Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge‐storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large‐scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two‐dimensional imine‐linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.
A highly controllable and scalable process for fabrication of large amounts of concentrated lignin nanoparticles (LNPs) is reported. These lignin core nanoparticles are formed through flash nanoprecipitation, however, scaling up of the fabrication process requires fundamental understanding of their operational formation mechanism and surface properties. It is shown how a semicontinuous synthesis system with a recirculation loop makes it possible to produce flash precipitated lignin nanoparticles in large amounts for practical applications. The roles of the process parameters, including flow rates and lignin concentration, are investigated and analyzed. The results indicate that the LNPs are formed by a process of continuous burst nucleation at the point of mixing without diffusive growth, which yields nanoparticles of highly uniform size following a modified LaMer nucleation and growth mechanism. This mechanism makes possible facile process control and scale‐up. Effective control of the resulting nanoparticle size is achieved through the initial concentration of lignin in the injected solution. The impressive capability to produce suspensions of any predesigned multimodal distribution is demonstrated. The resulting nanofabrication technique can produce large volumes of concentrated LNP suspensions of high stability and tightly controlled size distributions for biological or agricultural applications.
- Publication Date:
- NSF-PAR ID:
- 10456188
- Journal Name:
- Particle & Particle Systems Characterization
- Volume:
- 37
- Issue:
- 7
- ISSN:
- 0934-0866
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Sponsoring Org:
- National Science Foundation
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Abstract -
Abstract Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge‐storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large‐scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two‐dimensional imine‐linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.
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Lignin nanomaterials have wide application prospects in the fields of cosmetics delivery, energy storage, and environmental governance. In this study, we developed a simple and sustainable synthesis approach to produce uniform lignin nanoparticles (LNPs) by dissolving industrial lignin in deep eutectic solvents (DESs) followed by a self-assembling process. LNPs with high yield could be obtained through nanoprecipitation. The LNPs were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Distinct LNPs could be produced by changing the type of DES, lignin sources, pre-dropping lignin concentration, and the pH of the system. Their diameter is in the range of 20–200 nm and they show excellent dispersibility and superior long-term stability. The method of preparing LNPs from lignin–DES with water as an anti-solvent is simple, rapid, and environmentally friendly. The outcome aids to further the advancement of lignin-based nanotechnology.
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A novel and effective green system consisting of deep eutectic solvent (DES) was proposed to prepare lignin nanoparticles (LNPs) without any lignin modification. The LNPs are obtained through the dialysis of the kraft lignin-DES solution. The particle size distribution, Zeta potential and morphology of the LNPs are characterized by using dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The average diameter of LNPs is in the range 123.6 to 140.7 nm, and the LNPs show good stability and dispersibility in water. The composite beads composed of LNPs and sodium alginate (SA) are highly efficient (97.1%) at removing methylene blue (MB) from the aqueous solution compared to 82.9% and 77.4% by the SA/bulk kraft lignin composite and pure SA, respectively. Overall, the LNPs-SA bio-nanocomposite with high adsorption capacity (258.5 mg/g) could be useful in improving water quality and other related applications.
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