For the first time, the new microwave-assisted method for the synthesis of copper phyllosilicates on a commercial SiO2 carrier was developed. The application of microwave synthesis allowed to decrease the synthesis time from 9 to 6 h compared to the traditional DPU method of preparing chrysocolla. The synthesized catalysts were studied by N2 adsorption, TEM and XRD methods. Catalysts prepared by microwave method are highly effective in the selective hydrogenation of the С≡С bond in 1,4-butynediol to 1,4-butenediol and 2-phenylethinylaniline with a selectivity of 96.5% and 100% at full conversion for 2 and 0.5 h of the reaction, respectively.
In this study, novel SiO2- and Al2O3-supported Cu-Fe catalysts are developed for selective hydrogenation of 2-methyl-3-butyne-2-ol to 2-methyl-3-butene-2-ol under mild reaction conditions. TEM, XRD, and FTIR studies of adsorbed CO and TPR-H2 are performed to characterize the morphology, nanoparticle size, and particle distribution, as well as electronic state of deposited metals in the prepared catalysts. The deposition of Fe and Cu metal particles on the aluminum oxide carrier results in the formation of a mixed oxide phase with a strong interaction between the Fe and Cu precursors during the calcination. The highly dispersed nanoparticles of Fe2O3 and partially reduced CuOx, with an average size of 3.5 nm and with strong contact interactions between the metals in 5Cu-5Fe/Al2O3 catalysts, provide a high selectivity of 93% toward 2-methyl-3-butene-2-ol at complete conversion of the unsaturated alcohol.
Development of novel Cu-based catalysts has become one of the frontiers in the catalytic production of platform chemicals and in environment protection. However, the known methods of their synthesis are too complicated and result in materials that cannot be used instantly as commercial catalysts. In the present work, a novel material has been synthesized by the facile method of deposition–precipitation using thermal hydrolysis of urea. The conditions for Cu phyllosilicate formation have been revealed (molar ratio urea:copper = 10, 92 °C, 8–11 h). The prepared Cu-based materials were studied by TG–DTA, SEM, TEM, XRD, N2 adsorption and TPR-H2 methods, and it was found that the material involves nanoparticles of micro-mesoporous copper phyllosilicate phase with a chrysocolla-like structure inside the pores of a commercial meso-macroporous silica carrier. The chrysocolla-like phase is first shown to be catalytically active in the selective reduction of the nitro-group in trinitrobenzene to an amino-group with molecular hydrogen. Complete conversion of trinitrobenzene with a high yield of amines has been achieved in short time under relatively mild conditions (170 °C, 1.3 MPa) of nitroarene hydrogenation over a copper catalyst.
The cheap non-noble Cu–SiO2-based nanocatalysts are under intensive study in different reactions resulting in useful chemicals, yet their application in environment protection is poorly studied. In the present work, the influence of the Cu loading (3–15 wt%) on the catalytic behavior of Cu/SiO2 materials was first precisely studied in the hydrogenation of hazardous trinitrobenzene to valuable aromatic amines with molecular hydrogen. The catalysts have been synthesized by the method of deposition–precipitation using urea. The catalyst characterization by XRD, TPR-H2, SEM, TEM, and N2 adsorption methods confirmed that they include nanoparticles of the micro-mesoporous chrysocolla-like phase supported in the mesopores of a commercial SiO2 carrier, as well as revealed formation of the highly dispersed CuO phase in the sample with the highest Cu loading. Variation in reaction conditions showed the optimal ones (170 °C, 1.3 MPa H2) resulting in complete trinitrobenzene conversion with a triaminobenzene yield of 65% for the catalyst with a 15% Cu loading, and the best yield of 82% was obtained over the catalyst with 10% Cu calcined at 600 °C. The results show the potential of Cu phyllosilicate-based catalysts for the utilization of trinitroaromatic compounds via catalytic hydrogenation to amines and their possible applications in a remediation treatment system.