Molecular Engineering of Metal-Organic Frameworks for Boosting Photocatalytic Hydrogen Peroxide Production.

The development of novel metal-organic frameworks (MOFs) as efficient photocatalysts for hydrogen peroxide production from water and oxygen is particularly interesting, yet remains a challenge. Herein, we have prepared four cyclic trinuclear units (CTUs) based MOFs, exhibiting good light absorption ability and suitable band gaps for photosynthesis of H2O2. However, Cu-CTU-based MOFs are not able to photocatalyzed the formation of H2O2, while the alteration of metal nodes from Cu-CTU to Ag-CTU dramatically enhances the photocatalytic performance for H2O2 production and the production rates can reach as high as 17476 µmol g-1 h-1 with an apparent quantum yield of 4.72 %, at 420 nm, which is much higher than most reported MOFs. The photocatalytic mechanism is comprehensively studied by combining the isotope labeling experiments and DFT calculation. This study provides new insights into the preparation of MOF photocatalysts with high activity for H2O2 production through molecular engineering.

Gold(I)-Organic Frameworks as Catalysts for Carboxylation of Alkynes with CO2.

Construction of gold-based metal-organic frameworks (Au-MOFs) would bring the merits of gold chemistry into MOFs. However, it still remains challenging because gold cations are easily reduced to metallic gold under solvothermal conditions. Herein, we present the first example of Au-MOFs prepared from the networking of cyclic trinuclear gold(I) complexes by formal transimination reaction in a rapid (<15 min) and scalable (up to 1 g) fashion under ambient condition. The Au-MOFs feature uniform porosity, high crystallinity, and superior chemical stability toward base (i.e., 20 M NaOH). With open Au(I) sites in the skeleton, the Au-MOFs as heterogeneous catalysts delivered good performance and substrate tolerance for the carboxylation reactions of alkynes with CO2. This work demonstrates a facile approach to reticularly synthesize Au-MOFs by combining the coordination and dynamic covalent chemistry.

A Self-Assembled Capsule for Propylene/Propane Separation.

The development of energy-saving technology for the efficient separation of olefin and paraffin is highly important for the chemical industry. Herein, we report a self-assembled Fe4 L6 capsule containing a hydrophobic cavity, which can be used to encapsulate and separate propylene/propane. The successful encapsulation of propylene and propane by the Fe4 L6 cage in a water solution was documented by NMR spectroscopy. The binding constants K for the Fe4 L6 cage toward propylene and propane were determined to be (5.0±0.1)×103  M-1 and (2.1±0.7)×104  M-1 in D2 O at 25 °C, respectively. Experiments and theoretical studies revealed that the cage exhibited multiple weak interactions with propylene and propane. The polymer-grade propylene (>99.5 %) can be obtained from a mixture of propylene and propane by using the Fe4 L6 cage as a separation material in a U-shaped glass tube. This work provides a new strategy for the separation of olefin/paraffin.

Ultrathin Metal-Organic Framework Nanosheets Exhibiting Exceptional Catalytic Activity.

Two-dimensional (2D) metal-organic framework nanosheets (MONs) or membranes are classes of periodic, crystalline polymeric materials that may show unprecedented physicochemical properties due to their modular structures, high surface areas, and high aspect ratios. Yet preparing 2D MONs from multiple components and two different types of polymerization reaction remains challenging and less explored. Here, we report the synthesis of MOF films via interfacial polymerization, which involves three active monomers for simultaneous polycondensation and polycoordination taking place in a confined interface. The well-defined lamellar structure of the MOF films allowed feasible and scalable exfoliation to produce free-standing 2D MONs with high aspect ratio up to 2000:1 and ultrathin thickness (∼1.7 nm). The pore structure was revealed by high-resolution TEM images with near-atomic precision. The imide-linkage of MONs provided superior thermal (up to 530 °C) and good chemical stability in the pH range from 3 to 12. More importantly, the MONs exhibited exceptional catalytic activity and superior reusability for the hydroboration reactions of alkynes, in which the turnover frequency (TOF) reached 41734 h-1, which is 2-4 orders of magnitude greater than that reported for homogeneous and heterogeneous catalysts.

A cyclic trinuclear silver complex for photosynthesis of hydrogen peroxide.

The development of metal complexes for photosynthesis of hydrogen peroxide (H2O2) from pure water and oxygen using solar energy, especially in the absence of any additives (e.g., acid, co-catalysts, and sacrificial agents), is a worthwhile pursuit, yet still remains highly challenging. More importantly, the O2 evolution from the water oxidation reaction has been impeded by the classic bottleneck, the photon-flux-density problem of sunlight that could be attributed to rarefied solar radiation for a long time. Herein, we reported synthesis of boron dipyrromethene (BODIPY)-based cyclic trinuclear silver complexes (Ag-CTC), and they exhibited strong visible-light absorption ability, a suitable energy bandgap, excellent photochemical properties and efficient charge separation ability. The integration of BODIPY motifs as oxygen reduction reaction sites and silver ions as water oxidation reaction sites allows Ag-CTC to photosynthesize H2O2 either from pure water or from sea water in the absence of any additives with a high H2O2 production rate of 183.7 and 192.3 µM h-1, which is higher than that of other reported metal-based photocatalysts. The photocatalytic mechanism was systematically and ambiguously investigated by various experimental analyses and density functional theory (DFT) calculations. Our work represents an important breakthrough in developing a new Ag photocatalyst for the transformation of O2 into H2O2 and H2O into H2O2.

Acid-triggered interlayer sliding of two-dimensional copper(i)-organic frameworks: more metal sites for catalysis.

The interlay sliding of two-dimensional (2D) metal-organic and covalent-organic frameworks (MOFs and COFs) affects not only the layout features of the structures, but also the functional output of the materials. However, the control of interlay stacking is the major hurdle that needs to be overcome to construct new functional layer materials. Herein, we report the preparation of a pair of isostructural 2D copper(i) organic frameworks with an eclipsed AA stacking structure, namely JNM-3-AA, and a staggered ABC stacking topology, denoted JNM-3-ABC, by combining the chemistry of MOFs and COFs. The variation of interlayer stacking largely influences their functionality, including porosity (BET surface areas of 695.61 and 34.22 m2 g-1 for JNM-3-AA and JNM-3-ABC, respectively), chemical stability, and catalytic activities (less than 10% or ∼86% yield using JNM-3-AA or JNM-3-ABC as catalysts for click reaction, respectively). More interestingly, the structure transformation from JNM-3-ABC to JNM-3-AA is readily achieved by simple addition of trifluoroacetic acid accompanied by the extension of porosities from BET surface areas of 34.22 to 441.22 m2 g-1, resulting in in situ acceleration of the adoption rate (removal efficiency increases from ∼10 to 99.9%), which is rarely observed in 2D MOFs and COFs.