Conjugated polymers have sparked much interest as photocatalysts for hydrogen production. However, beyond basic considerations such as spectral absorption, the factors that dictate their photocatalytic activity are poorly understood. Here we investigate a series of linear conjugated polymers with external quantum efficiencies for hydrogen production between 0.4 and 11.6%. We monitor the generation of the photoactive species from femtoseconds to seconds after light absorption using transient spectroscopy and correlate their yield with the measured photocatalytic activity. Experiments coupled with modeling suggest that the localization of water around the polymer chain due to the incorporation of sulfone groups into an otherwise hydrophobic backbone is crucial for charge generation. Calculations of solution redox potentials and charge transfer free energies demonstrate that electron transfer from the sacrificial donor becomes thermodynamically favored as a result of the more polar local environment, leading to the production of long-lived electrons in these amphiphilic polymers.

Three series of conjugated microporous polymers (CMPs) were studied as photocatalysts for hydrogen production from water using a sacrificial hole scavenger. In all cases, dibenzo[b,d]thiophene sulfone polymers outperformed their fluorene analogues. A porous network, S-CMP3, showed the highest hydrogen evolution rates of 6076 μmol h −1 g −1 (λ > 295 nm) and 3106 μmol h −1 g −1 (λ > 420 nm), with an external quantum efficiency of 13.2% at 420 nm. S-CMP3 outperforms its linear structural analogue, P35, whereas in other cases, nonporous linear polymers are superior to equivalent porous networks. This suggests that microporosity might be beneficial for sacrificial photocatalytic hydrogen evolution, if suitable linkers are used that do not limit charge transport and the material can be wetted by water as studied here by water sorption and quasi-elastic neutron scattering.

Structure–property–activity relationships in solution processable polymer photocatalysts for hydrogen production from water were probed by varying the chemical structure of both the polymer side-chains and the polymer backbone.

Poly (3-hexylthiophene) (P3HT) was an early frontrunner in the development of donor polymers to be used in organic photovoltaics. A relatively straightforward and inexpensive synthesis suggests that it may be the most viable donor polymer to use in large-scale commercial organic solar cells. Replacing fullerenes with new electron acceptors has led to significant improvements in device performance and stability, with devices now able to exceed an efficiency of 7%. Past studies have reported a dependence of device performance on the molecular weight of the polymer in fullerenecontaining blends, however, with nonfullerene acceptors now showing promise a similar study was needed. P3HT blends, with two nonfullerene acceptors (O-IDTBR and EH-IDTBR), were probed using a number of polymer batches with varying molecular weights. O-IDTBR was shown to exhibit a dependence on the polymer molecular weight, with optimal performance achieved with a 34 kDa polymer, while EH-IDTBR displayed an independence in performance with varying polymer molecular weight. Probing the thermal and morphological behavior of the P3HT:O-IDTBR blends suggests that an optimal morphology with pronounced donor and acceptor domains was only achieved with the 34 kDa polymer, and a greater degree of mixing was exhibited in the other blends, likely leading to poorer device performance.

The bis and tris adducts of [6,6]phenyl-C(61)-butyric acid methyl ester (PCBM) offer lower reduction potentials than PCBM and are therefore expected to offer larger open-circuit voltages and more efficient energy conversion when blended with conjugated polymers in photovoltaic devices in place of PCBM. However, poor photovoltaic device performances are commonly observed when PCBM is replaced with higher-adduct fullerenes. In this work, we use transmission electron microscopy (TEM), steady-state and ultrafast time-resolved photoluminescence spectroscopy (PL), and differential scanning calorimetry (DSC) to probe the microstructural properties of blend films of poly(3-hexylthiophene-2,5-diyl) (P3HT) with the bis and tris adducts of PCBM. TEM and PL indicate that, in as-spun blend films, fullerenes become less soluble in P3HT as the number of adducts increases. PL indicates that upon annealing crystallization leads to phase separation in P3HT:PCBM samples only. DSC studies indicate that the interactions between P3HT and the fullerene become weaker with higher-adduct fullerenes and that all systems exhibit eutectic phase behavior with a eutectic composition being shifted to higher molar fullerene content for higher-adduct fullerenes. We propose two different mechanisms of microstructure development for PCBM and higher-adduct fullerenes. P3HT:PCBM blends, phase segregation is the result of crystallization of either one or both components and is facilitated by thermal treatments. In contrast, for blends containing higher adducts, the phase separation is due to a partial demixing of the amorphous phases. We rationalize the lower photocurrent generation by the higher-adduct fullerene blends in terms of film microstructure.