Details
| Original language | English |
|---|---|
| Pages (from-to) | 2726-2731 |
| Number of pages | 6 |
| Journal | CHEMCATCHEM |
| Volume | 12 |
| Issue number | 10 |
| Early online date | 16 Mar 2020 |
| Publication status | Published - 20 May 2020 |
Abstract
A paradigm for active constituents in (homogeneous) catalysis is that optimum performance requires maximum dispersion. Generally, aggregation results in a decline. This is a different case in supramolecular catalysis. A new concept based on surfactants equipped with functional heads is presented, which becomes a more active catalyst itself upon aggregation. The head group of the surfactants is composed of a diethylenetriamine-functionalized fullerene capable of coordinating to catalytically active metals like Co II. The improvement of catalytic properties upon aggregation is demonstrated via electrocatalytic water-splitting reaction as a model system. Detailed electrochemistry studies were performed at concentrations below and above the critical aggregation concentration (cac). While isolated surfactant molecules represent only moderately active catalysts, drastic improvement of efficiency in the hydrogen evolution (HER) as well as in the oxygen evolution reactions (OER) were detected, once vesicular structures have formed. Self-organization of the surfactants leads to an increase in turnover frequencies of up to 1300 % (HER). The strongly beneficial effect of aggregation arises from the favorable alignment of individual molecules, thus, facilitating intermolecular charge transfer processes in the vesicles.
Keywords
- catalysis, Fullerene, self-assembly, supramolecular chemistry, surfactant, water splitting
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Inorganic Chemistry
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
Sustainable Development Goals
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In: CHEMCATCHEM, Vol. 12, No. 10, 20.05.2020, p. 2726-2731.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Aggregation‐induced improvement of catalytic activity by inner‐aggregate electronic communication of metal‐fullerene‐based surfactants
AU - Kunkel, Marius
AU - Bitter, Stefan
AU - Sailer, Frank
AU - Winter, Rainer F.
AU - Polarz, Sebastian
N1 - Funding information: The current research was funded by an ERC consolidator grant (I?SURF; project 614606). We further thank Stephan Siroky for his support.
PY - 2020/5/20
Y1 - 2020/5/20
N2 - A paradigm for active constituents in (homogeneous) catalysis is that optimum performance requires maximum dispersion. Generally, aggregation results in a decline. This is a different case in supramolecular catalysis. A new concept based on surfactants equipped with functional heads is presented, which becomes a more active catalyst itself upon aggregation. The head group of the surfactants is composed of a diethylenetriamine-functionalized fullerene capable of coordinating to catalytically active metals like Co II. The improvement of catalytic properties upon aggregation is demonstrated via electrocatalytic water-splitting reaction as a model system. Detailed electrochemistry studies were performed at concentrations below and above the critical aggregation concentration (cac). While isolated surfactant molecules represent only moderately active catalysts, drastic improvement of efficiency in the hydrogen evolution (HER) as well as in the oxygen evolution reactions (OER) were detected, once vesicular structures have formed. Self-organization of the surfactants leads to an increase in turnover frequencies of up to 1300 % (HER). The strongly beneficial effect of aggregation arises from the favorable alignment of individual molecules, thus, facilitating intermolecular charge transfer processes in the vesicles.
AB - A paradigm for active constituents in (homogeneous) catalysis is that optimum performance requires maximum dispersion. Generally, aggregation results in a decline. This is a different case in supramolecular catalysis. A new concept based on surfactants equipped with functional heads is presented, which becomes a more active catalyst itself upon aggregation. The head group of the surfactants is composed of a diethylenetriamine-functionalized fullerene capable of coordinating to catalytically active metals like Co II. The improvement of catalytic properties upon aggregation is demonstrated via electrocatalytic water-splitting reaction as a model system. Detailed electrochemistry studies were performed at concentrations below and above the critical aggregation concentration (cac). While isolated surfactant molecules represent only moderately active catalysts, drastic improvement of efficiency in the hydrogen evolution (HER) as well as in the oxygen evolution reactions (OER) were detected, once vesicular structures have formed. Self-organization of the surfactants leads to an increase in turnover frequencies of up to 1300 % (HER). The strongly beneficial effect of aggregation arises from the favorable alignment of individual molecules, thus, facilitating intermolecular charge transfer processes in the vesicles.
KW - catalysis
KW - Fullerene
KW - self-assembly
KW - supramolecular chemistry
KW - surfactant
KW - water splitting
UR - http://www.scopus.com/inward/record.url?scp=85082947744&partnerID=8YFLogxK
U2 - 10.1002/cctc.202000412
DO - 10.1002/cctc.202000412
M3 - Article
VL - 12
SP - 2726
EP - 2731
JO - CHEMCATCHEM
JF - CHEMCATCHEM
SN - 1867-3880
IS - 10
ER -