Ph. D. Candidate at the University of Rochester
Exciting quantum dots to catalyze reactions efficiently and sustainably
Quantum dots are semiconducting nanocrystals whose properties change with size. They absorb a lot of light for their small size and can release that energy as photons and fluoresce, or can transfer the energy as an electron to neighboring molecules. We are exploiting these properties to use quantum dots to photocatalyze C-C bond forming reactions that are important for pharmaceutical applications. Quantum dots absorb more light, are more robust, are less expensive than traditional photocatalysts. Additionally, they can transfer energy at a wider range of redox potentials, meaning one quantum dot will work for a number of different reactions that would otherwise need a specially tuned catalyst. By changing the semiconducting material the quantum dots are made of we can access a wide range of potentials that have previously not been accessed for photocatalysis. This could lead to the discovery of new reactions or pathways not previously accessed, making organic reactions more efficient or allowing us to reach new synthetic targets.
Abstract: The subject of this review is the colloidal quantum dot (QD) and specifically the interaction of the QD with proximate molecules. It covers various functions of these molecules, including (i) ligands for the QDs, coupled electronically or vibrationally to localized surface states or to the delocalized states of the QD core, (ii) energy or electron donors or acceptors for the QDs, and (iii) structural components of QD assemblies that dictate QD-QD or QD-molecule interactions. Research on interactions of ligands with colloidal QDs has revealed that ligands determine not only the excited state dynamics of the QD but also, in some cases, its ground state electronic structure. Specifically, the article discusses (i) measurement of the electronic structure of colloidal QDs and the influence of their surface chemistry, in particular, dipolar ligands and exciton-delocalizing ligands, on their electronic energies; (ii) the role of molecules in interfacial electron and energy transfer processes involving QDs, including electron-to-vibrational energy transfer and the use of the ligand shell of a QD as a semipermeable membrane that gates its redox activity; and (iii) a particular application of colloidal QDs, photoredox catalysis, which exploits the combination of the electronic structure of the QD core and the chemistry at its surface to use the energy of the QD excited state to drive chemical reactions.
Pub.: 09 Aug '16, Pinned: 30 Jun '17
Abstract: Photoredox catalysis has become an essential tool in organic synthesis because it enables new routes to important molecules. However, the best available molecular catalysts suffer from high catalyst loadings and rely on precious metals. Here we show that colloidal nanocrystal quantum dots (QDs) can serve as efficient and robust, precious-metal free, photoassisted redox catalysts. A single-sized CdSe quantum dot (3.0 ± 0.2 nm) can replace several different dye catalysts needed for five different photoredox reactions (β-alkylation, β-aminoalkylation, dehalogenation, amine arylation, and decarboxylative radical formation). Even without optimization of the QDs or the reaction conditions, efficiencies rivaling the best available metal dyes were obtained.
Pub.: 11 Mar '17, Pinned: 29 Jun '17
Abstract: This paper describes the photo-redox catalysis of a C-C coupling reaction between 1-phenyl pyrrolidine (PhPyr) and phenyl trans-styryl sulfone (PhSO2) by visible light-absorbing colloidal CdS quantum dots (QDs), without a sacrificial oxidant or reductant, and without a co-catalyst. Simple kinetic analysis reveals that photo-oxidation of PhPyr by the QD is the rate-limiting step. Disordering of the ligand shell of the QDs by creating mixed monolayers of oleate and octylphosphonate increases the initial rate of the reaction by a factor of 2.3 and the energy efficiency (mol product / joule of incident photons) of the reaction by a factor of 1.6 by facilitating the hole transfer step.
Pub.: 16 Mar '17, Pinned: 29 Jun '17
Abstract: Titanium dioxide (TiO2) is a widely employed and inexpensive photocatalyst, but its use in organic synthesis has been limited by the short-wavelength ultraviolet irradiation typically used. We have discovered that TiO2 particles efficiently mediate photocatalytic radical cation Diels-Alder cycloadditions using a simple visible light source, enabled by the formation of a visible light absorbing complex of the substrate on the semiconductor surface.
Pub.: 04 Apr '17, Pinned: 29 Jun '17
Abstract: In the recent past, visible-light-mediated photoredox catalysis has made a huge impact on the development of new synthetic methods under very mild and ecologically benign conditions. Although semiconductor nanocrystals or quantum dots (QDs) possess suitable optoelectronic and redox properties for photoredox catalytic applications, surprisingly, their use for the activation of challenging chemical bonds in the synthesis of organic molecules is little explored. We report here the application of ZnSe/CdS core/shell QDs for the synthetically important photoredox catalytic activation of carbon–halogen bonds in dehalogenation and C–H arylation reactions using (hetero)aryl halides as bench-stable inexpensive bulk starting materials, under very mild reaction conditions. The outstanding catalytic activity of ZnSe/CdS core/shell QDs is a direct consequence of the high specific surface area and homogeneity of QDs in solution and their high photostability toward oxidation.
Pub.: 06 Jun '17, Pinned: 29 Jun '17
Abstract: Photosensitization of molecular catalysts to reduce CO2 to CO is a sustainable route to storable solar fuels. Crucial to the sensitization process is highly efficient transfer of redox equivalents from sensitizer to catalyst; in systems with molecular sensitizers, this transfer is often slow because it is gated by diffusion-limited collisions between sensitizer and catalyst. This article describes the photosensitization of a meso-tetraphenylporphyrin iron(III) chloride (FeTPP) catalyst by colloidal, heavy metal-free CuInS2/ZnS quantum dots (QDs) to reduce CO2 to CO using 450-nm light. The sensitization efficiency (turnover number per absorbed unit of photon energy) of the QD system is a factor of 18 greater than that of an analogous system with a fac-tris(2-phenylpyridine)iridium sensitizer. This high efficiency originates in ultrafast electron transfer between the QD and FeTPP, enabled by formation of QD/FeTPP complexes. Optical spectroscopy reveals that the electron transfer processes primarily responsible for the first two sensitization steps (Fe(III)TPP → Fe(II)TPP, and Fe(II)TPP → FeITPP) both occur in <200 fs.
Pub.: 14 Jun '17, Pinned: 29 Jun '17
Abstract: This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6–4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the QD exciton by transient absorption reveals that, for each step in the catalytic cycle, the sacrificial reductant, 3-mercaptopropionic acid, scavenges the excitonic hole in ∼5 ps to form QD•–; electron transfer to nitrobenzene or the intermediates nitrosobenzene and phenylhydroxylamine then occurs on the nanosecond time scale. The rate constants for the single-electron transfer reactions are correlated with the driving forces for the corresponding proton-coupled electron transfers. This result suggests, but does not prove, that electron transfer, not proton transfer, is rate-limiting for these reactions. Nuclear magnetic resonance analysis of the QD–molecule systems shows that the photoproduct aniline, left unprotonated, serves as a poison for the QD catalyst by adsorbing to its surface. Performing the reaction at an acidic pH not only encourages aniline to desorb but also increases the probability of protonated intermediates; the latter effect probably ensures that recruitment of protons is not rate-limiting.
Pub.: 19 Jan '16, Pinned: 29 Jun '17