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Light-Off in Plasmon-Mediated Photocatalysis.

ABSTRACT: In plasmon-mediated photocatalysis it is of critical importance to differentiate light-induced catalytic reaction rate enhancement channels, which include near-field effects, direct hot carrier injection, and photothermal catalyst heating. In particular, the discrimination of photothermal and hot electron channels is experimentally challenging, and their role is under keen debate. Here we demonstrate using the example of CO oxidation over nanofabricated neat Pd and Au₅₀Pd₅₀ alloy catalysts, how photothermal rate enhancement differs by up to 3 orders of magnitude for the same photon flux, and how this effect is controlled solely by the position of catalyst operation along the light-off curve measured in the dark. This highlights that small fluctuations in reactor temperature or temperature gradients across a sample may dramatically impact global and local photothermal rate enhancement, respectively, and thus control both the balance between different rate enhancement mechanisms and the way strategies to efficiently distinguish between them should be devised.

SUBMITTER: Tiburski C

PROVIDER: S-EPMC8320230 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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Light-Off in Plasmon-Mediated Photocatalysis.

Tiburski Christopher C Boje Astrid A Nilsson Sara S Say Zafer Z Fritzsche Joachim J Ström Henrik H Hellman Anders A Langhammer Christoph C

ACS nano 20210622 7

In plasmon-mediated photocatalysis it is of critical importance to differentiate light-induced catalytic reaction rate enhancement channels, which include near-field effects, direct hot carrier injection, and photothermal catalyst heating. In particular, the discrimination of photothermal and hot electron channels is experimentally challenging, and their role is under keen debate. Here we demonstrate using the example of CO oxidation over nanofabricated neat Pd and Au<sub>50</sub>Pd<sub>50</sub> ...[more]

PMID: 34156229

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Project description:The utilization of earth-abundant photosensitizers with visible light absorption to enable sustainable photocatalysis is a long-standing challenge. Overcoming such a challenge, in this work, two lanthanide (Ln3+ = Tb, Eu) based metal-organic frameworks (Ln-MOFs) have been synthesized utilizing a Co3+-based metalloligand. Both Ln-MOFs function as remarkable photocatalysts for the selective oxidation of assorted alcohols and sulfides to their corresponding aldehydes/ketones and sulfoxides using visible light. The photophysical behavior of both Ln-MOFs and mechanism of photocatalysis is comprehensively investigated using time-resolved transient absorption spectroscopy, electrochemical impedance spectroscopy, electron paramagnetic resonance spectroscopy, photoluminescence and phosphorescence studies. In both Ln-MOFs, a metalloligand acts as a light-harvester, being excited by visible light, while Ln3+ ions endow the resulting MOFs with long-lived triplet excited states. Ultrafast transient absorption spectroscopy, further supported by electron paramagnetic resonance spectra, revealed excited-state electron transfer from metalloligands to the Ln3+ ions and transient generation of Ln2+ sites alongside the facilitation of intersystem crossing. The excited Ln2+ ions transfer energy to the ground-state triplet oxygen (3O2) to generate singlet oxygen (1O2). The HOMO-LUMO positions of both Ln-MOFs support the generation of ˙O2 - and 1O2 but inhibit strongly-oxidizing yet non-selective ˙OH radicals. Scavenger experiments, 1O2 traps and electron paramagnetic resonance spectra confirmed the generation of singlet oxygen. The heavy-metal effect of a lanthanide ion in Ln-MOFs for the generation of triplet excitons is confirmed by the synthesis of a non-heavy-metal analogue involving a zinc ion via a single-crystal-to-single-crystal transformation strategy. The present results are noteworthy and may aid in the development of other earth-abundant metalloligand-based photocatalysts for challenging yet sustainable catalysis.

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Light-Off in Plasmon-Mediated Photocatalysis.

Publications

Light-Off in Plasmon-Mediated Photocatalysis.

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