NCH-Metallosurfactants as Active Polymerization Catalysts
2019-12-17, Donner, Adrian, Trepka, Bastian, Theiss, Sebastian, Immler, Fabian, Traber, Johanna, Polarz, Sebastian
Next-generation surfactants provide extended functionality apart from their amphiphilic properties. We present two novel metallosurfactants characterized by a N-heterocyclic carbene (NHC) head bearing Cu(I) and Fe(II). An innovative approach for their application in emulsion polymerizations under ATRP conditions was developed. Thereby the complexes fulfilled the role of emulsifiers, active catalysts and stabilization agents at once. Polymerization of methyl methacrylate (MMA) yielded stable PMMA colloids in water with the catalyst located at the surface of the colloids. The termination of PMMA with a bromine moiety enabled the subsequent co-polymerization with styrene via macroinitiation and PMMA-PS core-shell particles were obtained. Gel permeation chromatography (GPC) and selective gradient NMR experiments revealed a covalent linkage between the PMMA core and the PS shell.
Light-Triggered Boost of Activity of Catalytic Bola-Type Surfactants by a Plasmonic Metal-Support Interaction Effect
2019-05-01, Sutter, Sebastian, Trepka, Bastian, Siroky, Stephan, Hagedorn, Kay, Theiss, Sebastian, Baum, Peter, Polarz, Sebastian
The maximization of activity is a general aim in catalysis research. The possibility for light-triggered enhancement of a catalytic process, even if the process is not photochemical in nature, represents an intriguing concept. Here, we present a novel system for the exploration of the latter idea. A surfactant with a catalytically active head group, a protonated polyoxometalate (POM) cluster, is attached to the surface of a gold nanoparticle (Au NP) using thiol coupling chemistry. The distance of the catalytically active center to the gold surface could be adjusted precisely using surfactants containing hydrocarbon chains (Cn) of different lengths ( n = 4-10). Radiation with VIS-light has no effect on the catalytic activity of micellar aggregates of the surfactant. The situation changes, as soon as the surfactants have been attached to the Au NPs. The catalytic activity could almost be doubled. It was proven that the effect is caused by coupling the surface plasmon resonance of the Au NPs with the properties of the POM head group. The improvement of activity could only be observed if the excitation wavelength matches the absorption band of the used Au NPs. Furthermore, the shorter the distance between the POM group and the surface of the NP, the stronger is the effect. This phenomenon was explained by lowering the activation energy of the transition state relevant to the catalytic process by the strong electric fields in the vicinity of the surfaces of plasmonic nanoparticles. Because the catalytic enhancement is wavelength-selective, one can imagine the creation of complex systems in the future, a system of differently sized NPs, each responsible for a different catalytic step and activated by light of different colors.