Recent advances in synthesis of germanosilicate zeolites and their post-synthesis transformations to novel porous materials are reviewed. The structure-directing effect of Ge allows the synthesis of new zeolite structures with labile Ge−O bonds in aqueous solutions.

The host–guest synergy of carbon dots in porous materials boosts an emerging class of functional composite materials with intriguing optical and electrical properties. This Minireview highlights the recent progress in this field, and gives insightful prospects for the future development of CDs@PM composite materials.

Local structure modulations deviating from ideal framework-type structures are important fine-structural features within zeolite frameworks. By using (S)TEM with diffraction and imaging approaches, point, column and planar modulations can be observed in both reciprocal and real space.

Metal-containing zeolites outside the comfort zone: With a growing demand for the sustainable production of chemicals, new catalysts are vital. Here we highlight recent examples of metal-containing zeolite catalysts operating under harsh conditions in reactions such as high-temperature alkane conversion and biomass valorization in liquid water.

Both metal-organic frameworks and halide perovskites are important functional materials with significant scientific and industrial interest. The composite formed between these materials provides novel applications and synergistic functions. This Review introduces fundamental design principles and provides thoughts on future progress and key unanswered questions in this field.

A lean, mean, propylene machine: Subnanometer bimetallic Pt–Zn clusters are encapsulated inside silicalite-1 (S-1) zeolite via a ligand-protected direct hydrogen reduction method. In the propane dehydrogenation (PDH) reaction, the PtZn4@S-1-H catalyst exhibited a very high propylene selectivity of 99.3 % and specific activity of propylene formation of 65.5 mol  g_Pt⁻¹ h⁻¹ at 550 °C. Moreover, no obvious deactivation was observed over catalyst even after 13000 min on stream.

Pyrolysis–etching of a pyridine-coordinated polymer was used to prepare a porous carbon material with defect edge-enriched N-6/N-5 doping, high surface area, and rich distribution of N defects within the material. This carbonaceous material allows full utilization of surface-dominated capacitive K storage with ultrastable cycling.

Cooperative CO₂ chemisorption is achieved in a metal–organic framework functionalized with structurally diverse alcoholamines and alkoxyalkylamines. Solid-state NMR spectroscopy and DFT calculations indicate that CO₂ adsorption occurs via the formation and propagation of hydrogen bond-stabilized carbamic acid or ammonium carbamate structures.

ZSM-5 nanoboxes with low SARs: Rapid ageing of a sol gel synthesis mixture produces a parent zeolite with tetrahedral extra framework Al and a low silicon-to-aluminium ratio (SAR) value of ≈12, which is transformed to mesoporous ZSM-5 nanoboxes with low SARs of ≈16 during post-synthetic TPAOH treatment. The mesoporous ZSM-5 nanoboxes show comparatively enhanced mass transfer ability, catalytic cracking activity and longevity.

POP quiz: A molecular expansion strategy was developed to construct porous organic polymers (POPs) with high surface areas, well-defined nanopores, and excellent stability for methane storage. These hyper-crosslinked conjugated polymers (HCCPs) are among the few POPs with Brunauer-Emmett-Teller (BET) surface areas exceeding 3000 m² g⁻¹, and are stable in air, and strongly acid and alkaline environments.

A family of highly tunable MOFs are studied for their ability to form terminal metal–oxo species that can activate strong C−H bonds. For the Mn- and Fe-containing MOFs, a transition from ferromagnetic to antiferromagnetic coupling between the metal and terminal oxo ligand greatly reduces the barrier for C−H activation.

A high-entropy oxide material with mesoporous structure is prepared by an anchoring and merging process. It exhibits ultra-high catalytic activity for the oxidation of benzyl alcohol. Benzoic acid or benzaldehyde can be selectively optimized as the main product by rationally regulating the catalysis parameters.

Down to the atom: Through different imaging methods, electron microscopy can provide direct observation of oxygen atoms and sodium cations, pointing the way for the analysis of the local structure around heteroatoms in zeolite frameworks. The data provide clear evidence of Fe on tetrahedral sites within the MFI zeolite structure, clearly distinguished as single atoms.

Battery life on Mars: A photoinduced flexible Li-CO₂ battery with hierarchical, porous, and free-standing In₂S₃@CNT/SS as a bifunctional photoelectrode to accelerate both CO₂ reduction and evolution is presented. The Li-CO₂ battery achieved a record-high discharge voltage of 3.14 V (thermodynamic limit: 2.80 V), and an ultra-low charge voltage of 3.20 V, and a roundtrip efficiency of 98.1 %.

Supported rhodium catalysts anchored to mesoporous silica in three different locations demonstrate optimal tethering location, allowing for deployment in a fixed bed flow reactor for enantio- and regioselective C−H functionalization. Tuning silica particle size/shape enhances reactivity and the catalyst immobilization methodology is widely applicable.

Crucial intermediate: A surface gem-diol-type species is identified in the activation of acetone on the open Sn site of Sn-β zeolite by using solid-state NMR spectroscopy. This species promotes alcohol adsorption and provides an energy-favorable route for hydrogen transfer in the Meerwein–Ponndorf–Verley–Oppenauer reaction.

Trapping layers: The first layered cationic aluminum oxyhydroxide, JU-111, was synthesized, and its structure was determined from 3D electron diffraction tomography data. JU-111 is a promising candidate for trapping Cr^VI from aqueous solutions through anion exchange, showing high sorption capacity, ultrafast kinetics, broad working pH range, and excellent selectivity.

Calcium fluoride windows were functionalized to facilitate the growth of surface-mounted metal–organic frameworks (SURMOF). The resulting HKUST-1 SURMOF was measured by in situ IR spectroscopy during CO and NO adsorption. This work showcases the practicality for utilizing such calcium fluoride windows for in-depth in situ studies of various functional porous materials.

A single-site Mo-containing nanosized ZSM-5 zeolite with atomically dispersed framework-molybdenum is synthesized. The zeolite displays superior stability, maintaining the atomically dispersed Mo, structural integrity of the zeolite, and preventing the formation of silanols.

A design-led dual-templating approach was used to create a hierarchical zeotype catalyst with superior mass transport properties. Advanced probe-based characterization (including positron annihilation lifetime spectroscopy and probe-based IR spectroscopy) shows how the siliceous mesoporogen modulates the porosity and moderates the acidity of the zeotype framework, leading to enhanced catalytic performance.

A general composite-micelle-directed interfacial assembly method was developed to prepare mesoporous heterostructures (see picture). With their structural and compositional advantages, the unique sandwichlike mesoporous carbon@MXene@mesoporous carbon heterostructured nanosheets exhibited remarkable electrochemical performance as a cathode material for lithium–sulfur batteries.

Zeolite synthesis in an acidic medium is investigated. The isoelectric point (IEP) of the silica source is found to be the critical factor controlling the zeolite formation under acidic conditions. The zeolite crystalizes solely at a pH above the IEP when the silica particles are negatively charged.

An in situ bottom-up confined zeolite crystallization strategy is developed to construct micron-sized hierarchically ordered macro-mesoporous single-crystalline zeolite Beta with improved accessibility to active sites and outstanding (hydro)thermal stability for both gas-phase and liquid-phase acid-catalyzed reactions of bulky molecules.

Direct synthesis of Ga-ZSM-5 catalysts leads to dramatic enhancement in the production of aromatics from ethylene compared to post-synthesis preparation methods. Combined experiments and modeling reveal an energetic preference for Ga extra-framework sites to associate with select framework sites, suggesting the possibility of tailoring Lewis acid siting in zeolites by controlled heteroatom substitution in framework tetrahedral sites.

The functional porous hybrid material aza-MOF@COF is synthesised through post-synthesis modification of MOF@COF-LZU1 by a cycloaddition-based aza-Diels–Alder reaction. The aza-MOF@COF exhibits a high specific capacitance of 20.35 μF cm⁻² and an exceptional stack capacitance of 1.16 F cm⁻³.

A new class of mesoporous aluminosilicate adjuvants is created by controlling the surface coordination chemistry, which further adjusts the adjuvanticity. Nanoadjuvants modified with a binuclear octahedral aluminum-acetate complex, with a high density of six-coordinate ^VIAl−OH species and Brønsted basicity, show superior performance compared to counterparts modified with four-coordinate ^IVAl species with Brønsted acidity and a commercial product.

Green mining for palladium: As an alternative to platinum-group element (PGE) mining, a series of porous organic polymer nanotraps were rationally designed for their ability to recover Pd from aqueous solutions as a potential recycling method. Through intramolecular hydrogen bonding, the adsorbent–Pd complex could be stabilized, allowing for selective capture of Pd under environmentally relevant conditions.

Matching the geometry and stacking propensity of linkers allows for tetrathiafulvalene to be replaced with a nickel glyoximate core in a family of metal–organic frameworks with charge transport properties that are in line with their charge density.

Nanosheets to honeycombs: Superstructures have attracted extensive attention in material science and biology. The first centimeter-sized porous superstructure of carbon nanosheets was prepared by using MOF nanoparticles as a template, which exhibits a honeycomb-like morphology with wall-sharing carbon cages and shows great potential applications in electrochemical devices.

Robust COFs for separation: A general strategy for developing 3D chemically stable covalent organic frameworks through hydrophobic engineering is presented. The application of 3D COF materials for oil/water separation over a wide pH range is explored.

Defects in porous boron nitride enable the incorporation of boron atoms to the lattice of supported palladium nanoparticles, creating spatially isolated ensembles of metallic character. Evaluation in the continuous semi-hydrogenation of 1-hexyne demonstrates that the modification induced by the carrier can yield unparalleled performance compared to state-of-the-catalysts without the need for introducing further additives.

Training set: The 77K N₂ adsorption isotherms of porous carbons are used to train convolutional neural networks for prediction of gas separation performance. The approach allows exploration of a much broader porosity space to predict promising ones for higher CO₂/N₂ selectivity.

Full reduction: In situ Raman and X-ray absorption spectroscopy were combined with electrochemistry to study the relatively unknown CO₂ reduction to ethane mechanism. A model iodide-derived copper (ID-Cu) catalyst was studied owing to its relatively high selectivity towards ethane compared to other systems. Trace iodine species and positively charged Cu species on ID-Cu favored ethane production, which was shown to proceed via an ethoxy intermediate.

On top of the volcano: The importance of the anatase crystal phase in TiO₂-IrO₂ solid solutions in forming highly active Ir sites for the oxygen evolution reaction (OER), around the top of the volcano plot, is shown through theoretical and experimental studies. Such highly active Ir sites are indirectly obtained by creating Sr-deficient surfaces on SrTiO₃-SrIrO₃ solid solutions in situ.

A new type of MOS was successfully synthesized and employed for the construction of two new ZSA materials with MER and ABW underlying topologies. The introduction of this distinct MOS attests to the prospect of constructing new ZSA materials, and at the same time magnifies the plausible use of 4MR SBUs for the construction of ZMOFs.

A universal irregular-type mesostructured nanounit assembly method is developed to form hierarchically macro-/mesoporous polymer and carbon nanoshells on various functional materials. With structural and compositional advantages, Fe,N-doped porous carbon nanoshells exhibit enhanced electrocatalytic performance for the oxygen reduction reaction in an alkaline electrolyte.

Overcoming the mismatch between the rapid formation of nanoclusters and the slow crystallization of zeolites allows the in situ encapsulation of metal nanoclusters into zeolites in just a few minutes. The resultant Pt/Sn-ZSM-5 shows excellent activity and stability in the dehydrogenation of propane to propylene.

Cage to cage: Soluble, porous, and chemically stable quinoline cages are synthesized from salicylimine cages in one post-synthetic step. The cages show characteristic acidochromic behavior in bulk and solution, and as thin-films.

A moderate and reversible interaction dominated by the π-backbonding between NO₂ and adsorbent was achieved by inserting transition metals into porphyrin metal–organic frameworks. The accommodated Ni and Al-OH nodes serve as the active NO₂ adsorption sites.

Temperature-dependent ordering of colloidal zeolite LTA superballs leads to three-dimensional superstructures and chiral photonic superstructure films that can manipulate light in various ways including selective reflection of normal light, selective reflection of right-handed circularly polarized (RCP) light, negative circular dichroism, and left-handed circularly polarized (LCP) luminescence.

Vacant and distorted: The microstructure of hollow multishelled structure (HoMS) perovskite oxides combined with the dual-defects of surface oxygen vacancies and lattice distortion tuned the crystal-field splitting energy, which promotes the thermodynamic and kinetic processes for the oxygen evolution reaction (OER).

Electrochemical control over the synthesis of nanoparticles of the metal–organic framework (MOF) HKUST-1 is achieved using a nanopipette injection method to locally mix metal salt precursors and ligand reagents. The MOF nanocrystals are collected and characterised on a TEM grid. Single nanoparticle crystallisation is controlled and monitored in real time.

Teamwork: TiO₂ decorated with both platinum nanoparticles and CuO_x clusters enabled photocatalytic oxidative coupling of methane in a flow system at room temperature and atmospheric pressure with a high yield rate of 6.8 μmol h⁻¹ for the selective synthesis of C₂ hydrocarbons. It is proposed that Pt functions as an electron acceptor to facilitate charge separation, while holes may transfer to CuO_x to avoid deep dehydrogenation and overoxidation (see picture).

The selectivity of the methanol-to-olefins (MTO) reaction catalyzed by zeolites varies with cavity architecture and framework composition. The higher flexibility of the SAPO-34 framework as compared to SSZ-13 does not modify the relative diffusion rate of ethene and propene, but facilitates the accommodation of the bulkier cationic intermediates of the MTO reaction, increasing the production of propene and butene.

Two new tetraphenylethylene-based 3D MOFs are obtained. Sr-ETTB performs uncommon reversible thermo/piezofluorochromism and thermo/piezochromic behaviors which are driven by its characteristic crystalline framework flexibility. Non-emissive Co-ETTB exhibits a turn-on fluorescent enhancement under the stimulation of analyte histidine.