Cellulose-based hierarchical porous beads exhibit significant application potential in adsorption and separation systems due to their degradation and biocompatibility. However, the current fabrications of cellulose beads show poor mechanical properties and a difficult-to-regulate hierarchical porous structure, reducing their lifespan of use and limiting their application in fine separation. Here, we reported the facile creep-drop method to prepare cellulose beads that enabled systemic regulation of the macro-size, micropore structures, and mechanical properties by optimizing injection nozzle diameter, the composition of the coagulation bath, the temperature of the coagulation bath, and cellulose concentration. Notably, during the molding process, the H2SO4-Na2SO4 composite solidification bath endowed cellulose beads with a dense shell layer and a loose core layer, which achieved the integration of mechanical properties and high porosity. The cellulose beads exhibited high porosity (93.38-96.18%) and high sphericity (86.78-94.44%) by modulating the shell thickness of the cellulose beads. In particular, the cellulose beads exhibited excellent mechanical properties with a high compressive strength of 544.24 kPa at a 5% cellulose concentration. It is expected that these cellulose beads with tunable microstructures can realize their potential for applications in the fields of wastewater treatment, chemical engineering, bioengineering, medicine, and pharmaceuticals.

Herein, a facile yet efficient template method to fabricate macroporous cellulose beads (MCBs) is reported. In this method, micro-size CaCO3 is utilized to create macroporous structure for fast mass transfer, and tentacle-type poly(hydroxamic acid) as adsorption ligand is immobilized on the MCBs to improve adsorption capacity. The obtained tentacle-type poly(hydroxamic acid)-modified MCMs (TP-CMCBs) show uniform spherical shape (about 80 μm), bimodal pore system (macropores≈3.0 μm; diffusional pores≈14.5 nm), and high specific surface area (52.7 m2/g). The adsorption performance of TP-CMCBs is evaluated by heavy metal ions adsorption. TP-CMCBs exhibit not only high adsorption capacities (342.5, 261.5 and 243.2 mg/g for Cu2+, Mn2+ and Ni2+, respectively.), but also fast adsorption rate (>70% of its equilibrium uptake within 30 min). Additionally, TP-CMCBs have excellent reusability, as evidenced by that the adsorption capacities have no obvious change even after five-time consecutive adsorption-desorption cycles. All results demonstrate that the proposed TP-CMCBs have great potential in removal of heavy metal ions.

Due to strong activity, it is very difficult to remove low concentrations of bromide in medical wastewater by traditional method, thus highly effective and greener adsorbents should be utilized to design. In this work, the cellulose beads (CBs) were modified by the TEMPO-mediated oxidation and then bonded with Fe3+ to fabricate Fe(III)-complexed carboxylated cellulose beads (Fe-CCBs) adsorbents. Structure and properties of Fe-CCBs were analyzed using Energy dispersive spectrum (EDS), Scanning electron microscopy (SEM), Fourier transform infrared spectrum (FT-IR), total acidity and basicity groups, X-ray diffraction (XRD), N2 adsorption-desorption and Thermogravimetric (TGA). Moreover, batch adsorption experiments showed that the adsorption of Br- was better consistent with general-order kinetic model and Liu isotherm model, which could also further clarify the adsorption process mechanism. Meanwhile, the results revealed that removal of Br- was a spontaneous exothermic process and was more suitable to be carried out under neutral or acidic conditions. Furthermore, the mechanism of adsorption behavior of bromide ions on Fe-CCBs was based on a combination of electrostatic attraction and outer-sphere complexation. The results of this study can provide guidance for the design of novel material adsorbents and the removal of harmful anions from aqueous solutions.

In the present study, porous magnetic cellulose beads (CBs) were prepared and further modified using amines. The CBs appeared to have good spherical shape and three-dimensional (3D) porous structure. In the adsorption tests, the modified cellulose beads (MCBs) showed better adsorption capacities and shorter adsorption times on hyperin and 2\'-O-galloylhyperin than the commercial resins. The adsorption may be due to the hydrogen bonding between the target compounds and the amine groups of MCBs. After adsorption and desorption, the contents of hyperin and 2\'-O-galloylhyperin reached 1.32% and 3.92%, which were 4.08 and 4.23 times higher than those in the Pyrola extracts. Therefore, the prepared MCBs in this study make an excellent adsorbing material of hyperin and 2\'-O-galloylhyperin, and it may have potential for the separation of other natural compounds.

A novel super-macroporous monolithic composite cryogel was prepared by embedding macroporous cellulose beads into poly(hydroxyethyl methacrylate) cryogel. The cellulose beads were fabricated by using a microchannel liquid-flow focusing and cryopolymerization method, while the composite cryogel was prepared by cryogenic radical polymerization of the hydroxyethyl methacrylate monomer with poly(ethylene glycol) diacrylate as cross-linker together with the cellulose beads. After graft polymerization with (vinylbenzyl)trimethylammonium chloride, the composite cryogel was applied to separate immunoglobulin-G and albumin from human serum. Immunoglobulin-G with a mean purity of 83.2% and albumin with a purity of 98% were obtained, indicating the composite cryogel as a promising chromatographic medium in bioseparation for the isolation of important bioactive proteins like immunoglobulins and albumins.