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  1. Free, publicly-accessible full text available January 24, 2025
  2. Bipolar porous polymers bearing carbonyl and amine groups were designed and synthesized as cathode materials in Na-ion and K-ion batteries, demonstrating great promise for high-performance and sustainable batteries.

     
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    Free, publicly-accessible full text available August 8, 2024
  3. Controlling network growth and architecture of 3D-conjugated porous polymers (CPPs) is challenging and therefore has limited the ability to systematically tune the network architecture and study its impact on doping efficiency and conductivity. We have proposed that π-face masking straps mask the π-face of the polymer backbone and therefore help to control π–π interchain interactions in higher dimensional π-conjugated materials unlike the conventional linear alkyl pendant solubilizing chains that are incapable of masking the π-face. Herein, we used cycloaraliphane-based π-face masking strapped monomers and show that the strapped repeat units, unlike the conventional monomers, help to overcome the strong interchain π–π interactions, extend network residence time, tune network growth, and increase chemical doping and conductivity in 3D-conjugated porous polymers. The straps doubled the network crosslinking density, which resulted in 18 times higher chemical doping efficiency compared to the control non-strapped-CPP. The straps also provided synthetic tunability and generated CPPs of varying network size, crosslinking density, dispersibility limit, and chemical doping efficiency by changing the knot to strut ratio. For the first time, we have shown that the processability issue of CPPs can be overcome by blending them with insulating commodity polymers. The blending of CPPs with poly(methylmethacrylate) (PMMA) has enabled them to be processed into thin films for conductivity measurements. The conductivity of strapped-CPPs is three orders of magnitude higher than that of the poly(phenyleneethynylene) porous network.

     
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    Free, publicly-accessible full text available May 24, 2024
  4. Abstract

    Redox‐active polymers (RAPs) are promising organic electrode materials for affordable and sustainable batteries due to their flexible chemical structures and negligible solubility in the electrolyte. Developing high‐dimensional RAPs with porous structures and crosslinkers can further improve their stability and redox capability by reducing the solubility and enhancing reaction kinetics. This work reports two three‐dimensional (3D) RAPs as stable organic cathodes in Na‐ion batteries (NIBs) and K‐ion batteries (KIBs). Carbonyl functional groups are incorporated into the repeating units of the RAPs by the polycondensation of Tetrakis(4‐aminophenyl)methane and two different dianhydrides. The RAPs with interconnected 3D extended conjugation structures undergo multi‐electron redox reactions and exhibit high performance in both NIBs and KIBs in terms of long cycle life (up to 8000 cycles) and fast charging capability (up to 2 A g−1). The results demonstrate that developing 3D RAPs is an effective strategy to achieve high‐performance, affordable, and sustainable NIBs and KIBs.

     
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  5. null (Ed.)
    Abstract In the human neocortex coherent interlaminar theta oscillations are driven by deep cortical layers, suggesting neurons in these layers exhibit distinct electrophysiological properties. To characterize this potential distinctiveness, we use in vitro whole-cell recordings from cortical layers 2 and 3 (L2&3), layer 3c (L3c) and layer 5 (L5) of the human cortex. Across all layers we observe notable heterogeneity, indicating human cortical pyramidal neurons are an electrophysiologically diverse population. L5 pyramidal cells are the most excitable of these neurons and exhibit the most prominent sag current (abolished by blockade of the hyperpolarization activated cation current, I h ). While subthreshold resonance is more common in L3c and L5, we rarely observe this resonance at frequencies greater than 2 Hz. However, the frequency dependent gain of L5 neurons reveals they are most adept at tracking both delta and theta frequency inputs, a unique feature that may indirectly be important for the generation of cortical theta oscillations. 
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  6. A disulfide made by oxidation of 8-thioguanosine is a supergelator. The hydrogels are redox-responsive, as they disassemble upon either reduction or oxidation of the S–S bond. We also identified this disulfide, and 2 other compounds, as intermediates in oxidative desulfurization of 8-thioG to guanosine. 
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  7. Microfiber optic array structures are fabricated and employed as an optical structure overlaying a front-contact silicon solar cell. The arrays are synthesized through light-induced self-writing in a photo-crosslinking acrylate resin, which produces periodically spaced, high-aspect-ratio, and vertically aligned tapered microfibers deposited on a transparent substrate. The structure is then positioned over and sealed onto the solar cell surface. Their fiber optic properties enable collection of non-normal incident light, allowing the structure to mitigate shading loss through the redirection of incident light away from contacts and toward the solar cell. Angle-averaged external quantum efficiency increases nominally by 1.61%, resulting in increases in short-circuit current density up to 1.13 mA/cm2. This work demonstrates a new approach to enhance light collection and conversion using a scalable, straightforward, light-based additive manufacturing process. 
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  8. We report observations of photopolymerization driven phase-separation in a mixture of a photo-reactive monomer and inorganic nanoparticles. The mixture is irradiated with visible light possessing a periodic intensity profile that elicits photopolymerization along the depth of the mixture, establishing a competition between photo-crosslinking and thermodynamically favorable phase-separating behavior inherent to the system. In situ Raman spectroscopy was used to monitor the polymerization reaction and morphology evolution, and reveals a key correlation between irradiation intensity and composite morphology extending the entire depth of the mixture, i.e. unhindered phase-separation at low irradiation intensity and arrested phase-separation at high irradiation intensity. 3D Raman volume mapping and energy dispersive X-ray mapping confirm that the intensity-dependent irradiation process dictates the extent of phase separation, enabling single-parameter control over phase evolution and subsequent composite morphology. These observations can potentially enable a single-step route to develop polymer–inorganic composite materials with tunable morphologies. 
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