This work reports the reduction of 4-nitrophenol to 4-aminophenol using UiO-66(Zr) as a bifunctional photocatalyst and hydrogenation catalyst using methanol as the hydrogen source. In particular, a series of UiO-66(Zr)-X (X: NH, NO and H) and MIL-125(Ti)-NH catalysts have been screened as bifunctional catalysts for this process. UiO-66(Zr)-NH was found to be the most active material to promote light-assisted nitro hydrogenation under both UV-Vis and simulated sunlight irradiation. The tandem reaction occurs via hydrogen generation from a water/methanol mixture in the first step and, then, reduction of 4-nitrophenol to 4-aminophenol. UiO-66(Zr)-NH acts as a truly heterogeneous catalyst and can be reused several times without significant loss of activity, maintaining its crystallinity. This work shows the possibility of using MOFs as solar-driven bifunctional catalysts to promote the hydrogenation of organic compounds using methanol as the hydrogen source.
Silica-based monoliths offer higher separation efficiency per unit pressure drop compared to particle-packed columns. Their application is limited by the commercial availability of different column chemistries. Pentafluorophenyl ligands enable hydrogen bonding, dipole-dipole, π-π, and hydrophobic interactions, facilitating the separation of various compounds.
The catalytic efficiency of M-H2tpda pincer complexes (M = Mn(I), Fe(II), Co(III)) in CO2 hydrogenation, emphasizing the role of transition metal center variability have been discussed. The DFT analysis demonstrates that complexes with low αR values form weaker M-H bonds, enhancing catalyst reactivity with the elongation of M-H bond. The analysis further displays excellent catalytic performance for Mn-H2tpda (ΔE = 20.
Carbon dioxide hydrogenation to methanol is a key chemical reaction to store energy in chemical bonds, using carbon dioxide as an energy sink. Indium oxide is amongst the most promising candidates for replacing the copper and zinc oxide catalyst, which is industrially applied for syngas mixtures but less idoneous for educts with carbon dioxide due to instability reasons. The polymorph of indium oxide and the operating conditions remain to be optimized for optimal and stable performance.
In this study, a tetradentate Schiff-base ligand (HL), synthesized by the condensation of ethylenediamine with 2-hydroxy-3-methoxy-5-methylbenzaldehyde, was reacted with either manganese salts or manganese salts in the presence of various pseudohalides in methanol. This reaction resulted in the formation of five mononuclear Mn complexes: [Mn(L)(HO)](NO)·1/2HO·1/2CHOH (), [Mn(L)(HO)](ClO)·HO (), [Mn(L)(N)(HO)]·1/3HO (), [Mn(L)(NCS)(HO)] (), and [Mn(L)(HO)](dca) () (where dca is dicyanamide ion). X-ray crystallography revealed that the Mn centers adopt a hexa-coordinate pseudo-octahedral geometry, where the equatorial plane is constructed with phenoxo oxygen and imine nitrogen atoms from the Schiff base ligand, while the axial positions are occupied by water molecules or a combination of water and pseudohalides.
In the title solvate, CHNO·CHO, the dihedral angles between the formamidine backbone and the pendant 2-meth-oxy-phenyl and 2,6-di-methyl-phenyl groups are 14.84 (11) and 81.61 (12)°, respectively.
