Luminescent Metal-Organic Framework for Lithium Harvesting Applications

Nathan D. Rudd, Yanyao Liu, Kui Tan, Feng Chen, Yves J. Chabal, Jing Li

Research output: Contribution to journalArticle

Abstract

We have synthesized a stable luminescent metal-organic framework (LMOF) through modification of an established Zr-based structure. The three-dimensional porous network of LMOF-321 represents a step forward in the development of robust, dual-ligand Zr-MOFs. This material is based on Zr 6 -nodes, which underlie chemically and thermally stable frameworks. LMOF-321 exhibits notable durability in diverse types of water samples (deionized, acidic/basic, seawater). The porosity, luminescence, and specific functionality from LMOF-321 establishes itself as a fluorescent chemical sensor and adsorbent for aqueous analytes. Studies have been implemented to analyze interactions of LMOF-321 with Li + and other metals commonly found in water. The fluorescence intensity from LMOF-321 is responsive to Li + at a parts per billion level (3.3 ppb) and demonstrates high selectivity for Li + over other light metals, with detection ratios of 6.2, 14.3, and 44.9 for Li + /Na + , Li + /Ca 2+ , and Li + /Mg 2+ , respectively. These performances were maintained in ion-doped deionized and seawater samples, highlighting the potential of LMOF-321 for field applications. The Li + K SV value for LMOF-321 (6549 M -1 ) sets the standard for LMOF sensors. ICP-OES reveals the selective adsorption of Li + over other light metals, consistent with fluorescence measurements. LMOF-321 has a maximum uptake capacity of 12.18 mg/g, on par with lithium extraction materials. The adsorption data was fitted using Langmuir adsorption model with a high correlation factor (>0.999). XPS and FTIR studies provide insight to help understand the interaction mechanism between Li + and LMOF-321, focusing on the bis(sulfonyl)imide functionality in the pillaring coligand. No other MOFs have been utilized for both the detection and extraction of Li + , rendering this work one step further toward more efficient harvesting procedures.

Original languageEnglish
Pages (from-to)6561-6568
Number of pages8
JournalACS Sustainable Chemistry and Engineering
Volume7
Issue number7
DOIs
Publication statusPublished - Apr 1 2019

Fingerprint

lithium
Lithium
Metals
metal
Light Metals
Light metals
Seawater
Adsorption
adsorption
Fluorescence
Imides
fluorescence
sensor
Water
seawater
Chemical sensors
Adsorbents
luminescence
Luminescence
durability

Keywords

  • Fluorescence
  • Lithium harvesting
  • Lithium-ion detection
  • Luminescent metal-organic framework
  • Zr-MOF

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry
  • Chemical Engineering(all)
  • Renewable Energy, Sustainability and the Environment

Cite this

Luminescent Metal-Organic Framework for Lithium Harvesting Applications. / Rudd, Nathan D.; Liu, Yanyao; Tan, Kui; Chen, Feng; Chabal, Yves J.; Li, Jing.

In: ACS Sustainable Chemistry and Engineering, Vol. 7, No. 7, 01.04.2019, p. 6561-6568.

Research output: Contribution to journalArticle

Rudd, Nathan D. ; Liu, Yanyao ; Tan, Kui ; Chen, Feng ; Chabal, Yves J. ; Li, Jing. / Luminescent Metal-Organic Framework for Lithium Harvesting Applications. In: ACS Sustainable Chemistry and Engineering. 2019 ; Vol. 7, No. 7. pp. 6561-6568.
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AB - We have synthesized a stable luminescent metal-organic framework (LMOF) through modification of an established Zr-based structure. The three-dimensional porous network of LMOF-321 represents a step forward in the development of robust, dual-ligand Zr-MOFs. This material is based on Zr 6 -nodes, which underlie chemically and thermally stable frameworks. LMOF-321 exhibits notable durability in diverse types of water samples (deionized, acidic/basic, seawater). The porosity, luminescence, and specific functionality from LMOF-321 establishes itself as a fluorescent chemical sensor and adsorbent for aqueous analytes. Studies have been implemented to analyze interactions of LMOF-321 with Li + and other metals commonly found in water. The fluorescence intensity from LMOF-321 is responsive to Li + at a parts per billion level (3.3 ppb) and demonstrates high selectivity for Li + over other light metals, with detection ratios of 6.2, 14.3, and 44.9 for Li + /Na + , Li + /Ca 2+ , and Li + /Mg 2+ , respectively. These performances were maintained in ion-doped deionized and seawater samples, highlighting the potential of LMOF-321 for field applications. The Li + K SV value for LMOF-321 (6549 M -1 ) sets the standard for LMOF sensors. ICP-OES reveals the selective adsorption of Li + over other light metals, consistent with fluorescence measurements. LMOF-321 has a maximum uptake capacity of 12.18 mg/g, on par with lithium extraction materials. The adsorption data was fitted using Langmuir adsorption model with a high correlation factor (>0.999). XPS and FTIR studies provide insight to help understand the interaction mechanism between Li + and LMOF-321, focusing on the bis(sulfonyl)imide functionality in the pillaring coligand. No other MOFs have been utilized for both the detection and extraction of Li + , rendering this work one step further toward more efficient harvesting procedures.

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