Tailoring Amine-Functionalized Ti-MOFs via a Mixed Ligands Strategy for High-Efficiency CO2 Capture

Amine-functionalized metal-organic frameworks (MOFs) are a promising strategy for the high-efficiency capture and separation of CO2. In this work, by tuning the ratio of 1,3,5-benzenetricarboxylic acid (H3BTC) to 5-aminoisophthalic acid (5-NH2-H2IPA), we designed and synthesized a series of amine-functionalized highly stable Ti-based MOFs (named MIP-207-NH2-n, in which n represents 15%, 25%, 50%, 60%, and 100%). The structural analysis shows that the original framework of MIP-207 in the MIP-207-NH2-n (n = 15%, 25%, and 50%) composites remains intact when the mole ratio of ligand H3BTC to 5-NH2-H2IPA is less than 1 to 1 in the resulting MOFs. By the introduction of amino groups, MIP-207-NH2-25% demonstrates outstanding CO2 capture performance up to 3.96 and 2.91 mmol g−1, 20.7% and 43.3% higher than those of unmodified MIP-207 at 0 and 25 °C, respectively. Furthermore, the breakthrough experiment indicates that the dynamic CO2 adsorption capacity and CO2/N2 separation factors of MIP-207-NH2-25% are increased by about 25% and 15%, respectively. This work provides an additional strategy to construct amine-functionalized MOFs with the maintenance of the original MOF structure and a high performance of CO2 capture and separation.

PH Controlled the Supramolecular Assemblies of Two Guanosine Monophosphate Cadmium Metal Coordination Complexes: Structure and Chirality

In biological systems Chirality is important property from small molecules to macromolecules. The construction of homochiral coordination supramolecules in crystal and helical delivers the connection of molecular and macromolecular chirality. Complexity and properties in the presence of cadmium ion and bpe auxiliary ligand for bio-molecular guanosine-5- monophosphate disodium salt (GMP) was studied. The two Complexes 1 and 2 have been investigated the impact of auxiliary ligand bpe, hydroxy group on the sugar motif and pH for coordination of GMP ligands. The interaction of mixed ligands for growth and advancement of chiral complexes was controlled by the alteration of pH values for coordination of guanosine-5-monophosphate nucleotide with cadmium Cd (II) metal. The chirality of complexes 1 and 2 was studied with solid circular dichroism (CD) spectroscopy, including supramolecular chirality and extended auxiliary ligand (EAC) combining with the crystal structure analysis. The various hydrogen bonding and auxiliary ligand are the special means of transporting chirality from isolated molecules to dynamic supramolecular three-dimensional designs of GMP nucleotide crystals. The research results will be benefit to the controlling supramolecular assembly with well-defined structure and properties.

The Structure and Property of Two Different Metal-Organic Frameworks Based on N/O-Donor Mixed Ligands

Two different metal-organic frameworks (MOFs) [Cd2(AZN)(HAZN)(btc)(Hbtc)·4H2O]·2H2O (1), and [Zn3(AZN)2(btc)2·4H2O] (2) were synthesized by the reactions of different metal salts with mixed ligands of 1-(4-(1H-imidazol-5-yl)phenyl)-1H-1,2,4-triazole (AZN) and trimesic acid (H3btc). The different metal centers in the reaction condition have important impact on the resulting structures of MOFs 1 and 2. Compound 1 is a one-dimensional (1D) chain structure, while 2 features a three-dimensional (3D) framework with 3-fold interpenetration topology of Point (Schläfli) symbol of (6·82)4(62·82·102). Furthermore, the luminescent properties have been studied for MOFs 1 and 2.

Activation of anionic redox in d0 transition metal chalcogenides by anion doping

Expanding the chemical space for designing novel anionic redox materials from oxides to sulfides has enabled to better apprehend fundamental aspects dealing with cationic-anionic relative band positioning. Pursuing with chalcogenides, but deviating from cationic substitution, we here present another twist to our band positioning strategy that relies on mixed ligands with the synthesis of the Li2TiS3-xSex solid solution series. Through the series the electrochemical activity displays a bell shape variation that peaks at 260 mAh/g for the composition x = 0.6 with barely no capacity for the x = 0 and x = 3 end members. We show that this capacity results from cumulated anionic (Se2−/Sen−) and (S2−/Sn−) and cationic Ti3+/Ti4+ redox processes and provide evidence for a metal-ligand charge transfer by temperature-driven electron localization. Moreover, DFT calculations reveal that an anionic redox process cannot take place without the dynamic involvement of the transition metal electronic states. These insights can guide the rational synthesis of other Li-rich chalcogenides that are of interest for the development of solid-state batteries.