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Functionalized Li/NH2/MIL-101(Cr) and Li/NH2/MIL-100(Fe) for lithium adsorption and separation from aqueous solutions
Yanjia Zhou1, Xiaodong Tang1, Jingjing Li1
1Southwest Petroleum University, Department of Chemistry and Chemical Engineering, Chengdu, 610500, Sichuan, China. txda429@163.com.
Dalton Transactions (Cambridge, England : 2003)
|August 1, 2025
Summary
Functionalized Metal-Organic Frameworks (MOFs) show enhanced lithium-ion (Li+) adsorption for efficient recovery. These materials demonstrate high selectivity and reusability in complex solutions, crucial for sustainable lithium extraction.
Area of Science:
- Materials Science
- Chemical Engineering
- Environmental Science
Background:
- Metal-Organic Frameworks (MOFs), specifically MIL-101(Cr) and MIL-100(Fe), are known for high surface areas and tunable properties.
- These characteristics make them promising candidates for selective ion adsorption, particularly for lithium (Li+) recovery from aqueous solutions.
- Existing MOFs may require modification to enhance their adsorption capacity and selectivity for Li+.
Purpose of the Study:
- To synthesize functionalized MIL-type MOFs, Li/NH2/MIL-101(Cr) and Li/NH2/MIL-100(Fe), for improved Li+ extraction.
- To investigate the adsorption performance, kinetics, thermodynamics, and selectivity of these modified MOFs for Li+.
- To evaluate the reusability and practical applicability of the functionalized MOFs in lithium recovery processes.
Main Methods:
- Synthesis of MIL-101(Cr) and MIL-100(Fe) with introduced -NH2 functional groups using LiNO3 as a template and mineralizer.
- Adsorption experiments to determine Li+ adsorption capacities under varying conditions (mineralizer dosage, initial Li+ concentration, adsorbent dosage, pH, temperature).
- Kinetic (pseudo-first-order, pseudo-second-order) and thermodynamic (Langmuir, Freundlich) modeling to understand adsorption mechanisms.
- Selectivity tests in Mg-Li mixed solutions and multi-ion systems to assess separation capabilities.
Main Results:
- Functionalized MOFs, Li/NH2/MIL-101(Cr) and Li/NH2/MIL-100(Fe), exhibited enhanced Li+ adsorption capacities of 43.58 and 38.22 mg g-1, respectively.
- Adsorption followed monolayer chemisorption, was exothermic, and best described by pseudo-second-order kinetics and Langmuir/Freundlich models.
- Materials demonstrated excellent Li+ selectivity over Mg2+ (separation factor α > 80 at low Mg2+/Li+ ratio, ~50 at high ratio) and other cations (Li+ ≫ Mg2+ > Ca2+ > Na+ > K+).
- High reusability was observed, retaining over 85% capacity after four cycles.
Conclusions:
- The synthesized Li/NH2/MIL-101(Cr) and Li/NH2/MIL-100(Fe) are effective adsorbents for Li+ recovery.
- The functionalization strategy significantly improved adsorption capacity and selectivity, demonstrating practical potential for lithium extraction.
- The exothermic, chemisorption-based process and excellent reusability highlight the viability of these MOFs for sustainable lithium recovery.
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