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Although metal catalysts have dominated and defined a benchmark in the field of electrochemical CO2 reduction (CO2RR), recent research has shifted toward the use of metal-free carbon-based catalysts. The catalytic role of metal-free polymers has remained unexplored, and they are primarily used as interfacial modifiers and electrolytes for CO2RR. The present study bridges a gap in this direction wherein a redox-active, benzoquinone-pyrrole copolymer (BQ-Py) is proposed as a durable, metal-free catalyst for CO2RR. The polymer catalyzes the reduction of CO2 to CO, HCOOH, and H2 over a potential range of \u20131.4 to \u20131.8 V vs RHE. Using operando ATR-IR spectroscopy, Raman spectroscopy, and DFT calculations, the reaction pathway to formic acid is confirmed via the formation of the *HCOO intermediate on the C atom adjacent to pyrrolic N. This study highlights the crucial role of various pyrrolic N-environments in the catalyst on product formation and its distribution through different mechanistic pathways during CO2 reduction. It further demonstrates the catalytic competency of pyrrolic-N toward electrochemical CO2 reduction. Preliminary studies reveal the possibility of integrating the polymer catalyst into rechargeable Zn-CO2 batteries.<\/jats:p>","DOI":"10.1021\/acsami.6c11750","type":"journal-article","created":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T03:01:39Z","timestamp":1789441299000},"page":"50821-50832","source":"Crossref","is-referenced-by-count":0,"title":["Electrochemical Reduction of CO2 Using a Metal-Free Polymer Catalyst: Synergy of Pyrrole and Quinone Interfacial Sites"],"prefix":"10.1021","volume":"18","author":[{"given":"Gargi","family":"Dey","sequence":"first","affiliation":[{"name":"Indian Institute of Science , , ,","place":["Bangalore, India, 560012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-4195-6417","authenticated-orcid":true,"given":"Adil","family":"Fayaz","sequence":"additional","affiliation":[{"name":"Indian Institute of Science , , ,","place":["Bangalore, India, 560012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8373-9032","authenticated-orcid":true,"given":"Muthu Austeria","family":"P","sequence":"additional","affiliation":[{"name":"Jain (Deemed-to-be University) , , ,","place":["Bangalore, India, 562112"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0777-2161","authenticated-orcid":true,"given":"Srinivasan","family":"Sampath","sequence":"additional","affiliation":[{"name":"Indian Institute of Science , , ,","place":["Bangalore, India, 560012"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,14]]},"reference":[{"key":"2026100820073638700_cit1","doi-asserted-by":"publisher","DOI":"10.1016\/j.rser.2021.110846","article-title":"A Review of CO2 Emissions Reduction Technologies and Low-Carbon Development in the Iron and Steel Industry Focusing on China","volume":"143","author":"Ren","year":"2021","journal-title":"Reneweable Sustainable Energy Rev."},{"issue":"2","key":"2026100820073638700_cit2","doi-asserted-by":"publisher","first-page":"765","DOI":"10.1039\/D0EE02981E","article-title":"Recent Advances in Innovative Strategies for the CO2 Electroreduction Reaction","volume":"14","author":"Tan","year":"2021","journal-title":"Energy Environ. 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