The complex wastewater containing water-soluble dyes and water-insoluble oils has given rise to significant environmental concerns that demand urgent remediation. Herein, a novel “smart” multifunctional sponge (ZIF-8@PMS) stepwise decorated with ZIF-8 nanoparticles and CO2-responsive copolymer (poly(2-(diethylamino) ethyl methacrylate-co-3-(trimethoxysilyl)propyl acrylate-co-stearyl methacrylate) was successfully prepared for CO2 controllable oil/water separation and dyes removal. The results revealed that the sponge coated with CO2-responsive copolymer for three cycles (ZIF-8@PMS-3) exhibited optimal comprehensive properties. The ZIF-8@PMS-3 had excellent compressive-resilient characteristics and chemical stability. As expected, it displayed tunable wettability and charged state under the regulation of CO2. Based on these features, ZIF-8@PMS-3 presented highly efficient removal of oil and dyes, even for the dye-containing oil/water emulsions, via a synergistic combination of adsorption and separation methods. The adsorption capacity for oil and various organic solvents ranged from 21.3 to 50 g g–1. The maximum adsorption capacities toward anionic dyes: methyl orange with 1205.89 mg g–1 and methyl blue with 880.00 mg g–1 in the presence of CO2 through electrostatic interaction. In the absence of CO2, it achieved maximum adsorption capacities for cationic dyes, including malachite green with 1246.15 mg g–1 and rhodamine B with 203 mg g–1, primarily driven by π–π interactions. According to distinct adsorption mechanisms, ZIF-8@PMS-3 could selectively adsorb either anionic or cationic dyes by exploiting CO2 as a trigger. Furthermore, the separation efficiencies for both types of oil/water emulsions surpassed 99.9%, with respective fluxes of 1566.99 L m–2 h–1 (water-in-oil emulsion) and 310.37 L m–2 h–1 (oil-in-water emulsion). Additionally, the as-prepared sponges exhibited remarkable antibacterial properties and exceptional recyclability. Therefore, the ZIF-8@PMS-3 holds substantial promise for potential applications in practical industrial wastewater treatment.
