Efficient charge-transfer from diketopyrrolopyrroles to single-walled carbon nanotubes

Papadopoulos, Ilias; Menon, Arjun; Plass, Fabian; Molina, Desiré; Harreiß, Christina; Kahnt, Axel; Spiecker, Erdmann; Sastre‐Santos, Ángela; Guldi, Dirk M.

doi:10.1039/d1nr03105h

Cited by 5 publications

(6 citation statements)

References 42 publications

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“…Each corona phase can influence the fluorescence emission of the SWCNTs, due to its density and/or interactions with the SWCNT surface. Fluorescence emission of a certain chirality can be altered by the distinct dielectric environment that the corona phase induces around the SWCNTs or even charge transfer effects from the wrapping molecules to the SWCNT or vice versa. , Our PEG-dendrons are bound to the SWCNTs via end groups that differ in the type of their interaction with the graphene lattice. While π–π stacking of the SWCNT with the aromatic end groups is possible, hydrophobic interactions are expected in the case of the aliphatic end groups.…”

Section: Resultsmentioning

confidence: 99%

Dendron–Polymer Hybrids as Tailorable Responsive Coronae of Single-Walled Carbon Nanotubes

et al. 2021

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Functional composite materials that can change their spectral properties in response to external stimuli have a plethora of applications in fields ranging from sensors to biomedical imaging. One of the most promising types of materials used to design spectrally active composites are fluorescent single-walled carbon nanotubes (SWCNTs), noncovalently functionalized by synthetic amphiphilic polymers. These coated SWCNTs can exhibit modulations in their fluorescence spectra in response to interactions with target analytes. Hence, identifying new amphiphiles with interchangeable building blocks that can form individual coronae around the SWCNTs and can be tailored for a specific application is of great interest. This study presents highly modular amphiphilic polymer-dendron hybrids, composed of hydrophobic dendrons and hydrophilic polyethylene glycol (PEG) that can be synthesized with a high degree of structural freedom, for suspending SWCNTs in aqueous solution. Taking advantage of the high molecular precision of these PEG-dendrons, we show that precise differences in the chemical structure of the hydrophobic end groups of the dendrons can be used to control the interactions of the amphiphiles with the SWCNT surface. These interactions can be directly related to differences in the intrinsic near-infrared fluorescence emission of the various chiralities in a SWCNT sample. Utilizing the susceptibility of the PEG-dendrons toward enzymatic degradation, we demonstrate the ability to monitor enzymatic activity through changes in the SWCNT fluorescent signal. These findings pave the way for a rational design of functional SWCNTs, which can be used for optical sensing of enzymatic activity in the near-infrared spectral range.

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Section: Resultsmentioning

confidence: 99%

Dendron–Polymer Hybrids as Tailorable Responsive Coronae of Single-Walled Carbon Nanotubes

et al. 2021

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“…Henceforth, enormous research studies have been performed to develop thermodynamically stable and noncovalently functionalized CNTs, graphene, carbon dots, and their hybrids through van der Waals, hydrophilic-hydrophobic, charge transfer, and/or π-π stacking interactions. [55,114,115] In principle, some binding motifs for creating hybrids with SWCNTs are shown in Figure 8. [55] Preliminary investigation has revealed that small polycyclic aromatic hydrocarbons, for example, pyrenes, are suitable anchors for SWCNT functionalization because of their strong π-stacking abilities.…”

Section: Photo-induced Charge Transfermentioning

confidence: 99%

“…Very recently, the excited state charge-transfer interactions between SWCNTs and a variety of phenyl, 4bromophenyl, and thiophene substituted diketopyrrolopyrroles (DPPs) were reported to show about 81% transfer efficiencies for the one-electron oxidization of DPPs. [114] A similar strategy can be adapted for hybrid porous carbon nanostructures for efficient electrochemical energy conversion and storage devices and integrated energy systems. [55,[114][115][116][117][118]…”

Section: Photo-induced Charge Transfermentioning

confidence: 99%

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Charge transfer of carbon nanomaterials for efficient metal‐free electrocatalysis

Paul

Zhai

Roy

et al. 2022

Interdisciplinary Materials

103

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“…48 The simulation-based approach was also used for the treatment of the standard SWV curves, 49 and transient absorption spectroscopy allowed the straightforward determination of the lifetimes of the charge-separated excited states in CNT-diketopyrrolopyrrole hybrids. 50 However, VF-SWV has the great advantage of being a mapping technique which provides more details of the surface redox response under the umbrella of a single method. The VF-SWV time resolution is mostly determined by the maximum frequency of the square wave ramp of the hardware (1250 Hz for BioLogic SP-300).…”

Section: Interfacial Charge Migration Mechanismsmentioning

confidence: 99%

Mechanism-Driven Design of Heterogeneous Molecular Electrocatalysts for CO₂ Reduction

Marianov

Jiang

2022

Acc. Mater. Res.

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Conspectus The electrochemical reduction of CO2 (CO2ERR) in aqueous electrolytes is one of the most promising routes for commercial CO2 utilization. A switch from the currently used noble-metal-based catalysts to carbon-supported macrocyclic complexes could bring about a much-needed cost reduction, thus making the technology economically viable. However, the inherently low conductivity and the tendency of molecular catalysts to degrade during the long-term operation present a significant challenge to the material design which we endeavored to resolve using a mechanism-driven approach. This Account puts into perspective a series of our recent studies on the phenomena taking place during CO2ERR and the employment of these insights in the catalyst development. It is demonstrated that in a heterogeneous system CO2ERR relies on the sequential rather than simultaneous transfer of two electrons. This feature causes heterogeneous CO2ERR to be extremely dependent on the ability of the catalyst to support the interfacial charge migration. Using recently developed variable-frequency square wave voltammetry (VF-SWV), which allows one to map the interfacial charge transfer for the heterogeneous electrochemical systems, we also found that the fast heterogeneous charge transfer is confined to a thin layer of the complex at the interface between the supporting electrode and the bulk of the porphyrin complex. Hence, it is desirable to construct an electrode with a uniform dense layer of the complex strongly bound to the surface. These requirements are conveniently addressed using the covalent immobilization of the catalysts on the surface of carbonaceous electrodes. In this regard, electrografting of the cobalt tetraphenylporphyrin (CoTPP) onto the surface of carbon cloth yields a material exhibiting a TOF of 8.3 ± 0.9 s–1 at a 500 mV overpotential and a Faradaic efficiency to CO evolution (FE(CO)) of 62 ± 7%. The application of the chemical covalent immobilization to CNT-based supports further improves the FE(CO) to ∼100% and allows the complex to reach an impressive intrinsic TOF0 of 36.6 s–1. We also applied mechanistic investigations to tackle the challenging problem of catalyst durability in CO2ERR. It was determined that the loss of activity takes place because of the reductive carboxylation and co-occurring formation of the [CoIIITPP]OH complex. Thus, quite unexpectedly, the stability could be enhanced via the introduction of bulky donating substituents around the macrocyclic core. This insight allowed us to design and synthesize catalyst CoTPP-(OMe) 8 bearing eight −OMe groups around the lateral aromatic moieties which demonstrates no noticeable degradation during the repetitive long-run electrolyses. These design principles, combined with the recent advances in the development of gas diffusion electrodes (GDE) and heterogeneous molecular catalysts, could provide a low-cost and very stable catalytic system for industrial-scale CO2ERR.

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Efficient charge-transfer from diketopyrrolopyrroles to single-walled carbon nanotubes

Abstract: In this contribution, the excited state charge-transfer interactions between single walled carbon nanotubes (SWCNTs) and a variety of phenyl, 4-bromophenyl, and thiophene substituted diketopyrrolopyrroles (DPPs), is described. Atomic force microscopy...

Cited by 5 publications

References 42 publications

Dendron–Polymer Hybrids as Tailorable Responsive Coronae of Single-Walled Carbon Nanotubes

Dendron–Polymer Hybrids as Tailorable Responsive Coronae of Single-Walled Carbon Nanotubes

Charge transfer of carbon nanomaterials for efficient metal‐free electrocatalysis

Mechanism-Driven Design of Heterogeneous Molecular Electrocatalysts for CO₂ Reduction

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Efficient charge-transfer from diketopyrrolopyrroles to single-walled carbon nanotubes

Abstract: In this contribution, the excited state charge-transfer interactions between single walled carbon nanotubes (SWCNTs) and a variety of phenyl, 4-bromophenyl, and thiophene substituted diketopyrrolopyrroles (DPPs), is described. Atomic force microscopy...

Cited by 5 publications

References 42 publications

Dendron–Polymer Hybrids as Tailorable Responsive Coronae of Single-Walled Carbon Nanotubes

Dendron–Polymer Hybrids as Tailorable Responsive Coronae of Single-Walled Carbon Nanotubes

Charge transfer of carbon nanomaterials for efficient metal‐free electrocatalysis

Mechanism-Driven Design of Heterogeneous Molecular Electrocatalysts for CO2 Reduction

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Product

Resources

About

Mechanism-Driven Design of Heterogeneous Molecular Electrocatalysts for CO₂ Reduction