Self-supporting and hierarchical porous membrane of bacterial nanocellulose@metal-organic framework for ultra-high adsorption of Congo red.

The widespread use of synthetic dyes has serious implications for both the environment and human health. Therefore, there is an urgent need for the development of novel, high-efficiency adsorbents for these dyes. In this study, a Zirconium-based metal-organic framework (MOF) with controllable morphology was in-situ grown on bacterial nanocellulose (BC) via a solvothermal method. The resulting BC@MOF composite nanofibers have a high specific surface area of 651 m2/g and can be assembled into a self-supported porous membrane (BMMCa) through vacuum filtration with the assistance of calcium ions. The addition of Ca(II) significantly enhanced the mechanical properties of the membrane through dispersion effect and electrostatic interactions, as well as enhancing its adsorption performance through the salting-out effect. The BMMCa membrane, with its hierarchical porous structure and high flux, exhibits high selectivity for Congo red (CR) with an ultra-high adsorption capacity of 3518.6 mg/g. Furthermore, the self-supporting membrane achieved rapid and convenient removal of CR through circulating filtration adsorption. The adsorption mechanism and selectivity were verified through the molecular dynamics simulation calculations by Materials Studio (MS) software. This membrane-based adsorbent, with its ultra-high adsorption capacity, good selectivity, and recycling ability, has great potential for practical wastewater treatment applications.

Nanocellulose-based membranes with pH- and temperature-responsive pore size for selective separation.

Smart gating membranes have drawn much attention due to the controllable pore structure. Herein, a smart gating membrane with dual responsiveness was prepared from bacteria cellulose (BC) grafted with pH- and temperature-responsive polymers. By external stimulation, the average pore size of the membrane can be controlled from 33.75 nm to 144.81 nm, and the pure water flux can be regulated from 342 to 2118 L·m-2·h-1 with remarkable variation in the pH range of 1-11 and temperature range of 20-60 °C. The adjustability of pore size is able to achieve the gradient selective separation of particles and polymers with different sizes. In addition, owing to the underwater superoleophobicity and the nanoscale pore structure, the membrane separation efficiencies of emulsified oils are higher than 99 %. Moreover, the controllable pore size endows the membrane with good self-cleaning performance. This nanocellulose-based smart gating membrane has potential applications in the fields of controllable permeation, selective separation, fluid transport, and drug/chemical controlled release systems.

A smart gating nanocellulose membrane showing selective separation and self-cleaning performance.

A smart gating membrane based on thermal-sensitive poly (N-isopropyl acrylamide) (PNIPAM)-grafted nanocellulose and carbon nanotube (CNT) was prepared. The presence of PNIPAM shell on cellulose nanofibrils (CNFs) endow the composite membrane with thermal responsiveness. By external stimulation, an increase temperature from 10 °C to 70 °C allows the average pore size of the membrane to be controlled from 28 nm to 110 nm, as well as the water permeance from 440 L·m-2·h-1·bar-1 to 1088 L·m-2·h-1·bar-1. The gating ratio of the membrane can reach 2.47. The photothermal effect of CNT rapidly warms up the membrane to the lowest critical solution temperature in the water, avoiding the constraint that the whole water phase cannot be heated throughout the practical use process. The membrane can precisely control the nanoparticles to concentrate at 25.3 nm, 47.7 nm or 102 nm by adjust the temperature. In addition, the water permeance can be restored to 370 L·m-2·h-1·bar-1 by washing the membrane under light. The smart gating membrane has a wide application in substance multi-stage separation and selective separation, and it can realize self-cleaning.