Photoinduced Fano Resonances between Quantum Confined Nanocrystals and Adsorbed Molecular Catalysts

Yang, Wenxing; Liu, Yawei; Edvinsson, Tomas; Castner, Ashleigh T.; Wang, Shihuai; He, Sheng; Ott, Sascha; Hammarström, Leif; Lian, Tianquan

doi:10.1021/acs.nanolett.1c01739

Cited by 8 publications

(4 citation statements)

References 46 publications

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“…Transient IR spectra of the CO stretching mode shows a large positive feature that is consistent with the formation of Fano resonance (FR) signals (Figure S8). 52 These TRIR experiments were done with Cd 3 P 2 and varying amounts of ReC0A (0.25×, 1×, and 2× Re) in hexanes under 500 nm excitation at a high pump fluence to investigate. At this experiment's smallest concentration, 0.25× Re, the FR, a large positive peak, can be observed at ∼2025 cm −1 .…”

Section: ■ Introductionmentioning

confidence: 99%

Amine Hole Scavengers Facilitate Both Electron and Hole Transfer in a Nanocrystal/Molecular Hybrid Photocatalyst

et al. 2023

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A well-known catalyst, fac-Re(4,4′-R 2 -bpy)(CO) 3 Cl (bpy = bipyridine; R = COOH) (ReC0A), has been widely studied for CO 2 reduction; however, its photocatalytic performance is limited due to its narrow absorption range. Quantum dots (QDs) are efficient light harvesters that offer several advantages, including size tunability and broad absorption in the solar spectrum. Therefore, photoinduced CO 2 reduction over a broad range of the solar spectrum could be enabled by ReC0A catalysts heterogenized on QDs. Here, we investigate interfacial electron transfer from Cd 3 P 2 QDs to ReC0A complexes covalently bound on the QD surface, induced by photoexcitation of the QD. We explore the effect of triethylamine, a sacrificial hole scavenger incorporated to replenish the QD with electrons. Through combined transient absorption spectroscopic and computational studies, we demonstrate that electron transfer from Cd 3 P 2 to ReC0A can be enhanced by a factor of ∼4 upon addition of triethylamine. We hypothesize that the rate enhancement is a result of triethylamine possibly altering the energetics of the Cd 3 P 2 −ReC0A system by interacting with the quantum dot surface, deprotonation of the quantum dot, and preferential solvation, resulting in a shift of the conduction band edge to more negative potentials. We also observe the rate enhancement in other QD−electron acceptor systems. Our findings provide mechanistic insights into hole scavenger−quantum dot interactions and how they may influence photoinduced interfacial electron transfer processes.

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Section: ■ Introductionmentioning

confidence: 99%

Amine Hole Scavengers Facilitate Both Electron and Hole Transfer in a Nanocrystal/Molecular Hybrid Photocatalyst

et al. 2023

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“…An extensive list of examples can be found, for instance, in [1][2][3][4] and the references therein. Some of these applications extend from fields such as optoelectronics [5][6][7][8][9][10][11] and the design of nonlinear optical (NLO) materials [12] or, plasma Physics [13][14][15], to the development of qubits for quantum computing [16], or photovoltaics [17][18][19][20], where artificial photosynthesis has been the focus of several works [21,22]. Hydrogen storage and transportation also deserve special mention, both of which have attracted particular attention owing to the use of this gas as an effective, eco-friendly and clean alternative to fossil fuels [23][24][25].…”

Section: Introductionmentioning

confidence: 99%

Effects of size on the spectrum and stability of a confined on-center Hydrogen atom

2022

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In this work we studied the problem of the stability of confined atoms when they are released from confinement. We analyzed the confined Hydrogen atom inside a cage modelled by a square-well potential, in particular the effects of size on the energy and the electronic structure of the confined atom, by considering different internal radii of the confining cage. Starting from the confined wave function, we clarified the effect on the probability transition between different confined states, and characterized the stability of the atom when released from in term of both, the ionization probability and the transition probability to a bound state of the free atom. The values of the different atomic properties calculated present oscillations when they are studied as a function of the size of the confining cage. This behavior can be explained in terms of the shell structure of the atom.

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“…They can be quite informative on how molecular structures couple to an extended, solid-state environment. For example, Fano resonances describe plasmonic interactions between quantum nanocrystals and colloidal molecules 17 and adsorbed molecular catalysts 18 .…”

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confidence: 99%

Formation of the oxyl’s potential energy surface by the spectral kinetics of a vibrational mode

Cuk,

Stewart,

Zayka

et al. 2024

Preprint

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One of the most reactive intermediates for oxidative reactions is the oxyl radical, an electron-deficient oxygen atom. The discovery of a new vibration upon photoexcitation of the oxygen evolution catalysis detected the oxyl radical at the SrTiO3 surface. The vibration was assigned to a motion of the sub-surface oxygen underneath the titanium oxyl (Ti-O·-), created upon hole transfer to (or electron extraction from) a hydroxylated surface site. Evidence for such an interfacial mode derived from its spectral shape which exhibited a Fano resonance—a coupling of a sharp normal mode to continu-um excitations. Here, this Fano resonance is utilized to derive precise formation kinetics of the oxyl radical and its associ-ated potential energy surface (PES). From the Fano lineshape, the formation kinetics are obtained from the anti-resonance (the kinetics of the coupling factor), the resonance (the kinetics of the coupled continuum excitations), and the frequency integrated spectrum (the kinetics of the normal mode’s cross-section). All three perspectives yield a logistic function growth with a half-rise of 2.3 ± 0.3 ps and rate of 0.48 ± 0.09 ps. A non-equilibrium transient associated with photoexcitation is separated from the rise of the equilibrated PES. The logistic function characterizes the oxyl coverage at the very initial stages (t~0) to have an exponential growth rate that quickly decreases towards zero as a limiting coverage is reached. Such time-dependent reaction kinetics identify a dynamic activation barrier associated with the formation of a PES and quantify it for an oxyl radical coverage.

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Photoinduced Fano Resonances between Quantum Confined Nanocrystals and Adsorbed Molecular Catalysts

Cited by 8 publications

References 46 publications

Amine Hole Scavengers Facilitate Both Electron and Hole Transfer in a Nanocrystal/Molecular Hybrid Photocatalyst

Amine Hole Scavengers Facilitate Both Electron and Hole Transfer in a Nanocrystal/Molecular Hybrid Photocatalyst

Effects of size on the spectrum and stability of a confined on-center Hydrogen atom

Formation of the oxyl’s potential energy surface by the spectral kinetics of a vibrational mode

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