Outstanding enhancement of caproate production with microwave pyrolyzed highly reductive biochar addition

•Microwave-heating with carbon fiber cloth gives efficient biochar yield performance.•Microwave-pyrolyzed char (MW) enhanced caproate production and selectivity.•MW enriched the dominance of Parabacteroides, Bacteroides, and Macellibacteroides.•MW significantly promoted both RBO and fatty acid biosynthesis pathways. The integration of biochar into microbial Chain Elongation (CE) proves to be an effective tool of producing high-value bio-based products. This study innovatively applied biochar fabricated under microwave irradiation with carbon fiber cloth assistance into CE system. Results highlighted that microwave biochar achieved maximal CE efficiency yielding 8 g COD/L, with 3-fold increase to the blank group devoid of any biochar. Microwave biochar also obtained the highest substrate utilization rate of 94 %, while conventional biochar group recorded 90 % and the blank group was of 74 %. Mechanistic insights revealed that the reductive surface properties facilitated CE performance, which is relevant to fostering dominant genera of Parabacteroides, Bacteroides, and Macellibacteroides. By metagenomics, microwave biochar up-regulated functional genes and enzymes involved in CE process including ethanol oxidation, the reverse β-oxidation pathway, and the fatty acid biosynthesis pathway. This study effectively facilitated caproate production by utilizing a new microwave biochar preparation strategy.