Metal Sites in Zeolites: Synthesis, Characterization, and Catalysis.

Zeolites with ordered microporous systems, distinct framework topologies, good spatial nanoconfinement effects, and superior (hydro)thermal stability are an ideal scaffold for planting diverse active metal species, including single sites, clusters, and nanoparticles in the framework and framework-associated sites and extra-framework positions, thus affording the metal-in-zeolite catalysts outstanding activity, unique shape selectivity, and enhanced stability and recyclability in the processes of Brønsted acid-, Lewis acid-, and extra-framework metal-catalyzed reactions. Especially, thanks to the advances in zeolite synthesis and characterization techniques in recent years, zeolite-confined extra-framework metal catalysts (denoted as metal@zeolite composites) have experienced rapid development in heterogeneous catalysis, owing to the combination of the merits of both active metal sites and zeolite intrinsic properties. In this review, we will present the recent developments of synthesis strategies for incorporating and tailoring of active metal sites in zeolites and advanced characterization techniques for identification of the location, distribution, and coordination environment of metal species in zeolites. Furthermore, the catalytic applications of metal-in-zeolite catalysts are demonstrated, with an emphasis on the metal@zeolite composites in hydrogenation, dehydrogenation, and oxidation reactions. Finally, we point out the current challenges and future perspectives on precise synthesis, atomic level identification, and practical application of the metal-in-zeolite catalyst system.

Confinement of CsPbBr3 Perovskite Nanocrystals into Extra-large-pore Zeolite for Efficient and Stable Photocatalytic Hydrogen Evolution.

Metal halide perovskites (MHPs), renowned for their outstanding optoelectronic properties, hold significant promise as photocatalysts for hydrogen evolution reaction (HER). However, the low stability and insufficient exposure of catalytically active sites of bulky MHPs seriously impair their catalytic efficiency. Herein, we utilized an extra-large-pore zeolite ZEO-1 (JZO) as a host to confine and stabilize the CsPbBr3 nanocrystals (3.4 nm) for boosting hydrogen iodide (HI) splitting. The as-prepared CsPbBr3@ZEO-1 featured sufficiently exposed active sites, superior stability in acidic media, along with intrinsic extra-large pores of ZEO-1 that were favorable for molecule/ion adsorption and diffusion. Most importantly, the unique nanoconfinement effect of ZEO-1 led to the narrowing of the band gap of CsPbBr3, allowing for more efficient light utilization. As a result, the photocatalytic HER rate of the as-prepared CsPbBr3@ZEO-1 photocatalyst was increased to 1734 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3) under visible light irradiation compared with bulk CsPbBr3 (11 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3)), and the long-term durability (36 h) can be achieved. Furthermore, Pt was incorporated with well-dispersed CsPbBr3 nanocrystals into ZEO-1, resulting in a significant enhancement in activity (4826 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3)), surpassing most of the Pt-integrated perovskite-based photocatalysts. Density functional theory (DFT) calculations and charge-carrier dynamics investigation revealed that the dramatically boosted photocatalytic performance of Pt/CsPbBr3@ZEO-1 could be attributed to the promotion of charge separation and transfer, as well as to the substantially lowered energy barrier for HER. This work highlights the advantage of extra-large-pore zeolites as the nanoscale platform to accommodate multiple photoactive components, opening up promising prospects in the design and exploitation of novel zeolite-confined photocatalysts for energy harvesting and storage.

Systematic Analysis and Identification of Drought-Responsive Genes of the CAMTA Gene Family in Wheat (Triticum aestivum L.).

The calmodulin-binding transcription activator (CAMTA) is a Ca2+/CaM-mediated transcription factor (TF) that modulates plant stress responses and development. Although the investigations of CAMTAs in various organisms revealed a broad range of functions from sensory mechanisms to physiological activities in crops, little is known about the CAMTA family in wheat (Triticum aestivum L.). Here, we systematically analyzed phylogeny, gene expansion, conserved motifs, gene structure, cis-elements, chromosomal localization, and expression patterns of CAMTA genes in wheat. We described and confirmed, via molecular evolution and functional verification analyses, two new members of the family, TaCAMTA5-B.1 and TaCAMTA5-B.2. In addition, we determined that the expression of most TaCAMTA genes responded to several abiotic stresses (drought, salt, heat, and cold) and ABA during the seedling stage, but it was mainly induced by drought stress. Our study provides considerable information about the changes in gene expression in wheat under stress, notably that drought stress-related gene expression in TaCAMTA1b-B.1 transgenic lines was significantly upregulated under drought stress. In addition to providing a comprehensive view of CAMTA genes in wheat, our results indicate that TaCAMTA1b-B.1 has a potential role in the drought stress response induced by a water deficit at the seedling stage.

Arabidopsis G-Protein ß Subunit AGB1 Negatively Regulates DNA Binding of MYB62, a Suppressor in the Gibberellin Pathway.

Plant G proteins are versatile components of transmembrane signaling transduction pathways. The deficient mutant of heterotrimeric G protein leads to defects in plant growth and development, suggesting that it regulates the GA pathway in Arabidopsis. However, the molecular mechanism of G protein regulation of the GA pathway is not understood in plants. In this study, two G protein ß subunit (AGB1) mutants, agb1-2 and N692967, were dwarfed after exogenous application of GA3. AGB1 interacts with the DNA-binding domain MYB62, a GA pathway suppressor. Transgenic plants were obtained through overexpression of MYB62 in two backgrounds including the wild-type (MYB62/WT Col-0) and agb1 mutants (MYB62/agb1) in Arabidopsis. Genetic analysis showed that under GA3 treatment, the height of the transgenic plants MYB62/WT and MYB62/agb1 was lower than that of WT. The height of MYB62/agb1 plants was closer to MYB62/WT plants and higher than that of mutants agb1-2 and N692967, suggesting that MYB62 is downstream of AGB1 in the GA pathway. qRT-PCR and competitive DNA binding assays indicated that MYB62 can bind MYB elements in the promoter of GA2ox7, a GA degradation gene, to activate GA2ox7 transcription. AGB1 affected binding of MYB62 on the promoter of GA2ox7, thereby negatively regulating th eactivity of MYB62.

Surface Restructuring of Zeolite-Encapsulated Halide Perovskite to Activate Lattice Oxygen Oxidation for Water Electrolysis.

Metal-halide perovskites possess great potential for electrochemical water splitting that has not been realized due to their intolerance to water. Here, methylammonium lead halide perovskites (MAPbX3 ) are used to electrocatalyze water oxidation in aqueous electrolytes by creating MAPbX3 @AlPO-5 host-guest composites. Due to the protective feature of the zeolite matrix, halide perovskite nanocrystals (NCs) confined in aluminophosphate AlPO-5 zeolites achieve an excellent stability in water. The resultant electrocatalyst undergoes dynamic surface restructuring during the oxygen evolution reaction (OER) with the formation of an edge-sharing α-PbO2 active layer. The existence of charge-transfer interactions at the MAPbX3 /α-PbO2 interface significantly modulates the surface electron density of the α-PbO2 and optimizes the adsorption free energy of oxygen-containing intermediate species. Furthermore, the soft-lattice nature of halide perovskites enables more facile triggering of lattice-oxygen oxidation of nanostructured α-PbO2 , exhibiting pH-dependent OER activity and non-concerted proton-electron transfer for MAPbX3 @AlPO-5 composite. As a result, the developed MAPbBr3 @AlPO-5 composite manifests an ultralow overpotential of 233 mV at 10 mA cm-2 in 1 m KOH. These findings offer facile access to halide perovskite applied to water electrolysis with enhanced intrinsic activity, providing a new paradigm for designing high-efficiency OER electrocatalysts.