High-voltage lithium metal batteries (LMBs) are a promising high-energy density energy storage system. However, their practical implementations are impeded by short lifespan due to uncontrolled lithium dendrite growth, narrow electrochemical stability window, and safety concerns of liquid electrolytes. Here, a porous composite aerogel is reported as the gel electrolyte (GE) matrix, made of metal–organic framework (MOF)@bacterial cellulose (BC), to enable long-life LMBs under high voltage. The effectiveness of suppressing dendrite growth is achieved by regulating ion deposition and facilitating ion conduction. Specifically, two hierarchical mesoporous Zr-based MOFs with different organic linkers, that is, UiO-66 and NH2-UiO-66, are embedded into BC aerogel skeletons. The results indicate that NH2-UiO-66 with anionphilic linkers is more effective in increasing the Li+ transference number; the intermolecular interactions between BC and NH2-UiO-66 markedly increase the electrochemical stability. The resulting GE shows high ionic conductivity (≈1 mS cm−1), high Li+ transference number (0.82), wide electrochemical stability window (4.9 V), and excellent thermal stability. Incorporating this GE in a symmetrical Li cell successfully prolongs the cycle life to 1200 h. Paired with the Ni-rich LiNiCoAlO2 (Ni: Co: Al = 8.15:1.5:0.35, NCA) cathode, the NH2-UiO-66@BC GE significantly improves the capacity, rate performance, and cycle stability, manifesting its feasibility to operate under high voltage.
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Ionic Liquid Welding of the UIO-66-NH2 MOF to Cotton Textiles
Ionic liquid based fiber welding has been used to attach the metal−organic framework (MOF) UiO-66-NH2to cotton fibers. The results show that by controlling the extent of the welding process, it is possible to produce fibers that contain a high surface area (approximately 50−100 m2/ g), an X-ray diffraction pattern consistent with UiO-66-NH2, and fibers that
are chemically reactive to dimethyl 4-nitrophenyl phosphate (DMNP), a common chemical weapon simulant. The ionic liquid/MOF welding solution can be applied by directly placing the fabric in the welding solution or by utilizing an airbrushing technique. Both welding techniques are shown to be scalable with results collected on approximately 1×1, 5
×5, and 15.5×15.5 in. swatches. The results are also applicable to weaving methods where the MOF is welded to individual threads and subsequently woven into a textile. The results provide an industrially scalable method of attaching a wide variety of MOFs to cotton textiles, which does not require synthesizing the MOF in the presence of the textile.
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- Award ID(s):
- 1726263
- NSF-PAR ID:
- 10207558
- Date Published:
- Journal Name:
- Industrial engineering chemistry research
- Volume:
- 59
- Issue:
- 43
- ISSN:
- 1520-5045
- Page Range / eLocation ID:
- 19285-19298
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Current approaches to create zirconium‐based metal–organic framework (MOF) fabric composites for catalysis, water purification, wound healing, gas sorption, and other applications often rely on toxic solvents, long reaction/post processing times, and batch methods hindering process scalability. Here, a novel mechanism was reported for rapid UiO‐66‐NH2synthesis in common low‐boiling‐point solvents (water, ethanol, and acetic acid) and revealed acid–base chemistry promoting full linker dissolution and vapor‐based crystallization. The mechanism enabled scalable roll‐to‐roll production of mechanically resilient UiO‐66‐NH2fabrics with superior chemical protective capability. Solvent choice and segregated spray delivery of organic linker and metal salt MOF precursor solutions allowed for rapid MOF nucleation on the fiber surface and decreased the energy and time needed for post‐processing, producing an activated composite in less than 165 min, far outpacing conventional MOF‐fabric synthesis approaches. The MOF‐fabric hydrolyzed and blocked permeation of the chemical warfare agent soman, outperforming the protection‐standard activated carbon cloth. This work presents both chemical insights into Zr‐MOF powder and fabric composite formation by a rapid, industrially relevant approach and demonstrates its practicality and affordability for high‐performing personal protective equipment.
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Abstract Hybridization of metal–organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF–polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench‐top approach to covalently tethered nylon–MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO‐66‐NH2MOF with a growing polyamide fiber (PA‐66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl‐4‐nitrophenyl phosphate, DMNP) compared to MOFs that are non‐covalently, physically entrapped in nylon, thus highlighting the importance of MOF–polymer hybridization.
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Abstract Hybridization of metal–organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF–polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench‐top approach to covalently tethered nylon–MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO‐66‐NH2MOF with a growing polyamide fiber (PA‐66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl‐4‐nitrophenyl phosphate, DMNP) compared to MOFs that are non‐covalently, physically entrapped in nylon, thus highlighting the importance of MOF–polymer hybridization.
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A leading biotechnological advancement in the field of biocatalysis is the immobilization of enzymes on solid supports to create more stable and recyclable systems. Metal-organic frameworks (MOFs) are porous materials that have been explored as solid supports for enzyme immobilization. Composed of organic linkers and inorganic nodes, MOFs feature empty void space with large surface areas and have the ability to be modified post-synthesis. Our target enzyme system for immobilization is glucose oxidase (GOx) and chloroperoxidase (CPO). Glucose oxidase catalyzes the oxidation of glucose and is used for many applications in biosensing, biofuel cells, and food production. Chloroperoxidase is a fungal heme enzyme that catalyzes peroxide-dependent halogenation, oxidation, and hydroxylation. These two enzymes work sequentially in this enzyme system by GOx producing peroxide, which activates CPO that reacts with a suitable substrate. This study focuses on using a zirconium-based MOF, UiO-66-NH2, to immobilize the enzyme system via crosslinking with the MOF’s amine group on the surface of the MOF. This study investigates two different crosslinkers: disuccinimidyl glutarate (DSG) and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC)/N-hydroxysuccinidimide (NHS), providing stable crosslinking of the MOF to the enzymes. The two crosslinkers are used to covalently bond CPO and GOx onto UiO-66-NH2, and a comparison of the recyclability and enzymatic activity of the single immobilization of CPO and the doubly immobilized CPO and GOx is discussed through assays and characterization analyses. The DSG-crosslinked composites displayed enhanced activity relative to the free enzyme, and all crosslinked enzyme/MOF composites demonstrated recyclability, with at least 30% of the activity being retained after four catalytic cycles. The results of this report will aid researchers in utilizing CPO as a biocatalyst that is more active and has greater recyclability.more » « less
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Accepted Manuscript1.0
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