Herein, a new preparation strategy of chiral metal–organic frameworks (CMOFs) has been demonstrated. By adsorption and then post-synthetically modified (PSM) procedures, chiral salen(Co(III)) could be imprisoned within the cages of an MOF and remained in its free form. This is the first report on the successful application of CMOFs in heterogeneous asymmetric catalysis for coupling CO2 with epoxides to obtain optically active cyclic carbonates at room temperature.

•Two new MOFs constructed from novel six-coordinated tetranuclear Cu(II) SBUs have been synthesized.•The two MOFs present flu-3,6-Fddd and ant topological structures, respectively.•The two MOFs exhibit good size-selectivity for the epoxidation of different olefin substrates.•The possible catalytic mechanism for the reaction has been proposed.Two metal-organic frameworks (MOFs) constructed from new six-coordinated tetranuclear Cu(II) secondary building units (SBUs) and 1-(3,5-dicarboxyphenyl)-2,5-dimethyl-1H-pyrrole-3,4-dicarboxylic acid (H4ppdc) ligands have been synthesized under solvothermal condition. Their similar, high density tetranuclear Cu(II) SBUs but different, well-defined microporous structures encourage us to contrastively study their catalytic behaviour for the epoxidation reaction of olefins using TBHP or molecular oxygen as oxidants. The results show that the two MOFs exhibit good size-selectivity for the epoxidation of different olefin substrates. The catalytic mechanism investigation indicates that the reaction process indeed proceeds via radical epoxidation.Two MOFs constructed from new six-coordinated Cu(II) SBUs and H4ppdc ligands exhibit size-selectivity for the epoxidation of different olefin substrates.

•Inverse CeO2/CuO catalysts for the preferential CO oxidation in H2-rich steam.•An alternative synthetic approach using MOFs as a precursor for the inverse catalysts.•The structural merits of MOFs are beneficial to the dispersion of active sites of CeO2/CuO.•These catalysts exhibited excellent catalytic activity and selectivity for CO-PROX.Using heterobimetallic metal-organic frameworks (MOFs) as the precursor, a series of inverse CeO2/CuO catalysts, by which cerial nanoparticles were patched on a copper oxide support, were synthesized. These catalysts exhibited excellent catalytic activity and selectivity during preferential CO oxidation in the H2-rich stream. This new approach based on MOFs precursor has two advantages for optimizing the inverse CeO2/CuO catalysts with more copper-ceria interfacial sites: 1) the highly ordered metal-oxygen clusters were completely separated by the organic linkers; and 2) the Ce/Cu configuration can be modulated. We further found that the calcination temperature and heating rate of MOFs are critical for their catalytic activity.

Two new coordination polymers, [Ni(H2O)(Hpdcd)(H2O)2]·DMF (1) and [Co(H2O)(Hpdcd)(H2O)2]·DMF (2) (H3pdcd = 1-(4-carboxyphenyl)-2,5-dimethyl, 1H-pyrrole-3,4-dicarboxylic acid), which were designed based on a tertiary amine ligand, were synthesized and characterized using multiple spectroscopy techniques, including single-crystal X-ray diffraction. These two 1D linear chains possess the properties of both a Lewis acid and organic base, which was confirmed by temperature programmed desorption of ammonia and on-line mass spectrometry (NH3-TPD-MS), and selective sorption for carbon dioxide. Due to their acid–base properties, the compounds exhibited high catalytic activity, in the absence of co-catalysts, for solvent-free synthesis of chloropropene carbonate from CO2 and epichlorohydrin under atmospheric CO2 pressure. The yields of chloropropene carbonate were 88% and 87% for 1 and 2, respectively, under the optimized conditions.

A highly thermal stable metal–organic framework (MOF), MIL-120, was employed to incorporate low-cost nickel particles by simple impregnate method to obtain heterogeneous catalyst, Ni/MIL-120. The as-synthesized catalysts were evaluated by gas-phase benzene hydrogenation and exhibited excellent catalytic activities in comparison with classic Ni/Al2O3 catalyst. The X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) and transmission electron microscopic (TEM) results indicated that Ni species were well dispersed on the MOF matrix and the interaction between the Ni species and the MOF-support was weaker than that between the metal species and Al2O3, which facilitated the catalytic performance of catalyst for benzene hydrogenation.Graphical abstractHighlights► A stable MOF, MIL-120, was employed to incorporate Ni by impregnate method. ► The catalytic property of Ni/MIL-120 catalyst was studied using gas-phase benzene hydrogenation. ► NiO/MIL-120 showed great catalytic activity.

A 2D metal-organic framework [Cu2 (BPTC) (Im)4(H2O) (DMF)]n (1) with unsaturated coordinated Cu(II) sites has been prepared under solvothermal condition, and applied to the hydroxylation of phenol after activating. The catalytic results indicate that 1a (the activated 1) exhibits an obvious activity for phenol hydroxylation at 40 °C for 4 h. Compared to the control experiments where the free Cu(II) (from Cu(OAc)2 salt) has been utilized as the catalysts, 1a shows the higher selectivity to diphenols. This suggests that the coordinated environment of unsaturated coordinated Cu(II) sites in the 2D layer play the key role in the phenol hydroxylation.

Controlling the ratio of biphenyl-3,3′,4,4′-tetracarboxylic acid to piperazine produces two interesting organic crystals, respectively, containing 1D negatively charged rectangular tubes and a 2D neutral fes 4·82 network, and the two crystals are both sufficiently robust to retain crystallinity after the water molecules have been completely removed.

Employing metal–organic frameworks (MOFs) as precursor, a series of CuO/CeO2 catalysts with well-dispersed copper species were synthesized and applied for preferential CO oxidation in H2-rich stream. The catalyst with 5 wt.% Cu loading calcined at 600 °C for 6 h exhibited an excellent catalytic activity. The high activity of the CuO/CeO2 catalysts indicated that MOF precursor played a key role for improving the dispersion of metal active sites.Download full-size imageHighlights► Catalysts for preferential CO oxidation in H2-rich steam. ► Metal-organic framework (MOF) was applied to synthesis of CuO/CeO2 catalysts. ► The feature of MOF is beneficial to the dispersion of active sites on the support. ► The catalysts with well-dispersed active sites on the support. ► The catalysts exhibited excellent catalytical activities.

•UTSA-16 acted as catalyst for CO2 cycloaddition reaction under mild condition.•K+ species played crucial role in CO2 capture and conversion processes.•Co2+ and K+ decorated in the framework played synergistic catalytic effect.•Catalyst could be reused above five times without loss of catalytic activity.UTSA-16, The second highest porous MOF for CO2 capture, was for the first time employed for CO2 cycloaddition reaction. It combined the CO2 capture and conversion steps into one. Carbon dioxide was fixed and activated by potassium species decorated in the framework, prior to insertion into the active epoxides performed by the coordinated unsaturated metal sites Co. In the absence of co-catalyst, the catalyst showed activities to propylene oxide and some other epoxides under relatively mild conditions, performed true heterogeneous catalysis, could be reused five times without loss of catalytic activity.UTSA-16 acted as self-supported catalyst for the CO2 cycloaddition reaction dependent on the coordinated unsaturated Co(1) ion with K species, which played synergistic catalytic effect.

Two new coordination polymers, [Ni(H2O)(Hpdcd)(H2O)2]·DMF (1) and [Co(H2O)(Hpdcd)(H2O)2]·DMF (2) (H3pdcd = 1-(4-carboxyphenyl)-2,5-dimethyl, 1H-pyrrole-3,4-dicarboxylic acid), which were designed based on a tertiary amine ligand, were synthesized and characterized using multiple spectroscopy techniques, including single-crystal X-ray diffraction. These two 1D linear chains possess the properties of both a Lewis acid and organic base, which was confirmed by temperature programmed desorption of ammonia and on-line mass spectrometry (NH3-TPD-MS), and selective sorption for carbon dioxide. Due to their acid–base properties, the compounds exhibited high catalytic activity, in the absence of co-catalysts, for solvent-free synthesis of chloropropene carbonate from CO2 and epichlorohydrin under atmospheric CO2 pressure. The yields of chloropropene carbonate were 88% and 87% for 1 and 2, respectively, under the optimized conditions.