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Traditional methods of decontaminating water via enzyme catalysis have limitations, particularly due to the mass transfer resistance resulting from enzyme immobilization. In this study, we report a novel approach in which biochar (BC), a biomass\u2010derived porous material rich in surface functional groups, is integrated with polyacrylamide hydrogels to encapsulate the enzyme horseradish peroxidase (HRP). The resulting Gel\/BC\u2010HRP composite hydrogel exhibits superior biocatalytic activity for the oxidation of phenolic contaminants in the presence of hydrogen peroxide (H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    ). Our findings demonstrate that the Gel\/BC\u2010HRP composite greatly enhances mass transfer efficiency, achieving a reaction rate 91.4 times faster than the biochar\u2010free control, together with exceptionally high turnover frequency (TOF) values. The composite maintains approximately 60% efficiency for phenol removal even after eight reaction cycles. Mechanistic\u00a0investigations suggest that the polyacrylamide gel creates electron\u2010rich domains, while the biochar segments provide electron\u2010deficient domains, leading to the formation of an optimal microenvironment that concentrates both H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    and phenol in the vicinity of the HRP, thereby significantly accelerating the oxidation process. The innovative integration of biochar with hydrogel\u2010immobilized biocatalysts offers a promising and environmentally friendly solution for the degradation of organic pollutants in water remediation.\n                  <\/jats:p>","DOI":"10.1002\/adma.202517616","type":"journal-article","created":{"date-parts":[[2025,12,26]],"date-time":"2025-12-26T09:17:29Z","timestamp":1766740649000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["A Biochar\u2010Based Composite Hydrogel Microenvironment for Enhanced Biocatalysis"],"prefix":"10.1002","volume":"38","author":[{"ORCID":"https:\/\/orcid.org\/0009-0008-3364-7333","authenticated-orcid":false,"given":"Shengzhe","family":"Wang","sequence":"first","affiliation":[{"name":"Department of Biomedical Engineering College of Design and Engineering National University of Singapore  Singapore Singapore"},{"name":"NUS Environmental Research Institute (NERI) National University of 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