Metal-Organic Frameworks Marry Sponge: New Opportunities for Advanced Water Treatment.

Metal-organic frameworks (MOFs) have garnered attention across various fields due to their noteworthy features like high specific surface area, substantial porosity, and adjustable performance. In the realm of water treatment, MOFs exhibit great potential for eliminating pollutants such as organics, heavy metals, and oils. Nonetheless, the inherent powder characteristics of MOFs pose challenges in terms of recycling, pipeline blockage, and even secondary pollution in practical applications. Addressing these issues, the incorporation of MOFs into sponges proves to be an effective solution. Strategies like one-pot synthesis, in situ growth, and impregnation are commonly employed for loading MOFs onto sponges. This review comprehensively explores the synthesis strategies of MOFs and sponges, along with their applications in water treatment, aiming to contribute to the ongoing advancement of MOF materials.

High entropy alloying strategy for accomplishing quintuple-nanoparticles grafted carbon towards exceptional high-performance overall seawater splitting.

High entropy alloys (HEAs), a novel class of material, have been explored in terms of their excellent mechanical properties. Seawater electrolysis is a step towards sustainable production of carbon-neutral fuels such as H2, O2, and industrially demanding Cl2. Herein, we report a practically viable FeCoNiMnCr HEA nanoparticles system grafted on a conductive carbon matrix for promising seawater electrolysis. The comprehensive kinetics analysis of the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and chlorine evolution reaction (CER) confirms the effectiveness of our system. As an electrocatalyst, HEAs grafted on carbon black show trifunctionality with promising kinetics, selectivity and enduring performance, towards seawater splitting. We optimize high entropy alloy decorated/grafted carbon black (HEACB) catalysts, studying their synthesis temperature to scrutinize the effect of alloy formation variation on the catalysis efficacy. During the catalysis, selectivity between two mutually competing reactions, CER and OER, in the electrochemical catalysis of seawater is controlled by the reaction media pH. We employ Mott-Schottky measurements to probe the band structure of the intrinsically induced metal-semiconductor junction in the HEACB catalyst, where the carrier density and flat band potential are optimized. The HEACB sample provides promising results towards overall seawater electrolysis with a net half-cell potential of about 1.65 V with good stability, which strongly implies its broad practical applicability.

Strategic design of Fe and N co-doped hierarchically porous carbon as superior ORR catalyst: from the perspective of nanoarchitectonics.

In this study, we present microporous carbon (MPC), hollow microporous carbon (HMC) and hierarchically porous carbon (HPC) to demonstrate the importance of strategical designing of nanoarchitectures in achieving advanced catalyst (or electrode) materials, especially in the context of oxygen reduction reaction (ORR). Based on the electrochemical impedance spectroscopy and ORR studies, we identify a marked structural effect depending on the porosity. Specifically, mesopores are found to have the most profound influence by significantly improving electrochemical wettability and accessibility. We also identify that macropore contributes to the rate capability of the porous carbons. The results of the rotating ring disk electrode (RRDE) method also demonstrate the advantages of strategically designed double-shelled nanoarchitecture of HPC to increase the overall electron transfer number (n) closer to four by offering a higher chance of the double two-electron pathways. Next, selective doping of highly active Fe-N x sites on HPC is obtained by increasing the nitrogen content in HPC. As a result, the optimized Fe and N co-doped HPC demonstrate high ORR catalytic activity comparable to the commercial 20 wt% Pt/C in alkaline electrolyte. Our findings, therefore, strongly advocate the importance of a strategic design of advanced catalyst (or electrode) materials, especially in light of both structural and doping effects, from the perspective of nanoarchitectonics.

MOF-derived nanoporous carbons with diverse tunable nanoarchitectures.

Metal-organic frameworks (MOFs), or porous coordination polymers, are crystalline porous materials formed by coordination bonding between inorganic and organic species on the basis of the self-assembly of the reacting units. The typical characteristics of MOFs, including their large specific surface areas, ultrahigh porosities and excellent thermal and chemical stabilities, as well as their great potential for chemical and structural modifications, make them excellent candidates for versatile applications. Their poor electrical conductivity, however, has meant that they have not been useful for electrochemical applications. Fortuitously, the direct carbonization of MOFs results in a rearrangement of the carbon atoms of the organic units into a network of carbon atoms, which means that the products have useful levels of conductivity. The direct carbonization of zeolitic imidazolate framework (ZIF)-type MOFs, particularly ZIF-8, has successfully widened the scope of possible applications of MOFs to include electrochemical reactions that could be used in, for example, energy storage, energy conversion, electrochemical biosensors and capacitive deionization of saline water. Here, we present the first detailed protocols for synthesizing high-quality ZIF-8 and its modified forms of hollow ZIF-8, core-shell ZIF-8@ZIF-67 and ZIF-8@mesostuctured polydopamine. Typically, ZIF-8 synthesis takes 27 h to complete, and subsequent nanoarchitecturing procedures leading to hollow ZIF-8, ZIF-8@ZIF-67 and ZIF-8@mPDA take 6, 14 and 30 h, respectively. The direct-carbonization procedure takes 12 h. The resulting nanoporous carbons are suitable for electrochemical applications, in particular as materials for supercapacitors.

Modular assembly of MOF-derived carbon nanofibers into macroarchitectures for water treatment.

The organized assembly of nanoparticles into complex macroarchitectures opens up a promising pathway to create functional materials. Here, we demonstrate a scalable strategy to fabricate macroarchitectures with high compressibility and elasticity from hollow particle-based carbon nanofibers. This strategy causes zeolitic imidazolate framework (ZIF-8)-polyacrylonitrile nanofibers to assemble into centimetre-sized aerogels (ZIF-8/NFAs) with expected shapes and tunable functions on a large scale. On further carbonization of ZIF-8/NFAs, ZIF-8 nanoparticles are transformed into a hollow structure to form the carbon nanofiber aerogels (CNFAs). The resulting CNFAs integrate the properties of zero-dimensional hollow structures, one-dimensional nanofibers, and three-dimensional carbon aerogels, and exhibit a low density of 7.32 mg cm-3, high mechanical strength (rapid recovery from 80% strain), outstanding adsorption capacity, and excellent photo-thermal conversion potential. These results provide a platform for the future development of macroarchitectured assemblies from nanometres to centimetres and facilitate the design of multifunctional materials.

Surface Filtration in Mesoporous Au Films Decorated by Ag Nanoparticles for Solving SERS Sensing Small Molecules in Living Cells.

For surface-enhanced Raman spectroscopy (SERS) sensing of small molecules in the presence of living cells, biofouling and blocking of plasmonic centers are key challenges. Here, we have developed a mesoporous Au (AuM) film coated with a Ag nanoparticles (NPs) as a plasmonic sensor (AuM@Ag) to analyze aromatic thiols, which is an example of a small molecule, in the presence of a living cell strain (e.g., MDA-MB-231) as a model living system. The resulting AuM@Ag provides 0.1 nM sensitivity and high reproducibility for thiols sensing. Simultaneously, the AuM@Ag film filters large biomolecules, preventing Raman signals from overlapping produced by large biomolecules. After analysis, the AuM@Ag film undergoes recycling by the full dissolution of the Ag-thiol layer and removal of thiols from AuM. Furthermore, fresh AgNPs are formed for further SERS analysis, which circumvents the Ag oxidation issue. The ease of the AgNPs deposition allows up to 12 cycles of on-demand recycling and sensing even after utilization as a sensor in multicomponent media without enhancement and sensitivity loss. The reported mesoporous film with surface filtering ability and prominent recycling procedure promises to offer a new strategy for the detection of various small molecules in the presence of living cells.

Expeditious Electrochemical Synthesis of Mesoporous Chalcogenide Flakes: Mesoporous Cu2 Se as a Potential High-Rate Anode for Sodium-Ion Battery.

Nanostructured copper selenide (Cu2 Se) attracts much interest as it shows outstanding performance as thermoelectric, photo-thermal, and optical material. The mesoporous structure is also a promising morphology to obtain better performance for electrochemical and catalytic applications, thanks to its high surface area. A simple one-step electrochemical method is proposed for mesoporous chalcogenides synthesis. The synthesized Cu2 Se material has two types of mesopores (9 and 18 nm in diameter), which are uniformly distributed inside the flakes. These materials are also implemented for sodium (Na) ion battery (NIB) anode as a proof of concept. The electrode employing the mesoporous Cu2 Se exhibits superior and more stable specific capacity as a NIB anode compared to the non-porous samples. The electrode also exhibits excellent rate tolerance at each current density, from 100 to 1000 mA g-1 . It is suggested that the mesoporous structure is advantageous for the insertion of Na ions inside the flakes. Electrochemical analysis indicates that the mesoporous electrode possesses more prominent diffusion-controlled kinetics during the sodiation-desodiation process, which contributes to the improvement of Na-ion storage performance.

New Trends in Nanoarchitectured SERS Substrates: Nanospaces, 2D Materials, and Organic Heterostructures.

This article reviews recent fabrication methods for surface-enhanced Raman spectroscopy (SERS) substrates with a focus on advanced nanoarchitecture based on noble metals with special nanospaces (round tips, gaps, and porous spaces), nanolayered 2D materials, including hybridization with metallic nanostructures (NSs), and the contemporary repertoire of nanoarchitecturing with organic molecules. The use of SERS for multidisciplinary applications has been extensively investigated because the considerably enhanced signal intensity enables the detection of a very small number of molecules with molecular fingerprints. Nanoarchitecture strategies for the design of new NSs play a vital role in developing SERS substrates. In this review, recent achievements with respect to the special morphology of metallic NSs are discussed, and future directions are outlined for the development of available NSs with reproducible preparation and well-controlled nanoarchitecture. Nanolayered 2D materials are proposed for SERS applications as an alternative to the noble metals. The modern solutions to existing limitations for their applications are described together with the state-of-the-art in bio/environmental SERS sensing using 2D materials-based composites. To complement the existing toolbox of plasmonic inorganic NSs, hybridization with organic molecules is proposed to improve the stability of NSs and selectivity of SERS sensing by hybridizing with small or large organic molecules.

Electrochemical preparation of nano/micron structure transition metal-based catalysts for the oxygen evolution reaction.

Electrochemical water splitting is a promising technology for hydrogen production and sustainable energy conversion, but the existing electrolytic cells lack a sufficient number of robust and highly active anodic electrodes for the oxygen evolution reaction (OER). Electrochemical synthesis technology provides a feasible route for the preparation of independent OER electrodes with high utilization of active sites, fast mass transfer, and a simple preparation process. A comprehensive review of the electrochemical synthesis of nano/microstructure transition metal-based OER materials is provided. First, some fundamentals of electrochemical synthesis are introduced, including electrochemical synthesis strategies, electrochemical synthesis substrates, the electrolyte used in electrochemical synthesis, and the combination of electrochemical synthesis and other synthesis methods. Second, the morphology and properties of electrochemical synthetic materials are summarized and introduced from the viewpoint of structural design. Then, the latest progress regarding the development of transition metal-based OER electrocatalysts is reviewed, including the classification of metals/alloys, oxides, hydroxides, sulfides, phosphides, selenides, and other transition metal compounds. In addition, the oxygen evolution mechanism and rate-determining steps of transition metal-based catalysts are also discussed. Finally, the advantages, challenges, and opportunities regarding the application of electrochemical techniques in the synthesis of transition metal-based OER electrocatalysts are summarized. This review can provide inspiration for researchers and promote the development of water splitting technology.

Plasma-Induced Nanocrystalline Domain Engineering and Surface Passivation in Mesoporous Chalcogenide Semiconductor Thin Films.

The synthesis of highly crystalline mesoporous materials is key to realizing high-performance chemical and biological sensors and optoelectronics. However, minimizing surface oxidation and enhancing the domain size without affecting the porous nanoarchitecture are daunting challenges. Herein, we report a hybrid technique that combines bottom-up electrochemical growth with top-down plasma treatment to produce mesoporous semiconductors with large crystalline domain sizes and excellent surface passivation. By passivating unsaturated bonds without incorporating any chemical or physical layers, these films show better stability and enhancement in the optoelectronic properties of mesoporous copper telluride (CuTe) with different pore diameters. These results provide exciting opportunities for the development of long-term, stable, and high-performance mesoporous semiconductor materials for future technologies.

Material Nanoarchitectonics of Functional Polymers and Inorganic Nanomaterials for Smart Supercapacitors.

Smart supercapacitors are a promising energy storage solution due to their high power density, long cycle life, and low-maintenance requirements. Functional polymers (FPs) and inorganic nanomaterials are used in smart supercapacitors because of the favorable mechanical properties (flexibility and stretchability) of FPs and the energy storage properties of inorganic materials. The complementary properties of these materials facilitate commercial applications of smart supercapacitors in flexible smart wearables, displays, and self-generation, as well as energy storage. Here, an overview of strategies for the development of suitable materials for smart supercapacitors is presented, based on recent literature reports. A range of synthetic techniques are discussed and it is concluded that a combination of organic and inorganic hybrid materials is the best option for realizing smart supercapacitors. This perspective facilitates new strategies for the synthesis of hybrid materials, and the development of material technologies for smart energy storage applications.

Progress in Solid Polymer Electrolytes for Lithium-Ion Batteries and Beyond.

Solid-state polymer electrolytes (SPEs) for high electrochemical performance lithium-ion batteries have received considerable attention due to their unique characteristics; they are not prone to leakage, and they exhibit low flammability, excellent processability, good flexibility, high safety levels, and superior thermal stability. However, current SPEs are far from commercialization, mainly due to the low ionic conductivity, low Li+ transference number (tLi+ ), poor electrode/electrolyte interface contact, narrow electrochemical oxidation window, and poor long-term stability of Li metal. Recent work on improving electrochemical performance and these aspects of SPEs are summarized systematically here with a particular focus on the underlying mechanisms, and the improvement strategies are also proposed. This review could lead to a deeper consideration of the issues and solutions affecting the application of SPEs and pave a new pathway to safe, high-performance lithium-ion batteries.

Macroscopic MOF Architectures: Effective Strategies for Practical Application in Water Treatment.

Metal-organic frameworks (MOFs) have potential applications in removing pollutants such as heavy metals, oils, and toxins from water. However, due to the intrinsic fragility of MOFs and their fine powder form, there are still technical barriers to their practical application such as blockage of pipes, difficulty in recovery, and potential environmental toxicity. Therefore, attention has focused on approaches to convert nanocrystalline MOFs into macroscopic materials to overcome these limitations. Recently, strategies for shaping MOFs into beads (0D), nanofibers (1D), membranes (2D), and gels/sponges (3D) with macrostructures are developed including direct mixing, in situ growth, or deposition of MOFs with polymers, cotton, foams or other porous substrates. In this review, successful strategies for the fabrication of macroscopic materials from MOFs and their applications in removing pollutants from water including adsorption, separation, and advanced oxidation processes, are discussed. The relationship between the macroscopic performance and the microstructure of materials, and how the range of 0D to 3D macroscopic materials can be used for water treatment are also outlined.

Efficient lithium-ion storage using a heterostructured porous carbon framework and its in situ transmission electron microscopy study.

A heterostructured porous carbon framework (PCF) composed of reduced graphene oxide (rGO) nanosheets and metal organic framework (MOF)-derived microporous carbon is prepared to investigate its potential use in a lithium-ion battery. As an anode material, the PCF exhibits efficient lithium-ion storage performance with a high reversible specific capacity (771 mA h g-1 at 50 mA g-1), an excellent rate capability (448 mA h g-1 at 1000 mA g-1), and a long lifespan (75% retention after 400 cycles). The in situ transmission electron microscopy (TEM) study demonstrates that its unique three-dimensional (3D) heterostructure can largely tolerate the volume expansion. We envisage that this work may offer a deeper understanding of the importance of tailored design of anode materials for future lithium-ion batteries.

Phenyl-Modified Carbon Nitride Quantum Nanoflakes for Ultra-Highly Selective Sensing of Formic Acid: A Combined Experimental by QCM and Density Functional Theory Study.

Formic acid (HCOOH) is an important intermediate in chemical synthesis, pharmaceuticals, the food industry, and leather tanning and is considered to be an effective hydrogen storage molecule. Direct contact with its vapor and its inhalation lead to burns, nerve injury, and dermatosis. Thus, it is critical to establish efficient sensing materials and devices for the rapid detection of HCOOH. In the present study, we introduce a chemical sensor based on a quartz crystal microbalance (QCM) sensor capable of detecting trace amounts of HCOOH. This sensor is composed of colloidal phenyl-terminated carbon nitride (Ph-g-C3N4) quantum nanoflakes prepared using a facile solid-state method involving the supramolecular preorganization technology. In contrast to other synthetic methods of modified carbon nitride materials, this approach requires no hard templates, hazardous chemicals, or hydrothermal treatments. Comprehensive characterization and density functional theory (DFT) calculations revealed that the QCM sensor designed and prepared here exhibits enhanced detection sensitivity and selectivity for volatile HCOOH, which originates from chemical and hydrogen-bonding interactions between HCOOH and the surface of Ph-g-C3N4. According to DFT results, HCOOH is located close to the cavity of the Ph-g-C3N4 unit, with bonding to graphitic carbon and pyridinic nitrogen atoms of the nanoflake. The sensitivity of the Ph-g-C3N4-nanoflake-based QCM sensor was found to be the highest (128.99 Hz ppm-1) of the substances studied, with a limit of detection (LOD) of HCOOH down to a sub-ppm level of 80 ppb. This sensing technology based on phenyl-terminated attached-g-C3N4 nanoflakes establishes a simple, low-cost solution to improve the performance of QCM sensors for the effective discrimination of HCOOH, HCHO, and CH3COOH vapors using smart electronic noses.

KOH-Activated Hollow ZIF-8 Derived Porous Carbon: Nanoarchitectured Control for Upgraded Capacitive Deionization and Supercapacitor.

Herein, the synergistic effects of hollow nanoarchitecture and high specific surface area of hollow activated carbons (HACs) are reported with the superior supercapacitor (SC) and capacitive deionization (CDI) performance. The center of zeolite imidazolate framework-8 (ZIF-8) is selectively etched to create a hollow cavity as a macropore, and the resulting hollow ZIF-8 (HZIF-8) is carbonized to obtain hollow carbon (HC). The distribution of nanopores is, subsequently, optimized by KOH activation to create more nanopores and significantly increase specific surface area. Indeed, as-prepared hollow activated carbons (HACs) show significant improvement not only in the maximum specific capacitance and desalination capacity but also capacitance retention and mean desalination rates in SC and CDI, respectively. As a result, it is confirmed that well-designed nanoarchitecture and porosity are required to allow efficient diffusion and maximum electrosorption of electrolyte ions.

Nanoarchitectured Porous Conducting Polymers: From Controlled Synthesis to Advanced Applications.

Conductive polymers (CPs) integrate the inherent characteristics of conventional polymers and the unique electrical properties of metals. They have aroused tremendous interest over the last decade owing to their high conductivity, robust and flexible properties, facile fabrication, and cost-effectiveness. Compared to bulk CPs, porous CPs with well-defined nano- or microstructures possess open porous architectures, high specific surface areas, more exposed reactive sites, and remarkably enhanced activities. These attractive features have led to their applications in sensors, energy storage and conversion devices, biomedical devices, and so on. In this review article, the different strategies for synthesizing porous CPs, including template-free and template-based methods, are summarized, and the importance of tuning the morphology and pore structure of porous CPs to optimize their functional performance is highlighted. Moreover, their representative applications (energy storage devices, sensors, biomedical devices, etc.) are also discussed. The review is concluded by discussing the current challenges and future development trend in this field.

Enantioselective SERS sensing of pseudoephedrine in blood plasma biomatrix by hierarchical mesoporous Au films coated with a homochiral MOF.

Here, we present a new family of hierarchical porous hybrid materials as an innovative tool for ultrasensitive and selective sensing of enantiomeric drugs in complex biosamples via chiral surface-enhanced Raman spectroscopy (SERS). Hierarchical porous hybrid films were prepared by the combination of mesoporous plasmonic Au films and microporous homochiral metal-organic frameworks (HMOFs). The proposed hierarchical porous substrates enable extremely low limit of detection values (10-12 M) for pseudoephedrine in undiluted blood plasma due to dual enhancement mechanisms (physical enhancement by the mesoporous Au nanostructures and chemical enhancement by HMOF), chemical recognition by HMOF, and a discriminant function for bio-samples containing large biomolecules, such as blood components. We demonstrate the effect of each component (mesoporous Au and microporous AlaZnCl (HMOF)) on the analytical performance for sensing. The growth of AlaZnCl leads to an increase in the SERS signal (by around 17 times), while the use of mesoporous Au leads to an increase in the signal (by up to 40%). In the presence of a complex biomatrix (blood serum or plasma), the hybrid hierarchical porous substrate provides control over the transport of the molecules inside the pores and prevents blood protein infiltration, provoking competition with existing plasmonic materials at the limit of detection and enantioselectivity in the presence of a multicomponent biomatrix.

In Search of Excellence: Convex versus Concave Noble Metal Nanostructures for Electrocatalytic Applications.

Controlling the shape of noble metal nanoparticles is a challenging but important task in electrocatalysis. Apart from hollow and nanocage structures, concave noble metal nanoparticles are considered a new class of unconventional electrocatalysts that exhibit superior electrocatalytic properties as compared with those of conventional nanoparticles (including convex and flat ones). Herein, several facile and highly reproducible routes for synthesizing nanostructured concave noble metal materials reported in the literature are discussed, together with their advantages over noble metal nanoparticles with convex shapes. In addition, possible ways of optimizing the synthesis procedure and enhancing the electrocatalytic characteristics of concave metal nanoparticles are suggested. Nanostructured noble metals with concave features are found to show better catalytic activity and stability hence improve their practical applicability in electrocatalysis.

Nanoporous carbon nitride with a high content of inbuilt N site for the CO2 capture.

We report the nanoconfinement-mediated graphitic nanoporous carbon nitride (gNPCN) adsorbents with a high content of inbuilt basic nitrogen (N) (48%) by X-ray photoelectron spectroscopy (XPS) for efficient CO2 adsorption. The gNPCNs (gNPCN-150 and gNPCN-130) are synthesized using the mesoporous SBA-15 silica template and a single carbon-nitrogen (C-N) precursor (guanidine hydrochloride). The various adsorbents were utilized for investigating the influence of pore size (PS), surface area (SA), and type of adsorbent for CO2 adsorption performance. The capacity for CO2 capturing of gNPCN-150 reached 23.1 mmol/g at 0 °C under 30 bar pressure. This CO2 capturing capacity value was higher than the capacity gNPCN-130, SBA15, activated carbon (AC), and multiwalled carbon nanotube (MWCN) under identical conditions. The gNPCN materials exhibited superior CO2 adsorption ability that is ascribed to the presence of the highly organized mesoporosity, inbuilt high content of basic N site for adsorbing more CO2 through acid-base interaction, and tunable surface-structural properties. Moreover, the synthesis strategy is remarkably flexible in selecting C-N sources. This study features graphitic high-ordered nanoporous CN materials as a resourceful platform towards the efficient CO2 capture.