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However, most of the electrocatalysts currently used for MOR have drawbacks, such as inefficient reaction kinetics, low tolerance to carbon monoxide poisoning, and unstable performance. Herein, we report a novel hierarchical MOF heterostructure that is made up of Mn\u2010doped ZIF67 and Mn\u2010doped ZIF\u2010L (Mn\u2010ZIF67\/L) directly grown on carbon cloth to highly enhance the MOR performance. Such heterostructure integrates flake\u2010like Mn\u2010doped ZIF\u2010L with Mn\u2010doped ZIF\u201067 nanocrystals, forming a porous core\u2010shell framework with abundant active sites and enhanced charge transportation. More interesting, the Mn\u2010ZIF67\/L experiences dynamic reconstruction (Mn\u2010ZIF67\/L\u2010ac) that partial phases in CoMn LDHs are transformed into (Co,Mn)OOH during the electrochemical operation in which further boosting the catalytic performance and stability. The electrochemical results demonstrate that Mn\u2010ZIF67\/L\u2010ac remarkably improves the MOR performance with the much lower potential of 1.359\u00a0V at 10\u00a0mA cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    , outperforming commercial RuO\n                    <jats:sub>2<\/jats:sub>\n                    . The electrocatalyst also delivers the high MOR stability of \u223c97% retention after 130\u00a0h. This work demonstrates a robust strategy for nonnoble\u2010metal electrocatalysts and an efficient route to hydrogen production through MOR\u2010HER coupling.\n                  <\/jats:p>","DOI":"10.1002\/chem.202503102","type":"journal-article","created":{"date-parts":[[2025,12,24]],"date-time":"2025-12-24T06:42:03Z","timestamp":1766558523000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Hierarchical Manganese\u2010Doped ZIFs Heterostructure Electrocatalysts for Highly\u2010Efficient Methanol Oxidation Reaction"],"prefix":"10.1002","volume":"32","author":[{"given":"Weijian","family":"Sun","sequence":"first","affiliation":[{"name":"Institute of Energy Supply Technology for High\u2010end Equipment, Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering Nanjing University of Information Science &amp; Technology  Nanjing Jiangsu China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fangyan","family":"Li","sequence":"additional","affiliation":[{"name":"Institute of Energy Supply Technology for High\u2010end Equipment, Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering Nanjing University of Information Science &amp; Technology  Nanjing Jiangsu China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7517-4633","authenticated-orcid":false,"given":"Yachao","family":"Jin","sequence":"additional","affiliation":[{"name":"Institute of Energy Supply Technology for High\u2010end Equipment, Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering Nanjing University of Information Science &amp; Technology  Nanjing Jiangsu China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Li","family":"Song","sequence":"additional","affiliation":[{"name":"Institute of Energy Supply Technology for High\u2010end Equipment, Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering Nanjing University of Information Science &amp; Technology  Nanjing Jiangsu China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mingdao","family":"Zhang","sequence":"additional","affiliation":[{"name":"Institute of Energy Supply Technology for High\u2010end Equipment, Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment 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