Hierarchical Mesoporous Metal–Organic Frameworks for Enhanced CO2 Capture

Hierarchical porous materials are promising for catalyst, separation and sorption applications. A ligand‐assisted etching process is developed for template‐free synthesis of hierarchical mesoporous MOFs as single crystals and well‐intergrown membranes at 40 °C. At 223 K, the hierarchical porous structures significantly improve the CO₂ capture capacity of HKUST‐1 by more than 44 % at pressures up to 20 kPa and 13 % at 100 kPa. Even at 323 K, the enhancement of CO₂ uptake is above 25 % at pressures up to 20 kPa and 7 % at 100 kPa. The mesoporous structures not only enhance the CO₂ uptake capacity but also improve the diffusion and mass transportation of CO₂. Similarly, well‐intergrown mesoporous HKUST‐1 membranes are synthesized, which hold the potential for film‐like porous devices. Mesoporous MOF‐5 crystals are also obtained by a similar ligand‐assisted etching process. This may provide a facile way to prepare hierarchical porous MOF single crystals and membranes for wide‐ranging applications.     

CO2 Binding and Splitting by Boron–Boron Multiple Bonds

The room‐temperature, ambient‐pressure reactions of CO₂ with two species containing boron–boron multiple bonds led to the incorporation of either one or two CO₂ molecules. The structural characterization of a thermally unstable intermediate in one case indicates that an initial [2+2] cycloaddition is the key step in the reaction mechanism.     

Reduced Graphene Oxide‐Supported TiO2 Fiber Bundles with Mesostructures as Anode Materials for Lithium‐Ion Batteries

Although the synthesis of mesoporous materials is well established, the preparation of TiO₂ fiber bundles with mesostructures, highly crystalline walls, and good thermal stability on the RGO nanosheets remains a challenge. Herein, a low‐cost and environmentally friendly hydrothermal route for the synthesis of RGO nanosheet‐supported anatase TiO₂ fiber bundles with dense mesostructures is used. These mesostructured TiO₂‐RGO materials are used for investigation of Li‐ion insertion properties, which show a reversible capacity of 235 mA h g^?1 at 200 mA g^?1 and 150 mA h g^?1 at 1000 mA g^?1 after 1000 cycles. The higher specific surface area of the new mesostructures and high conductive substrate (RGO nanosheets) result in excellent lithium storage performance, high‐rate performance, and strong cycling stability of the TiO₂‐RGO composites.     

Ternary Sn‐Ti‐O Electrocatalyst Boosts the Stability and Energy Efficiency of CO2 Reduction

Simultaneously improving energy efficiency (EE) and material stability in electrochemical CO₂ conversion remains an unsolved challenge. Among a series of ternary Sn‐Ti‐O electrocatalysts, 3D ordered mesoporous (3DOM) Sn_0.3Ti_0.7O₂ achieves a trade‐off between active‐site exposure and structural stability, demonstrating up to 71.5 % half‐cell EE over 200 hours, and a 94.5 % Faradaic efficiency for CO at an overpotential as low as 430 mV. DFT and X‐ray absorption fine structure analyses reveal an electron density reconfiguration in the Sn‐Ti‐O system. A downshift of the orbital band center of Sn and a charge depletion of Ti collectively facilitate the dissociative adsorption of the desired intermediate COOH* for CO formation. It is also beneficial in maintaining a local alkaline environment to suppress H₂ and formate formation, and in stabilizing oxygen atoms to prolong durability. These findings provide a new strategy in materials design for efficient CO₂ conversion and beyond.     

Highly Ordered Mesoporous Few‐Layer Graphene Frameworks Enabled by Fe3O4 Nanocrystal Superlattices

While great progress has been achieved in the synthesis of ordered mesoporous carbons in the past decade, it still remains a challenge to prepare highly graphitic frameworks with ordered mesoporosity and high surface area. Reported herein is a simple synthetic methodology, based on the conversion of self‐assembled superlattices of Fe₃O₄ nanocrystals, to fabricate highly ordered mesoporous graphene frameworks (MGFs) with ultrathin pore walls consisting of three to six stacking graphene layers. The MGFs possess face‐centered‐cubic symmetry with interconnected mesoporosity, tunable pore width, and high surface area. Because of their unique architectures and superior structural durability, the MGFs exhibit excellent cycling stability and rate performance when used as anode materials for lithium‐ion batteries, thus retaining a specific capacity of 520 mAh g^?1 at a current density of 300 mA g^?1 after 400 cycles.     

3D Hexagonal Mesoporous Silica and Its Organic Functionalization for High CO2 Uptake

Highly ordered 3D‐hexagonal mesoporous silica HMS‐3 and its vinyl‐ and 3‐chloropropyl‐functionalized analogues HMS‐4 and ‐5, respectively, are synthesized under strongly alkaline conditions at 277 K. Tetraethyl orthosilicate, vinyltrimethoxysilane, and 3‐chloropropyltrimethoxysilane are used as silica sources, and cetyltrimethylammonium bromide as the structure‐directing agent. The 3D‐hexagonal pore structures of HMS‐3, 4‐, and ‐5 were confirmed by powder XRD and high‐resolution TEM studies. Brunauer–Emmett–Teller surface areas of these materials are 1353, 1211, and 603 m² g^?1 for HMS‐3, ‐4, and ‐5, respectively. Among these materials, vinyl‐functionalized mesoporous material HMS‐4 adsorbs the highest CO₂ (5.5 mmol g^?1, 24.3 wt %) under 3 bar pressure at 273 K. The 3D‐hexagonal pore openings, very high surface area, and cagelike mesopores as well as organic functionalization could be responsible for very high CO₂ uptakes of these materials compared to other related mesoporous silica‐based materials.     

Solvent Impedes CO2 Cycloaddition on Metal–Organic Frameworks

The catalytic performance of metal–organic frameworks (MOFs) for the synthesis of cyclic carbonate from carbon dioxide and epoxides has been explored under solvent and solvent‐free conditions, respectively. It was found that MOF catalysts have significantly improved catalytic activities in solvent‐free CO₂ cycloaddition reactions than those in solvent. The mechanism was discussed with regard to the competition of solvent with substrate to adhere MOF catalysts during the reaction process.     

Three‐Dimensional Nitrogen‐Doped Reduced Graphene Oxide–Carbon Nanotubes Architecture Supporting Ultrafine Palladium Nanoparticles for Highly Efficient Methanol Electrooxidation

A three‐dimensional (3D) nitrogen‐doped reduced graphene oxide (rGO)–carbon nanotubes (CNTs) architecture supporting ultrafine Pd nanoparticles is prepared and used as a highly efficient electrocatalyst. Graphene oxide (GO) is first used as a surfactant to disperse pristine CNTs for electrochemical preparation of 3D rGO@CNTs, and subsequently one‐step electrodeposition of the stable colloidal GO–CNTs solution containing Na₂PdCl₄ affords rGO@CNTs‐supported Pd nanoparticles. Further thermal treatment of the Pd/rGO@CNTs hybrid with ammonia achieves not only in situ nitrogen‐doping of the rGO@CNTs support but also extraordinary size decrease of the Pd nanoparticles to below 2.0 nm. The resulting catalyst is characterized by scanning and transmission electron microscopy, X‐ray diffraction, Raman spectroscopy, and X‐ray photoelectron spectroscopy. Catalyst performance for the methanol oxidation reaction is tested through cyclic voltammetry and chronoamperometry techniques, which shows exceedingly high mass activity and superior durability.     

Metal Oxide‐Coated Three‐Dimensional Graphene Prepared by the Use of Metal–Organic Frameworks as Precursors

A simple method for the preparation of metal‐oxide‐coated three‐dimensional (3D) graphene composites was developed. The metal–organic frameworks (MOFs) that served as the precursors of the metal oxides were first synthesized on the 3D graphene networks (3DGNs). The desired metal oxide/3DGN composites were then obtained by a two‐step annealing process. As a proof‐of‐concept application, the obtained ZnO/3DGN and Fe₂O₃/3DGN materials were used in a photocatalytic reaction and a lithium‐ion battery, respectively. We believe this method could be extended to the synthesis of other metal oxide/3DGN composites with 3D structures simply through the appropriate choice of specific MOFs as precursors.     

Boron‐Doped,Carbon‐Coated SnO2/Graphene Nanosheets for Enhanced Lithium Storage

Heteroatom doping is an effective method to adjust the electrochemical behavior of carbonaceous materials. In this work, boron‐doped, carbon‐coated SnO₂/graphene hybrids (BCTGs) were fabricated by hydrothermal carbonization of sucrose in the presence of SnO₂/graphene nanosheets and phenylboronic acid or boric acid as dopant source and subsequent thermal treatment. Owing to their unique 2D core–shell architecture and B‐doped carbon shells, BCTGs have enhanced conductivity and extra active sites for lithium storage. With phenylboronic acid as B source, the resulting hybrid shows outstanding electrochemical performance as the anode in lithium‐ion batteries with a highly stable capacity of 1165 mA h g^?1 at 0.1 A g^?1 after 360 cycles and an excellent rate capability of 600 mA h g^?1 at 3.2 A g^?1, and thus outperforms most of the previously reported SnO₂‐based anode materials.     

Directing the Structural Features of N2‐Phobic Nanoporous Covalent Organic Polymers for CO2 Capture and Separation

A family of azo‐bridged covalent organic polymers (azo‐COPs) was synthesized through a catalyst‐free direct coupling of aromatic nitro and amine compounds under basic conditions. The azo‐COPs formed 3D nanoporous networks and exhibited surface areas up to 729.6 m² g^?1, with a CO₂‐uptake capacity as high as 2.55 mmol g^?1 at 273 K and 1 bar. Azo‐COPs showed remarkable CO₂/N₂ selectivities (95.6–165.2) at 298 K and 1 bar. Unlike any other porous material, CO₂/N₂ selectivities of azo‐COPs increase with rising temperature. It was found that azo‐COPs show less than expected affinity towards N₂ gas, thus making the framework “N₂‐phobic”, in relative terms. Our theoretical simulations indicate that the origin of this unusual behavior is associated with the larger entropic loss of N₂ gas molecules upon their interaction with azo‐groups. The effect of fused aromatic rings on the CO₂/N₂ selectivity in azo‐COPs is also demonstrated. Increasing the π‐surface area resulted in an increase in the CO₂‐philic nature of the framework, thus allowing us to reach a CO₂/N₂ selectivity value of 307.7 at 323 K and 1 bar, which is the highest value reported to date. Hence, it is possible to combine the concepts of “CO₂‐philicity” and “N₂‐phobicity” for efficient CO₂ capture and separation. Isosteric heats of CO₂ adsorption for azo‐COPs range from 24.8–32.1 kJ mol^?1 at ambient pressure. Azo‐COPs are stable up to 350 °C in air and boiling water for a week. A promising cis/trans isomerization of azo‐COPs for switchable porosity is also demonstrated, making way for a gated CO₂ uptake.     

[Zn4O] Cluster‐Based Metal‐Organic Frameworks as Catalysts for Conversion of CO2

One unique two‐dimensional (2D) Zn‐MOF {Na[Zn_1.5(μ₄‐O)(L)]}_n ( 1 ) was synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction. Four Zn atoms are bridged through μ₄‐O to form [Zn₄O] clusters, which are further linked to form a 2D layer network through sharing Zn as vertexes. 1 exhibits high thermal stability up to 280 °C and keeps stable in common solvents and water solutions with pH ranging from 1 to 13. The catalytic studies reveal that compound 1 exhibits excellent catalytic activity for cycloaddition of CO₂ with epoxides into cyclic carbonates under mild conditions. Furthermore, 1 demonstrates good generality in CO₂ coupling reaction with extensive epoxides. Importantly, 1 can be reused for at least five times without significant reduction in catalytic ability.     

Membranes with Fast and Selective Gas‐Transport Channels of Laminar Graphene Oxide for Efficient CO2 Capture

Graphene oxide (GO) nanosheets were engineered to be assembled into laminar structures having fast and selective transport channels for gas separation. With molecular‐sieving interlayer spaces and straight diffusion pathways, the GO laminates endowed as‐prepared membranes with excellent preferential CO₂ permeation performance (CO₂ permeability: 100 Barrer, CO₂/N₂ selectivity: 91) and extraordinary operational stability (>6000 min), which are attractive for implementation of practical CO₂ capture.     

Tuning the Surface Polarity of Microporous Organic Polymers for CO2 Capture

CO₂ capture is very important to reduce the CO₂ concentration in atmosphere. Herein, we report the preparation of microporous polymers with tunable surface polarity for CO₂ capture. Porous polymers functionalized with ‐NH₂, ‐SO₃H, and ‐SO₃Li have been successfully prepared by using a post‐synthesis modification of microporous polymers (P‐PhPh₃ prepared with 1,3,5‐triphenylbenzene as the monomer and AlCl₃ as the catalyst) by chemical transformations, such as nitration–reduction, sulfonation, and cationic exchange. The CO₂ adsorption selectivity (CO₂/N₂ and CO₂/H₂) and isosteric heats of the microporous polymers increase markedly after modification, P‐PhPh₃‐NH₂ and P‐PhPh₃‐SO₃Li afford higher CO₂ uptake capacity than P‐PhPh₃ at pressures of less than 0.15 bar due to the enhanced interaction between CO₂ and the ‐NH₂ and ‐SO₃Li functional groups. Moreover, functionalized porous polymers could be stably used for CO₂ capture. Surface modification is an efficient approach to tune the CO₂ capture properties of porous polymers.     

β‐Cyclodextrin Functionalized Nanoporous Graphene Oxides for Efficient Resolution of Asparagine Enantiomers

Efficient resolution of racemic mixture has long been an attractive but challenging subject since Pasteur separated tartrate enantiomers in 19^th century. Graphene oxide (GO) could be flexibly functionalized by using a variety of chiral host molecules and therefore, was expected to show excellent enantioselective resolution performance. However, this combination with efficient enantioselective resolution capability has been scarcely demonstrated. Here, nanoporous graphene oxides were produced and then covalently functionalized by using a chiral host material‐β‐cyclodextrin (β‐CD). This chiral GO displayed enantioselective affinity toward the l ‐enantiomers of amino acids. In particular, >99 % of l ‐asparagine (Asn) was captured in a racemic solution of Asn while the adsorption of d ‐enantiomer was not observed. This remarkable resolution performance was subsequently modelled by using an attach‐pull‐release dynamic method. We expect this preliminary concept could be expanded to other chiral host molecules and be employed to current membrane separation technologies and finally show practical use for many other racemates.     

Importance of Micropore–Mesopore Interfaces in Carbon Dioxide Capture by Carbon‐Based Materials

Mesoporous carbonaceous materials (Starbons®) derived from low‐value/waste bio‐resources separate CO₂ from CO₂/N₂ mixtures. Compared to Norit activated charcoal (AC), Starbons® have much lower microporosities (8–32 % versus 73 %) yet adsorb up to 65 % more CO₂. The presence of interconnected micropores and mesopores is responsible for the enhanced CO₂ adsorption. The Starbons® also showed three–four times higher selectivity for CO₂ adsorption rather than N₂ adsorption compared to AC.     

N‐Heterocyclic Carbenes as Efficient Organocatalysts for CO2 Fixation Reactions

Getting a fix : N‐heterocyclic carbenes (NHCs) and NHC–CO₂ adducts serve as potent organocatalysts for carbonate synthesis by the addition of a CO₂ unit to propargylic alcohols or epoxides under mild and solvent‐free reaction conditions (see scheme). The enhanced Lewis basicity of imidazol‐2‐ylidenes bearing electron‐donating alkyl groups on the nitrogen atoms leads to utilizing CO₂ as a nucleophilic fragment in the chemical fixation processes.