of Materials and Energy Guangdong University of Technology  Guangzhou People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Junhua","family":"Yang","sequence":"additional","affiliation":[{"name":"Guangzhou Key Laboratory of Low\u2010Dimensional Materials and Energy Storage Devices School of Materials and Energy Guangdong University of Technology  Guangzhou People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-7700-6417","authenticated-orcid":false,"given":"Fu","family":"Li","sequence":"additional","affiliation":[{"name":"Institute of Materials Science Technical University of Darmstadt  Darmstadt Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qinyang","family":"Sheng","sequence":"additional","affiliation":[{"name":"Guangzhou Key Laboratory of Low\u2010Dimensional Materials and Energy Storage Devices School of Materials and Energy Guangdong University of Technology  Guangzhou People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6127-2753","authenticated-orcid":false,"given":"Kai","family":"Meng","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Technology For Materials Synthesis and Processing Wuhan University of Technology  Wuhan People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shiyun","family":"Xiong","sequence":"additional","affiliation":[{"name":"Guangzhou Key Laboratory of Low\u2010Dimensional Materials and Energy Storage Devices School of Materials and Energy Guangdong University of Technology  Guangzhou People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1035-8861","authenticated-orcid":false,"given":"Hongbin","family":"Zhang","sequence":"additional","affiliation":[{"name":"Institute of Materials Science Technical University of Darmstadt  Darmstadt Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3773-7981","authenticated-orcid":false,"given":"Qi","family":"Zhang","sequence":"additional","affiliation":[{"name":"Guangzhou Key Laboratory of Low\u2010Dimensional Materials and Energy Storage Devices School of Materials and Energy Guangdong University of Technology  Guangzhou People's Republic of China"},{"name":"State Key Laboratory of Silicon and Advanced Semiconductor Materials Zhejiang University  Hangzhou People's Republic of 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