The amalgamation of different disciplines is at the heart of reticular chemistry and has broadened the boundaries of chemistry by opening up an infinite space of chemical composition, structure, and material properties. Reticular design has enabled the precise prediction of crystalline framework structures, tunability of chemical composition, incorporation of various functionalities onto the framework backbone, and as a consequence, fine-tuning of metal-organic framework (MOF) and covalent organic framework (COF) properties beyond that of any other material class. Leveraging the unique properties of reticular materials has resulted in significant advances from both a fundamental and an applied perspective. Here, we wish to review the milestones in MOF and COF research and give a critical view on progress in their real-world applications. Finally, we briefly discuss the major challenges in the field that need to be addressed to pave the way for industrial applications.

The Current Status of MOF and COF Applications

At its core, reticular chemistry has translated the precision and expertise of organic and inorganic synthesis to the solid state. While initial excitement over metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) was undoubtedly fueled by their unprecedented porosity and surface areas, the most profound scientific innovation of the field has been the elaboration of design strategies for the synthesis of extended crystalline solids through strong directional bonds. In this contribution we highlight the different classes of reticular materials that have been developed, how these frameworks can be functionalized, and how complexity can be introduced into their backbones. Finally, we show how the structural control over these materials is being extended from the molecular scale to their crystal morphology and shape on the nanoscale, all the way to their shaping on the bulk scale.

25 Years of Reticular Chemistry.

Two-dimensional metal-organic frameworks (MOFs) have been explored as effective electrocatalysts for hydrogen evolution reaction (HER). However, the sluggish water activation kinetics and structural instability under ultrahigh-current density hinder their large-scale industrial applications. Herein, we develop a universal ligand regulation strategy to build well-aligned Ni-benzenedicarboxylic acid (BDC)-based MOF nanosheet arrays with S introducing (S-NiBDC). Benefiting from the closer p-band center to the Fermi level with strong electron transferability, S-NiBDC array exhibits a low overpotential of 310 mV to attain 1.0 A cm-2 with high stability in alkaline electrolyte. We speculate the newly-constructed triangular "Ni2-S1" motif as the improved HER active region based on detailed mechanism analysis and structural characterization, and the enhanced covalency of Ni-O bonds by S introducing stabilizes S-NiBDC structure. Experimental observations and theoretical calculations elucidate that such Ni sites in "Ni2-S1" center distinctly accelerate the water activation kinetics, while the S site readily captures the H atom as the optimal HER active site, boosting the whole HER activity. 

https://www.nature.com/articles/s41467-022-34278-6.pdf

Accelerated water activation and stabilized metal-organic framework via constructing triangular active-regions for ampere-level current density hydrogen production

PEDOT:PSS: From conductive polymers to sensors

The development of modern cutting-edge technology relies heavily on the huge success and advancement of nanotechnology, in which nanomaterials and nanostructures provide the indispensable material cornerstone. Owing to their nanoscale dimensions with possible quantum limit, nanomaterials and nanostructures possess a high surface-to-volume ratio, rich surface/interface effects, and distinct physical and chemical properties compared with their bulk counterparts, leading to the remarkably expanded horizons of their applications. Depending on their degree of spatial quantization, low-dimensional nanomaterials are generally categorized into nanoparticles (0D); nanorods, nanowires, and nanobelts (1D); and atomically thin layered materials (2D). This review article provides a comprehensive guide to low-dimensional nanomaterials and nanostructures. It begins with the classification of nanomaterials, followed by an inclusive account of nanofabrication and characterization. Both top-down and bottom-up fabrication approaches are discussed in detail. Next, various significant applications of low-dimensional nanomaterials are discussed, such as photonics, sensors, catalysis, energy storage, diverse coatings, and various bioapplications. This article would serve as a quick and facile guide for scientists and engineers working in the field of nanotechnology and nanomaterials.

/pdf/a-review-on-low-dimensional-nanomaterials-nanofabrication-2fk2k6rg.pdf

A Review on Low-Dimensional Nanomaterials: Nanofabrication, Characterization and Applications

Metal–organic frameworks (MOFs) offer disruptive potential in micro- and optoelectronics because of the unique properties of these microporous materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturized solid-state devices. Conventional MOF patterning methods suffer from low resolution and poorly defined pattern edges. Here, we demonstrate the resist-free, direct X-ray and electron-beam lithography of MOFs. This process avoids etching damage and contamination and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting high-quality patterns have excellent sub-50-nm resolution, and approach the mesopore regime. The compatibility of X-ray and electron-beam lithography with existing micro- and nanofabrication processes will facilitate the integration of MOFs in miniaturized devices. The low dielectric constants and high porosity of MOFs are of interest for applications in electronics and sensors, but patterning techniques for these materials are in their infancy. Here, direct X-ray and electron-beam lithography at sub-50-nm resolution are reported that leave porosity and crystallinity intact.

/pdf/direct-x-ray-and-electron-beam-lithography-of-halogenated-58ihtoa9lx.pdf

Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks

The landscape of possible polymorphs for some metal-organic frameworks (MOFs) can pose a challenge for controlling the outcome of their syntheses. Demonstrated here is the use of a template to control in the vapor-assisted formation of zeolitic imidazolate framework (ZIF) powders and thin films. Introducing a small amount of either ethanol or dimethylformamide vapor during the reaction between ZnO and 4,5-dichloroimidazole vapor results in the formation of the porous ZIF-71 phase, whereas other conditions lead to the formation of the dense ZIF-72 phase or amorphous materials. Time-resolved in situ small-angle X-ray scattering reveals that the porous phase is metastable and can be transformed into its dense polymorph. This transformation is avoided through the introduction of template vapor. The porosity of the resulting ZIF powders and films was studied by N2 and Kr physisorption, as well as positron annihilation lifetime spectroscopy. The templating principle was demonstrated for other members of the ZIF family as well, including the ZIF-7 series, ZIF-8_Cl, and ZIF-8_Br.

/pdf/template-mediated-control-over-polymorphism-in-the-vapor-55s7owqcb5.pdf

Template‐mediated control over polymorphism in the vapor‐assisted formation of zeolitic imidazolate framework powders and films

Flexible Metal Halide Perovskite Photodetector Arrays via Photolithography and Dry Lift-Off Patterning

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Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks

Template‐mediated control over polymorphism in the vapor‐assisted formation of zeolitic imidazolate framework powders and films

Flexible Metal Halide Perovskite Photodetector Arrays via Photolithography and Dry Lift-Off Patterning