Side-chain tuning in conjugated polymer photocatalysts for improved hydrogen production from water

Abstract

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.

Interfacial Engineering for Improved Photocatalysis in a Charge Storing 2D Carbon Nitride: Melamine Functionalized Poly(heptazine imide)

“…This is in line with previous observations by Cooper et al. for hydrophilic sulfone containing polymer photocatalysts, [ 67–69 ] where wettability was identified as crucial parameter for electron transfer during proton reduction. Our study demonstrates that interfacial effects in general are a bottleneck reaction, i.e., hole extraction, which is also important to enable efficient charge carrier separation and with it, high HER rates.…”

Structure–activity relationships in well-defined conjugated oligomer photocatalysts for hydrogen production from water

“…Previously, we showed that this approach yields results comparable to those measured using photoelectron spectroscopy, at least for amorphous polymers. 54,60 The results of these calculations (Fig. 3d), suggest for MeF1-MeF3 and S1-S3 that with increasing oligomer length the IP becomes less positive and EA less negative, and hence the driving force for triethylamine/Na 2 SO 3 /Na 2 S oxidation and proton reduction decreases with oligomer length.…”

Hydrogen evolution by polymer photocatalysts; a possible photocatalytic cycle

“…18,22,23 The dispersability of a polymer probably depends both on the size (distribution) of the polymer particles in suspension and the inherent wettability of the polymer or the sidegroups present. 24,25 Our empirical observations are in line with a classical semiconductor microscopic model where the exciton formed through the absorption of light either (i) spontaneously falls apart and the free electron and hole formed in the process reduce protons/SEA and oxidise water/SED, respectively, or, more likely due to the large exciton binding energy relative to k B T in polymers, (ii) drives one of the two solution half-reactions and the remaining free-electron/hole the other. 26,27 Transient spectroscopy of polymers under hydrogen evolution conditions 25,28 indeed suggest the presence of electron polarons, i.e.…”