High Oxygen Reduction Efficiency and Durability of Nano-Honeycomb Pt3(NiFeCo) Replenished by High-Entropy Metallic Glass Support.

Developing low-Pt oxygen reduction reaction (ORR) catalysts with high efficiency and robustness is critical for practical fuel cells. The most advanced ORR catalysts either feature high percentages of Pt (>70 at.%) or exhibit poor durability when reducing Pt loading. Herein, a multicomponent solid-solution Pt3(FeCoNi) honeycomb nano-framework supported by the specially designed high-entropy metallic glass (MG) is reported for efficient ORR. This hybrid catalyst with a low surface Pt loading of 5.79 µg cm-2 displays exceptional mass and specific activities of 7.02 A mgpt -1 and 8.15 mA cmPt -2 at 0.9 V, respectively, which are ≈15 and 22 times higher compared with commercial Pt/C. The analyses reveal the weakened chemisorption of oxygenated species, which is induced by the strong strain and ligand effects originating from the synergistic multicomponent alloying. This in turn enhances the intrinsic ORR activity. Moreover, benefiting from a unique replenishment behavior, the hybrid catalyst delivers ultra-high durability with negligible activity decay even after 50 000 potential cycles. This mechanism is achieved by sacrificing the interior MG supplementary support to dynamically compensate for the loss of catalytically active surface. The work provides an alternative way to design more efficient and durable low-Pt electrocatalysts for electrochemical devices.

Adhesion and morphology of mammalian cells on nanoporous and nonporous spherical carbon substrates.

Three spherical activated carbons (SACs) were used as substrates for mammalian cell proliferation. SACs were obtained by carbonizing styrene-co-divinylbenzene ion exchangers 35WET, XAD4, or 1200H. The new materials (XAD_C, WET_C, and H_C) were characterized by adsorption-desorption nitrogen isotherms and mercury intrusion porosimetry. XAD_C and WET_C exhibited well-developed BET surface areas, similar total pore volumes, and highly different pore size distributions. H_C was nonporous spherical material-reference material. The XAD_C was meso-macroporous, but the WET_C was micro-mesoporous. All SACs were not cytotoxic toward Leydig TM3 cells. The differences in porous structure and morphology of the carbon scaffolds led to morphological differences in adhered cells. The monolayer of cells was distributed flat over the entire WET_C and H_C surfaces. Leydig TM3 cells adhered to nonporous SAC but were easily washed out due to weak adhesion. The cells adhered in clusters to XAD_C and proliferated in clusters. As microscopic techniques and viability tests demonstrated, only nanoporous carbons provided a good surface for the attachment and proliferation of eukaryotic cells.

Decoding the nanoscale porosity in serpentinites from multidimensional electron microscopy and discrete element modelling.

Serpentinites, widespread in Earth's lithosphere, exhibit inherent nanoporosity that may significantly impact their geochemical behaviour. This study provides a comprehensive investigation into the characteristics, scale dependence, and potential implications of nanoporosity in lizardite-dominated serpentinites. Through a combination of multidimensional imaging techniques and molecular-dynamics-based discrete element modelling, we reveal that serpentinites function as nanoporous media with pore sizes predominantly less than 100 nm. Crystallographic relationships between olivine, serpentine, and nanoporosity are explored, indicating a lack of significant correlations. Instead, stochastic growth and random packing of serpentine grains within mesh cores may result in interconnected porosity. The analysis of pore morphology suggests that the irregular pore shapes align with the crystal form of serpentine minerals. Furthermore, the nanoporosity within brucite-rich layers at the serpentine-olivine interface is attributed to delamination along weak van der Waals planes, while pore formation within larger brucite domains likely results from low-temperature alteration processes. The fractal nature of the pore size distribution and the potential interconnectivity of porosity across different scales further support the presence of a pervasive nanoporous network within serpentinites. Confinement within these nanopores may introduce unique emergent properties, potentially influencing fluid transport, mineral solubility, and chemical reactions. As such, these processes may have profound implications for the geochemical evolution of serpentinites.

Chemical Imaging of Hierarchical Porosity Formation within a Zeolite Crystal Visualized by Small-Angle X-Ray Scattering and In-Situ Fluorescence Microscopy.

Introducing hierarchical porosity to zeolites is vital for providing molecular access to microporous domains. Yet, the dynamics of meso- and macropore formation has remained elusive and pore space ill-characterized by a lack of (in situ) microscopic tools sensitive to nanoporosity. Here, we probe hierarchical porosity formation within a zeolite ZSM-5 crystal in real-time by in situ fluorescence microscopy during desilication. In addition, we introduce small-angle X-ray scattering microscopy as novel characterization tool to map intracrystal meso- and macropore properties. It is shown that hierarchical porosity formation initiates at the crystal surface and propagates to the crystal core via a pore front with decreasing rate. Also, hierarchical porosity only establishes in specific (segments of) subunits which constitute ZSM-5. Such space-dependent meso- and macroporosity implies local discrepancies in diffusion, performance and deactivation behaviors even within a zeolite crystal.

Exploring the Porosity in Ceramics at the nm Scale: From Understanding Historical Ceramics to Innovative Materials Design.

Ceramics are complex objects and a rich source of information: they constitute a large part of the staple memory of past and present human activities. A deep understanding of traditional ceramics is an essential key to designing new ceramic materials. The demanding synthesis of ceramics with fine-tuned properties, such as enhanced mechanical, electrical, optical or magnetic characteristics, must be associated with cutting-edge analysis procedures in order to improve the engineering process. In this context, we describe a neutron-based non-destructive approach to investigating the nanoporosity of an historical pottery matrix as an effective investigation technique for exploring both traditional and advanced ceramic materials.

Single-Nanometer Changes in Nanopore Geometry Influence Curvature, Local Properties, and Protein Localization in Membrane Simulations.

Nanoporous surfaces are used in many applications in intracellular sensing and drug delivery. However, the effects of such nanostructures on cell membrane properties are still far from understood. Here, we use coarse-grained molecular dynamics simulations to show that nanoporous substrates can stimulate membrane-curvature effects and that this curvature-sensing effect is much more sensitive than previously thought. We define a series of design parameters for inducing a nanoscale membrane curvature and show that nanopore taper plays a key role in membrane deformation, elucidating a previously unexplored fabrication parameter applicable to many nanostructured biomaterials. We report significant changes in the membrane area per lipid and thickness at regions of curvature. Finally, we demonstrate that regions of the nanopore-induced membrane curvature act as local hotspots for an increased bioactivity. We show spontaneous binding and localization of the epsin N-terminal homology (ENTH) domain to the regions of curvature. Understanding this interplay between the membrane curvature and nanoporosity at the biointerface helps both explain recent biological results and suggests a pathway for developing the next generation of cell-active substrates.

Two-Dimensional Layered Hydroxide Nanoporous Nanohybrids Pillared with Zero-Dimensional Polyoxovanadate Nanoclusters for Enhanced Water Oxidation Catalysis.

The oxygen-evolution reaction (OER) is critical in electrochemical water splitting and requires an efficient, sustainable, and cheap catalyst for successful practical applications. A common development strategy for OER catalysts is to search for facile routes for the synthesis of new catalytic materials with optimized chemical compositions and structures. Here, nickel hydroxide Ni(OH)2 2D nanosheets pillared with 0D polyoxovanadate (POV) nanoclusters as an OER catalyst that can operate in alkaline media are reported. The intercalation of POV nanoclusters into Ni(OH)2 induces the formation of a nanoporous layer-by-layer stacking architecture of 2D Ni(OH)2 nanosheets and 0D POV with a tunable chemical composition. The nanohybrid catalysts remarkably enhance the OER activity of pristine Ni(OH)2 . The present findings demonstrate that the intercalation of 0D POV nanoclusters into Ni(OH)2 is effective for improving water oxidation catalysis and represents a potential method to synthesize novel, porous hydroxide-based nanohybrid materials with superior electrochemical activities.

Residual Silver Remarkably Enhances Electrocatalytic Activity and Durability of Dealloyed Gold Nanosponge Particles.

Percolation dealloying of multimetallic alloys entangles the selective dissolution of the less-noble elements with nanoscale restructuring of the more-noble components, resulting in the formation of spongelike, nanoporous architectures with a unique set of structural characteristics highly desirable for heterogeneous catalysis. Although the dealloyed nanoporous materials are compositionally dominated by the more-noble elements, they inevitably contain residual less-noble elements that cannot be completely removed through the percolation dealloying process. How to employ the less-noble elements to rationally guide the structural evolution and optimize the catalytic performances of the dealloyed noble metal nanocatalysts still remains largely unexplored. Here, we have discovered that incorporation of Ag into Au-Cu binary alloy nanoparticles substantially enhances the Cu leaching kinetics while effectively suppressing the ligament coarsening during the nanoporosity-evolving percolation dealloying of the alloy nanoparticles. The controlled coleaching of Ag and Cu from Au-Ag-Cu ternary alloy nanoparticles provides a unique way to optimize both the surface area-to-mass ratios and specific activities of the dealloyed nanosponge particles for the electrocatalytic oxidation of alcohols. The residual Ag in the fully dealloyed nanosponge particles plays crucial roles in stabilizing the surface active sites and maintaining the nanoporous architectures during the electrocatalytic reactions, thereby greatly enhancing the durability of the electrocatalysts. The insights gained from this work shed light on the underlying roles of residual less-noble elements that are crucial to the rational optimization of electrocatalysis on noble-metal nanostructures.

Macrocyclic weakly coordinating anions.

Herein, the concept of macrocyclic weakly coordinating anions (M-WCAs) is introduced. Synthetic methodologies are described how to access M-WCAs by thermodynamically controlled self-assembly in high yields, in particular through condensation and alkyne metathesis reactions. The anticipated properties and applications of M-WCAs in solid state and in solution are discussed, specifically for gas storage and separation, homogeneous and heterogeneous catalysis, and as liquid and solid electrolytes.

Nanoporous Graphene with Single-Atom Nickel Dopants: An Efficient and Stable Catalyst for Electrochemical Hydrogen Production.

Single-atom nickel dopants anchored to three-dimensional nanoporous graphene can be used as catalysts of the hydrogen evolution reaction (HER) in acidic solutions. In contrast to conventional nickel-based catalysts and graphene, this material shows superior HER catalysis with a low overpotential of approximately 50 mV and a Tafel slope of 45 mV dec(-1) in 0.5 M H2SO4 solution, together with excellent cycling stability. Experimental and theoretical investigations suggest that the unusual catalytic performance of this catalyst is due to sp-d orbital charge transfer between the Ni dopants and the surrounding carbon atoms. The resultant local structure with empty C-Ni hybrid orbitals is catalytically active and electrochemically stable.

Surface Composites Synthesized through the Incorporation of Atomic Layer Deposited AlOx into Nanoporous Fuzzy Tungsten.

The incorporation of energetic helium gaseous species into materials such as tungsten (W) imparts intrinsic surface fragility, yielding fuzzy tungsten. To enhance the robustness of the surface layers, aluminum oxide (AlOx) was deposited by atomic layer deposition into the fuzzy W. The conformally deposited ceramic yields a new class of surface composites. Structural characterization of the fuzzy W-AlOx composites through nanoindentation testing indicated enhanced indentation modulus (Eind) and hardness (Hind) and was modeled through various rules of mixtures approaches. The distribution of AlOx in fuzzy W was explored and a systematic study of the extent of incorporation of the AlOx into the fuzzy W was carried out. The synthesized composites may be utilized for improved structural characteristics, e.g., in reducing crack initiation and fracture.

Direct Observations of Ordered Nanoporosity in Deprotonated 2-(Acetoacetoxy)ethyl Methacrylate (AAEMA-) Polymer: Preliminary Results.

Polymers based on 2-(acetoacetoxy)ethyl methacrylate, charged with iron or sodium, were thermally heated at 150 °C. Both polymers were studied and characterized by SEM, TEM, STEM microscopy and SAEDF techniques. The morphological investigation revealed that, upon heating, both polymers were endowed with microholes, sometimes perfectly ordered, whose dimensions varied from 4-5 nm to approximately 500 nm. In the case of an Fe-containing copolymer, unexpectedly, iron did not fill in the cavities, thus implying that it was "dispersed" in the polymeric matrix. Electronic microdiffraction documented that both polymers exhibited a proto-crystallinity, likely induced by thermal heating.

Slippery lubricant-infused silica nanoparticulate film processing for anti-biofouling applications.

Microbial biofilm build-up in water distribution systems can pose a risk to human health and pipe material integrity. The impact is more devastating in space stations and to astronauts due to the isolation from necessary replacement parts and medical resources. As a result, there is a need for coatings to be implemented onto the inner region of the pipe to minimize the adherence and growth of biofilms. Lubricant-infused surfaces has been one such interesting material for anti-biofouling applications in which their slippery property promotes repellence to many liquids and thus prevents bacterial adherence. Textured and porous films are suitable substrate candidates to infuse and contain the lubricant. However, there is little investigation in utilizing a nanoparticulate thin film as the substrate material for lubricant infusion. A nanoparticulate film has high porosity within the structure which can promote greater lubricant infusion and retention. The implementation as a thin film structure aids to reduce material consumption and cost. In our study, we utilized a well-studied nanoporous thin film fabricated via layer-by-layer assembly of polycations and colloid silica and then calcination for greater stability. The film was further functionalized to promote fluorinated groups and improve affinity with a fluorinated lubricant. The pristine nanoporous film was characterized to determine its morphology, thickness, wettability, and porosity. The lubricant-infused film was then tested for its lubricant layer stability upon various washing conditions and its performance against bacterial biofilm adherence as a result of its slippery property. Overall, the modified silica nanoparticulate thin film demonstrated potential as a base substrate for lubricant-infused surface fabrication that repelled against ambient aqueous solvents and as an anti-biofouling coating that demonstrated low biofilm coverage and colony forming unit values. Further optimization to improve lubricant retention or incorporation of a secondary function can aid in developing better coatings for biofilm mitigation.

Spatio-temporal programming of lyotropic phase transition in nanoporous microfluidic confinements.

HYPOTHESIS: The nanoporous polydimethylsiloxane (PDMS) surfaces of a rectangular microfluidic channel, selectively uptakes water molecules, concentrating the solute molecules in an aqueous phase, that could drive phase transitions. Factors such as surface wettability, channel geometry, the surface-to-volume ratio, and surface topography of the confinements could play a key role in tuning the phase transitions spatio-temporally. EXPERIMENTS: Using a lyotropic chromonic liquid crystal as model biological material, confined within nanoporous microfluidic environments, we study molecular assembly driven by nanoporous substrates. By combining timelapse polarized imaging, quantitative image processing, and a simple mathematical model, we analyze the phase transitions and construct a master diagram capturing the role of surface wettability, channel geometry and embedded topography on programmable lyotropic phase transitions. FINDINGS: Intrinsic PDMS nanoporosity and confinement cross-section, together with the imposed wettability regulate the rate of the N-M phase transition; whereas the microfluidic geometry and embedded topography enable phase transition at targeted locations. We harness the emergent long-range order during N-M transition to actuate elasto-advective transport of embedded micro-cargo, demonstrating particle manipulation concepts governed by tunable phase transitions. Our results present a programmable physical route to material assembly in microfluidic environment, and offer a new paradigm for assembling genetic components, biological cargo, and minimal synthetic cells.

Recent Advancements in the Fabrication of Functional Nanoporous Materials and Their Biomedical Applications.

Functional nanoporous materials are categorized as an important class of nanostructured materials because of their tunable porosity and pore geometry (size, shape, and distribution) and their unique chemical and physical properties as compared with other nanostructures and bulk counterparts. Progress in developing a broad spectrum of nanoporous materials has accelerated their use for extensive applications in catalysis, sensing, separation, and environmental, energy, and biomedical areas. The purpose of this review is to provide recent advances in synthesis strategies for designing ordered or hierarchical nanoporous materials of tunable porosity and complex architectures. Furthermore, we briefly highlight working principles, potential pitfalls, experimental challenges, and limitations associated with nanoporous material fabrication strategies. Finally, we give a forward look at how digitally controlled additive manufacturing may overcome existing obstacles to guide the design and development of next-generation nanoporous materials with predefined properties for industrial manufacturing and applications.

How Fiber Surface Topography Affects Interactions between Cells and Electrospun Scaffolds: A Systematic Review.

Electrospun scaffolds have a 3D fibrous structure that attempts to imitate the extracellular matrix in order to be able to host cells. It has been reported in the literature that controlling fiber surface topography produces varying results regarding cell-scaffold interactions. This review analyzes the relevant literature concerning in vitro studies to provide a better understanding of the effect that controlling fiber surface topography has on cell-scaffold interactions. A systematic approach following PRISMA, GRADE, PICO, and other standard methodological frameworks for systematic reviews was used. Different topographic interventions and their effects on cell-scaffold interactions were analyzed. Results indicate that nanopores and roughness on fiber surfaces seem to improve proliferation and adhesion of cells. The quality of the evidence is different for each studied cell-scaffold interaction, and for each studied morphological attribute. The evidence points to improvements in cell-scaffold interactions on most morphologically complex fiber surfaces. The discussion includes an in-depth evaluation of the indirectness of the evidence, as well as the potentially involved publication bias. Insights and suggestions about dose-dependency relationship, as well as the effect on particular cell and polymer types, are presented. It is concluded that topographical alterations to the fiber surface should be further studied, since results so far are promising.

Two-Photon Laser Microprinting of Highly Ordered Nanoporous Materials Based on Hexagonal Columnar Liquid Crystals.

Nanoporous materials relying on supramolecular liquid crystals (LCs) are excellent candidates for size- and charge-selective membranes. However, whether they can be manufactured using printing technologies remained unexplored so far. In this work, we develop a new approach for the fabrication of ordered nanoporous microstructures based on supramolecular LCs using two-photon laser printing. In particular, we employ photo-cross-linkable hydrogen-bonded complexes, that self-assemble into columnar hexagonal (Colh) mesophases, as the base of our printable photoresist. The presence of photopolymerizable groups in the periphery of the molecules enables the printability using a laser. We demonstrate the conservation of the Colh arrangement and of the adsorptive properties of the materials after laser microprinting, which highlights the potential of the approach for the fabrication of functional nanoporous structures with a defined geometry. This first example of printable Colh LC should open new opportunities for the fabrication of functional porous microdevices with potential application in catalysis, filtration, separation, or molecular recognition.

Ordered Mesoporous Microcapsules from Double Emulsion Confined Block Copolymer Self-Assembly.

Polymeric microcapsules with shells containing homogeneous pores with uniform diameter on the nanometer scale are reported. The mesoporous microcapsules are obtained from confined self-assembly of amphiphilic block copolymers with a selective porogen in the shell of water-in-oil-in-water double emulsion drops. The use of double emulsion drops as a liquid template enables the formation of homogeneous capsules of 100s of microns in diameter, with aqueous cores encapsulated in a shell membrane with a tunable thickness of 100s of nanometers to 10s of microns. Microcapsules with shells that exhibit an ordered gyroidal morphology and three-dimensionally connected mesopores are obtained from the triblock terpolymer poly(isoprene)-block-poly(styrene)-block-poly(4-vinylpyridine) coassembled with pentadecylphenol as a porogen. The bicontinuous shell morphology yields nanoporous paths connecting the inside to the outside of the microcapsule after porogen removal; by contrast, one-dimensional hexagonally packed cylindrical pores, obtained from a traditional diblock copolymer system with parallel alignment to the surface, would block transport through the shell. To enable the mesoporous microcapsules to withstand harsh conditions, such as exposure to organic solvents, without rupture of the shell, we develop a cross-linking method of the nanostructured triblock terpolymer shell after its self-assembly. The microcapsules exhibit pH-responsive permeability to polymeric solutes, demonstrating their potential as a filtration medium for actively tunable macromolecular separation and purification. Furthermore, we report a tunable dual-phase separation method to fabricate microcapsules with hierarchically porous shells that exhibit ordered mesoporous membrane walls within sponge-like micron-sized macropores to further control shell permeability.

Influence of Functional Group Concentration on Hypercrosslinking of Poly(vinylbenzyl chloride) PolyHIPEs: Upgrading Macroporosity with Nanoporosity.

With the aim to study the influence of monomer ratio in poly(high internal phase emulsions) (polyHIPEs) on the polymer network architecture and morphology of poly(vinylbenzyl chloride-co-divinylbenzene-co-styrene) after hypercrosslinking via the internal Friedel-Crafts process, polyHIPEs with 80% overall porosity were prepared at three different initial crosslinking degrees, namely 2, 5, and 10 mol.%. All had typical interconnected cellular morphology, which was not affected by the hypercrosslinking process. Nitrogen adsorption and desorption experiments with BET and t-plot modelling were used for the evaluation of the newly introduced nanoporosity and in combination with elemental analysis for the evaluation of the extent of the hypercrosslinking. It was found that, for all three initial crosslinking degrees, the minimum amount of functional monomer, 4-vinylbenzyl chloride, was approximately 30 mol.%. Hypercrosslinking of polymers with lower concentrations of functional monomer did not result in induction of nanoporosity while the initial crosslinking degree had a much lower impact on the formation of nanoporosity.

Nanoscale Interfacial Smoothing and Dissolution during Unconventional Reservoir Stimulation: Implications for Hydrocarbon Mobilization and Transport.

Hydraulic fracturing of low-permeability rocks significantly enhances hydrocarbon production from unconventional reservoirs. However, fluid transport through low-permeability rocks and the influence of geochemical transformations on pore networks are poorly constrained. Mineral reactivity during interactions with injected water may alter the physical nature of the rock, which may affect hydrocarbon mobility. To assess alterations to the rock, we have previously conducted a hydrothermal experiment that reacted cubed rock samples (1 cm3) with synthetic hydraulic fracturing fluid (HFF) to simulate physicochemical reactivity during hydraulic fracturing. Here, we analyze unreacted and reacted rocks by small-angle neutron scattering and high-pressure mercury intrusion to determine how the pore networks of unconventional reservoir rocks are influenced by the reaction with hydraulic fracturing injectates. Our results suggest that fluid-rock interactions exhibit a two-fold influence on hydrocarbon recovery, promoting both hydrocarbon mobilization and transport. Pore-matrix interfaces smooth via the removal of clay mineral surface asperities, reducing the available surface area for hydrocarbon adsorption by 12-75%. Additionally, HFF-induced dissolution creates new pores with diameters ranging from 800-1400 nm, increasing the permeability of the rocks by a factor of 5-10. These two consequences of mineral dissolution likely act in concert to release hydrocarbons from the host rock and facilitate transport through the rock during unconventional reservoir production.