Templated 2D Polymer Heterojunctions for Improved Photocatalytic Hydrogen Production.

2D polymers have emerged as one of the most promising classes of organic photocatalysts for solar fuel production due to their tunability, charge-transport properties, and robustness. They are however difficult to process and so there are limited studies into the formation of heterojunction materials incorporating these components. In this work, a novel templating approach is used to combine an imine-based donor polymer and an acceptor polymer formed through Knoevenagel condensation. Heterojunction formation is shown to be highly dependent on the topological match of the donor and acceptor polymers with the most active templated material found to be between three and nine times more active for photocatalysis than its constituent components. Transient absorption spectroscopy reveals that this improvement is due to faster charge separation and more efficient charge extraction in the templated heterojunction. The templated material shows a very high hydrogen evolution rate of >20 mmol h-1 m-2 with an ascorbic acid hole scavenger but also produces hydrogen in the presence of only water and a cobalt-based redox mediator. This suggests the improved charge-separation interface and reduced trapping accessed through this approach could be suitable for Z-scheme formation.

Solution-processable polymers of intrinsic microporosity for gas-phase carbon dioxide photoreduction.

Four solution-processable, linear conjugated polymers of intrinsic porosity are synthesised and tested for gas phase carbon dioxide photoreduction. The polymers' photoreduction efficiency is investigated as a function of their porosity, optical properties, energy levels and photoluminescence. All polymers successfully form carbon monoxide as the main product, without the addition of metal co-catalysts. The best performing single component polymer yields a rate of 66 µmol h-1 m-2, which we attribute to the polymer exhibiting macroporosity and the longest exciton lifetimes. The addition of copper iodide, as a source of a copper co-catalyst in the polymers shows an increase in rate, with the best performing polymer achieving a rate of 175 µmol h-1 m-2. The polymers are active for over 100 h under operating conditions. This work shows the potential of processable polymers of intrinsic porosity for use in the gas phase photoreduction of carbon dioxide towards solar fuels.

Oligoethylene Glycol Side Chains Increase Charge Generation in Organic Semiconductor Nanoparticles for Enhanced Photocatalytic Hydrogen Evolution.

Organic semiconductor nanoparticles (NPs) composed of an electron donor/acceptor (D/A) semiconductor blend have recently emerged as an efficient class of hydrogen-evolution photocatalysts. It is demonstrated that using conjugated polymers functionalized with (oligo)ethylene glycol side chains in NP photocatalysts can greatly enhance their H2 -evolution efficiency compared to their nonglycolated analogues. The strategy is broadly applicable to a range of structurally diverse conjugated polymers. Transient spectroscopic studies show that glycolation facilitates charge generation even in the absence of a D/A heterojunction, and further suppresses both geminate and nongeminate charge recombination in D/A NPs. This results in a high yield of photogenerated charges with lifetimes long enough to efficiently drive ascorbic acid oxidation, which is correlated with greatly enhanced H2 -evolution rates in the glycolated NPs. Glycolation increases the relative permittivity of the semiconductors and facilitates water uptake. Together, these effects may increase the high-frequency relative permittivity inside the NPs sufficiently, to cause the observed suppression of exciton and charge recombination responsible for the high photocatalytic activities of the glycolated NPs.