RESUMO
The development of efficient and sustainable electrochemical systems able to provide clean-energy fuels and chemicals is one of the main current challenges of materials science and engineering. Over the last decades, significant advances have been made in the development of robust electrocatalysts for different reactions, with fundamental insights from both computational and experimental work. Some of the most promising systems in the literature are based on expensive and scarce platinum-group metals; however, natural enzymes show the highest per-site catalytic activities, while their active sites are based exclusively on earth-abundant metals. Additionally, natural biomass provides a valuable feedstock for producing advanced carbonaceous materials with porous hierarchical structures. Utilizing resources and design inspiration from nature can help create more sustainable and cost-effective strategies for manufacturing cost-effective, sustainable, and robust electrochemical materials and devices. This review spans from materials to device engineering; we initially discuss the design of carbon-based materials with bioinspired features (such as enzyme active sites), the utilization of biomass resources to construct tailored carbon materials, and their activity in aqueous electrocatalysis for water splitting, oxygen reduction, and CO2 reduction. We then delve in the applicability of bioinspired features in electrochemical devices, such as the engineering of bioinspired mass transport and electrode interfaces. Finally, we address remaining challenges, such as the stability of bioinspired active sites or the activity of metal-free carbon materials, and discuss new potential research directions that can open the gates to the implementation of bioinspired sustainable materials in electrochemical devices.
RESUMO
Ultrathin amorphous silica membranes with embedded organic molecular wires (oligo(p-phenylenevinylene), three aryl units) provide chemical separation of incompatible catalytic environments of CO2 reduction and H2O oxidation while maintaining electronic and protonic coupling between them. For an efficient nanoscale artificial photosystem, important performance criteria are high rate and directionality of charge flow. Here, the visible-light-induced charge flow from an anchored Ru bipyridyl light absorber across the silica nanomembrane to Co3O4 water oxidation catalyst is quantitatively evaluated by photocurrent measurements. Charge transfer rates increase linearly with wire density, with 5 nm-2 identified as an optimal target. Accurate measurement of wire and light absorber densities is accomplished by the polarized FT-IRRAS method. Guided by density functional theory (DFT) calculations, four wire derivatives featuring electron-donating (methoxy) and -withdrawing groups (sulfonate, perfluorophenyl) with highest occupied molecular orbital (HOMO) potentials ranging from 1.48 to 0.64 V vs NHE were synthesized and photocurrents evaluated. Charge transfer rates increase sharply with increasing driving force for hole transfer from the excited light absorber to the embedded wire, followed by a decrease as the HOMO potential of the wire moves beyond the Co3O4 valence band level toward more negative values, pointing to an optimal wire HOMO potential around 1.3 V vs NHE. Comparison with photocurrents of samples without nanomembrane indicates that silica layers with optimized wires are able to approach undiminished electron flux at typical solar intensities. Combined with the established high proton conductivity and small-molecule blocking property, the charge transfer measurements demonstrate that oxidation and reduction catalysis can be efficiently integrated on the nanoscale under separation by an ultrathin silica membrane.
