Interfacial charge-engineered Ag@ZIF-67/cellulose acetate membranes fabricated by synchronous electrospinning and electrospraying for enhanced PMS/visible-light degradation of tetracycline

Utilizing cellulose acetate (CA), a value-added derivative of biomass industrial crops to construct robust catalytic supports offers a sustainable solution to the bottlenecks of conventional powdered catalysts in advanced oxidation processes, such as poor particle stability, difficult separation and recovery, and rapid loss of photogenerated charge carriers. Herein, we propose an immobilization strategy based on cellulose acetate (CA) electrospun nanofibrous membrane (ENM), in which ZIF-67 and its Ag nanoparticle-modified derivative are efficiently anchored onto the fiber surface via synchronous electrospinning and electrospraying (SEE) to obtain a flexible and recyclable Ag@ZIF-67@CA ENM. The SEE process leads to uniform catalyst dispersion, robust stability and high accessibility of active sites on the fiber surface, while the incorporation of Ag nanoparticles enhances electrical conductivity and effectively inhibits photogenerated electron-hole recombination by driving interfacial electron transfer. Using tetracycline (TC) as a model contaminant, the Ag@ZIF-67@CA ENM exhibits outstanding synergistic degradation performance in the PMS/visible-light system, achieving 95.9% removal within 30 min with an apparent rate constant of 0.14486 min⁻¹. Radical quenching tests and ESR analyses indicate that multiple reactive species, including SO 4 • - , •OH, O 2 • - and 1 O 2 , jointly contribute to the degradation process. Photoelectrochemical measurements and DFT calculations further verify the formation of a built-in electric field and low-resistance pathways, confirming the efficient charge separation mechanism. This study presents a simple and scalable design for the advanced valorization of industrial crop-derived products, highlighting the potential of bio-based MOF composite membranes in advanced environmental remediation. • Crop-derived CA membranes via synchronous electrospinning and electrospraying. • SEE ensures uniform catalyst dispersion and superior mechanical stability. • Ag/ZIF-67 work-function mismatch promotes interfacial charge separation. • PMS/visible light enables 95.9% tetracycline removal within 30 min. • DFT and experiments confirm low-resistance electron-transfer pathways.