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 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

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

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.]

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

Rapid synthesis of supported single metal nanoparticles and effective removal of stabilizing ligands

A method is introduced to rapidly (<30 min) synthesize single metal nanoparticles with narrow size distribution in a simple way. It is based on the electrospraying of a metal precursor solution into a surfactant solution, which acts as a reducing and stabilizing agent. This synthesis method is demonstrated for the production of Ag and Au nanoparticles, which are incorporated onto carbonaceous and non-carbonaceous supports. The nanoparticle size depends on the internal diameter of the spraying nozzle. The removal of the stabilizing surfactant (dodecylamine; DDA) is also examined via thermal annealing and oxygen plasma treatments. Thermal annealing at a low temperature rate is found to be the most effective, as it completely removes DDA from the metal nanoparticles without inducing changes in their particle size. To verify that the supported Ag nanoparticles post calcination are surfactant-free and, thus, their surface sites are active, their oxygen reduction reaction (ORR) activity is measured in alkaline media, demonstrating similar values to the ones reported in the literature

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

A lung-inspired approach to scalable and robust fuel cell design

A lung-inspired approach is employed to overcome reactant homogeneity issues in polymer electrolyte fuel cells. The fractal geometry of the lung is used as the model to design flow-fields of different branching generations, resulting in uniform reactant distribution across the electrodes and minimum entropy production of the whole system. 3D printed, lung-inspired flow field based PEFCs with N = 4 generations outperform the conventional serpentine flow field designs at 50% and 75% RH, exhibiting a 20% and 30% increase in performance (at current densities higher than 0.8 A cm2) and maximum power density, respectively. In terms of pressure drop, fractal flow-fields with N = 3 and 4 generations demonstrate 75% and 50% lower values than conventional serpentine flow-field design for all RH tested, reducing the power requirements for pressurization and recirculation of the reactants. The positive effect of uniform reactant distribution is pronounced under extended current-hold measurements, where lung-inspired flow field based PEFCs with N = 4 generations exhibit the lowest voltage decay (B5 mV h1). The enhanced fuel cell performance and low pressure drop values of fractal flow field design are preserved at large scale (25 cm2), in which the excessive pressure drop of a large-scale serpentine flow field renders its use prohibitive

Precisely Engineered Supported Gold Clusters as a Stable Catalyst for Propylene Epoxidation

Designing a stable and selective catalyst with high H2 utilisation is of pivotal importance for the direct gas-phase epoxidation of propylene. This work describes a facile one-pot methodology to synthesise ligand-stabilised sub-nanometre gold clusters immobilised onto a zeolitic support (TS-1) to engineer a stable Au/TS-1 catalyst. A non-thermal O2 plasma technique is used for the quick removal of ligands with limited increase in particle size. Compared to untreated Au/TS-1 catalysts prepared using the deposition precipitation method, the synthesised catalyst exhibits improved catalytic performance, including 10 times longer lifetime (>20 days), increased PO selectivity and hydrogen efficiency in direct gas phase epoxidation. The structure-stability relationship of the catalyst is illustrated using multiple characterisation techniques, such as XPS, 31P MAS NMR, DR-UV/VIS, HRTEM and TGA. It is hypothesised that the ligands play a guardian role in stabilising the Au particle size, which is vital in this reaction. This strategy is a promising approach towards designing a more stable heterogeneous catalyst

Effect of extended short-circuiting in proton exchange membrane fuel cells

Short-circuiting is regularly utilized in Proton Exchange Membrane Fuel Cells (PEMFCs) to reverse short-term reversible catalyst degradation. However, do these improvements in fuel cell performance and durability still exist after extended operation? We provide an answer to this question by comparing the performance and durability of a PEMFC under open-circuit voltage (OCV) and a commercial short-circuiting protocol, against a PEMFC under OCV without short-circuiting for the same extended period (∼144 h). The experimental results demonstrate the detrimental effect of extended short-circuiting on the durability of the catalyst and the performance of the fuel cell. Electrochemically active surface area losses reach ∼46% for the short-circuiting case, compared to only ∼18% losses for the OCV without short-circuiting. TEM and XPS measurements are employed to monitor the morphological changes of the catalyst layer, revealing that Ostwald ripening, carbon corrosion, and Pt migration and precipitation into the polymer membrane are the main degradation mechanisms of the cathode catalyst layer. At the end of PEMFC operation, XPS measurements reveal that only ∼0.1% (atomic) of Pt remains on the surface of the cathode catalyst layer after OCV with short-circuiting, compared to the initial ∼0.4% Pt of the unused cathode MEA and ∼0.3% Pt for the cathode MEA after OCV without short-circuiting. These results show that short-circuiting can cause facile degradation of the catalyst layer and significant decrease in fuel cell performance, rendering this technique non-beneficial for extended operation