Enhancing humic acids production from cornstalk under fast hydrothermal conditions: Insights into new pathways of skeleton self-polymerization and branch growth.

Hydrochar, a sustainable fertilizer rich in humic substances, is made from lignocellulose through hydrothermal conversion. However, hydrothermal humification (HTH) is challenged by low yields and limited selectivity in the resulting hydrochar. This study proved humic-like acids production can be enhanced under fast non-catalytic conditions (260 ∼ 280 °C, 0 ∼ 1 h). A higher yield (by 14.1 %) and selectivity (by 40.2 %) in hydrochar of humic-like acids than conventional HTH (＜250 °C) were achieved. Meanwhile, decreased lignin derivatives, carbonyl and quinone groups, as well as increased sp-C structures in the humic-like acids were observed. The synthesized humic-like acids exhibited a lower degree of aromatization and a higher molecular weight than commercial variants. Two pathways of humic-like acids formation of self-polymerization and the development of branched sidechains were hypothesized based on mass mitigation, carbon flow and aqueous phase compositions. This research contributes a novel approach to producing humic-like acids rich hydrochar for environmentally friendly fertilizer production.