Size Control Research Articles

Ceramic Thin-Film Composite Membranes with Tunable Subnanometer Poresfor Molecular Sieving By Atomic Layer Deposition

Membranes with tunable, sub-nanometer pores are needed for molecular separations in applications including water treatment, critical mineral extraction, and recycling. Ceramic membranes are a promising alternative to the polymeric membranes typically used in such applications due to their robust operation under harsh chemical conditions. However, current fabrication technologies fail to construct ceramic membranes suitable for selective molecular separations. In this presentation, we describe a ceramic thin film composite (TFC) membrane fabrication method that achieves sub-nm pore size control using atomic layer deposition (ALD) by incorporating a molecular-scale porogen. By co-dosing alkyl alcohols along with the H2O coreactant during Al2O3 ALD, we incorporate alkoxide species in the film which create a continuous network of pores upon calcination. Varying the alkyl alcohol (methanol, ethanol, isopropanol) tunes the pore size. We use Fourier transform infrared absorption spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy to elucidate the surface chemistry and growth during the alcohol-modulated ALD as well as the subsequent pore formation. We evaluate the transport and separations properties of the ALD TFC membranes using a two-chamber diffusion cell with aqueous salt solutions. We measured a remarkable enhancement in the transport of Cl- compared to SO4 2- (8.6 times faster) matching the selectivity of state-of-the-art polymer membranes. We attribute this selectivity to the dehydration of the large divalent ions within the subnanometer pores. In addition, permeation studies using neutral adsorbates revealed average pore sizes of ~7Å, 13Å, and 19Å for ALD TFC membranes prepared using methanol, ethanol, and isopropanol, respectively. This work provides the scientific basis for the design of ceramic membranes with subnanometer pores for molecular sieving using ALD.

A Novel Wet Synthesis Method of High-Conductivity Sulfide Solid Electrolytes with Controlled Particle Size for All-Solid-State Batteries

Growing safety concerns regarding commercial lithium-ion batteries arise from the use of flammable organic liquid electrolytes. Consequently, all-solid-state batteries (ASSBs), free from such electrolytes and therefore posing no fire risk, are attracting significant attention as the next-generation battery system. Among various solid electrolytes (SEs), sulfide-based SEs stand out as promising candidates for commercialization due to their high ionic conductivity and superior processability. For the commercialization of ASSBs, a scalable and efficient wet synthesis process for mass production of solid electrolytes is essential.In previous research, we developed a novel method for preparing bulk-type argyrodite Li6PS5Cl (LPSCl) SEs with high ionic conductivity approaching 2 mS cm-1 using solution-phase synthesis with an additive and no high-energy ball-milling processes. Additionally, we investigated various solvents to understand the relationship between solvent properties and the purity of LPSCl SEs, finding that the characteristics of organic solvents play a significant role in lithium polysulfide formation. Despite these advancements, limitations in large-scale SE production may arise due to the use of petrochemical-derived toxic solvents. Therefore, we explored scalable production of cost-effective LPSCl-based sulfide SEs with high ionic conductivities exceeding 2 mS cm-1 using various green and sustainable solvents. However, the wet synthesis method introduced previously often produces SEs with large particle sizes, necessitating additional pulverization processes. This leads to increased costs and time, posing limitations to commercialization.This study introduces a novel, scalable, and cost-efficient wet synthesis approach for producing superionic conductive sulfide-based SEs. This pioneering process enables the creation of fine solid electrolyte particles by controlling the nucleation rate and strategically introducing Cl excess to enhance ionic conductivity. The synthesized Li5.5PS4.5Cl1.5 SE features a uniform size distribution (with an average particle diameter of 7 μm) and a high ionic conductivity of 4.98 mS cm-1, comparable to those produced by dry processes. The ability to control particle size allows the direct integration of these SEs with electrodes, eliminating the need for additional pulverization and facilitating the commercialization of ASSBs. The simulation results, including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations, confirm that the experimental data trends align with theoretical predictions. By utilizing green and sustainable solvents, we significantly reduced the environmental footprint of the production process, highlighting the importance of environmentally friendly methods in the sustainable commercialization of ASSBs.In conclusion, the novel wet synthesis method introduced in this study represents a major advancement in the field of ASSBs. By achieving high ionic conductivity through Cl excess and ensuring fine particle size control, we have addressed key barriers to commercialization. The ability to integrate these SEs directly with electrodes without additional pulverization processes further enhances the practical applicability of this method. As ASSBs continue to gain traction as the next-generation battery system, our findings provide a robust foundation for future developments and large-scale production. This study not only contributes to the technical advancement of battery technology but also underscores the importance of sustainable practices in the quest for high-performance energy storage solutions.

Large-Scale DFT Calculations on Size and Site Dependences of Atomic and Electronic Structures in Metallic Nanoparticle Catalysts

Size control of Pt nanoparticle catalysts is one of the key challenges in fuel cell development. Miniaturization of Pt nanoparticles is expected to increase activity and save the amount of Pt, while very small particles (e.g. sub-nano particles or clusters) have different electronic structures and stabilities from “nano” particles. To investigate the atomic and electronic structures of materials, first-principles density functional theory (DFT) calculation is a powerful tool. However, because of its high computational cost, the DFT applications have been limited mainly for small particles and clusters of tens to hundreds of atoms. In this study, by using our own large-scale DFT calculation method, we investigate the size and site dependences of atomic and electronic structures in Pt nanoparticles with the diameters of several nanometers, which are comparable to the sizes of the particles in practical use.The computational cost of the conventional DFT calculation methods scale cubically to the system size, i.e., the number of the atoms in the target system and the number of local functions for each atom, which are used to express electronic density. We have developed the multi-site support function (MSSF) method [1,2], in which local functions are constructed as the linear combinations of the atomic orbital functions belonging to not only the target atom but also its neighboring atoms. The MSSF method enables us to reduce the number of local functions to be the minimal-basis size, leading the dramatical computational cost reduction. The MSSF method is implemented in our large-scale DFT code CONQUEST [3,4].We optimized the structures of Pt nanoparticles with the diameters of 0.5 nm (13 atoms) - 5.5 nm (3871 atoms) and found that the Pt-Pt bond lengths inside the nanoparticle converge to those in bulk Pt when the nanoparticle size becomes large. The similar trend is found also in the electronic structures as shown in the figure. In the presentation, we compare the size dependence of the stability and atomic and electronic structures of Pt nanoparticle with other metallic nanoparticles. Site dependence of the electronic structures and reactivity with molecules are also investigated by using large-scale DFT together with statistical analysis.[1] A. Nakata, D. R. Bowler, T. Miyazaki, J. Phys. Soc. Jpn., 91, 091011 (2022). [2] A. Nakata, D. R. Bowler, T. Miyazaki, Phys. Chem. Chem. Phys. 17, 31427 (2015). [3] http://www.order-n.org/ [4] A. Nakata, J. S. Baker, S. Y. Mujahed, J. T. L. Poulton, S. Arapan, J. Lin, Z. Raza, S. Yadav, L. Truflandier, T. Miyazaki, D. R. Bowler, J. Chem. Phys., 152, 164112 (2020). Figure 1

Novel Rat Model of Embolic Cerebral Ischemia Using a Radiopaque Blood Clot and a Microcatheter Under Fluoroscopy.

Conventional rat models of thromboembolic stroke do not allow control of infarct size or spontaneous recanalization. We aimed to develop a novel rat thromboembolic stroke model that ensures highly reproducible infarct sizes and locations within the MCA territory and does not require arterial ligation. Twenty male Sprague-Dawley rats and two sham-operated rats were included. A microcatheter was navigated from the caudal ventral artery to the internal carotid artery using digital subtraction angiography. A blood clot (diameter, 0.86 mm; length, 3 mm) containing zirconium dioxide was advanced in the catheter. Fluoroscopy was performed at 1, 3, 6, and 24 h after stroke model creation, and TTC staining was conducted at 24 h. Neurological deficit scores were measured. In all embolized rats, the ACA and MCA bifurcation were selective. Median operating time was 6 min. The position of the radiopaque blood clot remained unchanged for 24 h after model creation in 19/20 rats. Median infarct volume was 242 mm3 (IQR, 239-262 mm3). We present a novel rat model of highly reproducible focal infarct in only the MCA territory. Fluoroscopy effectively identified any blood clot migration. This model could contribute to the development of new thrombolytic agents.

Rebuilding Peripheral F, Cl, Br Footprints on Acceptors Enables Binary Organic Photovoltaic Efficiency Exceeding 19.7 .

Given homomorphic fluorine (F), chlorine (Cl) and bromine (Br) atoms are featured with gradually enlarged polarizability/atomic radius but decreased electronegativity, the rational screen of halogen species and locations on small molecular acceptors (SMAs) is quite essential for acquiring desirable molecular packing to boost efficiency of organic solar cells (OSCs). Herein, three isomeric SMAs (CH-F, CH-C and CH-B) are constructed by delicately rebuilding peripheral F, Cl, Br footprints on both central and end units. Such a re-permutation of peripheral halogens could not only maintain the structural symmetry of SMAs to the maximum, but also acquire extra asymmetric benefits of enhanced dipole moment and intramolecular charge transfer, etc. Moreover, central brominating enhances molecular crystallinity of CH-B without introducing undesirable steric hindrance on end groups, thus rendering a better balance between high crystallization and domain size control in PM6:CH-B blend. Further benefitting from the large dielectric constant, small exciton binding energy, optimized molecular packing and great electron transfer integral, CH-B affords the first class binary OSC efficiency of 19.78 %, moreover, the highest efficiency of 18.35 % thus far when increasing active layer thickness to ~300 nm. Our successful screening in rebuilding peripheral halogen footprints provides the valuable insight into further rational design of SMAs for record-breaking OSCs.

Rebuilding Peripheral F, Cl, Br Footprints on Acceptors Enables Binary Organic Photovoltaic Efficiency Exceeding 19.7 %

AbstractGiven homomorphic fluorine (F), chlorine (Cl) and bromine (Br) atoms are featured with gradually enlarged polarizability/atomic radius but decreased electronegativity, the rational screen of halogen species and locations on small molecular acceptors (SMAs) is quite essential for acquiring desirable molecular packing to boost efficiency of organic solar cells (OSCs). Herein, three isomeric SMAs (CH−F, CH−C and CH−B) are constructed by delicately rebuilding peripheral F, Cl, Br footprints on both central and end units. Such a re‐permutation of peripheral halogens could not only maintain the structural symmetry of SMAs to the maximum, but also acquire extra asymmetric benefits of enhanced dipole moment and intramolecular charge transfer, etc. Moreover, central brominating enhances molecular crystallinity of CH−B without introducing undesirable steric hindrance on end groups, thus rendering a better balance between high crystallization and domain size control in PM6:CH−B blend. Further benefitting from the large dielectric constant, small exciton binding energy, optimized molecular packing and great electron transfer integral, CH−B affords the first class binary OSC efficiency of 19.78 %, moreover, the highest efficiency of 18.35 % thus far when increasing active layer thickness to ~300 nm. Our successful screening in rebuilding peripheral halogen footprints provides the valuable insight into further rational design of SMAs for record‐breaking OSCs.

Task-irrelevant stimuli reliably boost phasic pupil-linked arousal but do not affect decision formation

The arousal systems of the brainstem, specifically the locus coeruleus-noradrenaline system, respond “phasically” during decisions. These central arousal transients are accompanied by dilations of the pupil. Mechanistic attempts to understand the impact of phasic arousal on cognition would benefit from temporally precise experimental manipulations. Here, we evaluated a non-invasive candidate approach to manipulate arousal in humans: presenting task-irrelevant auditory stimuli at different latencies during the execution of a challenging task. Task-irrelevant auditory stimuli drive responses of brainstem nuclei involved in the control of pupil size, but it is unknown whether such sound-evoked responses mimic the central arousal transients evoked during cognitive computations. A large body of evidence has implicated central arousal transients in reducing bias during challenging perceptual decisions. We thus used challenging visual decisions as a testbed, combining them with task-irrelevant sounds of varying onset latency or duration. Across three experiments, the sounds consistently elicited well-controlled pupil responses that superimposed onto task-evoked responses. While we replicated a negative correlation between task-evoked pupil responses and bias, the task-irrelevant sounds had no behavioral effect. This dissociation suggests that cognitive task engagement and task-irrelevant sounds may recruit distinct neural systems contributing to the control of pupil size.

Kinetic Control over Social and Narcissistic Self‐Sorting from Multicomponent Mixtures in Seed‐Initiated Supramolecular Polymerization by Fine‐Tuning of Steric Effects

AbstractSupramolecular polymers offer an intriguing possibility to transfer molecular properties from the nano‐ to the mesoscale. Towards this achievement, seed‐initiated supramolecular polymerization has emerged as a powerful tool, as it prevents unlimited growth and enables size control of the assembly outcome. However, the potential application of the seeding method in the context of complex supramolecular systems is hitherto unclear. Herein we demonstrate that minute differences in molecular design in direct proximity to intermolecular recognition sites govern the molecular packing and in turn dictate the efficacy of seeded polymerization processes. We introduce a stepwise increase in steric demand in the central amino acid residue of a diamide system, which gradually increases the rotational displacement within the aggregated state. This fine‐tuning of the molecular packing directly affects the propensity of the different aggregates to act as seeds for the other supramolecular synthons. In turn this allows us to selectively target specific trapped monomer states in binary mixtures for social or narcissistic seeded polymerization.

Kinetic Control over Social and Narcissistic Self-Sorting from Multicomponent Mixtures in Seed-Initiated Supramolecular Polymerization by Fine-Tuning of Steric Effects.

Supramolecular polymers offer an intriguing possibility to transfer molecular properties from the nano- to the mesoscale. Towards this achievement, seed-initiated supramolecular polymerization has emerged as a powerful tool, as it prevents unlimited growth and enables size control of the assembly outcome. However, the potential application of the seeding method in the context of complex supramolecular systems is hitherto unclear. Herein we demonstrate that minute differences in molecular design in direct proximity to intermolecular recognition sites govern the molecular packing and in turn dictate the efficacy of seeded polymerization processes. We introduce a stepwise increase in steric demand in the central amino acid residue of a diamide system, which gradually increases the rotational displacement within the aggregated state. This fine-tuning of the molecular packing directly affects the propensity of the different aggregates to act as seeds for the other supramolecular synthons. In turn this allows us to selectively target specific trapped monomer states in binary mixtures for social or narcissistic seeded polymerization.

Stimuli-responsive self-regulating assembly of chiral colloids for robust size and shape control

Most synthetic self-assemblies grow indefinitely into size-unlimited structures, whereas some biological self-assemblies autonomously regulate their size and shape. One mechanism of such self-regulation arises from the chirality of building blocks, inducing their mutual twisting that is incompatible with their long-range ordered packing and thus halts the assembly’s growth at a certain stage. This self-regulation occurs robustly in thermodynamic equilibrium rather than kinetic trapping, and therefore is attractive yet elusive. Until now, studies of self-regulating assemblies have focused on non-responsive systems, whose equilibrium point and corresponding size and shape are hardly changeable. Here, we demonstrate a stimuli-responsive, self-regulating assembly. This assembly consists of chiral and magnetically orientable nanorods, where the effective chirality can be changed by balancing chirality-induced twisting and magnet-induced flattening between nanorods. Consequently, the strength of self-regulation in the assembly is modulable by magnetic field intensity, allowing robust, tunable, and reversible control of its size and shape. Our strategy would provide more biomimetic materials with precision and responsiveness.

Aperture size control in kirigami metamaterials: Towards enhanced performance and applications

Kirigami metamaterials, inspired by the ancient art of kirigami, have recently emerged as an innovative approach for creating metamaterials with a diverse range of properties. While many studies on 2D kirigami have focused on stretchability and multi-stable properties, the variation in aperture size throughout the unfolding process of kirigami is another significant geometric feature. In this study, two novel kirigami materials are introduced, based on the topological construction of traditional triangular kirigami designs. These novel kirigami materials exhibit a wide range of aperture sizes, offering significant flexibility and tunability in stretch ratio. The diverse range of aperture sizes presents numerous potential applications at both micro and macro scales. Additionally, a hollow technique is proposed for designing kirigami cellular structures, which undergo distinct stages during the compression process characterized by low-reaction response and high-reaction response. This research expands the design possibilities of kirigami metamaterials by enabling precise adjustments in aperture sizes.

Microfluidic Bubble-Templating Multinozzle 3D Printing for Preparations of Macroporous Hydrogels with Ordered Pores of Large Size Ranges.

A strategy for fabrication of macroporous hydrogels through 3D printing assisted by molding and multiple microfluidic bubble-templating nozzles is proposed here. This approach aims to address the challenges faced by methods for 3D printing macroporous hydrogels, such as difficulties in precisely controlling the spatial distribution of macropores, limited porosity, and low resolution of external boundaries due to the poor mechanical properties of hydrogel solutions as printing ink. In this method, fast-switching microfluidic bubble-templating nozzles of varying sizes allowed for precise control of target pore sizes over a wide range. Cavities of polydimethylsiloxane (PDMS) molds were used to define the overall external shape of the hydrogels and enhance the resolution of the boundaries. During the printing process, the laminar shear force generated by a coaxial microfluidic system generated microbubbles which were then injected into the PDMS mold cavities. The spatial distribution of the microbubble clusters within the cavities was controlled by a 3D motion module. Finally, macroporous hydrogels with a pore size range of 238-930 μm were fabricated while avoiding millimeter round corners on the boundaries. A control precision of pore sizes was about 60 μm. Most importantly, this strategy broke through the space occupancy limitations of pores in traditional 3D printing methods for macroporous hydrogels. The space occupancy of pores could reach a maximum of about 87% within a single layer.

Synthesis, Morphology, and Particle Size Control of Acidic Aqueous Polyurethane Dispersions.

A range of charge-stabilized aqueous polyurethane (PU) dispersions comprising hard segments formed from hydrogenated methylene diphenyl diisocyanate (H12MDI) with dimethylolpropionic acid (DMPA) and ethylenediamine, and soft segments of poly(tetramethylene oxide) of different molecular weights are synthesized. Characterization of the dispersions by mass spectrometry, gel permeation chromatography, small-angle X-ray scattering, atomic force microscopy, and infrared spectroscopy shows that they are composed of PUs self-assembled into spherical particles (primary population) and supramolecular structures formed by hydrogen-bonded H12MDI and DMPA acid-rich fragments (secondary population). Analysis of the scattering patterns of the dispersions, using a structural model based on conservation of mass, reveals that the proportion of supramolecular structures increases with DMPA content. It is also found that the PU particle radius follows the predictions of the particle surface charge density model, originally developed for acrylic statistical copolymers, and is controlled by hydrophile (DMPA) content in the PU molecules, where an increase in PU acidity results in a decrease in particle size. Moreover, there is a critical fractional coverage of hydrophiles stabilizing the particle surface for a given polyether soft-segment molecular weight, which increases with the polyether molecular weight, confirming that more acid groups are required to stabilize a more hydrophobic composition.

Bubble-Assisted Sample Preparation Techniques for Mass Spectrometry.

This review delves into the efficacy of utilizing bubbles to extract analytes into the gas phase, offering a faster and greener alternative to traditional sample preparation methods for mass spectrometry. Generating numerous bubbles in liquids rapidly transfers volatile and surface-active species to the gas phase. Recently, effervescence has found application in chemical laboratories for swiftly extracting volatile organic compounds, facilitating instantaneous analysis. In the so-called fizzy extraction, liquid matrices are pressurized with gas and then subjected to sudden decompression to induce effervescence. Alternatively, specifically designed effervescent tablets are introduced into the liquid samples. In situ bubble generation has also enhanced dispersion of extractant in microextraction techniques. Furthermore, droplets from bursting bubbles are collected to analyze non-volatile species. Various methods exist to induce bubbling for sample preparation. The polydispersity of generated bubbles and the limited control of bubble size pose critical challenges in the stability of the bubble-liquid interface and the ability to quantify analytes using bubble-based sample preparation techniques. This review covers different bubble-assisted sample preparation methods and gives practical guidance on their implementation in mass spectrometry workflows. Traditional, offline, and online approaches for sample preparation relying on bubbles are discussed. Unconventional bubbling techniques for sample preparation are also covered.

Stable Millivolt Range Resistive Switching in Percolating Molybdenum Nanoparticle Networks.

To overcome the limitations of the conventional Von Neumann architecture, inspiration from the mammalian brain has led to the development of nanoscale neuromorphic networks. In the present research, molybdenum nanoparticles (NPs), which were produced by means of gas phase condensation based on magnetron sputtering, are shown to be the constituents of electrically percolating networks that exhibit stable, complex, neuron-like spiking behavior at low potentials in the millivolt range, satisfying well the requirement of low energy consumption. Characterization of the NPs using both scanning electron microscopy and scanning transmission electron microscopy revealed not only pristine shape, size, and density control of Mo NPs but also a preliminary proof of the working mechanism behind the spiking behavior due to filament formations. Furthermore, electrostatics COMSOL Multiphysics simulations of the morphology of the NPs provided evidence that the stable switching is due to the as-deposited stellate Mo NPs creating high electric field strengths, while keeping them separated, not seen before in other percolating networks based on spherical NPs. Hence, our results show the working mechanism behind switching in percolating Mo NP networks and show that they are very promising for realistic neuromorphic systems.

Redispersible Acrylic Ester Polymers: Effect of Polymer Property Changes Due to Polymerization Method Modification and Functional Additives on the Performance of Polymer Cement Mortar.

This paper presents an experimental study aimed at improving the performance of polymer cement mortar by evaluating the properties of acrylic ester redispersible polymers, synthesized using a change in polymerization method from emulsion monomer to monomer dropwise addition methods, along with the use of a functional additive in the form of a foaming agent. To achieve the research objectives, a polymer with a glass transition temperature of -11 °C was synthesized by fixing the monomer ratio, particle-size distribution, and glass transition temperature, and the physical properties of the polymer cement mortar were assessed. The results showed that polymers synthesized using the modified polymerization method increased elongation at break and possessed a 35% smaller average particle size. The use of the foaming agent also resulted in enhanced tensile strength. The polymer cement mortars made with these respective polymers demonstrated improvements in compressive strength 11~25%, flexural strength 53~77%, bond strength 78~113%, volumetric changes 65~88%, and water absorption 30~70%. These findings suggest that changes in the polymerization method and the incorporation of functional additives influence the average particle size and air entrainment control properties of the polymers, thereby positively impacting the performance of the cement hydrates.

Ideal Bi-Based Hybrid Anode Material for Ultrafast Charging of Sodium-Ion Batteries at Extremely Low Temperatures

HighlightsMetallic nanoparticles with excellent size controllability and high loading rate are obtained via ultrafast high temperature shock method.The Bi/CNRs-15 electrode exhibits an unprecedented rate performance (237.9 mAh g−1 at 2 A g−1) at − 60 °C, while the energy density of the full cell can reach to 181.9 Wh kg−1 at − 40 °C.A novel strategy of high-rate activation is proposed to obtain high capacity and superior stability at low temperature by creating new active sites for interfacial reaction.

Precision Macroporous Monoliths Made Using High‐Throughput Microfluidic Emulsification

Materials with pore sizes ranging from micrometers to millimeters find use in thermal insulation, acoustics, separation, and energy‐related applications. While several routes have been developed to manufacture such macroporous materials, current fabrication technologies remain limited in either scalability or pore size control. Herein, a scalable microfluidic approach is reported to create macroporous materials with precisely controlled pore sizes from monodisperse emulsion templates. Emulsion droplets produced in a parallelized step emulsification device are assembled by gravity and converted into macroporous monoliths by polymerization and drying. Microstructural analysis and model filtration experiments show that the pore windows of the bulk macroporous material can be tightly controlled and used for the size‐selective separation of particles from suspensions. By heat treating macroporous structures of selected compositions, one can also create bulk carbon and silica glass monoliths with unique cellular architectures for potential applications as filters, separation membranes, or catalyst supports.

High-Throughput Measurement of Single-Fission Yeast Cell Volume Using Fluorescence Exclusion.

Cell volume is a critical parameter for the biology of living species and has an impact on virtually all cellular functions. In Schizosaccharomyces pombe, the regulation of cell size has been the focus of intense investigation, and mechanisms that couple size control with cell cycle progression have been identified. In fission yeast, cell length at division is generally used as a proxy for determining cell size. However, it only allows for an inaccurate evaluation of this critical parameter and neglects potential changes in cell morphology and diameter, which can strongly impact cell volume. Until recently, one of the major obstacles for studying the complexity of cell size regulation in fission yeast has been the lack of a robust method for high-throughput, direct measurement of single-cell volume. Here, we provide a comprehensive protocol for S. pombe cell volume determination based on the Fluorescence eXclusion method and microfluidics technologies. This approach makes it possible to reliably describe cell volume and its distribution in populations of fission yeast cells.

Efficient recovery of Pd(II) from nuclear wastewater using a functionalized covalent organic frameworks with uniform spherical structure: Size control, performance and mechanism insight

The efficient recovery of palladium from the spent nuclear fuel was of great significance to the sustainable development of nuclear energy. Herein, the uniform spherical COFs were constructed by a facile approach at room temperature, which were further surface functionalized by a thiol-ene “click” reaction to recover Pd(II). Microscopic and spectroscopic studies manifested that the formation mechanism and size of spherical COFs were greatly affected by the amount of catalyst and solvent type. The TAPB-BPTA-DTT and TAPB-BPTA-S-β-CD exhibited high Pd(II) recovery efficiency due to the introduction of sulfhydryl groups, and the maximum adsorption capacities were 489.3 and 234.3 mg/g, respectively. Meanwhile, the water environmental condition played an important role in the separation process, and the classical adsorption models demonstrated that monolayer chemisorption was the dominant removal mechanism. Mechanism analysis showed that the excellent adsorption performance was mainly attributed to the electrostatic interaction, physical absorption and chelation of N, O, and S groups with Pd(II). Thus, it is expected that this work could provide more insight into COFs materials, thereby promoting palladium removal advancements in the spent nuclear fuel.