A novel electrically conductive perylene diimide‐based MOF‐74 series featuring luminescence and redox activity

In this paper, we report the fabrication of highly conductive poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS)/cellulose nanofiber (CNF) nanocomposite paper with excellent flexibility through post-treatment with an organic solvent. The post-treated PEDOT:PSS/CNF porous nanocomposite papers showed a lower sulfur content, indicating the removal of residual PSS. The electrical conductivity of PEDOT:PSS/CNF porous nanocomposite paper was increased from 1.05 S/cm to 123.37 S/cm and 106.6 S/cm by post-treatment with dimethyl sulfoxide (DMSO) and ethylene glycol (EG), respectively. These values are outstanding in the development of electrically conductive CNF composites. Additionally, the highly conductive nanocomposite papers showed excellent bending stability during bending tests. Cyclic voltammetry (CV) showed a Faradaic redox reaction and non-Faradaic capacitance due to the redox activity of PEDOT:PSS and large surface area, respectively. Electrochemical energy storage ability was evaluated and results showed that capacitance improved after post-treatment. We believe that the highly conductive PEDOT:PSS/CNF porous nanocomposite papers with excellent flexibility described here are potential candidates for application in porous paper electrodes, flexible energy storage devices, and bioengineering sensors.

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Cryogenic atomic force microscopy

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100084570 ◽

1991 ◽

Vol 49 ◽

pp. 54-55

Author(s):

K. A. Fisher ◽

M. G. L. Gustafsson ◽

M. B. Shattuck ◽

J. Clarke

Keyword(s):

Room Temperature ◽

Rapid Freezing ◽

Cryogenic Temperatures ◽

Soft Or ◽

Electrically Conductive ◽

Force Microscopy ◽

Flexible Molecules ◽

Advantages And Disadvantages ◽

Atomic Force ◽

Chemical Perturbation

The atomic force microscope (AFM) is capable of imaging electrically conductive and non-conductive surfaces at atomic resolution. When used to image biological samples, however, lateral resolution is often limited to nanometer levels, due primarily to AFM tip/sample interactions. Several approaches to immobilize and stabilize soft or flexible molecules for AFM have been examined, notably, tethering coating, and freezing. Although each approach has its advantages and disadvantages, rapid freezing techniques have the special advantage of avoiding chemical perturbation, and minimizing physical disruption of the sample. Scanning with an AFM at cryogenic temperatures has the potential to image frozen biomolecules at high resolution. We have constructed a force microscope capable of operating immersed in liquid n-pentane and have tested its performance at room temperature with carbon and metal-coated samples, and at 143° K with uncoated ferritin and purple membrane (PM).

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Local heat transfer measurements using an electrically conductive coating for icing applications

10.2514/6.2000-485 ◽

2000 ◽

Author(s):

A. Feo ◽

J. Sanchez ◽

M. Urdiales

Keyword(s):

Heat Transfer ◽

Local Heat Transfer ◽

Local Heat ◽

Electrically Conductive ◽

Conductive Coating

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Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

10.26434/chemrxiv.10316681.v1 ◽

2019 ◽

Author(s):

Andrew Rosen ◽

M. Rasel Mian ◽

Timur Islamoglu ◽

Haoyuan Chen ◽

Omar Farha ◽

...

Keyword(s):

Density Functional ◽

Metal Organic Frameworks ◽

Redox Activity ◽

Screening Methods ◽

Bridging Ligands ◽

Metal Centers ◽

Computational Screening ◽

Open Metal Sites ◽

Metal Organic ◽

Unsaturated Metal Sites

Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O2 and N2 adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br-, μ-Cl-, μ-F-, μ-SH-, or μ-OH- groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O2 affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O2. In contrast with O2 adsorption, N2 adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V2+ open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl- ligands of M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH- groups would significantly enhance the strength of O2 adsorption at the open metal sites without a corresponding increase in the N2 affinity. Experimental investigation of Co2Cl2(BBTA) and Co2(OH)2(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O2 at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH- ligands and the presence of H-bonding interactions between the μ-OH- bridging ligands and the O2 adsorbate.

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Experimental Assessment of the Practical Oxidative Stability of Lithium Thiophosphate Solid Electrolytes

10.26434/chemrxiv.8014715.v1 ◽

2019 ◽

Author(s):

Georg Dewald ◽

Saneyuki Ohno ◽

Marvin Kraft ◽

Raimund Koerver ◽

Paul Till ◽

...

Keyword(s):

Cyclic Voltammetry ◽

Solid State ◽

Oxidative Stability ◽

Photoelectron Spectroscopy ◽

Solid Electrolytes ◽

Stability Limit ◽

Lithium Ion ◽

High Energy ◽

Redox Activity ◽

Solid State Batteries

All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use stepwisecyclic voltammetry to obtain information on the practical oxidative stability limit of Li10GeP2S12, a Li2S‑P2S5glass, as well as the argyrodite Li6PS5Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The stepwise cyclic voltammetryapproach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes.

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Experimental Assessment of the Practical Oxidative Stability of Lithium Thiophosphate Solid Electrolytes

10.26434/chemrxiv.8014715 ◽

2019 ◽

Author(s):

Georg Dewald ◽

Saneyuki Ohno ◽

Marvin Kraft ◽

Raimund Koerver ◽

Paul Till ◽

...

Keyword(s):

Cyclic Voltammetry ◽

Solid State ◽

Oxidative Stability ◽

Photoelectron Spectroscopy ◽

Solid Electrolytes ◽

Stability Limit ◽

Lithium Ion ◽

High Energy ◽

Redox Activity ◽

Solid State Batteries

All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use stepwisecyclic voltammetry to obtain information on the practical oxidative stability limit of Li10GeP2S12, a Li2S‑P2S5glass, as well as the argyrodite Li6PS5Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The stepwise cyclic voltammetryapproach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes.

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