Tracking charge transfer to residual metal clusters in conjugated polymers for photocatalytic hydrogen evolution

Tools

Sachs, Michael and Cha, Hyojung and Kosco, Jan and Aitchison, Catherine M. and Francàs, Laia and Corby, Sacha and Chiang, Chao-Lung and Wilson, Anna A. and Godin, Robert and Fahey-Williams, Alexander and Cooper, Andrew I. and Sprick, Reiner Sebastian and McCulloch, Iain and Durrant, James R. (2020) Tracking charge transfer to residual metal clusters in conjugated polymers for photocatalytic hydrogen evolution. Journal of the American Chemical Society, 142 (34). pp. 14574-14587. ISSN 1520-5126 (https://doi.org/10.1021/jacs.0c06104)

[thumbnail of Sachs-etal-JACS-2020-Tracking-charge-transfer-to-residual-metal-clusters-in-conjugated-polymers]
Preview
 Text. Filename: Sachs_etal_JACS_2020_Tracking_charge_transfer_to_residual_metal_clusters_in_conjugated_polymers.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (2MB)| Preview

Abstract

Semiconducting polymers are versatile materials for solar energy conversion and have gained popularity as photocatalysts for sunlight-driven hydrogen production. Organic polymers often contain residual metal impurities such as palladium (Pd) clusters that are formed during the polymerization reaction, and there is increasing evidence for a catalytic role of such metal clusters in polymer photocatalysts. Using transient and operando optical spectroscopy on nanoparticles of F8BT, P3HT, and the dibenzo[b,d]thiophene sulfone homopolymer P10, we demonstrate how differences in the time scale of electron transfer to Pd clusters translate into hydrogen evolution activity optima at different residual Pd concentrations. For F8BT nanoparticles with common Pd concentrations of >1000 ppm (>0.1 wt %), we find that residual Pd clusters quench photogenerated excitons via energy and electron transfer on the femto-nanosecond time scale, thus outcompeting reductive quenching. We spectroscopically identify reduced Pd clusters in our F8BT nanoparticles from the microsecond time scale onward and show that the predominant location of long-lived electrons gradually shifts to the F8BT polymer when the Pd content is lowered. While a low yield of long-lived electrons limits the hydrogen evolution activity of F8BT, P10 exhibits a substantially higher hydrogen evolution activity, which we demonstrate results from higher yields of long-lived electrons due to more efficient reductive quenching. Surprisingly, and despite the higher performance of P10, long-lived electrons reside on the P10 polymer rather than on the Pd clusters in P10 particles, even at very high Pd concentrations of 27000 ppm (2.7 wt %). In contrast, long-lived electrons in F8BT already reside on Pd clusters before the typical time scale of hydrogen evolution. This comparison shows that P10 exhibits efficient reductive quenching but slow electron transfer to residual Pd clusters, whereas the opposite is the case for F8BT. These findings suggest that the development of even more efficient polymer photocatalysts must target materials that combine both rapid reductive quenching and rapid charge transfer to a metal-based cocatalyst.

ORCID iDs

Sachs, Michael, Cha, Hyojung, Kosco, Jan, Aitchison, Catherine M., Francàs, Laia, Corby, Sacha, Chiang, Chao-Lung, Wilson, Anna A., Godin, Robert, Fahey-Williams, Alexander, Cooper, Andrew I., Sprick, Reiner Sebastian ORCID logoORCID: https://orcid.org/0000-0002-5389-2706, McCulloch, Iain and Durrant, James R.;
  • Item type:Article
    ID code:73810
    Dates:
    Date
    Event
    26 August 2020
    Published
    28 July 2020
    Published Online
    5 June 2020
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:15 Sep 2020 09:57
    Last modified:14 Dec 2024 09:43
    URI:https://strathprints.strath.ac.uk/id/eprint/73810
CORE (COnnecting REpositories)