As a new kind of organic-inorganic hybrid porous material, metal-organic frameworks (MOFs) exhibit a wide application prospect in gas storage and separation, catalysis and sensing due to their characteristics of large specific surface area, high porosity and coordination unsaturation. As more and more types of MOFs were reported, the synthetic strategies of MOFs-based materials have become a hot research topic. According to the morphological dimension, MOFs can be roughly divided into one-dimensional, two-dimensional and three-dimensional structures. Herein, we summarize the synthetic methods and principles of MOFs from multi-dimensional perspectives, and explore the growth mechanism of MOFs with different morphologies based on dynamic and thermodynamic tuning. Finally, based on the above summaries, the challenges and opportunities of MOFs in the future are discussed.

MFI zeolite characterized by uniform pore size, adjustable acidity, and high-temperature resistance has a broad application prospect in catalytic reactions. However, controlling the product distribution of zeolite as a catalyst is still confronting great challenges and applications. It is considered as an effective way to control the product distribution by developing and improving new zeolites to modulate their shape selective effect. In recent years, researchers have achieved remarkable successes in investigating the shape selective modulation of zeolites on catalytic reaction and molecular diffusion. The microporous channels of MFI zeolite are the main places for the entry and exit of reactants or product molecules. This review provides the research progress of the shape-selective modulation of MFI zeolite channels and its influence on a series of catalytic performances in recent years. The shape-selective modulation of microporous channels of zeolite, encapsulation of micropores to metals, catalysis of mesoporous zeolite, and the distribution of framework Al were all systematically discussed. The development of advanced catalysts still faces great challenges and potential applications. Finally, we discussed the problems to be addressed urgently in the field of zeolite catalysts in the future.

The synergistic promotion by photocatalysis and thermocatalysis is a promising approach for sustainable hydrogen (H₂) production. Herein, we rationally design a perovskite-based catalyst with three-dimensionally ordered macroporous structure (3DOM CaTiO₃-Au) for photothermal catalytic H₂ production from different substrates. The hierarchical 3DOM structure facilitates light harvesting and mass diffusion of the substrates, while the gold nanoparticles (Au NPs) promote charge separation. The photogenerated and hot electrons are oriented accumulated on the surface of Au NPs. The non-metallic gold species [Au(I)] show more activity for H₂ evolution. As a result, 3DOM CaTiO₃-Au exhibits excellent activity for H₂ production from glycerol and other substrates with hydroxyl groups. The present work demonstrates a feasible approach to improve sustainable H₂ production by rationally designing and fabricating efficient photothermal catalysts.

Direct hydrazine fuel cell is a promising portable energy conversion device due to its high energy density and free of carbon emissions. To realize the practical applications, the design of highly efficient electrocatalysts for hydrazine oxidation reaction (HzOR) is crucial. Metal nanocrystals with high-index facets have abundant step sites with reactivity. In this study, we prepared trapezohedral Pt nanocrystals (TPH Pt NCs) enclosed by {311} high-index facets and investigated the catalytic performance for hydrazine oxidation. TPH Pt NCs possess a specific activity of 39.1 mA·cm^-2 at 0.20 V, much higher than {111}-faceted octahedral (13.9 mA·cm^-2) and {100}-faceted cubic Pt NCs (9.11 mA·cm^-2). Meanwhile, TPH Pt NCs also show superior stability. Density functional theory (DFT) calculation indicates that Pt(311) facilitates the deprotonation of N₂H₄* to N₂H₃* (the rate-determining step) and improves the HzOR activity. This study is helpful for the design of advanced electrocatalysts for HzOR, especially high-index faceted Pt nanocatalysts.

Carbonic anhydrase (CA) is an important carbon fixation enzyme. Immobilization of CA can expand its application in the realm of adsorption, catalysis, and so on. As a typical metal-free framework, hydrogen-bonded organic frameworks (HOFs) featuring mild synthesis process, exquisite framework structure and good enzyme compatibility have been used for enzyme embedding. However, the catalytic performance of CA-embedded HOFs (CA@HOFs) is limited by the micropore size of HOFs and the slow adsorption of CO₂. Herein, CA@Lys-HOF-1 was synthesized by introducing lysine (Lys), a basic amino acid, during the coprecipitation of CA and HOFs for CO₂ fixation. The addition of Lys enlarged the average pore size of HOF-1 from 1.8 to 3.2 nm, whereas the introduced -NH₂ groups increased the initial adsorption of CO₂ from 0.55 to 1.21 cm³ g^-1. Compared to CA@HOF-1, the activity of CA@Lys-HOF-1 was enhanced by 71.25%, and the corresponding production of CaCO₃ was enhanced by 12.7%. After eight reaction cycles, CA@Lys-HOF-1 still maintained an output of 9.97 mg of CaCO₃ every 5 min, 83.7% of the initial production. It is hoped that the CA@Lys-HOF-1 reported offers a platform for efficient and continuous fixation of CO₂.

In recent years, it has become an urgent task to design new types of indole-based platform molecules for Nazarov-type cyclizations and develop organocatalytic Nazarov-type cyclizations for synthesizing indole derivatives. To fulfill this task, in this work, by changing the alkynyl terminal substituent from t-Bu to an aryl group, the reactivity of 3-alkynyl-2-indolylmethanols is modulated and the new platform molecules serve as competent substrates for Brønsted acid-catalyzed Nazarov-type cyclization. Based on this new reactivity, the first organocatalytic Nazarov-type cyclization of aryl-substituted 3-alkynyl-2-indolylmethanols with 2-naphthols is accomplished, leading to the efficient construction of a new class of axially chiral 3, 4-dihydrocyclopenta[b]indole scaffolds. This preliminary investigation of organocatalytic asymmetric Nazarov-type cyclization provides an optional strategy for the atroposelective construction of this new class of axially chiral cyclopenta[b]indole scaffolds. In addition, the first preparation of axially chiral 3, 4-dihydrocyclopenta[b]indole with optical purity is established through chiral resolution, which could serve as a complementary method to catalytic asymmetric approaches.

Chiral spirolactones, including spiropropyllactones, spirobutyrolactones, and spirovalerolactones, are important heterocyclic frameworks that attracted the attention of organic and medicinal chemists because these motifs constitute the core structure of several natural products and bioactive molecules. The absolute configuration and the substituents on the fully substituted spirocyclic stereocenter of the lactone can potentially enhance specificity for ligand-protein binding and enhance bioavailability, potency, and metabolic stability. So, intensive attention from chemists has been paid to the synthetic methods leading to such prominent structural motifs. The synthetic methods can be divided into two main classes. The first approach takes advantage of the presence of the existing lactone structure and focuses on its functionalization. The second approach is the lactone framework constructed from various precursors in a direct spirolactonization reaction. In this review, for convenience in reading, the recent advances in the synthesis of spirolactones are summarized and discussed according to the two major organocatalytic asymmetric synthetic routes: (i) using the lactone-related frameworks as building blocks; and (ii) direct spirolactonization reaction using various reagents. This review also describes both the mechanisms and related transformations, and gives some insights into challenging issues in this research field, which will enlighten the future development of this field.

Modulating the electrocatalytic performance of Palladium (Pd) with nonmetallic elements (e.g., H, B, C, N, O, P and S) has gained ever-increasing attention since their introduction has been proven to effectively modulate the 3d-electronic configuration and subsurface properties of Pd. In this review, the most advanced nonmetal-modified Pd-based catalysts are classified according to the different doped atoms (i.e., hydrides, borides, carbides, nitrides, oxides, phosphides and sulfides) and critically reviewed to emphasize the roles of nonmetallic elements doping on various electrocatalytic reactions. In each section, the synthetic strategies developed to incorporate nonmetals are discussed in detail. Furthermore, the optimized approaches of nonmetals-doped Pd-based catalysts and corresponding electrocatalytic enhancement mechanisms are also discussed clearly. Finally, the current challenges and future perspectives regarding nonmetal-modified Pd-based nanocatalysts are also outlined.