Low-valence platinum single atoms in sulfur-containing covalent organic frameworks for photocatalytic hydrogen evolution.

This study focuses on optimizing catalytic activity in photocatalytic hydrogen evolution reaction by precisely designing and modulating the electronic structure of metal single atoms. The catalyst, denoted as PtSA@S-TFPT, integrates low-valence platinum single atoms into sulfur-containing covalent organic frameworks. The robust asymmetric four-coordination between sulfur and platinum within the framework enables a high platinum loading of 12.

Intrareticular Exciton Effects Regulate Photocatalytic Activity in Donor-Acceptor Olefin-Linked Covalent Organic Frameworks.

Olefin-linked covalent organic frameworks (OL-COFs) show great promise for visible-light-driven photocatalysis. Manipulating atomic-level donor-acceptor interactions in OL-COFs is key to understanding their exciton effects in this system. Here, three OL-COFs are presented with orthorhombic lattice structures, synthesized via Knoevenagel polycondensation reaction of terephthalaldehyde and tetratopic monomers featuring phenyl, benzo[c][1,2,5]oxadiazole, and benzo[c][1,2,5]thiadiazole moieties.

Tailoring chelating sites in two-dimensional covalent organic framework nanosheets for enhanced uranium capture.

In this study, we intricately designed and synthesized two isoreticular two-dimensional covalent organic framework nanosheets, namely TAPA-COF-1 and TAPA-COF-2, distinguished by their unique spatial arrangement of hydroxyl groups. These precisely engineered nanosheets were employed as a tailored platform for the selective capture of uranium, due to their tunable chelating sites and characteristic sheet-like morphology. Notably, TAPA-COF-1, featuring -hydroxyl groups, demonstrated a significantly enhanced adsorption capacity for uranium capture originating from the additional oriented adjacent phenolic hydroxyl chelating sites in comparison to TAPA-COF-2 with -hydroxyl groups, which was proved by theoretical calculation.

Revolutionizing the structural design and determination of covalent-organic frameworks: principles, methods, and techniques.

Covalent organic frameworks (COFs) represent an important class of crystalline porous materials with designable structures and functions. The interconnected organic monomers, featuring pre-designed symmetries and connectivities, dictate the structures of COFs, endowing them with high thermal and chemical stability, large surface area, and tunable micropores. Furthermore, by utilizing pre-functionalization or post-synthetic functionalization strategies, COFs can acquire multifunctionalities, leading to their versatile applications in gas separation/storage, catalysis, and optoelectronic devices.

Recent Progress on Phase Engineering of Nanomaterials.

As a key structural parameter, phase depicts the arrangement of atoms in materials. Normally, a nanomaterial exists in its thermodynamically stable crystal phase. With the development of nanotechnology, nanomaterials with unconventional crystal phases, which rarely exist in their bulk counterparts, or amorphous phase have been prepared using carefully controlled reaction conditions.

Kagome-topology 2D covalent organic frameworks assembled from -symmetric and non-centrosymmetric -symmetric blocks for photothermal imaging.

In this study, we synthesized two new two-dimensional (2D) covalent organic frameworks (COFs), COF-TA and COF-DP, by combining 4-connected -symmetric and 2-connected non-centrosymmetric -symmetric building blocks. Unlike the typical sql topology, these COFs exhibit an unconventional topology characterized by a favorable anti-parallel stacking arrangement, which results in a lower energy configuration. Notably, COF-DP, with its unique D-A-D structural motif and photosensitive properties, demonstrates a narrow band gap and excellent photothermal conversion capabilities, making it a promising material for photothermal imaging applications.

Salt-Assisted Fabrication of a Water-Based Covalent Organic Framework Ink and Its Hybrid Films for Photothermal Actuators.

The exceptional properties of two-dimensional covalent organic framework materials (2D-COFs), including their large π-conjugated structure at the molecular level and π-π multilayer stacking, have attracted interest for soft photothermal actuator applications. However, the conventional synthesis of COFs as microcrystalline powders limits their processing in water due to their limited dispersibility. Herein, we present a simple and environmentally friendly method to fabricate water-suspended COF inks by adjusting the surface potential of COF powders through adsorption of ionic species such as Na and Cl.

Three-dimensional covalent organic frameworks with pto and mhq-z topologies based on Tri- and tetratopic linkers.

Three-dimensional (3D) covalent organic frameworks (COFs) possess higher surface areas, more abundant pore channels, and lower density compared to their two-dimensional counterparts which makes the development of 3D COFs interesting from a fundamental and practical point of view. However, the construction of highly crystalline 3D COF remains challenging. At the same time, the choice of topologies in 3D COFs is limited by the crystallization problem, the lack of availability of suitable building blocks with appropriate reactivity and symmetries, and the difficulties in crystalline structure determination.

Single Site Coordination Enabled Construction of Metal-Diketimine-Linked Covalent Organic Frameworks for Boosted Electrooxidation of Biomass Derivative.

Aromatic aldehydes are widely used for the construction of covalent organic frameworks (COFs). However, due to the high flexibility, high steric hindrance, and low reactivity, it remains challenging to synthesize COFs using ketones as building units, especially the highly flexible aliphatic ones. Here, the single nickel site coordination strategy is reported to lock the configurations of the highly flexible diketimine to transform discrete oligomers or amorphous polymers into highly crystalline nickel-diketimine-linked COFs (named as Ni-DKI-COFs).

Density Functional Theory Study of CO Hydrogenation on Transition-Metal-Doped Cu(211) Surfaces.

The massive emission of CO has caused a series of environmental problems, including global warming, which exacerbates natural disasters and human health. Cu-based catalysts have shown great activity in the reduction of CO, but the mechanism of CO activation remains ambiguous. In this work, we performed density functional theory (DFT) calculations to investigate the hydrogenation of CO on Cu(211)-Rh, Cu(211)-Ni, Cu(211)-Co, and Cu(211)-Ru surfaces.

growth strategy to construct perovskite quantum dot@covalent organic framework composites with enhanced water stability.

Metal halide perovskite quantum dots (QDs) have excellent optoelectronic properties; however, their poor stability under water or thermal conditions remains an obstacle to commercialization. Here, we used a carboxyl functional group (-COOH) to enhance the ability of a covalent organic framework (COF) to adsorb lead ions and grow CHNHPbBr(MAPbBr) QDsinto a mesoporous carboxyl-functionalized COF to construct MAPbBrQDs@COF core-shell-like composites to improve the stability of perovskites. Owing to the protection of the COF, the as-prepared composites exhibited enhanced water stability, and the characteristic fluorescence was maintained for more than 15 d.

Self-Assembly of Silver Clusters into One- and Two-Dimensional Structures and Highly Selective Methanol Sensing.

The development of new materials for the design of sensitive and responsive sensors has become a crucial research direction. Here, two silver cluster-based polymers (Ag-CBPs), including one-dimensional {[Ag(L1)(CFCO)](CHOH)} chain and two-dimensional {[Ag(L2)(COCF)(HO)(AgCOCF)](HNEt)} film, are designed and used to simulate the human nose, an elegant sensor to smells, to distinguish organic solvents. We study the relationship between the atomic structures of Ag-CBPs determined by x-ray diffraction and the electrical properties in the presence of organic solvents (e.

Ultrathin Covalent Organic Framework Nanosheets/TiCT-Based Photoelectrochemical Biosensor for Efficient Detection of Prostate-Specific Antigen.

Designable and ultrathin covalent organic framework nanosheets (CONs) with good photoelectric activity are promising candidates for the construction of photoelectrochemical (PEC) biosensors for the detection of low-abundance biological substrates. However, achieving highly sensitive PEC properties by using emerging covalent organic framework nanosheets (CONs) remains a great challenge due to the polymeric nature and poor photoelectric activity of CONs. Herein, we report for the first time the preparation of novel composites and their PEC sensing properties by electrostatic self-assembly of ultrathin CONs (called TTPA-CONs) with TiCT.

Ultrathin MOF nanosheet-based resistive sensors for highly sensitive detection of methanol.

Sensors with high-sensitivity for resistive methanol gas detection are highly desirable. Herein, we report newly designed ultrathin anionic metal-organic framework (MOF) nanosheets (NSs), with an average thickness of 10 nm and an electrical conductivity of 3.77 × 10 S cm.

A rigidity-flexibility balance strategy enabling highly photoluminescent two-dimensional covalent organic framework nanosheets.

The fluorescence quenching phenomenon commonly found in two-dimensional COFs is due to either the strong interlayer π-π stacking or the non-radiative decay caused by intramolecular rotation. Here, we report a rigidity-flexibility balance strategy for constructing highly photoluminescent 2D COF nanosheets the integration of rigid fluorescent molecular nodes with flexible non-planar building blocks. The prepared COF nanosheets, termed TPE-DBC-COF, achieve extremely high PLQY in common organic solvents, especially in tetrahydrofuran (43.

Synthesis and Visualization of Entangled 3D Covalent Organic Frameworks with High-Valency Stereoscopic Molecular Nodes for Gas Separation.

The structural diversity of three-dimensional (3D) covalent organic frameworks (COFs) are limited as there are only a few choices of building units with multiple symmetrically distributed connection sites. To date, 4 and 6-connected stereoscopic nodes with T , D , D and C symmetries have been mostly reported, delivering limited 3D topologies. We propose an efficient approach to expand the 3D COF repertoire by introducing a high-valency quadrangular prism (D ) stereoscopic node with a connectivity of eight, based on which two isoreticular 3D imine-linked COFs can be created.

Isoreticular Series of Two-Dimensional Covalent Organic Frameworks with the kgd Topology and Controllable Micropores.

Two-dimensional (2D) covalent organic frameworks (COFs) possess designable pore architectures but limited framework topologies. Until now, 2D COFs adopting the topology with ordered and rhombic pore geometry have rarely been reported. Here, an isoreticular series of 2D COFs with the topology and controllable pore size is synthesized by employing a -symmetric aldehyde, .

A reusable wet-transfer printing technique for manufacturing of flexible silver nanowire film-based electrodes.

To explore a simple and efficient way to fabricate thin film electrodes on flexible substrates is highly desired because of its high promising application in optoelectronics. Transfer printing technique plays a key role in the fabrication of flexible electrodes from conventional substrates to flexible substrates. Unfortunately, a simple, room temperature, environmental-friendly and reusable transfer printing technique still remains challenging.

Substoichiometric 3D Covalent Organic Frameworks Based on Hexagonal Linkers.

Covalent organic frameworks (COFs), a fast-growing field in crystalline porous materials, have achieved tremendous success in structure development and application exploration over the past decade. The vast majority of COFs reported to date are designed according to the basic concept of reticular chemistry, which is rooted in the idea that building blocks are fully connected within the frameworks. We demonstrate here that sub-stoichiometric construction of 2D/3D COFs can be accomplished by the condensation of a hexagonal linker with 4-connected building units.

A highly sensitive strain sensor with a sandwich structure composed of two silver nanoparticles layers and one silver nanowires layer for human motion detection.

The fabrication of strain sensors with high sensitivity, large sensing range and excellent stability is highly desirable because of their promising applications in human motion detection, human-machine interface and electric skin, etc. Herein, by introducing a highly conductive silver nanowire (AgNW) layer between two serried silver nanoparticle (AgNP) layers, forming a sandwich structure, a strain sensor with high sensitivity (a large gauge factor of 2.8 × 10), large sensing range (up to 80% strain) and excellent stability (over 1000 cycles) can be achieved.

Evoking ordered vacancies in metallic nanostructures toward a vacated Barlow packing for high-performance hydrogen evolution.

Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize.

Enhanced stability of silver nanowire transparent conductive films against ultraviolet light illumination.

Silver nanowires are susceptible to degradation under ultraviolet (UV) light illumination. Encapsulating silver nanowire transparent conductive films (AgNW TCFs) with UV shielding materials usually result in the increasing of the sheet resistance or the decrease of the visible light transparency. Herein, we combine a reducing species (FeSO) and a thin layer (overcoating) of UV shielding material to solve the stability and the optical performance issues simultaneously.

Intramolecular Hydrogen Bonding-Based Topology Regulation of Two-Dimensional Covalent Organic Frameworks.

Creating molecular networks with different topologies using identical molecular linkers is fundamentally important but requires precise chemistry control. Here, we propose an effective strategy to regulate the network topologies of two-dimensional (2D) covalent organic frameworks (COFs) through the conformational switching of molecular linkages. By simply altering the substituents of an identical molecular linker, the topology-selective synthesis of two highly crystalline 2D COFs can be readily achieved.

Selective Epitaxial Growth of Oriented Hierarchical Metal-Organic Framework Heterostructures.

Metal-organic framework (MOF) heterostructures have shown promising applications in gas adsorption, gas separation, catalysis, and energy, arising from the synergistic effect of each component. However, owing to the difficulty in controlling the size, shape, nucleation, and growth of MOFs, it remains a great challenge to construct MOF heterostructures with precisely controlled orientation, morphology, dimensionality, and spatial distribution of each component. Here, we report a seeded epitaxial growth method to prepare a series of hierarchical MOF heterostructures by engineering the structures, sizes, dimensionalities, morphologies, and lattice parameters of both MOF seeds and the secondary MOFs.

Two-dimensional metal-organic framework nanosheets: synthesis and applications.

Two-dimensional (2D) metal-organic framework (MOF) nanosheets are attracting increasing research attention due to their unique properties originating from their ultrathin thickness, large surface area and high surface-to-volume atom ratios. Many great advances have been made in the synthesis and application of 2D MOF nanosheets over the past few years. In this review, we summarize the recent advances in the synthesis of 2D MOF nanosheets by using top-down methods, e.