Authors:	Wang, Zi Jun
Title:	Conjugated porous polymers for heterogeneous visible light photocatalysis
Online publication date:	20-Jan-2016
Year of first publication:	2016
Language:	english
Abstract:	Conjugated porous polymers (CPP) conveniently combine photoactive electron polymer backbone with high interfacial surface area and have drawn tremendous interest from material scientists. Indeed, CPPs have been employed for many applications such as gas adsorption and light harvesting. In this work, we demonstrate that the excellent visible light absorptivity and highly porous nature of the CPPs make them promising candidates as metal free heterogeneous visible light photocatalysts for various organic transformations. A comprehensive study of this new class of materials on different aspects such as porosity, morphology, valence and conduction band positions, chemical composition etc., which effectively influenced their photocatalytic activity, is discussed in this work. First, we present that the valence and conduction band levels of the conjugated microporous (CMP) photocatalysts can be fine-tuned by molecular structural control method in order to optimize the photocatalytic efficiency for the photooxidative coupling of benzylamine and its derivatives under visible light irradiation. Next, we introduce macroporosity as well as microporosity and prepare CPPs with hierarchical porous structures via high internal phase emulsion polymerization technique and micropore engineering method. In addition to porosity and surface area control, another aspect, the chemical composition control of the CPP-based photocatalysts is also shown via incorporating electron acceptor-moiety into the only electron donor-containing polymer backbone structure. Significantly enhanced photocatalytic efficiencies for the photoreductive dehalogenation of alpha-bromo acetophenone and its derivatives are demonstrated. Apart from being used as visible light photocatalysts for organic chemical reactions, we also present that the conjugated porous polymers can act as effective heterogeneous visible light macromolecular photoinitiator for the free radical polymerization of methyl methacrylate under a 23 W household fluorescent lightbulb. Last, hybrid CPP photocatalyst with immobilized palladium nanocrystals has been synthesized and employed as heterogeneous visible light photocatalyst for the efficient photoinduced Suzuki-Miyaura cross-coupling reactions.
DDC:	540 Chemie 540 Chemistry and allied sciences
Institution:	Johannes Gutenberg-Universität Mainz
Department:	FB 09 Chemie, Pharmazie u. Geowissensch.
Place:	Mainz
ROR:	https://ror.org/023b0x485
DOI:	http://doi.org/10.25358/openscience-4210
URN:	urn:nbn:de:hebis:77-diss-1000000568
Version:	Original work
Publication type:	Dissertation
License:	In Copyright
Information on rights of use:	https://rightsstatements.org/vocab/InC/1.0/
Extent:	173 Seiten
Appears in collections:	JGU-Publikationen