Controlled Pore Size Research Articles

Metal-organic framework-based hybrids with photon upconversion.

Upconversion materials (UCMs) featuring an anti-Stokes type emission establish them as an important category of photoluminescent materials. Metal-organic frameworks (MOFs) are rapidly gaining prominence as a class of versatile materials with favourable physical and chemical properties, including high porosity, controllable pore size, flexible design, and diverse functional sites. To endow MOFs with upconversion capability and improve the properties and performance of UCMs, the hybrids integrating UCMs and MOFs are proven to be successful. This review focuses on the research advancements of upconverting MOF-based hybrids, encompassing classifications, luminescence mechanisms, designs, properties, and applications in energy, catalysis, and biomedical fields. The analyses on the functions of upconversion and MOFs, as well as the advantages and disadvantages of various upconverting MOF-based hybrids, are included. Future research directions spanning from properties and performance to applications are explored. This review will be valuable in highlighting the research accomplishments, inspiring more ideas, facilitating deeper investigations in diverse avenues, and further advancing the research field.

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.

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.

Nanometer-Scale Tunable mesopores in silica fillers for Facile enhancement of epoxy adhesion

Epoxy resins are essential polymeric materials for various industrial applications owing to their excellent adhesion, thermal properties, and processability. Reported improvement methods for overcoming the limitations of epoxy-resin adhesives involve incorporating fillers such as silica, clay, carbon nanotubes, and graphene. While silica nanoparticles are commonly used in industrial applications, their properties often require enhancement. In this study, mesoporous silica nanoparticles (MSNs) were synthesized using cetyltrimethylammonium bromide and novel swelling agents, 2,6-dihydroxybenzoic acid and decane, to control pore sizes within the 2–4 nm range. Transmission electron microscope and nitrogen adsorption analyses confirmed pore sizes of 2.0, 3.1, and 3.9 nm. Applying MSNs as nanofillers to epoxy resin adhesive resulted in enhanced adhesive properties with increasing pore size, particularly with 0.5 wt% MSN-4 nm, achieving a 51.4 % improvement in shear strength compared to that of bare epoxy resin. This enhancement is attributed to the increased specific surface area of the MSNs, providing more interaction sites with the epoxy resin and improving resin penetration and interaction. These findings highlight the critical role of nanopore size in optimizing adhesion in nanofiller applications and emphasize the potential of MSNs as superior nanofillers for future industrial applications.

Controlled Nanopore Sizes in Supraparticle Supports for Enhanced Propane Dehydrogenation with GaPt SCALMS Catalysts.

The efficient immobilization of GaPt liquid metal alloy droplets onto tailored supports improves catalytic performance by preventing coalescence and subsequent loss of active surface area. Herein, we use tailored supraparticle (SP) supports with controlled nanopores to systematically study the influence of pore sizes on the catalytic stability of GaPt supported catalytically active liquid metal solution (SCALMS) in propane dehydrogenation (PDH). Initially, GaPt droplets were prepared via an atom-efficient and scalable ultrasonication method with recycling loops to yield droplets <300 nm. Subsequently, these droplets were immobilized onto SiO2-based SPs with controlled pore sizes ranging from 45 to 320 nm. Catalytic evaluations in PDH revealed that GaPt immobilized on SPs with larger pores demonstrated superior stability over 15 h time-on-stream evidenced by reduced deactivation rates from 0.046 to 0.026 h-1. Nanocomputed tomography and identical location SEM confirmed the successful immobilization of GaPt droplets within the interstitial sites formed by the primary particles constituting the SPs. These remained unchanged before and after the catalytic reaction, demonstrating efficient coalescence prevention. Our findings underscore the importance of support pore size engineering for improving the stability of GaPt SCALMS catalysts and highlight, particularly, the high potential of using SPs in this context.

Upcycling Waste Polyethylene Terephthalate to Produce Nitrogen-Doped Porous Carbon for Enhanced Capacitive Deionization

Porous carbon with a high surface area and controllable pore size is needed for energy storage. It is still a significant challenge to produce porous carbon in an economical way. Nitrogen-doped porous carbon (N-PC) was prepared through carbonization of a mixture of waste PET-derived metal–organic frameworks (MOFs) and ammonium. The obtained N-PC exhibits a large surface area and controlled pore size. When utilized as an electrode material for supercapacitors, the N-PC exhibits a specific capacitance of 224 F g−1, significantly surpassing that of commercial activated carbon (AC), which has a capacitance of 111 F g−1. In the subsequent capacitive deionization (CDI) tests, the N-PC demonstrated a maximum salt adsorption capacity of 19.9 mg g−1 at 1.2 V in a NaCl electrolyte (0.5 g L−1), and the salt adsorption capacity increased to 24.7 mg g−1 at 1.4 V. The N-PC electrode also exhibited superior regeneration. The present work not only presents a potential approach to develop cost-effective electrodes for seawater purification but also paves the way for recycling of waste plastics into high value-added products.

Construction of PTFE/PI-PI/PANI-PA composite nanofibrous membrane for efficient photothermal membrane distillation and VOCs interception

Water-soluble volatile organic compounds (VOCs) are one of the difficult substances in seawater and industrial wastewater treatment. Photothermal membrane distillation (PMD) technology has great advantages in solving the problems of low energy conversion efficiency and serious pollution of traditional membrane distillation (MD) technology, but it still faces the challenge that VOCs cannot be effectively removed.To solve this problem, we prepared photothermal Polytetrafluoroethylene/Polyimide-Polyimide/Polyaniline-Polyamide (PTFE/PI-PI/PANI-PA) composite membranes with VOCs interception. The composite membrane was fabricated by applying the previously studied PTFE/PI-PI/PANI/PANI membrane by interfacially polymerising an ultrathin PA layer with controllable pore sizes. Among them, the PTFE/PI-PI/PANI base membrane in the composite membrane not only provides strong support and durability as a backbone structure, but the PANI photothermal layer also provides photothermal conversion for effective PMD operation. In addition, the ultra-thin PA layer acts as a molecular sieve separator to effectively intercept VOCs in the feed solution. When the feed solution was 35 g⋅L−1 NaCl, the average permeate flux of the #M-PA-0.1 membrane was 1.44 ± 0.02 L⋅m−2⋅h−1 with a salt interception rate of 99.99 % or more after 80 h of PMD testing. Meanwhile, when 50 mg⋅L−1 of VOCs was added to the feed solution, the VOCs retention rate >99.35 %, and the concentration of VOCs on the permeate side was much lower than the corresponding concentration in the drinking water standards recommended by the World Health Organisation (WHO) and the US Environmental Protection Agency (EPA). This study effectively combines the molecular sieve effect with the solar-powered evaporation process, which provides a research basis for the preparation of high-performance PMD membranes that can effectively remove volatile organic compounds.

Recoverable and reusable light-induced multi-arm azobenzenes-Fe3O4 hybrid sorbent for enrichment of phthalate plasticizer and utilized as a SALDI substrate for the detection of 2-naphthol

The construction, structural identifications along with compositional properties, using TEM, FT-IR, and XPS spectroscopies, of an innovative light-induced multi-arm azobenzenes based Fe3O4 magnetic nanoparticles (Azo-Fe3O4 MNPs) are being reported. Such organic (light-sensitive dendrimers-like structure), inorganic (magnet core), hybrid material has been applied as an efficient recoverable/reusable extractive sorbent for the detection of phthalate plasticizers from acetate buffer solution. The extraction study was controlled within consecutive procedures via UV-light exposure to achieve pore-size control which then further subjected for the evaluation of the analytes’ retention, separation, and release as well as the detection of the phthalate pollutants using GCMS–. Various experimental conditions, such as time of extraction, salt concentration, pH, and desorption time, were studied and adjusted. Additionally, the extraction repeatability (RSD from 0.46 % to 6.12%, n = 5) of the studied sorbent was comparable to other published work. The linear range extended from 6.25 to 100 μg L-¹ and detection limits (LOD) within the range of 41- 150 ng L-1 were achieved, demonstrating good linearity with values ranging from 0.9992 to 0.9892. The inter-batch and intra-batch RSD ranged from 0.46 % to 6.12 %, respectively. Additionally, it provides effective detection of 2-naphthol when used as a SALDI substrate.

The Chemistry of Metal–Organic Frameworks for Multicomponent Gas Separation

AbstractAdsorbents‐based gas separation technologies are regarded as the potential energy‐efficient alternatives towards current thermal‐driven methods, and the study on multi‐component gas separation is essential to deepen our understanding of the adsorbents for practical use. Relative to the ideal two‐component mixtures, both the adsorption behavior and separation mechanisms are obviously more complex in multiple gas mixtures due to their close or even overlapped sizes and properties. The emergence of metal–organic frameworks with controllable pore size and pore chemistry provides the platform for the tailor‐made pore structure to satisfy the harsh requirements of multi‐component gas separation. This minireview highlights the recent advance of multi‐component gas separation using metal–organic frameworks, including multiple impurities removal and selective molecular capture. Combining with the typical cases of hydrocarbon separations (C2, C4, and C8), the detailed discussion about the developed strategies (e.g. self‐adaptive binding sites, multiple binding spaces, synergistic binding sites, synergistic sorbent separation technology, gate‐opening effect, size and thermodynamic combine effect) that are adaptive to different scenarios would be provided. The review will conclude with our perspective on the existing barriers and the future direction of this topic.

Cell migration within porous electrospun nanofibrous scaffolds in a mouse subcuticular implantation model.

Cellular infiltration into electrospun nanofibers (NFs) is limited due to the dense structure and small pore sizes. We developed a programmed NF collector that can fabricate porous NFs with desired pore sizes and thickness. Previously we demonstrated improved cellular proliferation and differentiation of osteoblasts, osteoclasts, and fibroblasts with increased pore sizes of polycaprolactone (PCL) NF in-vitro. This study investigated in-vivo host cell migration and vascular ingrowth within porous NF sheets implanted subcutaneously in a mouse model. Two types of PCL NFs with well-defined pore sizes were created using varying speeds of the NF collector: NF-zero (no movement, pore size 14.4 ± 8.9 µm2) and NF-high (0.232 mm/min, pore size 286.7 ± 381.9 µm2). The NF obtained by using classical flat NF collector (2D NF, pore size 1.09 ± 1.7 µm2) was a control. The three formulae of NFs were implanted subcutaneously in 18 BALB/cJ mice. Animals were killed 7 and 28-days after implantation (n = 3 per group per time point). The tissue with implanted NFs were collected for histologic analysis. Overall, 7-day samples showed little inflammatory response. At 28-days, the degree of tissue penetration of PCL NF sheet matrices was linked to pore size and area. NFs with the largest pore area had more efficient tissue migration and new blood vessel formation compared to those with smaller pore sizes. No newly formed blood vessels were observed in the 2D NF group. A porous NF scaffold with controllable pore size has potential for tissue repair/regeneration in situ with potential for many applications in orthopaedics.

Design and optimization of pore structure in three-dimensional micro-nano hierarchical SnOx supercapacitor electrodes for enhanced ion diffusion

This paper introduced a novel continuous electrochemical synthesis strategy to address the challenges of slow ion/electron transport rates and low electrode reaction efficiency in Sn-based electrode materials. This approach leveraged the induction and confinement of bubble templates to assist atoms deposition, generating micron-sized tin skeletons. Subsequently, these skeletons were transformed into a secondary nanoporous structure through dissolution-deposition etching effects. From liquid-phase ions to metal skeletons to porous oxides, the sequential material transformations realized the innovative design of three-dimensional (3D) hierarchical structures. This strategy ingeniously exploited the diffusion advantages of the electrolyte in the micro-nano hierarchical structure to achieve the diffusion enhancement of ions, thus solving the “dead surface” problem in the energy storage process. This study revealed the thermodynamic and kinetic feasibility of the constructed 3D micro-nano hierarchical structure through electrochemical evaluations and theoretical calculations, and elucidated the constitutive relationship in which the electrochemical performance of the electrode materials was enhanced with decreasing pore size. In addition, design optimization of pore structures and modelling exploration of pore size limit values were conducted based on density functional theory (DFT) simulations. These simulations demonstrated the advantages of hierarchical structures with controllable pore sizes in facilitating electrolyte ion diffusion, predicting an optimal pore size of 55 μm for 3D hierarchical porous SnOx electrodes. The integration of this innovative structural design with simulation insights offered significant implications for enhancing the sluggish electrode reaction kinetics of metal oxide electrode materials, advancing the controllable fabrication of high-performance energy storage devices.

The Chemistry of Metal-Organic Frameworks for Multicomponent Gas Separation.

Adsorbents-based gas separation technologies are regarded as the potential energy-efficient alternatives towards current thermal-driven methods, and the study on multi-component gas separation is essential to deepen our understanding of the adsorbents for practical use. Relative to the ideal two-component mixtures, both the adsorption behavior and separation mechanisms are obviously more complex in multiple gas mixtures due to their close or even overlapped sizes and properties. The emergence of metal-organic frameworks with controllable pore size and pore chemistry provides the platform for the tailor-made pore structure to satisfy the harsh requirements of multi-component gas separation. This minireview highlights the recent advance of multi-component gas separation using metal-organic frameworks, including multiple impurities removal and selective molecular capture. Combining with the typical cases of hydrocarbon separations (C2, C4, and C8), the detailed discussion about the developed strategies (e.g. self-adaptive binding sites, multiple binding spaces, synergistic binding sites, synergistic sorbent separation technology, gate-opening effect, size and thermodynamic combine effect) that are adaptive to different scenarios would be provided. The review will conclude with our perspective on the existing barriers and the future direction of this topic.

Pore engineering of Porous Materials: Effects and Applications.

Porous materials, characterized by their controllable pore size, high specific surface area, and controlled space functionality, have become cross-scale structures with microenvironment effects and multiple functions and have gained tremendous attention in the fields of catalysis, energy storage, and biomedicine. They have evolved from initial nanopores to multiscale pore-cavity designs with yolk-shell, multishells, or asymmetric structures, such as bottle-shaped, multichambered, and branching architectures. Various synthesis strategies have been developed for the interfacial engineering of porous structures, including bottom-up approaches by using liquid-liquid or liquid-solid interfaces "templating" and top-down approaches toward chemical tailoring of polymers with different cross-linking degrees, as well as interface transformation using the Oswald ripening, Kirkendall effect, or atomic diffusion and rearrangement methods. These techniques permit the design of functional porous materials with diverse microenvironment effects, such as the pore size effect, pore enrichment effect, pore isolation and synergistic effect, and pore local field enhancement effect, for enhanced applications. In this review, we delve into the bottom-up and top-down interfacial-oriented synthesis approaches of porous structures with advanced structures and microenvironment effects. We also discuss the recent progress in the applications of these collaborative effects and structure-activity relationships in the areas of catalysis, energy storage, electrochemical conversion, and biomedicine. Finally, we outline the persisting obstacles and prospective avenues in terms of controlled synthesis and functionalization of porous engineering. The perspectives proposed in this paper may contribute to promote wider applications in various interdisciplinary fields within the confined dimensions of porous structures.

Efficient construction of self-assembled starch colloidosomes for controlled-release of pesticides

Biodegradable colloidosomes have attracted increasing attention for their applications to enhance the efficacy and reduce wastage of pesticides in agriculture. In this study, we present a continuous and highly efficient method for production of starch colloidosomes. The starch particles with an average particle size of 230.2 nm and good dispersibility were prepared using surface modification technology, and then used as environment-friendly shell materials to form self-assembled starch colloidosomes using spray drying technology. The influences of inlet temperature, feed rate and air flow rate on the morphologies of colloidosomes were also studied. This strategy enables the construction of starch colloidosomes with uniform spherical morphology and controllable pore sizes under different pH, and can be used for pesticide encapsulation. After loading pyraclostrobin (PYR), the regular spherical colloidosomes not only achieve a small mean diameter of 2.35 µm, but also realize a high encapsulation efficiency of 82 %. The release performance of PYR has an obvious pH response and follows the segmented Ritger-Pepapes model of sustained-release. The colloidosomes were used to prevent the photodegradation of pesticides. The PYR loaded colloidosomes exhibit excellent UV resistance with a retention rate of 72.7 %. In addition, the loading of Fe3O4 nanoparticles and the embedding of carbon dots were also explored.

Electrodeposited Porous Ni-Fe-Co Thin Films By Hydrogen Templating Onto an Inverted Recessed Disk Electrode

Porous electrodes are advantageous for a variety of applications to enhance surface area per volume. Hydrogen templating is one well-known method to generate a porous metal, where metal deposits around generated gas bubbles from the same electrode surface. The technique has been demonstrated with noble (e.g., Au, Ag, Cu) and less noble (e.g., Ni) elemental deposits, but few alloy system.1 Ni-Fe-Co is of interest due to its electrocatalytic ability towards the oxygen evolution reaction for alkaline water splitting. Rafailović et al.2 galvanostatically electrodeposited an alloy at very high current density at pH 2 having 20 micron pore size with nano scale dendritic features, and Li and Podlaha3 potentiostatically electrodeposited Ni-Fe-Co alloys at pH < 0.5 into polycarbonate templates along with hydrogen templating to create pores in nanowires. There was a large distribution of pore size between 10 and 100 nm with the largest percentage between 20 and 40 nm. To better understand the control of pore size in the Ni-Fe-Co alloy system an inverted rotating disk electrode was used to control the limiting current of the proton reduction reaction during alloy electrodeposition. A boric acid, simple salt electrolyte was used with a three-electrode system to generate polarization curves and electrodeposits at different electrode rotation rates. The influence of mass transport and hydrogen bubble formation at different rotation rates were examined and affected porosity. Porosity was characterized by scanning electron microscopy (SEM) and the inspection of current during ferri/ferrocyanide polarization. Porous films were observed for deposits galvanostatically fabricated at current densities above the proton reduction limiting current density, but before water reduction, producing pore sizes on the order of 10s to 100s of nm, but below a micron. The ratio of the applied current density to proton reduction limiting current density was an important factor. J. Plowman, L. A. Jones, and S. K. Bhargava, Chemical Communications, 51, 4331-4346 (2015).D. Rafailović, C. Gammer, C. Rentenberger, T. Trišović, C. Kleber, and H. P. Karnthaler, Nano Energy, 2, 523-529 (2013).D. Li and E. J. Podlaha, Nano Letters, 19, 3569-3574 (2019).

High‐Pressure Molecular Sieving of High‐Humidity C2H4/C2H6 Mixture by a Hydrophobic Flexible Metal–Organic Framework

AbstractMolecular sieving is an ideal separation mechanism, but controlling pore size, restricting framework flexibility, and avoiding strong adsorption are all very challenging. Here, we report a flexible adsorbent showing molecular sieving at ambient temperature and high pressure, even under high humidity. While typical guest‐induced transformations are observed, a high transition pressure of 16.6 atm is observed for C2H4 at 298 K because of very weak C2H4 adsorption (~16 kJ mol−1). Also, C2H6 is completely excluded below the pore‐opening pressure of 7.7 atm, giving single‐component selectivity of ca. 300. Quantitative high‐pressure column breakthrough experiments using 1 : 1 C2H4/C2H6 mixtures at 10 atm as input confirm molecular sieving with C2H4 adsorption of 0.73 mmol g−1 or 32 cm3(STP) cm−3 and negligible C2H6 adsorption of 0.001(2) mmol g−1, and the adsorbent can be completely regenerated by inert gas purging. Furthermore, it is highly hydrophobic with negligible water adsorption, and the C2H4/C2H6 separation performance is unaffected at high humidity.

High-Pressure Molecular Sieving of High-Humidity C2H4/C2H6 Mixture by a Hydrophobic Flexible Metal-Organic Framework.

Molecular sieving is an ideal separation mechanism, but controlling pore size, restricting framework flexibility, and avoiding strong adsorption are all very challenging. Here, we report a flexible adsorbent showing molecular sieving at ambient temperature and high pressure, even under high humidity. While typical guest-induced transformations are observed, a high transition pressure of 16.6 atm is observed for C2H4 at 298 K because of very weak C2H4 adsorption (~16 kJ mol-1). Also, C2H6 is completely excluded below the pore-opening pressure of 7.7 atm, giving single-component selectivity of ca. 300. Quantitative high-pressure column breakthrough experiments using 1 : 1 C2H4/C2H6 mixtures at 10 atm as input confirm molecular sieving with C2H4 adsorption of 0.73 mmol g-1 or 32 cm3(STP) cm-3 and negligible C2H6 adsorption of 0.001(2) mmol g-1, and the adsorbent can be completely regenerated by inert gas purging. Furthermore, it is highly hydrophobic with negligible water adsorption, and the C2H4/C2H6 separation performance is unaffected at high humidity.

Influence of carbon template and ultrasound irradiation on combustion design of nanostructured calcium manganese oxides used in biodiesel production

Biodiesel, derived from renewable biomass, serves as a sustainable alternative to diesel produced from fossil fuels. This study explores the use of nanostructured MgO/Ca2Mn3O8 catalysts for biodiesel production through transesterification. Ca2Mn3O8 was synthesized as a support catalyst via combustion synthesis, employing carbon templates to control pore size. MgO was impregnated as the active phase using ultrasonic irradiation to enhance particle dispersion. Various characterization techniques, including XRD, FESEM, AFM, TEM, EDX, BET-BJH, and TPD-CO2, were utilized to analyse morphology, porosity, basicity, and active phase dispersion. The use of carbon templates increased pore diameters compared to catalysts without templates, while ultrasonic irradiation improved MgO dispersion. The MgO/Ca2Mn3O8 catalyst with a 10 wt% carbon template and ultrasonic irradiation achieved a maximum conversion rate of 95.5%. Its mesoporous structure, resembling a sponge, facilitated triglyceride diffusion. Stability tests indicated a 90% conversion rate after five reuses. The nanostructured MgO/Ca2Mn3O8 catalyst, with its tailored porosity and structure, demonstrated excellent performance in biodiesel production. Systematically adjusting support porosity and active site dispersion provides a viable approach for designing effective heterogeneous catalysts.

3D carbonaceous substrates synthesized from melamine sponges for energy storage: Influence of pyrolysis temperature in physicochemical and electrochemical properties

High-energy global requirements have caused a renewed interest in studying and developing new and improved energy storage devices and, precisely, the electrode materials that compose them, which play a fundamental role in determining the device’s performance. Carbon materials are first-class candidates due to their high electrical conductivity, chemical stability, and surface area. Although several carbon materials and their precursors have been studied, melamine sponges stand out for their nitrogen content, allowing them to act as a template and precursor for N-doped, ultralight carbon materials with good mechanical properties and a controlled pore size distribution. This work reports a simple and quick methodology to form ultralight and flexible carbon foam, along with the influence of the pyrolysis temperature on the physicochemical and electrochemical properties of 3D carbonaceous substrates used for energy storage and synthesized from melamine sponges. The substrates exhibit higher 3D porous structure than previously reported materials, with an average pore diameter of 80–90 µm. This morphology, added to the N content, promotes the remarkable electrochemical behavior (MS–950 °C) and cycling stability (MS–1000 °C) of almost 100% of capacitance retention after 10,000 cycles (≈ 60 F/g @1 A/g).

Accelerating Anhydrous Proton Transport in Covalent Organic Frameworks: Pore Chemistry and its Impacts

AbstractProton conduction is important in both fundamental research and technological development. Here we report designed synthesis of crystalline porous covalent organic frameworks as a new platform for high‐rate anhydrous proton conduction. By developing nanochannels with different topologies as proton pathways and loading neat phosphoric acid to construct robust proton carrier networks in the pores, we found that pore topology is crucial for proton conduction. Its effect on increasing proton conductivity is in an exponential mode other than linear fashion, endowing the materials with exceptional proton conductivities exceeding 10−2 S cm−1 over a broad range of temperature and a low activation energy barrier down to 0.24 eV. Remarkably, the pore size controls conduction mechanism, where mesopores promote proton conduction via a fast‐hopping mechanism, while micropores follow a sluggish vehicle process. Notably, decreasing phosphoric acid loading content drastically reduces proton conductivity and greatly increases activation energy barrier, emphasizing the pivotal role of well‐developed proton carrier network in proton transport. These findings and insights unveil a new general and transformative guidance for designing porous framework materials and systems for high‐rate ion conduction, energy storage, and energy conversion.