Closing the Loop in the Carbon Cycle: Enzymatic Reactions Housed in Metal-Organic Frameworks for CO Conversion to Methanol.

The preparation of value-added chemicals from carbon dioxide (CO) can act as a way of reducing the greenhouse gas from the atmosphere. Industrially significant C1 chemicals like methanol (CHOH), formic acid (HCOOH), and formaldehyde (HCHO) can be formed from CO. One sustainable way of achieving this is by connecting the reactions catalyzed by the enzymes formate dehydrogenase (FDH), formaldehyde dehydrogenase (FALDH), and alcohol dehydrogenase (ADH) into a single cascade reaction where CO is hydrogenated to CHOH.

Water sorption studies with mesoporous multivariate monoliths based on UiO-66.

Hierarchical linker thermolysis has been used to enhance the porosity of monolithic UiO-66-based metal-organic frameworks (MOFs) containing 30 wt% 2-aminoterephthalic acid (BDC-NH) linker. In this multivariate ( mixed-linker) MOF, the thermolabile BDC-NH linker decomposed at ∼350 °C, inducing mesopore formation. The nitrogen sorption of these monolithic MOFs was probed, and an increase in gas uptake of more than 200 cm g was observed after activation by heating, together with an increase in pore volume and mean pore width, indicating the creation of mesopores.

Chiral "doped" MOFs: an electrochemical and theoretical integrated study.

This work reports on the electrochemical behaviour of Fe and Zn based metal-organic framework (MOF) compounds, which are "doped" with chiral molecules, namely: cysteine and camphor sulfonic acid. Their electrochemical behaviour was thoroughly investigated via "solid-state" electrochemical measurements, exploiting an "" tailored experimental set-up: a paste obtained by carefully mixing the MOF with graphite powder is deposited on a glassy carbon (GC) surface. The latter serves as the working electrode (WE) in cyclic voltammetry (CV) measurements.

Hydrogenation of Carbon Dioxide to Formate by Noble Metal Catalysts Supported on a Chemically Stable Lanthanum Rod-Metal-Organic Framework.

The conversion of carbon dioxide to formate is of great importance for hydrogen storage as well as being a step to access an array of olefins. Herein, we have prepared a JMS-5 metal-organic framework (MOF) using a bipyridyl dicarboxylate linker, with the molecular formula [La(bpdc)(dmf)(OAc)]·dmf. The MOF was functionalized by cyclometalation using Pd(II), Pt(II), Ru(II), Rh(III), and Ir(III) complexes.

Two novel metal-organic frameworks functionalised with pentamethylcyclopentadienyl iridium(III) chloride for catalytic conversion of carbon dioxide to formate.

Hydrogenation of CO to formate is a vital reaction, because formate is an excellent hydrogen carrier, which yields blue hydrogen. Blue hydrogen is comparatively cheaper and attractive as the world envisions the hydrogen economy. In this work, two isostructural lanthanide-based MOFs (JMS-6 and JMS-7 [Ln(bpdc)(dmf)(HO)]) were prepared and used as support materials for molecular catalysts.

Selective Cu and Ni-MOFs as pre-catalysts for the hydrogenation of furfural to furfuryl alcohol.

In this work, we report the design of one-dimensional (1D) metal-organic framework containing Cu(II) and Ni(II) active sites using a ,'-bis-(4-pyridyl)isophthalamide linker to form MOF 1 [Cu(L1)(NO)·DMF] and MOF 2 [NiL1Cl]. The MOFs were evaluated as heterogeneous catalysts for the hydrogenation of furfural to furfuryl alcohol. MOF 2 catalyst showed impressive performance with conversion of FF (81%) and selectivity towards FA (100%).

A Co-Crystallised Cobalt(II) Cluster of Pyridinedicarboxylic Acid (PDC) as a Luminescent Material for Selective Sensing of Methanol.

A luminescent Cobalt(II) co-crystal [Co(PDC)(HO).7HO] 1 (where HPDC = 2,6-pyridinedicarboxylic acid) have been prepared by oven-heating and slow evaporation of solvent. Single crystal X-ray diffraction (SCXRD) analysis revealed that 1 is a mixture of complexes that crystallizes in the triclinic space group P-1 and the geometry around the Co(II) ions is octahedral.

Synthesis and Characterization of 2D Metal-Organic Frameworks for Adsorption of Carbon Dioxide and Hydrogen.

The reaction of Cd(NO)·4HO and Zn(NO)·6HO with the bipyridyl dicarboxylate ligand Hbpydc (2,2'-bipyridine-4,4'-dicarboxylic acid) afforded two porous metal organic frameworks [Cd(bpydc)(DMF)·2DMF] (JMS-3) and [Zn(bpydc)(DMF)·DMF] (JMS-4). X-ray diffraction studies revealed that both JMS-3 and JMS-4 crystallize in the monoclinic crystal. The MOFs possess 2D interdigited networks with () topology.

Palladium(II) Immobilized on Metal-Organic Frameworks for Catalytic Conversion of Carbon Dioxide to Formate.

In this work, we report the design of a two-dimensional (2D) isostructural metal-organic framework containing Pd(II) active sites, using a bipyridyl dicarboxylate linker (Mg(bpdc)(DMF)PdCl] (Pd@Mg:JMS-2) and [Mn(bpdc)(DMF)PdCl](Pd@Mn:JMS-2)). The activated MOFs Pd@Mg:JMS-2a and Pd@Mn:JMS-2a were evaluated as heterogeneous catalysts for the hydrogenation of carbon dioxide (CO) to formate. Under optimal conditions, the MOFs exhibited impressive catalytic activity with formate turnover numbers of 7272 and 9808 for Pd@Mg:JMS-2a and Pd@Mn:JMS-2a, respectively, after 24 h.

Cyclometalation of lanthanum(iii) based MOF for catalytic hydrogenation of carbon dioxide to formate.

The hydrogenation of carbon dioxide (CO) to formic acid is of great importance due to its useful properties in the chemical industry. In this work, we have prepared a novel metal-organic framework (MOF), JMS-1, using bipyridyl dicarboxylate linkers, with molecular formula [La(bpdc)(DMF)] . Network analysis of JMS-1 revealed a new 7-connected topology ().

A new class of thermo- and solvatochromic metal-organic frameworks based on 4-(pyridin-4-yl)benzoic acid.

Using 4-(pyridin-4-yl)benzoic acid, 44pba (1) as a ligand, two new metal-coordination networks [Co(4)(44pba)(8)](n)·[(DMF)(3)·(EtOH)(0.25)·(H(2)O)(4)](n) (2) and [Ni(4)(44pba)(8)](n)·[(DMF)(3.5)·(EtOH)·(H(2)O)(1.