Titanium metal–organic frameworks (Ti‐MOFs), as an appealing type of artificial photocatalyst, have shown great potential in the field of solar energy conversion due to their well‐studied photoredox ...activity (similar to TiO2) and good optical responsiveness of linkers, which serve as the antenna to absorb visible‐light. Although much effort has been dedicated to developing Ti‐MOFs with high photocatalytic activity, their solar energy conversion performances are still poor. Herein, we have implemented a covalent‐integration strategy to construct a series of multivariate Ti‐MOF/COF hybrid materials PdTCPP⊂PCN‐415(NH2)/TpPa (composites 1, 2, and 3), featuring excellent visible‐light utilization, a suitable band gap, and high surface area for photocatalytic H2 production. Notably, the resulting composites demonstrated remarkably enhanced visible‐light‐driven photocatalytic H2 evolution performance, especially for the composite 2 with a maximum H2 evolution rate of 13.98 mmol g−1 h−1 (turnover frequency (TOF)=227 h−1), which is much higher than that of PdTCPP⊂PCN‐415(NH2) (0.21 mmol g−1 h−1) and TpPa (6.51 mmol g−1 h−1). Our work thereby suggests a new approach to highly efficient photocatalysts for H2 evolution and beyond.
A series of covalently connected multivariate Ti‐MOF/COF hybrid materials were constructed demonstrating outstanding photocatalytic H2 evolution performance with a maximum H2 evolution rate of 13.98 mmol g−1 h−1 (TOF=227 h−1), much higher than the prototypical counterparts.
The indoor air quality is of prime importance for human daily life and health, for which the adsorbents like zeolites and silica‐gels are widely used for air dehumidification and harmful gases ...capture. Herein, we develop a pore‐nanospace post‐engineering strategy to optimize the hydrophilicity, water‐uptake capacity and air‐purifying ability of metal‐organic frameworks (MOFs) with long‐term stability, offering an ideal candidate with autonomous multi‐functionality of moisture control and pollutants sequestration. Through variant tuning of organic‐linkers carrying hydrophobic and hydrophilic groups in the pore‐nanospaces of prototypical UiO‐67, a moderately hydrophilic MOF (UiO‐67‐4Me‐NH2‐38 %) with high thermal, hydrolytic and acid‐base stability is screened out, featuring S‐shaped water sorption isotherms exactly located in the recommended comfortable and healthy ranges of relative humidity for indoor ventilation (45 %–65 % RH) and adverse health effects minimization (40–60 % RH). Its exceptional attributes of water‐uptake working capacity/efficiency, contaminants removal, recyclability and regeneration promise a great potential in confined indoor environment application.
A moderately hydrophilic MOF of UiO‐67‐4Me‐NH2‐38 % with high thermal, hydrolytic and acid‐base stability has been obtained by a pore‐nanospace post‐engineering strategy, which shows ideal S‐shaped water‐sorption isotherm, high water‐uptake working capacity and efficiency in the ASHRAE recommended humidity range, and prior capture ability of harmful organic and inorganic vapors, providing a promising candidate for autonomous indoor humidity control and air purification.
The separation of racemic compounds is important in many fields, such as pharmacology and biology. Taking advantage of the intrinsically strong chiral environment and specific interactions featured ...by biomolecules, here we contribute a general strategy is developed to enrich chirality into covalent organic frameworks (COFs) by covalently immobilizing a series of biomolecules (amino acids, peptides, enzymes) into achiral COFs. Inheriting the strong chirality and specific interactions from the immobilized biomolecules, the afforded biomolecules⊂COFs serve as versatile and highly efficient chiral stationary phases towards various racemates in both normal and reverse phase of high‐performance liquid chromatography (HPLC). The different interactions between enzyme secondary structure and racemates were revealed by surface‐enhanced Raman scattering studies, accounting for the observed chiral separation capacity of enzymes⊂COFs.
COF chirality: A general and efficient strategy has been developed to introduce chirality into covalent organic frameworks (COFs) by covalently immobilizing biomolecules into achiral COFs. The biomolecules⊂COFs can serve as chiral stationary phases for efficient chiral separation of a broad range of racemates.
Design of stable adsorbents for selective gold recovery with large capacity and fast adsorption kinetics is of great challenge, but significant for the economy and the environment. Herein, we show ...the design and preparation of an irreversible amide‐linked covalent organic framework (COF) JNU‐1 via a building block exchange strategy for efficient recovery of gold. JNU‐1 was synthesized through the exchange of 4,4′‐biphenyldicarboxaldehyde (BA) in mother COF TzBA consisting of 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline (Tz) and BA with terephthaloyl chloride. The irreversible amide linked JNU‐1 gave good stability, unprecedented fast kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. X‐ray photoelectron spectroscopy along with thermodynamic study and quantum mechanics calculation reveals that the excellent performance of JNU‐1 for gold recovery results from the formation of hydrogen bonds C(N)−H⋅⋅⋅Cl and coordinate interaction of O and Au. The rational design of irreversible bonds as both inherent linkage and functional groups in COFs is a promising way to prepare stable COFs for diverse applications.
Going for gold: A building‐block exchange strategy gave an irreversible amide‐linked covalent organic framework (COF). The irreversible‐amide linked COF gave good stability, unprecedented fast adsorption kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery.
Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral ...catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application.
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•Metal-catalyzed asymmetric difunctionalization of conjugated dienes in a highly regioselective fashion are realized.•Eight metal catalysts are introduced by the number of ...frequency.•Exquisite choosing diene coupling partners and reaction conditions are crucial for the high efficiency.
1,3-Dienes and derivatives are either feedstock chemicals or easily available materials. Catalytic difunctionalization of 1,3-diene is one of the most powerful methods for carboncarbon bond formation with rapid increase of the molecular complexity and synthetic value in an atom economic way. By choosing proper metals and chiral ligands, a variety of catalytic asymmetric difunctionalization of conjugated dienes in a highly regioselective fashion have been reported. In this digest review, we will summarize recent advances on this topic based on different metals. We will also introduce unique phenomena that include reversal of regio- and diastereoselectivity.
The diverse structures and pore topologies, accessible cages and tunnels, and high surface areas make metal–organic frameworks attractive as novel media in separation sciences. Here we report the ...slurry-packed MIL-101(Cr) column for high-performance liquid chromatographic separation of substituted aromatics. The MIL-101(Cr) packed column (5 cm long × 4.6 mm i.d.) offered high-resolution separation of ethylbenzene (EB) and xylene, dichlorobenzene and chlorotoluene isomers, and EB and styrene. The typical impurities of toluene and o-xylene in EB and styrene mixtures were also efficiently separated on the MIL-101(Cr) packed column. The column efficiencies for EB, m-dichlorobenzene, and m-chlorotoluene are 20000, 13000, and 10000 plates m–1, respectively. The relative standard deviation for five replicate separations of the substituted aromatics was 0.2–0.7%, 0.9–2.9%, 0.5–2.1%, and 0.6–2.7% for the retention time, peak area, peak height, and half peak width, respectively. The MIL-101(Cr) offered high affinity for the ortho-isomer, allowing fast and selective separation of the ortho-isomer from the other isomers within 3 min using dichloromethane as the mobile phase. The effects of the mobile phase composition, injected sample mass, and temperature were investigated. The separation of xylene, dichlorobenzene, and chlorotoluene on MIL-101(Cr) was controlled by entropy change, while the separation of EB and styrene on MIL-101(Cr) was governed by enthalpy change.
Subtropical evergreen broadleaved forests (EBLFs) inhabit large areas of East Asia. Although paleovegetation reconstructions have revealed that the subtropical EBLFs existed in Southwest China during ...the Miocene, the historical construction of these forests remains poorly known. Here, we used the tea family (Theaceae), a characteristic component of the subtropical EBLFs, to gain new insights into the assembly of this important biome.
Using a robust phylogenetic framework of Theaceae based on plastome and nuclear ribosomal DNA sequence data, the temporal history of the family was reconstructed. Data from other characteristic components of subtropical EBLFs, including Fagaceae, Lauraceae and Magnoliaceae, were also integrated.
Most of the essential elements of the subtropical EBLFs appear to have originated around the Oligocene–Miocene (O–M) boundary. However, small woody lineages (e.g. Camellia, Hartia) from Theaceae were dated to the late Miocene. Accelerated net diversification rates within Theaceae were also detected near the O–M transition period and the late Miocene.
Our results suggest that two independent intensifications of the East Asian summer monsoon (EASM) around the O–M boundary and the late Miocene may have facilitated the historical assembly of the subtropical EBLFs in East Asia.
A visible-light-induced copper-catalyzed intermolecular hydroamination of alkenes using commercially accessible primary and secondary amines has been established. This effective method exhibits good ...tolerance of a broad range of functional groups and provides a facile access to an array of valuable amines with Markovnikov regioselectivity. The process can be positively expected to be used in bioactive amines, and it may provide new potential in the discovery of copper-catalyzed hydrofunctionalization reactions.
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