The adsorption capacity of synthetic NaX zeolite for Pb²⁺, Cd²⁺, Cu²⁺ and Zn²⁺ in single and multi-component systems were investigated. The effects of electronegativity and hydration energy on the selective adsorption, as well as potential selective adsorption mechanism of the NaX zeolite for Pb²⁺, Cd²⁺, Cu²⁺ and Zn²⁺ were also discussed. The maximum adsorption capacity order of the heavy metals in the single system was Pb²⁺ > Cd²⁺ > Cu²⁺ > Zn²⁺, and this could be related to their hydration energy and electronegativity. The values of the separation factors (α) and affinity constant (K_EL) in different binary systems indicated that Pb²⁺ was preferentially adsorbed, and Zn²⁺ presented the lowest affinity for NaX zeolite. The selective adsorption capacities of the metals were in the order, Pb²⁺ > Cd²⁺ ≈ Cu²⁺ > Zn²⁺. The trend for the selective adsorption of NaX zeolite in ternary and quaternary systems was consistent with that in the binary systems. Pb²⁺ and Cu²⁺ reduced the stability of the Si-O-Al bonds and the double six-membered rings in the NaX framework, due to the high electronegativity of Pb²⁺ and Cu²⁺ than that of Al³⁺. The selective adsorption mechanism of NaX zeolite for the high electronegative metal ions could mainly result from the negatively charged O in the Si-O-Al structure of the NaX zeolite, hence heavy metal ions with high electronegativity display a strong affinity for the electron cloud of the oxygen atoms in the Si-O-Al. This study could evaluate the application and efficiency of zeolite in separating and recovering certain metal ions from industrial wastewater.

Background: Although laccase has a good catalytic oxidation ability, free laccase shows a poor stability. Enzyme immobilization is a common method to improve enzyme stability and endow the enzyme with reusability. Adsorption is the simplest and common method. Modified biochar has attracted great attention due to its excellent performance.Results: In this paper, cetyltrimethylammonium bromide (CTAB)-KOH modified biochar (CKMB) was used to immobilize laccase by adsorption method (laccase@CKMB). Based on the results of the single-factor experiments, the optimal loading conditions of laccase@CKMB were studied with the assistance of Design-Expert 12 and response surface methods. The predicted optimal experimental conditions were laccase dosage 1.78 mg/mL, pH 3.1 and 312 K. Under these conditions, the activity recovery of laccase@CKMB was the highest, reaching 61.78%. Then, the CKMB and laccase@CKMB were characterized by TGA, FT-IR, XRD, BET and SEM, and the results showed that laccase could be well immobilized on CKMB, the maximum enzyme loading could reach 57.5 mg/g. Compared to free laccase, the storage and pH stability of laccase@CKMB was improved greatly. The laccase@CKMB retained about 40% of relative activity (4 °C, 30 days) and more than 50% of relative activity at pH 2.0–6.0. In addition, the laccase@CKMB indicated the reusability up to 6 reaction cycles while retaining 45.1% of relative activity. Moreover, the thermal deactivation kinetic studies of laccase@CKMB showed a lower k value (0.00275 min^− 1) and higher t_1/2values (252.0 min) than the k value (0.00573 min^− 1) and t_1/2values (121.0 min) of free laccase.Conclusions: We explored scientific and reasonable immobilization conditions of laccase@CKMB, and the laccase@CKMB possessed relatively better stabilities, which gave the immobilization of laccase on this cheap and easily available carrier material the possibility of industrial applications.

Laccases have enormous potential as promising ‘green’ biocatalysts in environmental applications including wastewater treatment and polluted soil bioremediation. The catalytic oxidation reaction they perform uses only molecular oxygen without other cofactors, and the only product after the reaction is water. The immobilization of laccase offers several improvements such as protected activity and enhanced stability over free laccase. In addition, the reusability of immobilized laccase is adistinct advantage for future applications. This review covers the sources of and progress in laccase research, and discusses the different methodologies of laccase immobilization that have emerged in the recent 5–10 years, as well as its applications to environmental fields, and evaluates these emerging technologies. Abbreviations: (2,4,6-TCP): 2,4,6-trichlorophenol; (2,4-DCP): 2,4-dichlorophenol; (ABTS), 2,2-azinobis (3-ethylbenzothiazoline-6-sulfonic acid); (ACE), acetaminophen; (BC-AS), almond shell; (BC-PM), pig manure; (BC-PW), pine wood; (BPA), bisphenol A; (BPA), bisphenol A; (BPF), bisphenol F; (BPS), bisphenol S; (C₆₀), fullerene; (Ca-AIL), calcium-alginate immobilized laccase; (CBZ), carbamazepine; (CETY), cetirizine; (CHT-PGMA-PEI-Cu (II) NPs), Cu (II)-chelated chitosan nanoparticles; (CLEAs), cross-linked enzyme aggregates; (CMMC), carbon-based mesoporous magnetic composites; (COD), chemical oxygen demand; (CPH), ciprofloxacin hydrochloride; (CS), chitosan; (CTC), chlortetracycline; (Cu-AIL), copper-alginate immobilized laccase; (DBR K-4BL), Drimarene brilliant red K-4BL; (DCF), diclofenac; (E1),estrone; (E2), 17 β-estradiol; (EDC), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride; (EDCs), endocrine disrupting chemicals; (EE2), 17α-ethinylestradiol; (EFMs), electrospun fibrous membranes; (FL), free laccase; (fsMP), fumed silica microparticles; (GA-CBs), GLU-crosslinked chitosan beads; (GA-CBs), glutaraldehyde-crosslinked chitosan beads; (GA-Zr-MOF), graphene aerogel-zirconium-metal organic framework; (GLU), glutaraldehyde; (GO), graphene oxide; (HMCs), hollow mesoporous carbon spheres; (HPEI/PES), hyperbranched polyethyleneimine/polyether sulfone; (IC), indigo carmine; (IL), immobilized laccase; (k_cat), catalytic constant; (K_m), Michealis constant; (M-CLEAs), Magnetic cross-linked enzyme aggregates; (MMSNPs-CPTS-IDA-Cu²⁺), Cu²⁺-chelated magnetic mesoporous silica nanoparticles; (MSS), magnetic mesoporous silica spheres; (MWNTs), multi-walled carbon nanotubes; (MWNTs), multi-walled carbon nanotubes; (NHS), N-hydroxy succinimide; (O-MWNTs), oxidized-MWNTs; (P(AAm-NIPA)), poly(acrylamide-N-isopropylacrylamide); (p(GMA)), poly(glycidyl methacrylate); (p(HEMA)), poly(hydroxyethyl methacrylate); (p(HEMA-g-GMA)-NH₂, poly(glycidyl methacrylate) brush grafted poly(hydroxyethyl methacrylate); (PA6/CHIT), polyamide 6/chitosan; (PAC), powdered active carbon; (PAHs), polycyclic aromatic hydrocarbons; (PAM-CTS), chitosan grafted polyacrylamide hydrogel; (PAN/MMT/GO), polyacrylonitrile/montmorillonite/graphene oxide; (PAN/PVdF), polyacrylonitrile/polyvinylidene fluoride; (PEG), poly ethylene glycol; (PEI), Poly(ethyleneimine); (poly(4-VP)), poly(4-vinyl pyridine); (poly(GMA-MAA)), poly(glycidyl methacrylate-methacrylic acid); (PVA), polyvinyl alcohol; (RBBR), Remazol Brilliant Blue R; (SDE), simulated dye effluent; (semi-IPNs), semi-interpenetrating polymer networks; (TC), tetracycline; (TCH), tetracycline hydrochloride; (TCS), triclosan; (Vmax), maximum activity; (Zr-MOF, MMU), micro-mesoporous Zr-metal organic framework.

Immobilization of laccase helps protect the laccase and realizes repeated use. However, excessive encapsulation protection will also limit the release of laccase activity. This work introduces an effective one-pot method encapsulating laccase in the porous material of metal organic framework (MOF) containing specific metal ions, which provided a new way to solve the problem of limited laccase activity. The immobilization process was mathematically modeled. The morphological and encapsulated properties of the prepared materials were confirmed by the characterization results of SEM, FTIR, XRD, TGA, XPS and CLSM. The results showed that laccase was successfully encapsulated, and the Cu (PABA) with Cu²⁺ as the central structure promoted the laccase activity, the activity of immobilized laccase increased by 1.7 times. The prepared laccase@Cu (PABA) (Lac@Cu (PABA)) showed enhanced stability to extreme pH, high temperature and storage time. More importantly, the Lac@Cu (PABA) exhibited superior reusability, maintaining 70% removal rate of Direct Red 31 (DR31) even after 10 cycles. The dye removal rate of immobilized laccase reached 92% in 6 h under optimal conditions. This research improved the stability of laccase while releasing the activity of laccase, which not only broadened the applicable environment of laccase, but also increased the rate of degradation, and provided a new idea for the clean and efficient treatment of water pollution in textile industry.