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    Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution.

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    Type
    Article
    Authors
    Sachs, Michael cc
    Cha, Hyojung
    Kosco, Jan cc
    Aitchison, Catherine M cc
    Francàs, Laia cc
    Corby, Sacha cc
    Chiang, Chao-Lung
    Wilson, Anna A
    Godin, Robert
    Fahey-Williams, Alexander
    Cooper, Andrew I
    Sprick, Reiner Sebastian
    McCulloch, Iain cc
    Durrant, James R. cc
    KAUST Department
    Chemical Science Program
    Physical Science and Engineering (PSE) Division
    KAUST Solar Center (KSC)
    KAUST Grant Number
    OSR-2015-CRG4-2572
    Date
    2020-08-14
    Online Publication Date
    2020-07-28
    Print Publication Date
    2020-08-26
    Embargo End Date
    2021-08-14
    Submitted Date
    2020-06-05
    Permanent link to this record
    http://hdl.handle.net/10754/664753
    
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    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.
    Citation
    Sachs, M., Cha, H., Kosco, J., Aitchison, C. M., Francàs, L., Corby, S., … Durrant, J. R. (2020). Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution. Journal of the American Chemical Society. doi:10.1021/jacs.0c06104
    Sponsors
    M.S. is grateful to Imperial College for a President’s Ph.D. Scholarship and to the EPSRC for a Doctoral Prize Fellowship. J.R.D. and I.M. acknowledge support from KAUST (project numbers OSR-2015-CRG4-2572 and OSR-2018-CRG7-3749.2). C.M.A., A.I.C., and R.S.S. acknowledge the Engineering and Physical Sciences Research Council (EPSRC, EP/N004884/1). L.F. thanks the EU for a Marie Curie fellowship(658270). S.C. thanks Imperial College London for a Schrödinger Scholarship. R.G. is grateful to the FRQNT for a postdoctoral award and NSERC Discovery Grant funding. C.-L.C. appreciates his colleague, Dr. Bing-Jian Su, for his kind support and assistance. All plotted data have been deposited on the open-access repository Zenodo and can be accessed via dx. doi.org/10.5281/zenodo.3932340.
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.0c06104
    10.1021/jacs.0c12455
    PubMed ID
    32786800
    Additional Links
    https://pubs.acs.org/doi/10.1021/jacs.0c06104
    https://pubs.acs.org/doi/pdf/10.1021/jacs.0c06104
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    • [Dataset]
      Sachs, M., Hyojung Cha, Kosco, J., Aitchison, C. M., Francàs, L., Corby, S., Chao-Lung Chiang, Wilson, A. A., Godin, R., Fahey-Williams, A., Cooper, A. I., Sprick, R. S., McCulloch, I., & Durrant, J. R. (2020). Data for article "Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution" [Data set]. Zenodo. https://doi.org/10.5281/ZENODO.3932339. DOI: 10.5281/zenodo.3932339 Handle: 10754/664924
    ae974a485f413a2113503eed53cd6c53
    10.1021/jacs.0c06104
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Solar Center (KSC)

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