Substituent engineering in g-C3N4/COF heterojunctions for rapid charge separation and high photo-redox activity

Science China Chemistry - The heterojunction constructed of covalent organic frameworks (COFs) with adjustable structure and other photocatalysts has great potential in the field of photocatalysis....     

A window-space-directed assembly strategy for the construction of supertetrahedron-based zeolitic mesoporous metal–organic frameworks with ultramicroporous apertures for selective gas adsorption

Despite their scarcity due to synthetic challenges, supertetrahedron-based metal–organic frameworks (MOFs) possess intriguing architectures, diverse functionalities, and superb properties that make them in-demand materials. Employing a new window-space-directed assembly strategy, a family of mesoporous zeolitic MOFs have been constructed herein from corner-shared supertetrahedra based on homometallic or heterometallic trimers [M₃(OH/O)(COO)₆] (M₃ = Co₃, Ni₃ or Co₂Ti). These MOFs consisted of close-packed truncated octahedral cages possessing a sodalite topology and large β-cavity mesoporous cages (∼22 Å diameter) connected by ultramicroporous apertures (∼5.6 Å diameter). Notably, the supertetrahedron-based sodalite topology MOF combined with the Co₂Ti trimer exhibited high thermal and chemical stability as well as the ability to efficiently separate acetylene (C₂H₂) from carbon dioxide (CO₂).

A series of supertetrahedron (ST)-based sodalite (sod)-topology zeolitic MOFs specimens ST-sod-MOFs featuring ultramicroporous square windows and a mesoporous sodcage have been synthesized via a window-space-directed assembly approach.     

Chiral Frustrated Lewis Pair@Metal-Organic Framework as a New Platform for Heterogeneous Asymmetric Hydrogenation

Asymmetric hydrogenation, a seminal strategy for the synthesis of chiral molecules, remains largely unmet in terms of activation by non-metal sites of heterogeneous catalysts. Herein, as demonstrated by combined computational and experimental studies, we present a general strategy for integrating rationally designed molecular chiral frustrated Lewis pair (CFLP) with porous metal–organic framework (MOF) to construct the catalyst CFLP@MOF that can efficiently promote the asymmetric hydrogenation in a heterogeneous manner, which for the first time extends the concept of chiral frustrated Lewis pair from homogeneous system to heterogeneous catalysis. Significantly, the developed CFLP@MOF, inherits the merits of both homogeneous and heterogeneous catalysts, with high activity/enantio-selectivity and excellent recyclability/regenerability. Our work not only advances CFLP@MOF as a new platform for heterogeneous asymmetric hydrogenation, but also opens a new avenue for the design and preparation of advanced catalysts for asymmetric catalysis.     

Kinetic Control via Binding Sites within the Confined Space of Metal Metalloporphyrin-Frameworks for Enhanced Shape-Selectivity Catalysis

One striking feature of enzyme is its controllable ability to trap substrates via synergistic or cooperative binding in the enzymatic pocket, which renders the shape-selectivity of product by the confined spatial environment. The success of shape-selective catalysis relies on the ability of enzyme to tune the thermodynamics and kinetics for chemical reactions. In emulation of enzyme's ability, we showcase herein a targeting strategy with the substrate being anchored on the internal pore wall of metal-organic frameworks (MOFs), taking full advantage of the sterically kinetic control to achieve shape-selectivity for the reactions. For this purpose, a series of binding site-accessible metal metalloporphyrin-frameworks (MMPFs) have been investigated to shed light on the nature of enzyme-mimic catalysis. They exhibit a different density of binding sites that are well arranged into the nanospace with corresponding distances of opposite binding sites. Such a structural specificity results in a facile switch in selectivity from an exclusive formation of the thermodynamically stable product to the kinetic product. Thus, the proposed targeting strategy, based on the combination of porous materials and binding events, paves a new way to develop highly efficient heterogeneous catalysts for shifting selectivity.     

One-pot hydrothermal preparation of hierarchical manganese oxide nanorods for high-performance symmetric supercapacitors

An eco-friendly,new,and controllable approach for the preparation of manganese oxide(a-MnO₂)nanorods has been introduced using hydrothermal reaction for supercapacitor application.The in-depth crystal structure analysis ofα-MnO₂ is analyzed by X-ray Rietveld refinement by using Full Prof program with the help of pseudo-Voigt profile function.The developed a-MnO₂ electrode attains a remarkable capacitance of 577.7 F/g recorded at a current density value of 1 A/g with an excellent cycle life when is used for 10,000 repeated cycles due to the porous nanorod-morphology assisting the ease penetration of electrolyte ions into the electroactive sites.The diffusive and capacitive contributions of the electrode have been estimated by considering standard numerical packages in Python.After successfully assembling the aqueous symmetric supercapacitor(SSC)cell by utilizing the as-preparedα-MnO₂,an excellent capacitance of 163.5 F/g and energy density of 58.1 Wh/kg at the constant current density of 0.5 A/g are obtained with an expanded potential frame of 1.6 V.Moreover,the cell has exceptionally withstood up to 10,000 cycles with an ultimate capacitance retention of 94.1%including the ability to light an LED for 18 s.Such findings recommend the developed a-MnO₂ electrode to be a highly felicitous electrode for the field of energy storage.     

A Microporous Metal-Organic Framework with Unique Aromatic Pore Surfaces for High Performance C2H6/C2H4 Separation

Developing adsorptive separation processes based on C₂H₆-selective sorbents to replace energy-intensive cryogenic distillation is a promising alternative for C₂H₄ purification from C₂H₄/C₂H₆ mixtures, which however remains challenging. During our studies on two isostructural metal–organic frameworks ( Ni-MOF 1 and Ni-MOF 2 ), we found that Ni-MOF 2 exhibited significantly higher performance for C₂H₆/C₂H₄ separation than Ni-MOF-1 , as clearly established by gas sorption isotherms and breakthrough experiments. Density-Functional Theory (DFT) studies showed that the unblocked unique aromatic pore surfaces within Ni-MOF 2 induce more and stronger C−H⋅⋅⋅π with C₂H₆ over C₂H₄ while the suitable pore spaces enforce its high C₂H₆ uptake capacity, featuring Ni-MOF 2 as one of the best porous materials for this very important gas separation. It generates 12 L kg⁻¹ of polymer-grade C₂H₄ product from equimolar C₂H₆/C₂H₄ mixtures at ambient conditions.