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 ortho-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 para-hydroxyl groups, which was proved by theoretical calculation. The impressive features of TAPA-COF-1, including its notable selectivity, rapid adsorption kinetics, and high uptake capacity (657.2 mg g-1), endow it as a highly promising candidate for uranium capture.

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. Our review provides a comprehensive account of the latest advancements in the principles, methods, and techniques for structural design and determination of COFs. These cutting-edge approaches enable the rational design and precise elucidation of COF structures, addressing fundamental physicochemical challenges associated with host-guest interactions, topological transformations, network interpenetration, and defect-mediated catalysis.

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. Together these methods are beginning to enable phase engineering of nanomaterials (PEN), i.e., the synthesis of nanomaterials with unconventional phases and the transformation between different phases, to obtain desired properties and functions. This Review summarizes the research progress in the field of PEN. First, we present representative strategies for the direct synthesis of unconventional phases and modulation of phase transformation in diverse kinds of nanomaterials. We cover the synthesis of nanomaterials ranging from metal nanostructures such as Au, Ag, Cu, Pd, and Ru, and their alloys; metal oxides, borides, and carbides; to transition metal dichalcogenides (TMDs) and 2D layered materials. We review synthesis and growth methods ranging from wet-chemical reduction and seed-mediated epitaxial growth to chemical vapor deposition (CVD), high pressure phase transformation, and electron and ion-beam irradiation. After that, we summarize the significant influence of phase on the various properties of unconventional-phase nanomaterials. We also discuss the potential applications of the developed unconventional-phase nanomaterials in different areas including catalysis, electrochemical energy storage (batteries and supercapacitors), solar cells, optoelectronics, and sensing. Finally, we discuss existing challenges and future research directions in PEN.

Kagome-topology 2D covalent organic frameworks assembled from D2h-symmetric and non-centrosymmetric C2-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 D2h-symmetric and 2-connected non-centrosymmetric C2-symmetric building blocks. Unlike the typical sql topology, these COFs exhibit an unconventional kgm 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-. This technique effectively prevents the accumulation and aggregation of COF powder, resulting in an aqueous COF ink that can be easily cast into homogeneous hybrid COF films by Mayer-rod coating. In addition, the resulting photothermal actuator exhibited a fast response time within 3 s at a curvature of 2.35 cm-1 in the near-infrared light. This facile and practical approach to fabricating water-based COFs ink represents a promising strategy for the development of practical applications of COFs in photothermal actuators.

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. Herein, we report two highly crystalline 3D COFs with pto and mhq-z topologies designed by rationally selecting rectangular-planar and trigonal-planar building blocks with appropriate conformational strains. The pto 3D COFs show a large pore size of 46 Å with an extremely low calculated density. The mhq-z net topology is solely constructed from totally face-enclosed organic polyhedra displaying a precise uniform micropore size of 1.0 nm. The 3D COFs show a high CO2 adsorption capacity at room temperature and can potentially serve as promising carbon capture adsorbents. This work expands the choice of accessible 3D COF topologies, enriching the structural versatility of COFs.

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). The strategy has been successfully extended to the synthesis of a series of Ni-DKI-COFs by the condensation of three flexible diketones with two tridentate amines. Thanks to the ABC stacking model with high amount and easily accessible single nickel (II) sites on their 1D channels, Ni-DKI-COFs are exploited as well-defined electrocatalyst platforms for efficiently electro-upgrading biomass-derived 5-Hydroxymethylfurfural (HMF) into value-added 2,5-furandicarboxylic acid (FDCA) with a 99.9% yield and a 99.5% faradaic efficiency as well as a high turnover frequency of 0.31 s-1 .

In situgrowth 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 CH3NH3PbBr3(MAPbBr3) QDsin situinto a mesoporous carboxyl-functionalized COF to construct MAPbBr3QDs@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. These MAPbBr3QDs@COF composites can be used to fabricate white light-emitting diodes with a color comparable to natural white emission. This work demonstrates the importance of functional groups for thein situgrowth of perovskite QDs, and coating with a porous structure is an effective way to improve the stability of metal halide perovskites.

Density Functional Theory Study of CO2 Hydrogenation on Transition-Metal-Doped Cu(211) Surfaces.

The massive emission of CO2 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 CO2, but the mechanism of CO2 activation remains ambiguous. In this work, we performed density functional theory (DFT) calculations to investigate the hydrogenation of CO2 on Cu(211)-Rh, Cu(211)-Ni, Cu(211)-Co, and Cu(211)-Ru surfaces. The doping of Rh, Ni, Co, and Ru was found to enhance CO2 hydrogenation to produce COOH. For CO2 hydrogenation to produce HCOO, Ru plays a positive role in promoting CO dissociation, while Rh, Ni, and Co increase the barriers. These results indicate that Ru is the most effective additive for CO2 reduction in Cu-based catalysts. In addition, the doping of Rh, Ni, Co, and Ru alters the electronic properties of Cu, and the activity of Cu-based catalysts was subsequently affected according to differential charge analysis. The analysis of Bader charge shows good predictions for CO2 reduction over Cu-based catalysts. This study provides some fundamental aids for the rational design of efficient and stable CO2-reducing agents to mitigate CO2 emission.

Ultrathin Covalent Organic Framework Nanosheets/Ti3C2Tx-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 Ti3C2Tx. The prepared TTPA-CONs/Ti3C2Tx composites can be used as photocathodes for PEC detection of prostate-specific antigen (PSA) with high sensitivity, low detection limit, and good stability. This work not only expands the application of CONs but also opens new avenues for the development of efficient PEC sensing platforms.

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 × 10-4 S cm-1. The ultrathin MOF NSs can be used as the active material in an electronic methanol gas sensor, which exhibits high sensitivity toward methanol gas at room temperature, i.e., high Rair/Rgas (363.2 at 100 ppm), fast gas response/recovery speed (6 s/2 s at 20 ppm), long-term stability, and superior cross-selectivity against other interfering gases.

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 via 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 (43.5%). Besides, the prepared TPE-DBC-COF exhibits excellent sensitivity and selectivity to tetracycline hydrochloride and high cycling stability, so it can be used as a high-efficiency fluorescent sensor for the detection of tetracycline hydrochloride down to the ppm level.

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 Td , D3h , D3d and C3 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 (D4h ) stereoscopic node with a connectivity of eight, based on which two isoreticular 3D imine-linked COFs can be created. Low-dose electron microscopy allows the direct visualization of their 2-fold interpenetrated bcu networks. These 3D COFs are endowed with unique pore architectures and strong molecular binding sites, and exhibit excellent performance in separating C2 H2 /CO2 and C2 H2 /CH4 gas pairs. The introduction of high-valency stereoscopic nodes would lead to an outburst of new topologies for 3D COFs.

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 kgd topology with ordered and rhombic pore geometry have rarely been reported. Here, an isoreticular series of 2D COFs with the kgd topology and controllable pore size is synthesized by employing a C6-symmetric aldehyde, i.e., hexa(4-formylphenyl)benzene (HFPB), and C3-symmetric amines i.e., tris(4-aminophenyl)amine (TAPA), tris(4-aminophenyl)trazine (TAPT), and 1,3,5-tris[4-amino(1,1-biphenyl-4-yl)]benzene (TABPB), as building units, referred to as HFPB-TAPA, HFPB-TAPT, and HFPB-TABPB, respectively. The micropore dimension down to 6.7 Å is achieved in HFPB-TAPA, which is among the smallest pore size of reported 2D COFs. Impressively, both the in-plane network and stacking sequence of the 2D COFs can be clearly observed by low-dose electron microscopy. Integrating the unique kgd topology with small rhombic micropores, these 2D COFs are endowed with both short molecular diffusion length and favorable host-guest interaction, exhibiting potential for drug delivery with high loading and good release control of ibuprofen.

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. Here we demonstrated a novel water-based wet-transfer printing technique that is simple, room temperature, environmental-friendly and reusable by taking advantage of the adjustment of the intermolecular hydrogen bonding between thin film and substrates. This effective and practical transfer technique may provide an effective route to develop electronic flexible devices with high performance.

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. It is worth noting that the partially connected frameworks were successfully reticulated for 3D COFs for the first time, representing the highest BET surface area among imine-linked 3D COFs to data. The unreacted benzaldehydes in COF frameworks can enhance C2H2 and CO2 adsorption capacity and selectivities between C2H2/CH4 and C2H2/CO2 for sub-stoichiometric 2D COFs, while the reserved benzaldehydes control the interpenetrated architectures for the 3D case, achieving a rare non-interpenetrated pts topology for 3D COFs. This work not only paves a new avenue to build new COFs and endows residual function groups with further applications but also prompts redetermination of reticular frameworks in highly connected and symmetrical COFs.

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 × 105), large sensing range (up to 80% strain) and excellent stability (over 1000 cycles) can be achieved. A combination of experimental and mechanism studies shows that the high performance of the obtained strain sensor is ascribed to the synergy of the highly conductive AgNW layer, astatic AgNP layers and the presence of large cracks in stretching. As a proof-of-concept application, the obtained strain sensor can be used for highly effective human motion detection ranging from large scale motions, i.e. kneel bending and wrist flexion, to subtle scale motions, i.e. pulse and swallowing.

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. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H2O in the HER.

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 (FeSO4) and a thin layer (overcoating) of UV shielding material to solve the stability and the optical performance issues simultaneously. The AgNW TCFs show excellent stability under continuous UV light illumination for 14 h, and their sheet resistance varies only 6%. The dramatic enhancement of the stability against UV light illumination for as-obtained TCFs will make them viable for real-world applications in touch panels and displays.

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. Their distinct crystal structures are observed and determined by low-dose, high-resolution transmission electron microscopy imaging, indicating that the driving force for linkage conformation switching is intramolecular hydrogen bonding. Our strategy would greatly diversify the COF topologies and enable vast postsynthetic modifications such as boron complexation, endowing these structures with a unique optical property such as fluorescence turn on and aggregation-induced emission.