Surmounting the inhomogeniety issue of gas sensors and realizing their reproducible ppb‐level gas sensing are highly desirable for widespread deployments of sensors to build networks in applications of industrial safety and indoor/outdoor air quality monitoring. Herein, a strategy is proposed to substantially improve the surface homogeneity of sensing materials and gas sensing performance via chip‐level pyrolysis of as‐grown ZIF‐L (ZIF stands for zeolitic imidazolate framework) films to porous and hierarchical zinc oxide (ZnO) nanosheets. A novel approach to generate adjustable oxygen vacancies is demonstrated, through which the electronic structure of sensing materials can be fine‐tuned. Their presence is thoroughly verified by various techniques. The sensing results demonstrate that the resultant oxygen vacancy‐abundant ZnO nanosheets exhibit significantly enhanced sensitivity and shortened response time toward ppb‐level carbon monoxide (CO) and volatile organic compounds encompassing 1,3‐butadiene, toluene, and tetrachloroethylene, which can be ascribed to several reasons including unpaired electrons, consequent bandgap narrowing, increased specific surface area, and hierarchical micro–mesoporous structures. This facile approach sheds light on the rational design of sensing materials via defect engineering, and can facilitate the mass production, commercialization, and large‐scale deployments of sensors with controllable morphology and superior sensing performance targeted for ultratrace gas detection.

CO 2 emission has raised worldwide concerns because of its potential effects on climate change, species extinction, and plant nutrition deterioration. Metal-organic frameworks (MOFs) are one class of crystalline adsorbent materials that are believed to be of huge potential in CO 2 capture applications because of their advantages such as ultrahigh porosity, boundless chemical tunability, and surface functionality over traditional porous zeolites and activated carbon. In terms of chemistry, there are already many studies devoted to the synthesis of new functional MOFs. Some of the synthesized MOFs have been evaluated for CO 2 capture at laboratory-scale. Several reviews have been published on this topic, but mainly from a chemistry and materials point of view. In this review, the authors focus on the engineering perspective on this topic, with emphases on material evaluation, performance judgment, and process design to address the engineering issues of these materials to be used as adsorbents in industrial CO 2 capture. The current engineering evaluation approaches for MOFs are summarized, in a manner that could also be applied to other adsorbent materials.

Metal-organic cages (MOCs) are discrete molecular assemblies formed by coordination bonds between metal nodes and organic ligands. The application of MOCs has been greatly limited due to their poor stability, especially in aqueous solutions. In this work, we thoroughly investigate the stability of several Zr-MOCs and reveal their excellent stability in aqueous solutions with acidic, neutral, and weak basic conditions. In addition, we present for the first time a process-tracing study on the postassembly modification of one MOC, ZrT-1-NH, highlighting the excellent stability and versatility of Zr-MOCs as a new type of molecular platform for various applications.

The direct synthesis of metal−organic frameworks (MOFs) with strong Brønsted acidity is challenging because the functional groups exhibiting Brønsted acidity (e.g., sulfonic acid groups) often jeopardize the framework integrity. Herein, we report the direct synthesis of two hierarchically porous MOFs named NUS-6 composed of either zirconium (Zr) or hafnium (Hf) clusters with high stability and strong Brønsted acidity. Via the modulated hydrothermal (MHT) synthesis, these two MOFs can be easily synthesized at a low temperature (80 °C) with high throughput. They exhibit BET surface areas of 550 and 530 m 2 g −1 for Zr and Hf one, respectively, and a unique hierarchically porous structure of coexisting micropores (∼0.5, ∼0.7, and ∼1.4 nm) and mesopores (∼4.0 nm) with dangling sulfonic acid groups. Structural analysis reveals that the hierarchical porosity of NUS-6 is a result of missing linkers and clusters of the parental UiO-66 framework. These unique features make NUS-6 highly efficient and selective solid acid catalysts for dehydration of fructose to 5hydroxymethylfurfural (HMF), in which NUS-6(Hf) demonstrates a superior performance versus that of NUS-6(Zr) because of the stronger Brønsted acidity contributed from Hf-μ 3 -OH groups as well as smaller pore sizes suitable for the restriction of unwanted side reactions. Our results have demonstrated for the first time the unique attributes of Hf-MOFs featured by superior stability and Brønsted acidity that can be applied as heterogeneous catalysts in biobased chemical synthesis.

As primary feedstocks in the petrochemical industry, light olefins such as ethylene and propylene are mainly obtained from steam cracking of naphtha and short chain alkanes (ethane and propane). Due to their similar physical properties, the separations of olefins and paraffins—pivotal processes to meet the olefin purity requirement of downstream processing—are typically performed by highly energy‐intensive cryogenic distillation at low temperatures and high pressures. To reduce the energy input and save costs, adsorptive olefin/paraffin separations have been proposed as promising techniques to complement or even replace cryogenic distillation, and growing efforts have been devoted to developing advanced adsorbents to fulfill this challenging task. In this Review, a holistic view of olefin/paraffin separations is first provided by summarizing how different processes have been established to leverage the differences between olefins and paraffins for effective separations. Subsequently, recent advances in the development of porous materials for adsorptive olefin/paraffin separations are highlighted with an emphasis on different separation mechanisms. Last, a perspective on possible directions to push the limit of the research in this field is presented.

A series of 12-connected lanthanide cluster based metal-organic frameworks (MOFs) have been constructed by [Ln(μ-OH)(COO-)] secondary building units (SBUs) and 2-aminobenzenedicarboxylate (BDC-NH) ligands. These obtained materials exhibit high chemical stability and generic thermal stability, especially in acidic and basic conditions. They also present commendable CO adsorption capacity, and Yb-BDC-NH was further confirmed by a breakthrough experiment under both dry and wet conditions. Moreover, these materials possess both Lewis acid and Brønsted base sites that can catalyze one-pot tandem deacetalization-Knoevenagel condensation reactions.

This review offers a holistic perspective on Hf and Ce(iv) based metal–organic frameworks (MOFs), with a focus on Hf/Ce(iv)-clusters, topologies, ligand structures, synthetic strategies, and practical applications of these promising MOFs.

Metal–organic frameworks (MOFs) are a class of crystalline inorganic–organic hybrid materials that have demonstrated huge potential in gas separation due to their ultrahigh porosity, boundless chemical tunability, as well as surface functionality. Most gas separations realized in MOFs are under an equilibrium state and are dependent on the difference in thermodynamic affinities of gases to MOFs, whereas nonequilibrium separation such as kinetic and molecular sieving separation attracting growing attention in the past decade is achieved based on the difference in the size and diffusivity of gas molecules. In this perspective, we first discuss the pore size, temperature, and pressure effect on gas diffusion as well as nonequilibrium gas separation in MOFs. Second, we introduce current techniques reported to measure intracrystalline gas diffusivity. Third, we review recent progress in MOF-based nonequilibrium N2/O2 separation, CO2 capture, and hydrocarbon separation. In addition, we describe the hydrogen isotope separation based on kinetic quantum sieving in MOFs as a special scenario of kinetic gas separation. Lastly, we summarize general design strategies toward MOF-based nonequilibrium gas separation and propose several directions to advance the study in this exciting area.