RESUMO
Conjugated polymer frameworks (CPFs) have recently sparked tremendous research interest due to their broad potentials in various frontline application areas such as photocatalysis, sensing, gas storage, energy storage, etc. These framework materials, without sidechains or functional groups on their backbone, are generally insoluble in common organic solvents and less solution processable for further device applications. There are few reports on metal-free electrocatalysis, especially oxygen evolution reaction (OER) using CPF. Herein, we have developed two triazine-based donor-acceptor conjugated polymer frameworks by coupling a 3-substituted thiophene (donor) unit with a triazine ring (acceptor) through a phenyl ring spacer. Two different sidechains, alkyl and oligoethylene glycol, were rationally introduced into the 3-position of thiophene in the polymer framework to investigate the effect of side-chain functionality on the electrocatalytic property. Both the CPFs demonstrated superior electrocatalytic OER activity and long-term durability. The electrocatalytic performance of CPF2, which achieved a current density of 10 mA/cm2 at an overpotential (η) of 328 mV, is much superior to CPF1, which reached the same current density at an overpotential of 488 mV. The porous and interconnected nanostructure of the conjugated organic building blocks, which allowed for fast charge and mass transport processes, could be attributed to the higher electrocatalytic activity of both CPFs. However, the superior activity of CPF2 compared to CPF1 may be due to the presence of a more polar oxygen-containing ethylene glycol side chain, which enhances the surface hydrophilicity, promotes better ion/charge and mass transfer, and increases the accessibility of the active sites toward adsorption through lower π-π stacking compared to hexyl side chain present in CPF1. The DFT study also supports the plausible better performance toward OER for CPF2. This study confirms the promising potentiality of metal-free CPF electrocatalysts for OER and further sidechain modification to improve their electrocatalytic property.
RESUMO
This Research Article demonstrates a very simple approach of a moisture-induced power-generating phenomenon using water-soluble rod-coil conjugated block copolymer (poly(3-hexythiophene)-block-poly(4-styrenesulfonic acid) (P3HT-b-PSSA)-modified reduced graphene oxide. The block copolymer-modified reduced graphene oxide (BCP-RGO) was prepared by noncovalent surface functionalization cum in situ reduction of graphene oxide. A simple device made from BCP-RGO can generate voltage upon exposure to water vapor or under different humidity conditions. The open-circuit voltage generated from the diode-like device varies with respect to the relative humidity, and the device can act as a self-powered humidity sensor. The as-prepared BCP-RGO is able to produce a maximum power density of 1.15 µW/cm2 (short-circuit current density J SC = 6.40 µA/cm2) at a relative humidity of 94%. Meanwhile, the BCP-RGO device produces a very high power density of 0.7 mW/cm2 (at a short-circuit current density of 1.06 mA/cm2) after 91% water absorption. We believe that the material presented here will be very useful for a self-biased humidity sensor and moisture-induced energy harvesting. The diode-like response of the BCP-RGO device with humidity or after water absorption will make the material applicable for self-biased humidity-controlled electronic switching.
