50446-44-1Relevant articles and documents
Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium–Organic Frameworks
López-Maya, Elena,Padial, Natalia M.,Castells-Gil, Javier,Ganivet, Carolina R.,Rubio-Gaspar, Ana,Cirujano, Francisco G.,Almora-Barrios, Neyvis,Tatay, Sergio,Navalón, Sergio,Martí-Gastaldo, Carlos
, p. 11868 - 11873 (2021)
We introduce the first example of isoreticular titanium–organic frameworks, MUV-10 and MUV-12, to show how the different affinity of hard Ti(IV) and soft Ca(II) metal sites can be used to direct selective grafting of amines. This enables the combination of Lewis acid titanium centers and available -NH2 sites in two sizeable pores for cooperative cycloaddition of CO2 to epoxides at room temperature and atmospheric pressure. The selective grafting of molecules to heterometallic clusters adds up to the pool of methodologies available for controlling the positioning and distribution of chemical functions in precise positions of the framework required for definitive control of pore chemistry.
Independent verification of the saturation hydrogen uptake in MOF-177 and establishment of a benchmark for hydrogen adsorption in metal-organic frameworks
Furukawa, Hiroyasu,Miller, Michael A.,Yaghi, Omar M.
, p. 3197 - 3204 (2007)
Hydrogen isotherms for MOF-177, Zn4O(1,3,5-benzenetribenzoate) 2, crystals were independently measured by volumetric and gravimetric methods at 77 K to confirm its hydrogen uptake capacity and to establish the importance of calibrating gas adsorption instrumentation prior to evaluating H2 storage capacities. Reproducibility of hydrogen adsorption experiments is important because non-systematic errors in measurements can easily occur leading to erroneous reports of capacities. The surface excess weight percentage of hydrogen uptake in MOF-177 samples is 7.5 wt% at 70 bar, which corresponds to an absolute adsorbed amount of 11 wt%. These values are in agreement with our previous report and with those found independently by Southwest Research Institute. Considering its well-known structure and its significant H2 uptake properties, we believe MOF-177 is an excellent material to serve as a benchmark adsorber. The Royal Society of Chemistry.
Structures and H2 adsorption properties of porous scandium metal-organic frameworks
Ibarra, Ilich A.,Lin, Xiang,Yang, Sihai,Blake, Alexander J.,Walker, Gavin S.,Barnett, Sarah A.,Allan, David R.,Champness, Neil R.,Hubberstey, Peter,Schroeder, Martin
, p. 13671 - 13679 (2010)
Two new three-dimensional ScIII metal-organic frameworks {[Sc3O(L1)3(H2O)3] ·Cl0.5(OH)0.5(DMF)4(H2O) 3}∞ (1) (H2L1=1,4-benzene- dicarboxylic acid) and {[Sc3O(L2)2(H 2O)3](OH)(H2O)5(DMF)} ∞ (2) (H3L2=1,3,5-tris(4-carboxyphenyl) benzene) have been synthesised and characterised. The structures of both 1 and 2 incorporate the trinuclear trigonal planar [Sc3(O)(O 2CR)6] building block featuring three ScIII centres joined by a central μ3-O2- donor. Each Sc III centre is further bound by four oxygen donors from four different bridging carboxylate anions, and a molecule of water located trans to the μ3-O2- donor completes the six coordination at the metal centre. Frameworks 1 and 2 show high thermal stability with retention of crystallinity up to 350 °C. The desolvated materials 1 a and 2 a, in which the solvent has been removed from the pores but with water or hydroxide remaining coordinated to ScIII, show BET surface areas based upon N2 uptake of 634 and 1233 M2 g-1, respectively, and pore volumes calculated from the maximum N2 adsorption of 0.25 Cm3 g-1 and 0.62 Cm3 g-1, respectively. At 20 Bar and 78 K, the H2 isotherms for desolvated 1 a and 2 a confirm 2.48 and 1.99 Wt % total H2 uptake, respectively. The isosteric heats of adsorption were estimated to be 5.25 and 2.59 KJ mol -1 at zero surface coverage for 1 a and 2 a, respectively. Treatment of 2 with acetone followed by thermal desolvation in vacuo generated free metal coordination sites in a new material 2 b. Framework 2 b shows an enhanced BET surface area of 1511 M2 g-1 and a pore volume of 0.76 Cm3 g-1, with improved H2 uptake capacity and a higher heat of H2 adsorption. At 20 Bar, H2 capacity increases from 1.99 Wt % in 2 a to 2.64 Wt % for 2 b, and the H2 adsorption enthalpy rises markedly from 2.59 to 6.90 KJ mol-1. It's ScIIIandalous: {[Sc3O(L1)3(H 2O)3]·Cl0.5OH0.5(DMF) 4(H2O)3}∞ (1) (H 2L1=1,4-benzenedicarboxylic acid) and {[Sc 3O(L2)2(H2O)3]OH(H 2O)5(DMF)}∞ (2) (H3L 2=1,3,5-tris(4-carboxyphenyl)benzene) incorporate the trinuclear trigonal planar [Sc3(O)(O2CR)6] building block. After appropriate thermal treatment on the acetone-exchanged sample 2, the generation of free metal coordination sites has been achieved to give an increase in the BET surface area in 2 b. Copyright
A metal oxide catalytic oxidation three 1, 3, 5 - (4 - carboxyl phenyl) benzene method (by machine translation)
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Paragraph 0028; 0030; 0031; 0032, (2018/07/30)
The invention discloses a metal oxide catalytic oxidation process for preparing 1, 3, 5 - three (4 - carboxyl phenyl) benzene method. The method comprises the following steps: 1) the 1, 3, 5 - three (4 - methyl phenyl) benzene, organic metal catalyst, a ligand and an additive in a solvent after mixing, under the action of the oxidizing agent, in the 80 - 130 °C temperature, 0.5 - 5.5 mpa gauge pressure under the conditions of the reaction 5 - 22 the H; 2) after the end of the oxidation reaction, filtering to remove the organic metal catalyst, then adding the extraction reagent and water, by extraction to obtain the organic phase and aqueous phase; 3) organic phase sequentially through the drying, filtering, concentrating and purifying processing, to obtain 1, 3, 5 - three (4 - carboxyl phenyl) benzene. The invention adopts the metal oxide as the catalyst, hydrogen peroxide, air or oxygen as the oxidizing agent, can effectively reduce the cost, reduce the production of three wastes, environmental protection, mild reaction conditions, high product yield, is suitable for industrial production. (by machine translation)
Method for preparation of 1, 3, 5-tris(4-carboxyphenyl)benzene by catalytic oxidation of Anderson polyacid
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Paragraph 0031; 0033; 0035; 0037; 0038; 0039, (2018/09/20)
The inventon discloses a method for preparation of 1, 3, 5-tris(4-carboxyphenyl)benzene by catalytic oxidation of Anderson polyacid. The specific steps include: 1) subjecting 1, 3, 5-tris(4-methylphenyl)benzene, a catalyst, an oxidant and an additive to oxidation reaction in a solvent, wherein the oxidant is air, oxygen or hydrogen peroxide, and the catalyst is an Anderson type polyacid catalyst;and 2) at the end of the oxidation reaction, filtering out the catalyst, then adding an extracting solvent and water for extraction so as to obtain an organic phase and an aqueous phase, and carryingout drying, filtering, concentration and purification on the organic phase in order to obtain the1, 3, 5-tris(4-carboxyphenyl)benzene. The method adopts Anderson polyacid as the catalyst, which has the characteristics of high reaction activity, mild reaction conditions and environmental friendliness, high specific selectivity, and recyclability, and adopts hydrogen peroxide, air or oxygen as the oxidant, can low the cost and reduce the production of three wastes, and is suitable for industrial production.
