Nature-inspired electrocatalysts and devices for energy conversion

The main obstacles toward further commercialization of electrochemical devices are the development of highly efficient, cost-effective and robust electrocatalysts, and the suitable integration of those catalysts within devices that optimally translate catalytic performance at the nanoscale to practically relevant length and time scales. Over the last decades, advancements in manufacturing technology, computational tools, and synthesis techniques have led to a range of sophisticated electrocatalysts, mostly based on expensive platinum group metals. To further improve their design, and to reduce overall cost, inspiration can be derived from nature on multiple levels, considering nature's efficient, hierarchical structures that are intrinsically scaling, as well as biological catalysts that catalyze the same reactions as in electrochemical devices. In this review, we introduce the concept of nature-inspired chemical engineering (NICE), contrasting it to the narrow sense in which biomimetics is often applied, namely copying isolated features of biological organisms irrespective of the different context. In contrast, NICE provides a systematic design methodology to solve engineering problems, based on the fundamental understanding of mechanisms that underpin desired properties, but also adapting them to the context of engineering applications. The scope of the NICE approach is demonstrated via this comparative state-of-the-art review, providing examples of bio-inspired electrocatalysts for key energy conversion reactions and nature-inspired electrochemical devices

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

Nature-inspired optimization of hierarchical porous media for catalytic and separation processes

Hierarchical materials combining pore sizes of different length scales are highly important for catalysis and separation processes, where optimization of adsorption and transport properties is required. Nature can be an excellent guide to rational design, as it is full of hierarchical structures that are intrinsically scaling, efficient and robust. However, much of the “inspiration” from nature is, at present, empirical; considering the huge design space, we advocate a methodical, fundamental approach based on mechanistic features

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

Cost Effectiveness Analysis for Renewable Energy Sources Integration in the Island of Lemnos, Greece

The development of more efficient and least cost energy management interventions is of great importance for isolated energy systems. Islands are typical examples of isolated regions, often highly dependent on imported fossil fuels but with a significant and often unexploited Renewable Energy (RE) potential. This paper presents a least cost planning approach towards the integration of Renewable Energy Sources (RES) in such systems, which is applied to the island of Lemnos, Greece. The approach involves the application of Cost-Effectiveness Analysis (CEA) and Incremental Cost Analysis (ICA) for screening possible alternatives and determining the most economically efficient and effective plan for their implementation. The objective of the application of the proposed approach in the specific case study is to meet through the use of RE technologies all the additional electricity and thermal energy demand, compared to 2007. Various supply side options are evaluated, and an implementation plan is derived. The results indicate that the excess of both electricity and thermal energy demand can be met in the near future without any significant changes in existing infrastructure, while other options should be considered for a more extended time horizon

One-pot Synthesis of Hierarchical, Micro-macroporous Zeolites with Encapsulated Metal Particles as Sinter-resistant, Bifunctional Catalysts

We report a new one-pot synthesis procedure for hierarchical zeolites with intracrystalline macropores and metal particles encapsulated within the zeolitic walls. The synthesis allows to prepare macroporous zeolites of MFI topology with different heteroatoms (silicalite-1, ZSM-5 and TS-1) and different encapsulated noble metal particles, such as gold, platinum and palladium. The hierarchically structured zeolites contain large macropores with diameters around 400 nm, which are well distributed and interconnected and should significantly enhance mass transport properties. The encapsulation of metal nanoparticles within the zeolitic walls leads to remarkable sinter resistance of the particles. Encapsulated gold nanoparticles (2.6 nm) do not significantly change in size during an 18-hour treatment at 600 °C under air, while non-encapsulated gold particles sinter heavily during the same treatment. Catalytic experiments for the direct epoxidation of propene with hydrogen and oxygen show that both catalytic functions of a macroporous TS-1 sample that encapsulates gold particles are accessible and active. This catalyst displays high activity, although PO selectivity could still be improved. These materials show great potential for use in catalytic applications, due to their bifunctional nature, high sintering resistance, shape selective properties and hierarchical structure

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

Optimizing the architecture of lung-inspired fuel cells

A finite-element model of a polymer electrolyte membrane fuel cell (PEMFC) with fractal branching, lung-inspired flow-field is presented. The effect of the number of branching generations N on the thickness of the gas diffusion layer (GDL) and fuel cell performance is determined. Introduction of a fractal flow-field to homogenize reactant concentration at the flow-field | GDL interface allows for the use of thinner GDLs. The model is coupled with an optimized cathode catalyst layer microstructure with respect to platinum utilization and power density, revealing that the 2020 DoE target of ~8 kW/gPt is met at N = 4 generations, and a platinum utilization of ~36 kW/gPt is achieved at N = 6 generations. In terms of the overall fuel cell stack architecture, our results indicate that either the platinum loading or the number of cells in the stack can be reduced by ~75%, the latter option of which, when combined with a 100 µm GDL, can lead to >80% increase in the volumetric power density of the fuel cell stack

Bioinspired supramolecular macrocycle hybrid membranes with enhanced proton conductivity

Enhancing the proton conductivity of proton exchange membranes (PEMs) is essential to expand the applications of proton exchange membrane fuel cells (PEMFCs). Inspired by the proton conduction mechanism of bacteriorhodopsin, cucurbit[n]urils (CB[n], where n is the number of glycoluril units, n = 6, 7, or 8) are introduced into sulfonated poly(ether ether ketone) (SPEEK) matrix to fabricate hybrid PEMs, employing a nature-inspired chemical engineering (NICE) methodology. The carbonyl groups of CB[n] act as proton-conducting sites, while the host–guest interaction between CB[n] and water molecules offers extra proton-conducting pathways. Additionally, the molecular size of CB[n] aids in their dispersion within the SPEEK matrix, effectively bridging the unconnected proton-conducting sulfonic group domains within the SPEEK membrane. Consequently, all hybrid membranes exhibit significantly enhanced proton conductivity. Notably, the SPEEK membrane incorporating 1 wt.% CB[8] (CB[8]/SPEEK-1%) demonstrates the highest proton conductivity of 198.0 mS·cm−1 at 60 °C and 100% relative humidity (RH), which is 228% greater than that of the pure SPEEK membrane under the same conditions. Moreover, hybrid membranes exhibit superior fuel cell performance. The CB[8]/SPEEK-1% membrane achieves a maximum power density of 214 mW·cm−2, representing a 140% improvement over the pure SPEEK membrane (89 mW·cm−2) at 50 °C and 100% RH. These findings serve as a foundation for constructing continuous proton-conducting pathways within membranes by utilizing supramolecular macrocycles as fuel cell electrolytes and in other applications. [Figure not available: see fulltext.]

Optimization of mesoporous titanosilicate catalysts for cyclohexene epoxidation via statistically guided synthesis

An efficient approach to improve the catalytic activity of titanosilicates is introduced. The Doehlert matrix (DM) statistical model was utilized to probe the synthetic parameters of mesoporous titanosilicate microspheres (MTSM), in order to increase their catalytic activity with a minimal number of experiments. Synthesis optimization was carried out by varying two parameters simultaneously: homogenizing temperature and surfactant weight. Thirteen different MTSM samples were synthesized in two sequential ‘matrices’ according to Doehlert conditions and were used to catalyse the epoxidation of cyclohexene with 'tert'-butyl hydroperoxide. The samples (and the corresponding synthesis conditions) with superior catalytic activity in terms of product yield and selectivity were identified. In addition, this approach revealed the limiting values of each synthesis parameter, beyond which the material becomes catalytically ineffective. This study demonstrates that the DM approach can be broadly used as a powerful and time-efficient tool for investigating the optimal synthesis conditions of heterogeneous catalysts