TY - JOUR
T1 - Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution.
AU - Sachs, Michael
AU - Cha, Hyojung
AU - Kosco, Jan
AU - Aitchison, Catherine M
AU - Francàs, Laia
AU - Corby, Sacha
AU - Chiang, Chao-Lung
AU - Wilson, Anna A
AU - Godin, Robert
AU - Fahey-Williams, Alexander
AU - Cooper, Andrew I
AU - Sprick, Reiner Sebastian
AU - McCulloch, Iain
AU - Durrant, James R.
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): OSR-2015-CRG4-2572
Acknowledgements: 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.
PY - 2020/8/14
Y1 - 2020/8/14
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/664753
UR - https://pubs.acs.org/doi/10.1021/jacs.0c06104
U2 - 10.1021/jacs.0c06104
DO - 10.1021/jacs.0c06104
M3 - Article
C2 - 32786800
SN - 0002-7863
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -