Nature-Inspired Electrocatalysts for CO_{2} Reduction to C_{2+} Products

The electrocatalytic reduction reaction of carbon dioxide (CO2RR) has gained significant attention as a promising approach to mitigate carbon dioxide emissions and generate valuable chemicals and fuels. However, the practical application of CO2RR has been hindered by the lack of efficient and selective electrocatalysts, particularly to produce multi-carbon (C2+) products. Nature serves as an ideal source of inspiration for the development of CO2RR electrocatalysts, as biological organisms can efficiently catalyze the same reaction and possess robust structures that are inherently scaling. In this review, recent advances in the nature-inspired design of electrocatalysts for CO2RR to C2+ products are summarized and categorized based on their inspiration source, including the coordination sphere of metalloenzymes and the cascade reactions within the enzyme, as well as the local environment. The importance of understanding the fundamental mechanisms and the different contexts between nature and technological application in the design process is highlighted, with the aim to improve the nature-inspired design of electrocatalysts for CO2RR to C2+ products

From Biomimicking to Bioinspired Design of Electrocatalysts for CO2 Reduction to C1 Products

The electrochemical reduction of CO2 (CO2RR) is a promising approach to maintain a carbon cycle balance and produce value-added chemicals. However, CO2RR technology is far from mature, since the conventional CO2RR electrocatalysts suffer from low activity (leading to currents 200 mA cm−2, >8000 h, >90 % selectivity). Significant improvements are possible by taking inspiration from nature, considering biological organisms that efficiently catalyze the CO2 to various products. In this minireview, we present recent examples of enzyme-inspired and enzyme-mimicking CO2RR electrocatalysts enabling the production of C1 products with high faradaic efficiency (FE). At present, these designs do not typically follow a methodical approach, but rather focus on isolated features of biological systems. To achieve disruptive change, we advocate a systematic design methodology that leverages fundamental mechanisms associated with desired properties in nature and adapts them to the context of engineering applications

Nature-inspired flow-fields and water management for PEM fuel cells

Flow-field design is crucial to polymer electrolyte membrane fuel cell (PEMFC) performance, since non-uniform transport of species to and from the membrane electrode assembly (MEA) results in significant power losses. The long channels of conventional serpentine flow-fields cause large pressure drops between inlets and outlets, thus large parasitic energy losses and low fuel cell performance. Here, a lung-inspired approach is used to design flow-fields guided by the structure of a lung. The fractal geometry of the human lung has been shown to ensure uniform distribution of air from a single outlet (trachea) to multiple outlets (alveoli). Furthermore, the human lung transitions between two flow regimes: 14-16 upper generations of branches dominated by convection, and 7-9 lower generations of space-filling acini dominated by diffusion. The upper generations of branches are designed to slow down the gas flow to a rate compatible with the rate in the diffusional regime (Pé ~ 1), resulting in uniform distribution of entropy production in both regimes. By employing a three-dimensional (3D) fractal structure as flow-field inlet channel, we aim to yield similar benefits from replicating these characteristics of the human lung. The fractal pattern consists of repeating “H” shapes where daughter “H’s” are located at the four tips of the parent “H”. The fractal geometry obeys Murray’s law, much like the human lung, hereby leading to minimal mechanical energy losses. Furthermore, the three-dimensional branching structure provide uniform local conditions on the surface of the catalyst layer as only the outlets of the fractal inlet channel are exposed to the MEA. Numerical simulations were conducted to determine the number of generations required to achieve uniform reactant distribution and minimal entropy production. The results reveal that the ideal number of generations for minimum entropy production lies between N = 5 and 7. Guided by the simulation results, three flow-fields with N = 3, 4 and 5 (10 cm2 surface area) were 3D printed via direct metal laser sintering (DMLS), and experimentally validated against conventional serpentine flow-fields. The fractal flow-fields with N = 4 and 5 generations showed ~20% and ~30% increase in performance and maximum power density over serpentine flow-fields above 0.8 A cm-2 at 50% RH. At fully humidified conditions, though, the performance of fractal N = 5 flow-field significantly deteriorates due to flooding issues. Another defining characteristic of the fractal approach is scalability, which is an important feature in nature. Fractal flow-fields can bridge multiple length scales by adding further generations, while preserving the building units and microscopic function of the system. Larger, 3D printed fractal flow-fields (25 cm2 surface area) with N = 4 are compared to conventional serpentine flow-field based PEMFCs. Performance results show that fractal and serpentine flow-field based PEMFCs have similar polarization curves, which is attributed to the significantly higher pressure drop (~ 25 kPa) of large serpentine flow-fields compared to fractal flow-fields. However, such excessive pressure drop renders the use of a large scale serpentine flow-field prohibitive, thus favouring the fractal flow-field. A major shortcoming of using fractal flow-field is, though, susceptibility to flooding in the gas channels due to slow gas velocity. This problem has led to the development of a nature-inspired water management mechanism that draws inspiration from the ability of the Thorny Devil (Australian lizard) to passively transport liquid water across its skin using capillary pressure. We have recently integrated this strategy with the fractal N = 4 flow-fields and verified the viability of the strategy using neutron imaging at Helmholtz-Zentrum Berlin (HZB). Implementation of this water management strategy is expected to circumvent remaining problems of high-generation fractal flow-fields

Titanium(IV)-induced cristobalite formation in titanosilicates and its potential impact on catalysis

Cristobalite, a crystalline form of silica, is shown to be formed within an amorphous titanosilicate, at previously unknown conditions. Mesoporous titanosilicate microspheres (MTSM) were synthesized as efficient catalysts for the epoxidation of cyclohexene with 'tert'-butyl hydroperoxide. High-resolution transmission electron microscopy revealed the presence of crystals in this predominantly amorphous material, after calcination at 750 °C. When calcined at 800 °C, the crystals were identified via PXRD as predominantly cristobalite, which possibly marks its first observation in titanosilicates at such a low temperature, without adding any alkali metals during synthesis. Catalytic experiments conducted with MTSM materials calcined at temperatures varying from 650 to 950 °C, reveal that the amount of cristobalite formed increases with temperature, and that it has a significant impact on the pore structure, and, remarkably, correlates with the catalytic activity of titanosilicates

Effects of an easy-to-implement water management strategy on performance and degradation of polymer electrolyte fuel cells

Intermittent switching between wet and dry reactant gases during operation in a polymer electrolyte fuel cell (PEFC) can improve performance stability, alleviating the effects of flooding by controlling the water content within the system. However, lifetime durability may be affected due to membrane electrode assembly (MEA) boundary delamination and membrane damage. Two relative humidity (RH) control strategies were investigated, using electrochemical performance and MEA degradation as critical indicators. It was found that intermittent switching between wet and dry gases does not accelerate fuel cell degradation if the duration of the dry gas period is set reasonably (dry gases stops before the voltage reaches the apex of the hump). Additionally, current and temperature distribution mapping was utilised to capture the dynamic response between these transitional stages. The switching of dry gases first makes the current density distribution homogeneous, and the maximum current density is reduced subsequently. Then, the current density near the inlet keeps decreasing. Intermittent switching between wet and dry reactant gases is easy to implement and overcomes limitations in mass transfer at medium and high current densities

CeO₂ Surface Oxygen Vacancy Concentration Governs in Situ Free Radical Scavenging Efficacy in Polymer Electrolytes

Nonstoichiometric CeO₂ and Ce_0.25Zr_0.75O₂ nanoparticles with varying surface concentrations of Ce³⁺ were synthesized. Their surface Ce³⁺ concentration was measured by XPS, and their surface oxygen vacancy concentrations and grain size were estimated using Raman spectroscopy. The surface oxygen vacancy concentration was found to correlate well with grain size and surface Ce³⁺ concentration. When incorporated into a Nafion polymer electrolyte membrane (PEM), the added nonstoichiometric ceria nanoparticles effectively scavenged PEM-degradation-inducing free radical reactive oxygen species (ROS) formed during fuel cell operation. A 3-fold increase in the surface oxygen vacancy concentration resulted in an order of magnitude enhancement in the efficacy of free radical ROS scavenging by the nanoparticles. Overall, the macroscopic PEM degradation mitigation rate was lowered by up to 2 orders of magnitude using nonstoichiometric ceria nanoparticles with high surface oxygen vacancy concentration

X-ray micro-tomography as a diagnostic tool for the electrode degradation in vanadium redox flow batteries

Micro-tomography (CT) can be successfully employed to characterize ex situ the structural changes occurring in graphite felt electrodes during vanadium redox flow battery (VRFB) operation. Coupled high resolution X-ray and electron microscopy in conjunction with XPS are used to elucidate the microstructural and chemical changes to the high voltage RFB carbon electrode. The results reveal the onset of corrosion of the carbon felt structure relatively early in the VRFB life-cycle, extended operation is expected to result in extensive microstructural evolution effects. Keywords: X-ray micro-tomography, Vanadium redox flow battery, Electrode degradatio