SEM Image Processing Assisted by Deep Learning to Quantify Mesoporous γ-Alumina Spatial Heterogeneity and Its Predicted Impact on Mass Transfer.

The pore network architecture of porous heterogeneous catalyst supports has a significant effect on the kinetics of mass transfer occurring within them. Therefore, characterizing and understanding structure-transport relationships is essential to guide new designs of heterogeneous catalysts with higher activity and selectivity and superior resistance to deactivation. This study combines classical characterization via N2 adsorption and desorption and mercury porosimetry with advanced scanning electron microscopy (SEM) imaging and processing approaches to quantify the spatial heterogeneity of γ-alumina (γ-Al2O3), a catalyst support of great industrial relevance. Based on this, a model is proposed for the spatial organization of γ-Al2O3, containing alumina inclusions of different porosities with respect to the alumina matrix. Using original, advanced SEM image analysis techniques, including deep learning semantic segmentation and porosity measurement under gray-level calibration, the inclusion volume fraction and interphase porosity difference were identified and quantified as the key parameters that served as input for effective tortuosity factor predictions using effective medium theory (EMT)-based models. For the studied aluminas, spatial porosity heterogeneity impact on the effective tortuosity factor was found to be negligible, yet it was proven to become significant for an inclusion content of at least 30% and an interphase porosity difference of over 20%. The proposed methodology based on machine-learning-supported image analysis, in conjunction with other analytical techniques, is a general platform that should have a broader impact on porous materials characterization.

Machine Learning Assisted Experimental Characterization of Bubble Dynamics in Gas-Solid Fluidized Beds.

This study introduces a machine learning (ML)-assisted image segmentation method for automatic bubble identification in gas-solid quasi-2D fluidized beds, offering enhanced accuracy in bubble recognition. Binary images are segmented by the ML method, and an in-house Lagrangian tracking technique is developed to track bubble evolution. The ML-assisted segmentation method requires few training data, achieves an accuracy of 98.75%, and allows for filtering out common sources of uncertainty in hydrodynamics, such as varying illumination conditions and out-of-focus regions, thus providing an efficient tool to study bubbling in a standard, consistent, and repeatable manner. In this work, the ML-assisted methodology is tested in a particularly challenging case: structured oscillating fluidized beds, where the spatial and time evolution of the bubble position, velocity, and shape are characteristics of the nucleation-propagation-rupture cycle. The new method is validated across various operational conditions and particle sizes, demonstrating versatility and effectiveness. It shows the ability to capture challenging bubbling dynamics and subtle changes in velocity and size distributions observed in beds of varying particle size. New characteristic features of oscillating beds are identified, including the effect of frequency and particle size on the bubble morphology, aspect, and shape factors and their relationship with the stability of the flow, quantified through the rate of coalescence and splitting events. This type of combination of classic analysis with the application of the ML assisted techniques provides a powerful tool to improve standardization and address the reproducibility of hydrodynamic studies, with the potential to be extended from gas-solid fluidization to other multiphase flow systems.

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

The electrochemical reduction of CO2 (CO2 RR) is a promising approach to maintain a carbon cycle balance and produce value-added chemicals. However, CO2 RR technology is far from mature, since the conventional CO2 RR electrocatalysts suffer from low activity (leading to currents <10 mA cm-2 in an H-cell), stability (<120 h), and selectivity. Hence, they cannot meet the requirements for commercial applications (>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 CO2 RR 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.

Bioinspired 3D microprinted cell scaffolds: Integration of graph theory to recapitulate complex network wiring in lymph nodes.

Physical networks are ubiquitous in nature, but many of them possess a complex organizational structure that is difficult to recapitulate in artificial systems. This is especially the case in biomedical and tissue engineering, where the microstructural details of 3D cell scaffolds are important. Studies of biological networks-such as fibroblastic reticular cell (FRC) networks-have revealed the crucial role of network topology in a range of biological functions. However, cell scaffolds are rarely analyzed, or designed, using graph theory. To understand how networks affect adhered cells, 3D culture platforms capturing the complex topological properties of biologically relevant networks would be needed. In this work, we took inspiration from the small-world organization (high clustering and low path length) of FRC networks to design cell scaffolds. An algorithmic toolset was created to generate the networks and process them to improve their 3D printability. We employed tools from graph theory to show that the networks were small-world (omega factor, ω = -0.10 ± 0.02; small-world propensity, SWP = 0.74 ± 0.01). 3D microprinting was employed to physicalize networks as scaffolds, which supported the survival of FRCs. This work, therefore, represents a bioinspired, graph theory-driven approach to control the networks of microscale cell niches.

Surface barriers to mass transfer in nanoporous materials for catalysis and separations.

Surface barriers to mass transfer in various nanoporous materials have been increasingly identified. These past few years especially, a significant impact on catalysis and separations has come to light. Broadly speaking, there are two types of barriers: internal barriers, which affect intraparticle diffusion, and external barriers, which determine the uptake and release rates of molecules into and out of the material. Here, we review the literature on surface barriers to mass transfer in nanoporous materials and describe how the existence and influence of surface barriers has been characterized, aided by molecular simulations and experimental measurements. As this is a complex, evolving research topic, without consensus from the scientific community at the time of writing, we present various current viewpoints, not always in agreement, on the origin, nature, and function of such barriers in catalysis and separation. We also emphasize the need for considering all the elementary steps of the mass transfer process in optimally designing new nanoporous and hierarchically structured adsorbents and catalysts.

Enhanced Structural Control of Soft-Templated Mesoporous Inorganic Thin Films by Inert Processing Conditions.

Mesoporous thin films are widely used for applications in need of high surface area and efficient mass and charge transport properties. A well-established fabrication process involves the supramolecular assembly of organic molecules (e.g., block copolymers and surfactants) with inorganic materials obtained by sol-gel chemistry. Typically, subsequent calcination in air removes the organic template and reveals the porous inorganic network. A significant challenge for such coatings is the anisotropic shrinkage due to the volume contraction related to solvent evaporation, inorganic condensation, and template removal, affecting the final porosity as well as pore shape, size, arrangement, and accessibility. Here, we show that a two-step calcination process, composed of high-temperature treatment in argon followed by air calcination, is an effective fabrication strategy to reduce film contraction and enhance structural control of mesoporous thin films. Crucially, the formation of a transient carbonaceous scaffold enables the inorganic matrix to fully condense before template removal. The resulting mesoporous films retain a higher porosity as well as bigger pores with extended porous order. Such films present favorable characteristics for mass transport of large molecules. This is demonstrated for lysozyme adsorption into the mesoporous thin films as an example of enzyme storage.

Gold nanoparticles with tailored size through ligand modification for catalytic applications.

The active sites of catalysts can be tuned by using appropriate organic moieties. Here, we describe a facile approach to synthesise gold nanoparticles (AuNPs) using various Au(I) precursors. The core size of these AuNPs can be precisely tailored by varying the steric hindrance imposed by bound ligands. An interesting relationship is deduced that correlates the steric hindrance around the metal to the final size of the nanoparticles. The synthesised AuNPs are immobilised onto TS-1 zeolite (Au/TS-1) with minimal change in the final size of the AuNPs. The catalytic performance of Au/TS-1 catalyst is evaluated for the direct gas phase epoxidation of propylene with hydrogen and oxygen, an environmentally friendly route to produce propylene oxide. The results indicate that smaller AuNPs exhibit enhanced catalytic activity and selectivity. Furthermore, this synthetic approach is beneficial when tailored synthesis of gold nanoparticles of specific sizes is required.

Mixed-dimensional membranes: chemistry and structure-property relationships.

Tremendous progress in two-dimensional (2D) nanomaterial chemistry affords abundant opportunities for the sustainable development of membranes and membrane processes. In this review, we propose the concept of mixed dimensional membranes (MDMs), which are fabricated through the integration of 2D materials with nanomaterials of different dimensionality and chemistry. Complementing mixed matrix membranes or hybrid membranes, MDMs stimulate different conceptual thinking about designing advanced membranes from the angle of the dimensions of the building blocks as well as the final structures, including the nanochannels and the bulk structures. In this review, we survey MDMs (denoted nD/2D, where n is 0, 1 or 3) in terms of the dimensions of membrane-forming nanomaterials, as well as their fabrication methods. Subsequently, we highlight three kinds of nanochannels, which are 1D nanochannels within 1D/2D membranes, 2D nanochannels within 0D/2D membranes, and 3D nanochannels within 3D/2D membranes. Strategies to tune the physical and chemical microenvironments of the nanochannels as well as the bulk structures based on the size, type, structure and chemical character of nanomaterials are discussed. Some representative applications of MDMs are illustrated for gas molecular separations, liquid molecular separations, ionic separations and oil/water separation. Finally, current challenges and a future perspective on MDMs are presented.

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, 31 P 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 External Surface Diffusion Barriers on Platinum/Beta-Catalyzed Isomerization of n-Pentane.

We have developed a generalizable strategy to quantify the effect of surface barriers on zeolite catalysis. Isomerization of n-pentane, catalyzed by Pt/Beta, is taken as a model reaction system. Firstly, the surface modification by chemical liquid deposition of SiO2 was carried out to control the surface barriers on zeolite Beta crystals. The deposition of SiO2 leads to a very slight change in the physical properties of Beta crystals, but an obvious reduction in Brønsted acid sites. Diffusion measurements by the zero-length column (ZLC) method show that the apparent diffusivity of n-pentane can be more than doubled after SiO2 deposition, indicating that the surface barriers have been weakened. Catalytic performance was tested in a fixed-bed reactor, showing that the apparent catalytic activity improved by 51-131 % after SiO2 deposition. These results provide direct proof that reducing surface barriers can be an effective route to improve zeolite catalyst performance deteriorated by transport limitations.

Nature-Inspired Chemical Engineering for Process Intensification.

A nature-inspired solution (NIS) methodology is proposed as a systematic platform for innovation and to inform transformative technology required to address Grand Challenges, including sustainable development. Scalability, efficiency, and resilience are essential to nature, as they are to engineering processes. They are achieved through underpinning fundamental mechanisms, which are grouped as recurring themes in the NIS approach: hierarchical transport networks, force balancing, dynamic self-organization, and ecosystem properties. To leverage these universal mechanisms, and incorporate them effectively into engineering design, adaptations may be needed to accommodate the different contexts of nature and engineering applications. Nature-inspired chemical engineering takes advantage of the NIS methodology for process intensification, as demonstrated here in fluidization, catalysis, fuel cell engineering, and membrane separations, where much higher performance is achieved by rigorously employing concepts optimized in nature. The same approach lends itself to other applications, from biomedical engineering to information technology and architecture.

Increased E. coli bio-adsorption resistance of microfiltration membranes, using a bio-inspired approach.

Cells have inherent anti-fouling properties. The mechanisms underpinning these natural properties inform the design of an anti-biosorption coating for a polyethersulfone microfiltration membrane, which includes polydopamine and chitosan layers. This tri-layered membrane is created using quick and easy synthesis method. Its ability to resist bio-adsorption and membrane extracellular polymeric substances (EPS) formation is investigated using the bacterium E. coli (ATCC 11775, 1.5 × 107 CFU/mL). In addition, the proliferative bio-adsorption process is explored on the microfiltration membrane surface, using natural water under static and shaken conditions, while monitoring the bio-adsorption kinetics and EPS dynamic changes. The characterization results show that the modification by polydopamine and chitosan change the membrane surface morphology and increase its hydrophilicity. After 10 min dipping in 5 g/L chitosan solution, the pure water flux of the modified membrane is 5469 ± 30 L/(m2·h) (0.2 bar) and the contact angle decreases to 36.7 ± 1.0°, compared with 9889 ± 23 L/(m2·h) (0.2 bar) and 60.3 ± 1.5° for the unmodified polyethersulfone membrane, respectively. In proliferative bio-adsorption tests, the modified membrane is shown to decrease bio-adsorption by 0.4-2.3 orders of magnitude. However, no antimicrobial function is observed, probably due to the alkaline environment and insufficient functional amino groups. A series of linear and non-linear kinetic models is applied to fit the proliferative bio-adsorption process. The pseudo-second-order model is found to describe the proliferative bio-adsorption process best. Neither total organic carbon (TOC) nor protein is detected on the modified membrane surface. In contrast, on the unmodified PES membrane the ratios of protein/TOC (%), TOC/abundance ((µg/cm2)/CFU (log)) and protein/abundance ((µg/cm2)/CFU(log)) are 10%-16%, 0.17-0.28 and 0.02-0.04, respectively. No significant difference (p > 0.05) is found between static and shaken conditions. All these results point to improved anti-biosorption properties for water treatment applications, encouraging further studies on this membrane.

A Hydrogel-Integrated Culture Device to Interrogate T Cell Activation with Physicochemical Cues.

The recent rise of adoptive T cell therapy (ATCT) as a promising cancer immunotherapy has triggered increased interest in therapeutic T cell bioprocessing. T cell activation is a critical processing step and is known to be modulated by physical parameters, such as substrate stiffness. Nevertheless, relatively little is known about how biophysical factors regulate immune cells, such as T cells. Understanding how T cell activation is modulated by physical and biochemical cues may offer novel methods to control cell behavior for therapeutic cell processing. Inspired by T cell mechanosensitivity, we developed a multiwell, reusable, customizable, two-dimensional (2D) polyacrylamide (PA) hydrogel-integrated culture device to study the physicochemical stimulation of Jurkat T cells. Substrate stiffness and ligand density were tuned by concentrations of the hydrogel cross-linker and antibody in the coating solution, respectively. We cultured Jurkat T cells on 2D hydrogels of different stiffnesses that presented surface-immobilized stimulatory antibodies against CD3 and CD28 and demonstrated that Jurkat T cells stimulated by stiff hydrogels (50.6 ± 15.1 kPa) exhibited significantly higher interleukin-2 (IL-2) secretion, but lower proliferation, than those stimulated by softer hydrogels (7.1 ± 0.4 kPa). In addition, we found that increasing anti-CD3 concentration from 10 to 30 µg/mL led to a significant increase in IL-2 secretion from cells stimulated on 7.1 ± 0.4 and 9.3 ± 2.4 kPa gels. Simultaneous tuning of substrate stiffness and stimulatory ligand density showed that the two parameters synergize (two-way ANOVA interaction effect: p < 0.001) to enhance IL-2 secretion. Our results demonstrate the importance of physical parameters in immune cell stimulation and highlight the potential of designing future immunostimulatory biomaterials that are mechanically tailored to balance stimulatory strength and downstream proliferative capacity of therapeutic T cells.

Rethinking Cancer Immunotherapy by Embracing and Engineering Complexity.

The meteoric rise of cancer immunotherapy in the past decade has led to promising treatments for a number of hard-to-treat malignancies. In particular, adoptive T cell therapy has recently reached a major milestone with two products approved by the US FDA. However, the inherent complexity of cell-based immunotherapies means that their manufacturing time, cost, and controllability limit their effectiveness and geographic reach. One way to address these issues may lie in complementing the dominant, reductionistic mentality in modern medicine with complex systems thinking. In this opinion article, we identify key concepts from complexity theory to address manufacturing challenges in cell-based immunotherapies and raise the possibility of a unifying framework upon which future bioprocessing strategies may be designed.

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.

Understanding the Role of Internal Diffusion Barriers in Pt/Beta Zeolite Catalyzed Isomerization of n-Heptane.

Applications of zeolites in catalysis are plagued by strong diffusion resistance, which results from limitations to molecular transport in micropores, across external crystal surfaces, but also across internal interfaces. The first type of diffusion resistance is well understood, the second is receiving increasing attention, while the diffusion barriers at internal interfaces remain largely unclear. We take Pt/Beta catalyzed isomerization of n-heptane as the model system to explore the role of internal diffusion barriers in zeolite catalysis. The two as-synthesized Pt/Beta catalysts have an identical Pt loading, similar Beta particle size and acidity, but different internal structures. A Pt/Beta crystal with no observable internal interfaces can be 180 % higher in activity and 22 % higher in selectivity than its counterpart with numerous internal interfaces. This can only be attributed to the strong transport barriers across internal interfaces, as supported by directly comparing the apparent diffusivities of the two Beta samples.

Re-designing materials for biomedical applications: from biomimicry to nature-inspired chemical engineering.

Gathering inspiration from nature for the design of new materials, products and processes is a topic gaining rapid interest among scientists and engineers. In this review, we introduce the concept of nature-inspired chemical engineering (NICE). We critically examine how this approach offers advantages over straightforward biomimicry and distinguishes itself from bio-integrated design, as a systematic methodology to present innovative solutions to challenging problems. The scope of application of the nature-inspired approach is demonstrated via examples from the field of biomedicine, where much of the inspiration is still more narrowly focused on imitation or bio-integration. We conclude with an outlook on prospective future applications, offered by the more systematic and mechanistically based NICE approach, complemented by rapid progress in manufacturing, computation and robotics. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology'.

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.

Confinement Facilitated Protein Stabilization As Investigated by Small-Angle Neutron Scattering.

While mesoporous silicas have been shown to be a compelling candidate for drug delivery and the implementation of biotechnological applications requiring protein confinement and immobilization, the understanding of protein behavior upon physical adsorption into silica pores is limited. Many indirect methods are available to assess general adsorbed protein stability, such as Fourier-transform infrared spectroscopy and activity assays. However, the limitation of these methods is that spatial protein arrangement within the pores cannot be assessed. Mesoporous silicas pose a distinct challenge to direct methods, such as transmission electron microscopy, which lacks the contrast and resolution required to adequately observe immobilized protein structure, and nuclear magnetic resonance, which is computationally intensive and requires knowledge of the primary structure a priori. Small-angle neutron scattering can surmount these limitations and observe spatial protein arrangement within pores. Hereby, we observe the stabilization of fluid-like protein arrangement, facilitated by geometry-dependent crowding effects in cylindrical pores of ordered mesoporous silica, SBA-15. Stabilization is induced from a fluid-like structure factor, which is observed for samples at maximum protein loading in SBA-15 with pore diameters of 6.4 and 8.1 nm. Application of this effect for prevention of irreversible aggregation in high concentration environments is proposed.

Polymer-Magnetic Composite Fibers for Remote-Controlled Drug Release.

An efficient method is reported, for the fabrication of composite microfibers that can be magnetically actuated and are biocompatible, targeting controlled drug release. Aqueous solutions of polyvinyl alcohol, incorporated with citric acid-coated Fe3O4 magnetic nanoparticles (MNPs), are subject to infusion gyration to generate 100-300 nm diameter composite fibers, with controllable MNP loading. The fibers are stable in polar solvents, such as ethanol, and do not show any leaching of MNPs for over 4 weeks. Using acetaminophen as an example, we demonstrate that this material is effective in immobilization and triggered release of drugs, which is achieved by a moving external magnetic field. The remote actuation ability, coupled with biocompatibility and lightweight property, renders enormous potential for these fibers to be used as a smart drug release agent.