Bioinspired and Bioderived Aqueous Electrocatalysis

Abstract

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 CO 2 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.

FeNC Oxygen Reduction Electrocatalyst with High Utilisation Penta-coordinated sites

“…Moreover, ex situ X-ray absorption spectroscopy and low-temperature Mössbauer spectroscopy suggest the presence of penta-coordinated Fe sites, which were further studied by density functional theory calculations.resonance. [9,10] Some of them bearing close resemblance to biological systems, [11] such as N axially coordinated FeN4 sites resembling heme. [12] However, spectroscopic discernibility is often challenging in these typically heterogeneous FeNC catalysts, [13] therefore experimental structure-activity correlations are hard to conclude.…”

“…resonance. [9,10] Some of them bearing close resemblance to biological systems, [11] such as N axially coordinated FeN4 sites resembling heme. [12] However, spectroscopic discernibility is often challenging in these typically heterogeneous FeNC catalysts, [13] therefore experimental structure-activity correlations are hard to conclude.…”

Reaching the Fundamental Limitation in CO2 Reduction to CO with Single Atom Catalysts

“…Moving forwards, there are two routes to improving beyond the state-of-the art (a) finding compounds that preferentially accelerate the CO2 activation step relative to *CO desorption, for instance by manipulating the spin state of MNC catalysts [63] (b) or emulating enzymes such as nitrogenase so that we engineer the catalysts to yield more energy rich C2+ products. [64,65]…”

Biologically Assisted Construction of Advanced Electrode Materials for Electrochemical Energy Storage and Conversion

“…Considering the favorable effect of hydrophobic structure on promoting gas diffusion, analogous biomimetic design is also frequently conducted in other gas consuming systems, including nitrogen reduction reaction (NRR) and ORR. [128,129] For example, Liu, et al got inspiration from the gas-trapping hydrophobic hair of subaquatic spider and synthesized aerophilic ultrathin porous Bi 5 O 7 I nanotubes for efficient NRR electrocatalysis. [130] Tang, et al mimicked the waxy epidermis of diving flies and coated a layer of hydrophobic polytetrafluoroethylene (PTFE) on Co 3 O 4 nanosheets for promoting ORR efficiency.…”