- Deciphering the potentiometric properties of (porphinato)zinc(ii)-derived supramolecular polymers and related superstructures
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Because modulating the structure-function relationships of π-conjugated superstructures opens fresh opportunities to tune the electronic structures of semiconducting materials, self-assembled architectures have emerged as pivotal candidates to engineer optoelectronic devices. While the photophysical and electrical properties of 1-dimensional supramolecular polymers have been extensively explored, establishing their fundamental potentiometric properties using reliable electrochemical measurements has been less scrutinized and would benefit the engineering of semiconducting materials. In this regard, elucidating the energy level of valence and conduction bands that delineate the electronic structure of self-assemblies is critical to unveiling the parameters that regulate their structure-function properties. In the present contribution, design principles to engineer 2-dimensional nanosheets, nanowires, fibers and amorphous solids from (porphinato)zinc(ii) (PZn) building blocks have been elucidated by modifying the structural properties of the side chains that flank PZn-based cores. As these self-assemblies feature identical redox-active building blocks but evidence different solid-state morphologies, the elucidation of their potentiometric properties reveals important structural parameters that regulate the potentials at which holes and electrons are injected into the valence and conduction bands of these hierarchical materials. While self-assembly conformations modestly impact valence band energies, superstructures built from H-type aggregates feature a conduction band energy stabilized by more than 350 meV with respect to those constructed from J-type aggregates.
- Liu, Chuan,Liu, Kaixuan,Klutke, Jared,Ashcraft, Adam,Steefel, Samantha,Olivier, Jean-Hubert
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supporting information
p. 11980 - 11991
(2018/11/26)
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- Ammonium cation-containing organic salt
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PROBLEM TO BE SOLVED: To provide a novel ammonium cation-containing organic salt that has high hydrophobicity and excellent fluidity. SOLUTION: There is provided the ammonium cation-containing organic salt that includes quarternary ammonium cation part and an anion part represented by formula (1). (R1 is a substituted/non-substituted C6-100 linear alkyl group; at least 1 of the carbon atoms of the linear alkyl group may be an atom selected from Si, P, As or Se; R2 and R3 are each independently a substituted/non-substituted C6-100 branched alkyl group; at least 1 of the carbon atoms of the branched alkyl group may be an atom selected from Si, P, As or Se; R4 is a monovalent organic group; X is an anion, however, R1 to R3 do not contain, in the main chain and terminal, an atom that has an electronegativity higher than carbon.). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0044; 0045
(2017/01/31)
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- Selective recovery of a pyridine derivative from an aqueous waste stream containing acetic acid and succinonitrile with solvent impregnated resins
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Solvent impregnated resins (SIRs) were evaluated for the recovery of pyridine derivatives from an aqueous waste-stream containing also acetic acid and succinonitrile. For this purpose, a new solvent was developed, synthesized and impregnated in Amberlite XAD4. Sorption studies were used to determine the capacity, selectivity and the mass-transfer rate. A high capacity of 21 g 4-cyanopyridine (CP) per kg SIR was found, with very high selectivity toward CP over the other solutes of at least 570. A modified Langmuir equation could describe the equilibrium sorption isotherm. Both the linear driving force model and a Fickian diffusion model were evaluated. The Fick-model described both regeneration and loading best. The CP-diffusivity through the solvent phase was estimated at 6.53 · 10-13 ± 2.5% m2 s-1. The model was validated using fixed-bed column experiments. The R2 values for this model ranged between 0.94 at a flow rate of 5 mL/min and 0.99 at a flow rate of 1 mL/min during the loading cycle. Due to mass-transfer limitations the breakthrough profiles were broad and breakthrough occurred after 5 or 23 bed volumes, for flow rates of 5 and 1 mL/min, respectively. Both acetic acid and succinonitrile broke through immediately due to the very high CP-selectivity of the SIR.
- Bokhove,Visser,Schuur,De Haan
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