Objectives Conventional fertilizers often face difficulties in controlling nutrient release rates and exhibit relatively low utilization efficiency. Thus, environment-responsive fertilizers that modulate nutrient release in response to environmental changes are progressively emerging as pivotal technological approaches for advancing sustainable agriculture.

Methods Lignin (L) was hydrolyzed using Urea/NaOH (UR/SH) at low temperatures to obtain hydrolyzed lignin (HL). The hydrolyzed lignin was then cross-linked with polyethylene glycol diglycidyl ether (PEGDGE) to prepare a hydrolyzed lignin hydrogel (HLHG). The HLHG was subsequently employed as a carrier for diammonium phosphate (DAP) fertilizer to create a pH-responsive hydrogel fertilizer.

Results The optimal hydrolysis conditions were determined to be 18 h and −10℃. Under these conditions, the contents of hydroxyl (―OH) and carboxyl (―COOH) groups reached their maximum levels, increasing by approximately 68% and 99%, respectively, compared to untreated L. The obtained pH-responsive lignin hydrogel (HLHG-(−10℃)-18 h) showed an equilibrium swelling ratio of 1216%, with a water retention swelling ratio of 163% after 11 hours. These values were approximately 3 and 12 times greater than those of the unhydrolyzed lignin hydrogel (LHG), respectively. pH responsiveness analysis indicated that the hydrogel demonstrated significant pH sensitivity, with equilibrium swelling ratio of 364%, 518%, and 634% at pH 6, 7, and 8, respectively. The increases in equilibrium swelling ratios between adjacent pH levels were 154% and 116%, representing significant improvements of 41% and 70% compared to LHG, respectively. SEM analysis demonstrated pH-dependent microstructural evolution of the lignin hydrogel. As the pH increased from 5 to 8, the honeycomb network exhibited a progressive pore channel expansion with concomitant wall thinning. When the pH increased to 9, the network structure contracted, resulting in a reduction in pore channels and thickening of the pore wall. This pH-responsive behavior was mechanistically attributed to the ionization/protonation equilibria of abundant ―OH and ―COOH groups in lignin, as validated through integrated functional group quantification and pH responsiveness assays. Furthermore, the pH-responsive hydrogel was employed as a carrier for DAP to control the release of phosphate fertilizer nutrients. The nutrient release results showed that the cumulative release of P₂O₅ from the lignin hydrogel fertilizer in the period of 60 h was 61%, 76%, and 85% at pH 6, 7, and 8, respectively, exhibiting a prominent pH-responsive tendency.

Conclusion UR/SH hydrolysis of lignin effectively modifies the content of active functional groups and the internal spatial network structure of lignin, it is possible to create pH-responsive lignin hydrogels with enhanced water absorption and retention capacities. Utilizing this pH-responsive lignin-based hydrogel as a carrier for fertilizers offers a valuable reference for the effective utilization of lignin resources and the design of bio-based green fertilizer for nutrient control release.