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Simultaneously achieving long\u2010term thermal stability and strong infrared reflectivity remains particularly challenging, as these functionalities tend to deteriorate under sustained thermal loading. Here, we develop a strong ligand\u2010coordination strategy in which reactive metal precursors are stabilized by carboxylic acids to form a homogeneous multicomponent sol. Assisted by buffering phase zirconia between the alumina skeleton and infrared\u2010reflective titanium oxide species, the resulting ceramic nanofibers exhibit mechanical robustness, outstanding thermal insulation capability, and infrared reflection under harsh conditions. Notably, the fibers sustain reliable operation at temperatures up to 1300\u00b0C even at high titania loading, which is attributed to the collective lattice confinement effect of the alumina matrix and zirconia strengthening phase. Furthermore, thermal conductivity measurements conducted on dense pellets prepared from grounded fibers with the transient laser flash method reveal a continuous decrease in thermal conductivity, giving direct evidence of intensified phonon scattering at elevated temperatures. This work provides an effective strategy for designing flexible ceramic fibers integrating exceptional thermal insulation and multifunctionality for operation in extreme environments.<\/jats:p>","DOI":"10.1002\/smll.202600062","type":"journal-article","created":{"date-parts":[[2026,4,13]],"date-time":"2026-04-13T07:20:27Z","timestamp":1776064827000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Strong Ligand Coordination Enabled Multiphase Ceramic Nanofibers for Simultaneously Enhancing Structural Stability and Infrared Reflection"],"prefix":"10.1002","volume":"22","author":[{"given":"Jin","family":"Dai","sequence":"first","affiliation":[{"name":"State Key Laboratory of Advanced Fiber Materials Donghua University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fan","family":"Wu","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Shanghai University of Engineering Science  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hualei","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Shanghai University of Engineering Science  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Siyu","family":"Qiang","sequence":"additional","affiliation":[{"name":"College of Textile Science and Engineering Jiangnan University  Wuxi China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Liqian","family":"Huang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Fiber Materials Donghua University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaoyan","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Fiber Materials Donghua University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sam","family":"Sukgoo Yoon","sequence":"additional","affiliation":[{"name":"School of Mechanical and Engineering Korea University  Seoul Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jianyong","family":"Yu","sequence":"additional","affiliation":[{"name":"Innovation Center for Textile Science and Technology Donghua University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1382-9622","authenticated-orcid":false,"given":"Yi\u2010Tao","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Fiber Materials Donghua University  Shanghai China"},{"name":"Innovation Center for Textile Science and Technology Donghua University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bin","family":"Ding","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Fiber Materials Donghua University  Shanghai China"},{"name":"School of Materials Science and Engineering Shanghai University of Engineering Science  Shanghai China"},{"name":"College of Textile Science and Engineering Jiangnan University  Wuxi China"},{"name":"School of Energy and Materials Shanghai Polytechnic University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,4,13]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.joule.2020.02.010"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010024\u201046753\u20103"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.pecs.2019.03.002"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ensm.2017.05.013"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cis.2024.103352"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.4c00347"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.201904815"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/nmat4687"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022\u20103093(97)00430\u20104"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/cm402900y"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.7b04800"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1007\/s42765\u2010022\u201000133\u2010y"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.coco.2022.101290"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1080\/00405009008658717"},{"key":"e_1_2_8_16_1","first-page":"363","article-title":"Nextel\u2122 650 Ceramic Oxide Fiber: New Alumina\u2010Based Fiber for High Temperature Composite Reinforcement","volume":"21","author":"Wilson D. 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