Anodic Alumina Membranes Research Articles

Continuously tunable negative pressure for engineering high-symmetry nanocrystalline phases

In this work, the phenomenon of strain induced by a mismatch in thermal expansion coefficients between a thin film and its substrate is harnessed in a new context, replacing the canonical planar support with a three-dimensional (3-D), nanoconfining scaffold in which we embed a material of interest. In this manner, we demonstrate a general approach to exert a continuously tunable, triaxial, tensile strain, defying the Poisson ratio of the embedded material and achieving the exotic condition of "negative pressure." This approach is hypothetically generalizable to materials of low modulus and high thermal expansion coefficient, and we use it here to achieve negative pressure in perovskite-phase CsPbI3 embedded within the cylindrical pores of anodic aluminum oxide membranes. Through controlled thermal hysteresis, the perovskite crystal structure can be continuously tuned toward higher symmetry when confined in a scaffold with pore size <40 nm, in contrast with the symmetry-reducing action of any other mechanical perturbation. We use this effect to control the octahedral rotation angle that is critical to the remarkable photovoltaic attributes of halide perovskites. Under hundreds of megapascals of apparent negative pressure, the bandgap tunability is observed to follow the same quantitative trend observed for hydrostatic positive pressure, exploring the negative pressure region and demonstrating the relative dominance of bond stretching effects over average octahedral rotation angle on electronic structure. This study reveals and quantifies the structural and electronic consequences of 3D tensile strain present by design and provides a framework for understanding adventitious strain present in all nanocomposite materials.

Illuminating Biomimetic Nanochannels: Unveiling Macroscopic Anticounterfeiting and Photoswitchable Ion Conductivity via Polymer Tailoring.

Artificial photomodulated channels represent a significant advancement toward practical photogated systems because of their remote noncontact stimulation. Ion transport behaviors in artificial photomodulated channels, however, still require further investigation, especially in multiple nanochannels that closely resemble biological structures. Herein, we present the design and development of photoswitchable ion nanochannels inspired by natural channelrhodopsins (ChRs), utilizing photoresponsive polymers grafted anodic aluminum oxide (AAO) membranes. Our approach integrates spiropyran (SP) as photoresponsive molecules into nanochannels through surface-initiated atom transfer radical polymerization (SI-ATRP), creating a responsive system that modulates ionic conductivity and hydrophilicity in response to light stimuli. A key design feature is the reversible ring-opening photoisomerization of spiropyran groups under UV irradiation. This transformation, observable at the molecular level and macroscopically, allows the surface inside the nanochannels to switch between hydrophobic and hydrophilic states, thus efficiently modulating ion transport via changing water wetting behaviors. The patternable and erasable polySP-grafted AAO, based on a controllable and reversible photochromic effect, also shows potential applications in anticounterfeiting. This study pioneers achieving macroscopic anticounterfeiting and photoinduced photoswitching through reversible surface chemistry and expands the application of polymer-grafted structures in multiple nanochannels.

Pinhole small-angle neutron scattering based approach for desmearing slit ultra-small-angle neutron scattering data.

Presented here is an effective approach to desmearing slit ultra-small-angle neutron scattering (USANS) data, based on complementary small-angle neutron scattering (SANS) measurements, leading to a seamless merging of these data sets. The study focuses on the methodological aspects of desmearing USANS data, which can then be presented in the conventional manner of SANS, enabling a broader pool of data analysis methods. The key innovation lies in the use of smeared SANS data for extrapolating slit USANS, offering a self-consistent integrand function for desmearing with Lake's iterative method. The proposed approach is validated through experimental data on porous anodized aluminium oxide membranes, showcasing its applicability and benefits. The findings emphasize the importance of accurate desmearing for merging USANS and SANS data in the crossover q region, which is particularly crucial for complex scattering patterns.

Effects of Heat Treatment on Anodic Porous Alumina Membranes for Mass Spectrometry

Abstract Desorption ionization using through-hole alumina membrane (DIUTHAME) method is a mass spectrometry imaging (MSI) method that uses an anodic porous alumina membrane (APAM) with an array of submicron-sized through-holes as a surface-assisted laser desorption/ionization (SALDI) substrate. The DIUTHAME method is particularly promising for MSI because it does not generate interfering peaks in the low-molecular-weight region. However, the SALDI effect cannot be obtained if the nanostructures of the substrate are destroyed owing to laser irradiation before sample vaporization. APAMs that maintain their structures after irradiation with a high-intensity laser must be fabricated to realize highly sensitive measurements. In this study, we investigated the role of heat treatment suppressing the laser irradiation induced fracture of APAMs. We found that heat treatment at higher temperatures more effectively suppressed APAM fracture associated with laser irradiation. This result was attributed to the reduction of anion-derived impurities in APAMs upon heat treatment. The resulting heat-treated APAM is expected to serve as a substrate for highly sensitive and robust MSI.

Structurally Defined Amphiphilic AAO Membranes Using UV-Assisted Thiol-Yne Chemistry: Applications in Anti-Counterfeiting and Electronics.

In this study, we fabricate and characterize amphiphilic anodic aluminum oxide (AAO) membranes using UV-triggered thiol-yne click reactions and photomasks for various innovative applications, including driven polymer nanopatterns, anti-counterfeiting, and conductive pathways. Specifically, we synthesize 10-undecynyl-terminated-AAO membranes and subsequently prepare amphiphilic AAO membranes with superhydrophilic and superhydrophobic regions. Various analytical methods, including grazing angle X-ray photoelectron spectroscopy (GIXPS), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), nanofocused synchrotron X-ray techniques (nano-XRD and nano-XRF), and water contact angle measurements, confirm the modifications and distinct properties of the modified areas. This work achieves a series of applications, such as driven polymer nanopatterns, solvent- and light-triggered anti-counterfeiting, and region-selective conductive pathways using silver paint with lower resistivity. Besides, the amphiphilic AAO membrane exhibits successful stability, durability, and reusability. To sum up, this study highlights the versatility and potential of amphiphilic AAO membranes in advanced material design and smart applications.

Nanofluidic ion-exchange membranes: Can their conductance compete with polymeric ion-exchange membranes?

Nanofluidic membranes (NFMs) are gaining prominence as alternative ion-exchange membranes, because of their distinct selectivity mechanism, which does not rely on functional groups on a polymeric backbone but rather on charged nanopores that allow straight ion-conductive pathways for efficient ion transport. We measured the conductivity of commercial anodized aluminum oxide membranes with different pore sizes under different current densities and electrolyte concentrations. We also simulated a nanopore channel with charged walls between two electrolyte reservoirs. Our findings indicate that electrolyte concentration is the main parameter that determines NFM conductivity, with a linear dependence at least up to 1 M. Our study shows that the optimal pore length is between 0.5 and 5 μm considering the trade-off between selectivity and conductance. On the other hand, the conductance is not sensitive to the pore diameter. Conical nanopores are a way to increase conductance, but according to our results, this increase comes at the expense of selectivity. Our findings suggest that NFMs can outperform polymeric ion-exchange membranes in certain electrochemical applications, such as reverse electrodialysis, but not in applications that use low electrolyte concentrations on both sides of the membrane.

(Invited) The Influence of Magnetic Fields on the Oxygen Evolution Reaction Catalyzed By Cobalt-Iron Oxide Nanowire Arrays

To mitigate climate change through the establishment of a renewable energy infrastructure, advancements in energy storage technologies are imperative. Electrochemical water splitting via electrolyzers enables the conversion of electrical energy into chemical energy. However, the performance of these devices, particularly that of the oxygen evolution reaction (OER) occurring at the anode, still needs to be improved. Previous studies have demonstrated that magnetic fields can induce convective flow to the electrode through Lorentz and Kelvin force effects, thereby improving the mass transport.[1] In contrast to the Lorentz force, the Kelvin force can be substantially increased by introducing magnetic nanostructures to create high magnetic field gradients in the vicinity of the electrode surface.[2] Given the magnetic properties inherent to many earth-abundant metal-based and nanostructured electrocatalysts promising for the OER, there is potential for intelligently designing electrodes to leverage magnetic field effects in the future. However, a comprehensive understanding of these magnetic field effects is currently lacking. In the scope of this work, we aimed to systematically investigate the influence of magnetic fields on the oxygen evolution reaction. Considering the substantial magnetic field gradients generated by magnetic nanowires, we fabricated arrays of freestanding cobalt-iron oxide nanowires to explore the influence of magnetic fields on the oxygen evolution reaction catalyzed by these nanostructured electrocatalysts. Templated electrodeposition of cobalt-iron alloy into the pores of anodic aluminum oxide membranes enabled a straightforward control over nanowire diameter and length. Subsequent removal of the aluminum oxide template in alkaline solution yielded cobalt-iron oxide nanowires composed to 60% of Fe and 40% of Co standing freely on an electrochemically stable gold substrate. Superimposing a magnetic field during water oxidation on the so-prepared nanowire arrays resulted in an increase in the measured oxidation current (see Figure). To deconvolute the contributions of the Lorentz and Kelvin force, experiments were conducted in two different magnetic field orientations: either parallel or perpendicular to the electrode surface. In the parallel orientation, a linear correlation between the increase in current and the strength of the applied magnetic field was observed. In contrast, when the magnetic field was aligned perpendicular to the electrode surface, a plateau in the current enhancement manifested at higher magnetic field strengths, indicating different dominant effects in the two configurations.[1] K. Ngamchuea, K. Tschulik, R. G. Compton, Magnetic control: Switchable ultrahigh magnetic gradients at Fe3O4 nanoparticles to enhance solution-phase mass transport, Nano Res. 2015, 8, 3293–3306.[2] L. M. Monzon, J. Coey, Magnetic fields in electrochemistry: The Kelvin force. A mini-review, Electrochem. commun. 2014, 42, 42–45. Figure 1

(Invited) Engineering of Nanostructured Aluminum-Based and Polymer-Based Platforms for SERS Sensing

There has been great hope for ultrasensitive detection methods with the application of Surface Enhanced Raman Spectroscopy (SERS) because of its impressive advancements. Nevertheless, a major challenge is the creation of large-scale, controllable, and reproducible substrates with high SERS activity [1]. As a basis for SERS detection, we report here the fabrication of different types of aluminum-based and polymer-based SERS platforms with the synthesis of gold nanoparticle (AuNP) arrays on them. The tunability of the AuNPs size and distribution is achieved by methodically controlling the aluminum substrates nanostructuration and the subsequent processes for the synthesis of the AuNP. This research presents a scalable and dependable approach for creating ordered Au patterns on nanostructured aluminum and polymer substrates.For both aluminum-based and polymer-based platforms, the initial formation of nanoporous anodic alumina (NAA) on an aluminum substrate by electrochemical anodization [2] is essential. The electrolytes used (sulphuric, oxalic, or phosphoric acid) and its respective concentration determines the ideal voltage for anodization and the electrolyte temperature [3,4]. The formed NAA layer is chemically removed obtaining a nanostructured aluminum substrate with a hexagonally ordered distribution of nanoconcavities [5,6]. The distance between nanocavities ranges from tens to hundreds of nanometers depending on the electrolyte used [7]. The polymer-based nanostructured substrates are formed with the deposition of the selected polymer on the obtained aluminum nanoconcavities substrates and peeled off when dried. Instead of nanoconcavities, it presents a distribution of nanosemispheres that corresponds to the imprinting of the aluminum nanoconcavities on the polymer.The final SERS platforms are obtained with the gold sputtering on the nanoconcavities aluminum substrates and the polymer substrates, followed by a thermal annealing process [8]. The result is a scalable, ordered and controlled distribution of AuNPs on the nanostructured substrates (Fig. 1). An evaluation of the sputtering time and the thermal annealing paramenters (time and temperature) is presented. Over a large surface area of several square centimeters, the AuNPs size, shape, and interparticle spacing may be controlled by using the flexible manufacturing method discussed in this work.All these AuNPs nanostructured platforms have shown high and interesting amplifications of the Raman signal demonstrating its suitability for SERS detection of several molecules like 4-Mercaptopyridine, rhodamine, streptavidine, melamine, etc. Acknowledgments This work was supported by the Spanish Ministerio de Ciencia e Innovación (MICINN/FEDER) PDI2021-128342OB-I00, by the Agency for Management of University and Research Grants (AGAUR) ref. 2021-SGR-00739 and by the Catalan Institution for Research and Advanced Studies (ICREA) under the ICREA Academia Award. Has also received funding from the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No. 945413. References Di Anibal, Carolina V., Lluís F. Marsal, M. Pilar Callao, and Itziar Ruisánchez. "Surface Enhanced Raman Spectroscopy (SERS) and multivariate analysis as a screening tool for detecting Sudan I dye in culinary spices." Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy87 (2012): 135-141.Macias, Gerard, Laura P. Hernández-Eguía, Josep Ferré-Borrull, Josep Pallares, and Lluís F. Marsal. "Gold-coated ordered nanoporous anodic alumina bilayers for future label-free interferometric biosensors." ACS applied materials & interfaces5, no. 16 (2013): 8093-8098.Kumeria, Tushar, Abel Santos, Mohammad Mahbubur Rahman, Josep Ferré-Borrull, Lluís F. Marsal, and Dusan Losic. "Advanced structural engineering of nanoporous photonic structures: Tailoring nanopore architecture to enhance sensing properties." Acs Photonics1, no. 12 (2014): 1298-1306.Santos, Abel, Josep M. Montero-Moreno, Julien Bachmann, Kornelius Nielsch, Pilar Formentín, Josep Ferré-Borrull, Josep Pallares, and Lluís F. Marsal. "Understanding pore rearrangement during mild to hard transition in bilayered porous anodic alumina membranes." ACS applied materials & interfaces3, no. 6 (2011): 1925-1932.Hernández-Eguía, Laura P., Josep Ferré-Borrull, Gerard Macias, Josep Pallarès, and Lluís F. Marsal. "Engineering optical properties of gold-coated nanoporous anodic alumina for biosensing." Nanoscale Research Letters9 (2014): 1-8.Palacios, R., P. Formentín, J. Ferré‐Borrull, J. Pallarés, and L. F. Marsal. "Polymer nanopillars using self‐ordered nanoporous alumina templates." physica status solidi c6, no. 7 (2009): 1584-1586.Vojkuvka, Lukas, Lluís F. Marsal, Josep Ferré-Borrull, Trifon Trifonov, and Josep Pallarés. "Fabrication of self-ordered nanoporous alumina for optical and structural characterization." Contributions to science4, no. 2 (2008): 219-222.Dar, Gohar Ijaz, Elisabet Xifre‐Perez, and Lluis F. Marsal. "Fabrication of Au‐Decorated Al Nanoconcavities Platform for Augmented SERS." Advanced Materials Interfaces(2023): 2300560. Figure 1

Synaptic Response of Fluidic Nanopores: The Connection of Potentiation with Hysteresis.

Iontronic fluidic ionic/electronic components are emerging as promising elements for artificial brain-like computation systems. Nanopore ionic rectifiers can be operated as a synapse element, exhibiting conductance modulation in response to a train of voltage impulses, thus producing programmable resistive states. We propose a model that replicates hysteresis, rectification, and time domain response properties, based on conductance modulation between two conducting modes and a relaxation time of the state variable. We show that the kinetic effects observed in hysteresis loops govern the potentiation phenomena related to conductivity modulation. To illustrate the efficacy of the model, we apply it to replicate rectification, hysteresis and conductance modulation of two different experimental systems: a polymer membrane with conical pores, and a blind-hole nanoporous anodic alumina membrane with a barrier oxide layer. We show that the time transient analysis of the model develops the observed potentiation and depression phenomena of the synaptic properties.

Mesoporous silica modified alumina improves pressure stability of supported ionic liquid membranes

Supported liquid membranes (including those containing ionic liquids) offer the opportunity for high selectivity for a target gas imparted by the properties of the functional liquid or liquid mixture, along with high flux resulting from gas permeation through a liquid rather than a solid. One disadvantage of supported liquid membranes is limitations on the transmembrane pressure (TMP) they can sustain. Liquids held in the pores of the support by capillary forces are prone to “blow-out” at relatively modest TMP values. Here, we modify anodic aluminum oxide (AAO) membranes with uniformly sized ∼6–8 nm diameter cylindrical silica mesopores to improve the blow-out TMP. This modification increases the feasible TMP for various ionic liquids from ∼4 bar to more than ∼20 bar. Additionally, the liquid in the membrane at depths where the AAO membrane has not been modified (i.e., greater than a few microns) is expelled from the large pores, reducing the effective thickness of the liquid in the membrane and increasing permeance. This approach is analogous to asymmetric polymeric membranes, which are the standard of the commercial membrane industry. These findings open up the opportunity for investigation and use of supported liquid membranes at much higher TMPs than has been previously possible.

Closed Bipolar Nanoelectrode Array for Ultra-Sensitive Detection of Alkaline Phosphatase and Two-Dimensional Imaging of Epidermal Growth Factor Receptors.

The combination of closed bipolar electrodes (cBPE) with electrochemiluminescence (ECL) imaging has demonstrated remarkable capabilities in the field of bioanalysis. Here, we established a cBPE-ECL platform for ultrasensitive detection of alkaline phosphatase (ALP) and two-dimensional imaging of epidermal growth factor receptor (EGFR). This cBPE-ECL system consists of a high-density gold nanowire array in anodic aluminum oxide (AAO) membrane as the cBPE coupled with ECL of highly luminescent cadmium selenide quantum dots (CdSe QDs) luminophores to achieve cathodic electro-optical conversion. When an enzyme-catalyzed amplification effect of ALP with 4-aminophenyl phosphate monosodium salt hydrate (p-APP) as the substrate and 4-aminophenol (p-AP) as the electroactive probe is introduced, a significant improvement of sensing sensitivity with a detection limit as low as 0.5 fM for ALP on the cBPE-ECL platform can be obtained. In addition, the cBPE-ECL sensing system can also be used to detect cancer cells with an impressive detection limit of 50 cells/mL by labeling ALP onto the EGFR protein on A431 human epidermal cancer cell membranes. Thus, two-dimensional (2D) imaging of the EGFR proteins on the cell surface can be achieved, demonstrating that the established cBPE-ECL sensing system is of high resolution for spatiotemporal cell imaging.

Thermally-driven electrokinetic power generation system utilizing microporous NiO wicks and nanoporous AAO membranes for low-grade heat harvesting

Low-grade heat (T<100 ℃) exists ubiquitously in the environment, but it is difficult to harvest and utilize due to existing technology’s limitations. It would be significant to harvest this kind of energy through effective acquisition techniques. Here, we propose a micro/nano porous membranes low-grade heat harvesting system based on the thermoelectric effect, which uses the temperature gradient to induce the separation and transmission of electrolyte solution ions in the porous membrane to convert low-grade thermal energy into electrical energy. Two power generation materials of microporous nickel oxide (NiO) wicks and nanoporous anodic aluminum oxide (AAO) membranes were investigated experimentally. In the porous NiO wick experiment, it is observed that the wick significantly improves the thermoelectric conversion performance. In particular, when the temperature difference is 50 ℃, the open circuit voltage of the system reaches 215 mV, which is about 300 % higher than the case without the porous NiO wick. In addition, in the AAO porous membranes experiment, we found that at the low concentration, by collecting ambient heat with a temperature difference of 5 ℃, the system obtained the output power of about 6 nW, which improved the 2 ∼ 3 orders of magnitude compared with the previous research reports. This work offers a promising method for developing high-performance and low-cost low-grade heat harvesting systems.

A Rapid, Efficient Method for Anodic Aluminum Oxide Membrane Room-Temperature Multi-Detachment from Commercial 1050 Aluminum Alloy.

For commercial processes, through-hole AAO membranes are fabricated from high-purity aluminum by chemical etching. However, this method has the disadvantages of using heavy-metal solutions, creating large amounts of material waste, and leading to an irregular pore structure. Through-hole porous alumina membrane fabrication has been widely investigated due to applications in filters, nanomaterial synthesis, and surface-enhanced Raman scattering. There are several means to obtain freestanding through-hole AAO membranes, but a fast, low-cost, and repetitive process to create complete, high-quality membranes has not yet been established. Here, we propose a rapid and efficient method for the multi-detachment of an AAO membrane at room temperature by integrating the one-time potentiostatic (OTP) method and two-step electrochemical polishing. Economical commercial AA1050 was used instead of traditional high-cost high-purity aluminum for AAO membrane fabrication at 25 °C. The OTP method, which is a single-step process, was applied to achieve a high-quality membrane with unimodal pore distribution and diameters between 35 and 40 nm, maintaining a high consistency over five repetitions. To repeatedly detach the AAO membrane, two-step electrochemical polishing was developed to minimize damage on the AA1050 substrate caused by membrane separation. The mechanism for creating AAO membranes using the OTP method can be divided into three major components, including the Joule heating effect, the dissolution of the barrier layer, and stress effects. The stress is attributed to two factors: bubble formation and the difference in the coefficient of thermal expansion between the AAO membrane and the Al substrate. This highly efficient AAO membrane detachment method will facilitate the rapid production and applications of AAO films.

Flexible plasmonic display featuring differentiated and localized control over transmission and reflection

Structural colors using metal materials, plasmonic color generation, can confine optical excitation beyond the diffraction limit owing to nanoscale metals with high efficiency in light absorption and scattering. They have several advantages over conventional display technology, including superior resolution and long-term preservation. However, most research on plasmonic color generation has been conducted for the development of static color generation, and dynamic tuning remains a challenging issue. To develop dynamic plasmonic colors, electrochemical, liquid crystal, and electromechanical methods have been proposed; however, there have been limitations in repeatability, flexibility, and scale-up processes. To address these problems, this work proposes a flexible dynamic plasmonic display using dielectric elastomer actuators (DEAs) to isotropically control the interdistance between the metal nanostructures, which can show dynamic coloration without polarization distortion. To replace the expensive and small-scale manufacturing approach, shadow masking and transfer technique with the anodic aluminum oxide (AAO) membrane was applied to realize large-scale and uniformly distributed Au nanodisc array. The differentiated and localized color change in the transmission and reflection modes, such as Janus's face, is realized by proper design of Au nanodisc array on the patterned transparent compliant electrodes formed by silver nanowires and PEDOT:PSS composites. Apparent and locally active color changes appeared in the transmission mode, but almost no color changes were observed in the reflection model by DEA actuation. The proposed system has the potential to activate color filters, cryptographic characters, and next generation display technologies.

Advancing Nanopore Technology: Anodic Aluminum Oxide Membranes with Anisotropic Pores through Controlled Stretching for Applications in Nanopatterning

Advancing Nanopore Technology: Anodic Aluminum Oxide Membranes with Anisotropic Pores through Controlled Stretching for Applications in Nanopatterning

Self-Assembly of Ionic Superdiscs in Nanopores.

Discotic ionic liquid crystals (DILCs) consist of self-assembled superdiscs of cations and anions that spontaneously stack in linear columns with high one-dimensional ionic and electronic charge mobility, making them prominent model systems for functional soft matter. Compared to classical nonionic discotic liquid crystals, many liquid crystalline structures with a combination of electronic and ionic conductivity have been reported, which are of interest for separation membranes, artificial ion/proton conducting membranes, and optoelectronics. Unfortunately, a homogeneous alignment of the DILCs on the macroscale is often not achievable, which significantly limits the applicability of DILCs. Infiltration into nanoporous solid scaffolds can, in principle, overcome this drawback. However, due to the experimental challenges to scrutinize liquid crystalline order in extreme spatial confinement, little is known about the structures of DILCs in nanopores. Here, we present temperature-dependent high-resolution optical birefringence measurement and 3D reciprocal space mapping based on synchrotron X-ray scattering to investigate the thermotropic phase behavior of dopamine-based ionic liquid crystals confined in cylindrical channels of 180 nm diameter in macroscopic anodic aluminum oxide membranes. As a function of the membranes' hydrophilicity and thus the molecular anchoring to the pore walls (edge-on or face-on) and the variation of the hydrophilic-hydrophobic balance between the aromatic cores and the alkyl side chain motifs of the superdiscs by tailored chemical synthesis, we find a particularly rich phase behavior, which is not present in the bulk state. It is governed by a complex interplay of liquid crystalline elastic energies (bending and splay deformations), polar interactions, and pure geometric confinement and includes textural transitions between radial and axial alignment of the columns with respect to the long nanochannel axis. Furthermore, confinement-induced continuous order formation is observed in contrast to discontinuous first-order phase transitions, which can be quantitatively described by Landau-de Gennes free energy models for liquid crystalline order transitions in confinement. Our observations suggest that the infiltration of DILCs into nanoporous solids allows tailoring their nanoscale texture and ion channel formation and thus their electrical and optical functionalities over an even wider range than in the bulk state in a homogeneous manner on the centimeter scale as controlled by the monolithic nanoporous scaffolds.

High-performance separation for ultra-low concentration nanoparticles with mesoporous silica thin membrane

Mesoporous silica thin film membrane (MSTF) emerges as an ideal ultrafiltration membrane for the removal of nanoparticles, ensuring the production of particle-free water. This is mainly ascribed to its uniform and narrow pore size distribution, having vertical nanochannels with low tortuosity, and being ultrathin, which helps enhance its selectivity and permeability. In this study, we demonstrated the potential of MSTF overlayed on macroporous anodic aluminum oxide (AAO) support for separating gold nanoparticles even at a very low concentration. Moreover, with the addition of pore-expanding agents, E-MSTF⊥AAO (pore size 3.12 nm) and D-MSTF⊥AAO (pore size 5.26 nm) membranes are formed, and both membranes indeed showed high rejection efficiency towards 150 ppb gold nanoparticles of sizes 10 nm and 5 nm, ∼99 %, and ∼96 %, respectively. It is also worth noting that as compared to the state-of-the-art conventional UF membranes, the E-MSTF⊥AAO membrane showed significantly high permeance of 114.1 ± 12.76 L m−2 h−1 bar−1 and 104.1 ± 50.6 L m−2 h−1 bar−1 while efficiently separating 150 ppb and 50 ppb 5 nm gold nanoparticles, respectively. Moreover, the promising long-term stability and chemical stability of the MSTF⊥AAO membrane paved a promising path for applying mesoporous silica membranes for effective nanoparticle separation in wastewater treatment and particle-free water production in industries.

In-situ growth of Cs5Cu3Cl6I2 nanocrystals within AAO arrays for X-ray imaging

Lead-free halide perovskites have shown promising application for indirect X-ray detection as fascinating scintillator. The fabrication of pixelated scintillator films leveraging directional confinement allows high-resolution imaging, yet process complexity and the potential crystal structure damage pose challenges that compromises the corresponding scintillator performance. In this work, a facile in-situ strategy for growing scintillation perovskite of Cs5Cu3Cl6I2 within anodic aluminum oxide (AAO) membrane is developed as scintillator Cs5Cu3Cl6I2@AAO film. The as-fabricated pixelated scintillator array with an enhanced light directional confinement for high-resolution X-ray imaging is demonstrated. The corresponding film achieves a spatial resolution of approximately 20 lp mm−1 and a detection limit of 0.152 Gy·s−1. Moreover, the Cs5Cu3Cl6I2@AAO film performs excellent stability under long-term X-ray irradiation, making it a reliable option for cost-effective pixelated indirect X-ray imaging.

Surface Modification of Nanopores in an Anodic Aluminum Oxide Membrane through Dopamine-Assisted Codeposition with a Zwitterionic Polymer.

Surface modification through dopamine-assisted codeposition with functional zwitterionic polymers can provide a simple and one-step functionalization under ambient conditions with robust and stable dopamine-surface interactions to improve the hydrophilicity of nanoporous membranes, thereby expanding their applicability to nanofiltration, ion transport, and blood purification. However, a significant knowledge gap remains in our comprehension of the mechanisms underlying the formation and deposition of dopamine/polymer aggregated coatings within nanoscale confinement. This study explores a feasible method for membrane modification through the codeposition of dopamine hydrochloride (DA) and poly(sulfobetaine methacrylate) (PSBMA) on nanopores of anodic aluminum oxide (AAO) membranes. Our findings demonstrate that the aggregated coatings of DA and PSBMA nanocomposites can effectively deposit on the surfaces within cylindrical AAO nanopores, significantly enhancing the hydrophilicity of the nanoporous membranes. The morphology and homogeneity of the nanocomposite coatings within the nanopores are further investigated by varying PSBMA molecular weights and AAO pore sizes, revealing that higher molecular weights result in more uniform deposition. This work sheds light on understanding the codeposition of DA and zwitterionic polymers in nanoscale environments, highlighting a straightforward and stable surface modification process of nanoporous membranes involving functional polymers.

Quantum Griffiths Singularity in Ordered Artificial Superconducting-Islands-Array on Graphene.

Quantum Griffiths phase (QGP) is a novel quantum phenomenon of quantum phase transition in two-dimensional (2D) superconductors, and the emergence of inhomogeneous superconducting rare regions immersed in a metallic matrix is theoretically related to the quantum Griffiths singularity (QGS). However, the theoretical proposal of superconducting rare regions still lacks intuitive experimental verification. Here, we construct an artificial ordered superconducting-islands-array on monolayer graphene with the aid of an anodic aluminum oxide (AAO) membrane. The QGS under both in-plane and out-of-plane magnetic fields is evidenced by the divergent dynamical critical exponent and is in compliance with the direct activated scaling behavior. The phase diagram clearly shows that the QGP is indeed bred in the rare superconducting regions within isolated superconducting islands with a vanished quantum coherence. Our results reveal the universal features of QGP in artificial heterostructured systems and provide a visualized platform for the theoretical proposal of QGS.