Electrocatalytic acetylene semihydrogenation is a promising alternative to thermocatalytic acetylene hydrogenation due to its environmental benignity and economic efficiency, but its performance is far below that of the thermocatalytic reaction because of strong competition from side reactions, including hydrogen evolution, overhydrogenation and carbon–carbon coupling reactions. We develop N–heterocyclic carbene–metal complexes, with electron–rich metal centers owing to the strongly σ–donating N–heterocyclic carbene ligands, as electrocatalysts for selective acetylene semihydrogenation. Experimental and theoretical investigations reveal that the copper sites in N–heterocyclic carbene–copper facilitate the absorption of electrophilic acetylene and the desorption of nucleophilic ethylene, ultimately suppressing the side reactions during electrocatalytic acetylene semihydrogenation, and exhibit superior semihydrogenation performance, with faradaic efficiencies of ≥98 % under pure acetylene flow. Even in a crude ethylene feed containing 1 % acetylene (1 × 104 ppm), N–heterocyclic carbene–copper affords a specific selectivity of >99 % during a 100–h stability test, continuous ethylene production with only ~30 ppm acetylene, a large space velocity of up to 9.6 × 105 mL·gcat−1·h−1, and a turnover frequency of 2.1 × 10−2 s−1, dramatically outperforming currently reported thermocatalysts.
For designing water-soluble responsive materials, utilizing crown ethers as main building blocks has been rarely explored in contrast to their linear poly(ethylene glycol) counterparts. In the current study, we report the robust thermoresponsive properties of the benzo-21-crown-7 (B21C7) family with lower critical solution temperature (LCST) and upper critical solution temperature (UCST) behavior. Different substituent groups on the benzene ring exhibit significant effects on water solubility and thermoresponsiveness. B21C7 and its cyano derivative display LCST phenomena, while B21C7-based carboxylic acid derivative presents UCST followed by LCST phase behavior. Supramolecular interactions with KCl provide an additional tuning approach for this crown ether system. These results demonstrate that B21C7s can serve as an easily accessible toolbox to develop new thermosensitive systems and prepare thermally responsive materials.
Four new three-dimensional isostructural lanthanide-cadmium metal-organic frameworks (Ln-Cd MOFs), [LnCd(2)(imdc)(2)(Ac)(H(2)O)(2) ]·H(2)O (Ln=Pr (1), Eu (2), Gd (3), and Tb (4); H(3)imdc=4,5-imidazoledicarboxylic acid; Ac=acetate), have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, inductively coupled plasma (ICP) analysis, and X-ray diffraction. Single-crystal X-ray diffraction shows that two Ln(III) ions are surrounded by four Cd(II) ions to form a heteronuclear building block. The blocks are further linked to form 3D Ln-Cd MOFs by the bridging imdc(3-) ligand. Furthermore, the left- and right-handed helices array alternatively in the lattice. Eu-Cd and Tb-Cd MOFs can emit characteristic red light with the Eu(III) ion and green light with the Tb(III) ion, respectively, while both Gd-Cd and Pr-Cd MOFs generate blue emission when they are excited. Different concentrations of Eu(3+) and Tb(3+) ions were co-doped into Gd-Cd/Pr-Cd MOFs, and tunable luminescence from yellow to white was achieved. White-light emission was obtained successfully by adjusting the excitation wavelength or the co-doping ratio of the co-doped Gd-Cd and Pr-Cd MOFs. These results show that the relative emission intensity of white light for Gd-Cd:Eu(3+),Tb(3+) MOFs is stronger than that of Pr-Cd:Eu(3+),Tb(3+) MOFs, which implies that the Gd complex is a better matrix than the Pr complex to obtain white-light emission materials.
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