Inorganic-Organic Nanoarchitectonics: MXene/Covalent Organic Framework Heterostructure for Superior Microextraction.

One of the difficulties limiting covalent organic frameworks (COFs) from becoming excellent adsorbents is their stacking/aggregation architectures owing to poor morphology/structure control during the synthesis process. Herein, an inorganic-organic nanoarchitectonics strategy to synthesize the MXene/COF heterostructure (Ti3 C2 Tx /TAPT-TFP) is developed by the assembly of ß-ketoenamine-linked COF on the Ti3 C2 Tx MXene nanosheets. The as-prepared Ti3 C2 Tx /TAPT-TFP retains the 2D architecture and high adsorption capacity of MXenes as well as large specific surface area and hierarchical porous structure of COFs. As a proof of concept, the potential of Ti3 C2 Tx /TAPT-TFP for solid-phase microextraction (SPME) of trace organochlorine pesticides (OCPs) is investigated. The Ti3 C2 Tx /TAPT-TFP based SPME method achieves low limits of detection (0.036-0.126 ng g-1 ), wide linearity ranges (0.12-20.0 ng g-1 ), and acceptable repeatabilities for preconcentrating trace OCPs from fruit and vegetable samples. This study offers insights into the potential of constructing COF or MXene-based heterostructures for the microextraction of environmental pollutants.

Superstructures of Zeolitic Imidazolate Frameworks to Single- and Multiatom Sites for Electrochemical Energy Conversion.

The exploration of electrocatalysts with high catalytic activity and long-term stability for electrochemical energy conversion is significant yet remains challenging. Zeolitic imidazolate framework (ZIF)-derived superstructures are a source of atomic-site-containing electrocatalysts. These atomic sites anchor the guest encapsulation and self-assembly of aspheric polyhedral particles produced using microreactor fabrication. This review provides an overview of ZIF-derived superstructures by highlighting some of the key structural types, such as open carbon cages, 1D superstructures, hollow structures, and the interconversion of superstructures. The fundamentals and representative structures are outlined to demonstrate the role of superstructures in the construction of materials with atomic sites, such as single- and dual-atom materials. Then, the roles of ZIF-derived single-atom sites for the electroreduction of CO2 and electrochemical synthesis of H2 O2 are discussed, and their electrochemical performance for energy conversion is outlined. Finally, the perspective on advancing single- and dual-atom electrode-based electrochemical processes with enhanced redox activity and a low-impedance charge-transfer pathway for cathodes is provided. The challenges associated with ZIF-derived superstructures for electrochemical energy conversion are discussed.

Synthesis and Optical Properties of MnS­ZnS and MnS­CdS Nanoparticles in Montmorillonite.

The incorporation of metal sulfide mixture, manganese sulfide and zinc sulfide (MnS­ZnS) or manganese sulfide and cadmium sulfide (MnS­CdS), in two types of montmorillonites (sodium montmorillonite and cetyltrimethylammonium modified montmorillonite) was investigated. The hybrids were characterized by powder X-ray diffraction, thermogravimetric-differential thermal analysis, transmission electron microscopy (TEM), and Raman, UV-visible and photoluminescence spectroscopies. The experimental evidences such as the expansion of the interlayer spaces and the presence of the absorption and photoluminescence due to MnS, ZnS and/or CdS revealed that the mixed metal sulfides formed in the interlayer space of montmorillonites. TEM images of the hybrids showed diskor plate-shaped nanoparticles with a mean diameter of ca. 2 nm. The increase of the luminescence intensities of the hybrids was assumed to be caused by quantum confinement effect in the interlayer space of montmorillonite.

Cadmium Telluride-Titanium Dioxide Nanocomposite for Photodegradation of Organic Substance.

Cadmium telluride-titanium dioxide nanocomposite was prepared by hydrothermal reaction of sol-gel derived titanium dioxide and organically modified cadmium telluride. The crystallinity of titanium dioxide in the nanocomposite was higher than that of pure titanium dioxide obtained by the reaction under the same temperature and pressure conditions, showing that cadmium telluride induced the crystallization of titanium dioxide. Diffuse reflectance spectrum of the nanocomposite showed the higher absorption efficiency in the UV-visible region due to band-gap excitation of titanium dioxide. The nanocomposite significantly showed the improvement of photocatalytic activity for 4-chlorophenol with UV light.

Precise Regulation of Interlayer Stacking Modes in Trinuclear Copper Organic Frameworks for Efficient Photocatalytic Reduction of Uranium(VI).

The interlayer stacking modes of 2D covalent-organic frameworks (COFs) directly influence their structural features, ultimately determining their functional output. However, controllably modulating the interlayer stacking structure in traditional 2D metal-free COFs, based on the same building blocks, remains challenging. Here, two trinuclear copper organic frameworks are synthesized successfully with different interlayer stacking structures: eclipsed AA stacking in Cu3-PA-COF-AA and staggered ABC stacking in Cu3-PA-COF-ABC, using the same monomers. Remarkably, various functionalities, including porosity and electronic and optical properties, can be effectively regulated by interlayer stacking. As a result, Cu3-PA-COF-AA and Cu3-PA-COF-ABC exhibit significantly different activities toward the photoreduction of U(VI), presenting a promising strategy for removing radioactive uranium pollution. Due to its broader visible-light absorption range and superior photogenerated carrier migration and separation efficiency, Cu3-PA-COF-AA achieves a U(VI) removal ratio of 93.6% without additional sacrificial agents in an air atmosphere-≈2.2 times higher than that of Cu3-PA-COF-ABC (42.0%). To the best of the knowledge, this is the first study to elucidate the effect of interlayer stacking in COFs on the photocatalytic activity of U(VI) reduction. This finding may inspire further exploration of the structure-function relationship in COFs as photocatalysts and their potential for photoinduced removal of radionuclides.

Control of particle growth and enhancement of photoluminescence, adsorption efficiency, and photocatalytic activity for zinc sulfide and cadmium sulfide using CoAl-layered double hydroxide system.

The fabrication of zinc sulfide (ZnS) and cadmium sulfide (CdS) hybrids was carried out by the sulfidization of Zn(II) or Cd(II) adsorbed in dodecylsulfate modified CoAl-layered double hydroxide through solid-liquid reaction. The TEM images showed the nanocrystals of ZnS (2.61 nm) or CdS (3.29 nm) orderly distributed on the nanosheets. The BET surface area of ZnS (1.13 m2/g) and CdS (0.78 m2/g) was largely improved by intercalating in the interlayer space of CoAl-layered double hydroxide system (15-20 m2/g). The spectroscopic observations further confirmed the formation of ZnS or CdS nanoparticles in the hybrid as the evidence of the blue-shifted absorption onset (39-44 nm), and the increase of the photoluminescence intensity (3-4 times) relative to those of bare ZnS and CdS. The nanohybrids could be applicable as the adsorbent and photocatalyst on purifying wastewater contaminated with Congo red dye. By the adsorptive removal, the hybrids exhibited the maximum adsorption capacity of 216-234 mg/g, resulting from the effect of CoAl-layered double hydroxide. In addition, the photocatalytic degradation was completely conducted by using CdS hybrid with the rate constant of 0.0115 min-1, because the host-guest and/or guest-guest interactions promoted the greater optical performance, and adsorption and photocatalytic efficiencies.

Unlocking Catalytic Potential: Encasing CoP Nanoparticles within Mesoporous CoFeP Nanocubes for Enhanced Oxygen Evolution Reaction.

Efficient and durable electrocatalysts fabricated by using nanosized nonprecious-metal-based materials have attracted considerable attention for use in the oxygen evolution reaction (OER). Understanding performance disparities and structure-property relationships of various nonprecious-metal-based nanostructures is crucial for optimizing their applications. Herein, CoP nanoparticles encompassed within a CoFeP shell (named CoP/CoFeP) are fabricated. The mesoporous CoFeP shell enables effective mass transport, affords abundant active sites, and ensures the accessibility of hybrid interfaces between CoP and CoFeP. Therefore, encased CoP/CoFeP nanocubes exhibit excellent OER catalytic activity with an overpotential of 266 mV at a current density of 10 mA cm-2 in alkaline media, superior to reference hollow CoFeP nanocubes and commercial RuO2. Experimental characterization and theoretical calculations show that the encased structure of CoP/CoFeP with a rich Fe-doped shell enables electronic interactions between CoP and CoFeP, as well as accelerates structural reconstruction that exposes more active sites, yielding an enhanced OER performance. This study aims to inspire further work on nonprecious-metal catalysts with tailored nanostructures and electronic properties for the OER.

Photoactive nanoarchitectures based on clays incorporating TiO2 and ZnO nanoparticles.

Thought as raw materials clay minerals are often disregarded in the development of advanced materials. However, clays of natural and synthetic origin constitute excellent platforms for developing nanostructured functional materials for numerous applications. They can be easily assembled to diverse types of nanoparticles provided with magnetic, electronic, photoactive or bioactive properties, allowing to overcome drawbacks of other types of substrates in the design of functional nanoarchitectures. Within this scope, clays can be of special relevance in the production of photoactive materials as they offer an advantageous way for the stabilization and immobilization of diverse metal-oxide nanoparticles. The controlled assembly under mild conditions of titanium dioxide and zinc oxide nanoparticles with clay minerals to give diverse clay-semiconductor nanoarchitectures are summarized and critically discussed in this review article. The possibility to use clay minerals as starting components showing different morphologies, such as layered, fibrous, or tubular morphologies, to immobilize these types of nanoparticles mainly plays a role in i) the control of their size and size distribution on the solid surface, ii) the mitigation or suppression of the nanoparticle aggregation, and iii) the hierarchical design for selectivity enhancements in the catalytic transformation and for improved overall reaction efficiency. This article tries also to present new steps towards more sophisticated but efficient and highly selective functional nanoarchitectures incorporating photosensitizer elements for tuning the semiconductor-clay photoactivity.

Control of the optical properties of cadmium selenide nanoparticles using magadiite.

The preparation of cadmium selenide nanoparticles in the interlayer space of magadiite, a layered sodium silicate, modified with the cetyltrimethylammonium cation was studied. The preparation was based on the formation of cadmium selenide by the reaction between the cetyltrimethylammonium modified magadiite and an aqueous mixture of cadmium sulfate and sodium selenosulfite at room temperature. The resulting hybrids were characterized by XRD, FT-IR, HRTEM, TG-DTA, as well as UV-visible and photoluminescence spectroscopy. The expansion of the interlayer spaces as well as TG-DTA results indicated the presence of the cetyltrimethylammonium cation and cadmium selenide in the hybrids. The HRTEM images showed the presence of cadmium selenide in the diameter range of 2-3 nm in the interlayer space of magadiite. The luminescence intensity of the cadmium selenide varied depending on the particle size, which was controlled by the loading amount of cadmium selenide precursor.

Simple preparation of a cadmium selenide-montmorillonite hybrid.

The immobilization of organically modified cadmium selenide on montmorillonite was investigated by the reaction of modified cadmium selenide nanoparticles with montmorillonite. The intercalation of the nanoparticles was indicated by the expansion of the interlayer space and spectroscopic observations. The diffuse reflectance absorption spectrum of the product showed absorption onset at 567 nm. In comparison to the bulk cadmium selenide, the blue shift of the absorption onset of the hybrid was ascribed to the quantum size effect of the modified cadmium selenide nanoparticles. This study provides a new method for introducing nanoparticles into the interlayer space of layered inorganic materials.

Formation of mixed-ligand zinc(II) complex-montmorillonite hybrids by solid-solid reactions.

Two luminescent hybrids, Znqb- and Znqp-montmorillonites (q = 8-hydroxyquinoline, b = 2,2'-bipyridine, p = 1,10-phenanthroline), were prepared by solid-solid reactions between Zn(II)-montmorillonite and two ligands (8-hydroxyquinoline and 2,2'-bipyridine or 1,10-phenanthroline) at room temperature. The intercalation and in situ complex formation of the two ligands into an interlayer space of Zn(II)-montmorillonite were confirmed by powder XRD, TG-DTA, as well as FT-IR, UV-vis and photoluminescence spectroscopies. The emission band of Znqb-montmorillonite was red-shifted compared to that of the mixture of Znq-montmorillonite and Znb-montmorillonite, confirming the formation of Znqb complex in montmorillonite. The photoluminescence intensity of Znqb-montmorillonite was higher than that of Znqp-montmorillonite, indicating that 2,2'-bipyridine enhanced the emission intensity of zinc(8-hydroxyquinoline) complex in montmorillonite, while the coordination of 1,10-phenanthroline quenched the intensity of the immobilized chelate.