A multi-functional Ru Mo bimetallic catalyst for ultra-efficient C3 alcohols production from liquid phase hydrogenolysis of glycerol

Ru and Mo bimetallic catalysts supported on active carbon modified by phosphotungstic acid(PW)were designed and applied in glycerol hydrogenolysis reaction.The physicochemical properties of the catalysts were characterized and the presence of active sites was investigated from the perspective of the glycerol hydrogenolysis performance.The MoOxis highly selective for the C—O bond cleavage of glycerol molecules,which can reasonably regulate the strong C—C bond cleavage activity of Ru nanoparticles.By using sequential deposition of Ru and Mo supported on mesoporous PW-C,the characterization results show that the combination of isolated low-valence MoOxwith metal Ru particles can form“MoOx-Ru-PW”,which provides highly catalytic activity toward C—O bond cleavage,selectively producing more C3 alcohols(mainly 1,2(3)-propanediol).The glycerol conversion of 1%Mo/Ru/PW-C catalyst was 59.6%,the selectivity of C3 alcohol was 96.1%,and the selectivity of propanediol(1,2(3)-propanediol)was 94.9%.It is noteworthy that the selectivity of 1,3-propanediol reached 20.7%when the PW was 21.07%(mass).This study provides experimental evidence for the tandem dehydration and hydrogenation mechanism of the multifunctional Mo/Ru/PW-C catalyst.

Solvent-free partial oxidation of cyclohexane to KA oil over hydrotalcitederived Cu-MgAlO mixed metal oxides

A highly efficient and stable hydrotalcite-derived Cu-MgAlO catalyst was developed for the partial oxidation of cyclohexane with molecular oxygen.The physical–chemical properties of Cu-MgAlO catalysts were studied,and the results indicated that the copper component had been successfully introduced into the hydrotalcite unit layer structure.The catalytic reaction results showed that copper as the active species could activate CAH bond and effectively promote the decomposition of cyclohexyl hydroperoxide(CHHP)to the mixture of cyclohexanol and cyclohexanone(KA oil).8.3%of cyclohexane conversion and 82.9%of selectivity for KA oil were obtained over 9%Cu-MgAlO catalyst at 150℃with 0.6 MPa of oxygen pressure for 2 h.Especially,its catalytic performance was still stable after five runs.

Highly uniform Ni particles with phosphorus and phosphorus and adjacent defects catalyze 1,5-dinitronaphthalene hydrogenation with excellent catalytic performance

This work proposes a modified activated carbon support,with defects and heteroatoms(N,P-ACs)by nitrogen and phosphorus doping to load non-noble nickel to catalyze aromatic compound hydrogenation.The Ni/N,P-ACs-900(prepared at 900℃)showed promising catalytic activity in liquid-phase 1,5-dinitronaphthalene hydrogenation with a 1,5-diaminonaphthalene yield of 95.8% under the mild condition of 100℃,which is comparable to the commercial Pd/C catalyst.The nitrogen species were burned off at 900℃,causing more defects for nickel metal loading,facilitating the interaction between the supports and the nickel metal,and resulting in highly dispersed metal particles.The computational study of the nickel binding energy has been conducted using density functional theory.It exhibits that the defects formed by heteroatom doping are beneficial to nickel anchoring and deposition to form highly uniform nickel particles.The phosphorus species in combination with the defects are suitable for H_(2) adsorption and dissociation.These results reveal that the heteroatomic doping on the active carbon shows significant effects in the hydrogenation of the liquid-phase aromatic compounds.These findings could provide a promising route for the rational design of aromatic compound hydrogenation catalysts to significantly decrease the cost by instead using noble metal catalysts in the industry.

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene

Metal salts with highly electronegative cations have been used to effectively catalyze the liquid-phase nitration of benzene by NO2 to nitrobenzene under solventfree conditions. Several salts including FeCl3, ZrCl4, AlCl3, CuCl2, NiCl2, ZnCl2, MnCl2, Fe（NO3）3-9H2O, Bi （NO3）3·5H2O, Zr（NO3）4-SH2O, Cu（NO3）2.6H2O, Ni （NO3）2·6H2O, Zn（NO3）2·6H2O, Fe2（SO4）3, and CuSO4 were examined and anhydrous FeCl3 exhibited the best catalytic performance under the optimal reaction conditions. The benzene conversion and selectivity to nitrobenzene were both over 99%. In addition, it was determined that the metal counterion and the presence of water hydrates in the salt affects the catalytic activity. This method is simple and efficient and may have potential industrial application prospects.

Zinc modification of Ni-Ti as efficient Ni_(x)Zn_(y)Ti_(1)catalysts with both geometric and electronic improvements for hydrogenation of nitroaromatics

The catalytic hydrogenation of nitroaromatics is an environmentally friendly technology for aniline production,and it is crucial to develop noble-metal-free catalysts that can achieve chemoselective hydrogenation of nitroaromatics under mild reaction conditions.In this work,zinc-modified Ni-Ti catalysts(Ni_(x)Zn_(y)Ti_(1))were fabricated and applied for the hydrogenation of nitroaromatics hydrogenation.It was found that the introduction of zinc effectively increases the surface Ni density,enhances the electronic effect,and improves the interaction between Ni and TiO_(2),resulting in smaller Ni particle size,more oxygen vacancies,higher dispersion and greater concentration of Ni on the catalyst surface.Furthermore,the electron-rich Ni^(δ-) obtained by electron transfer from Zn and Ti to Ni effectively adsorbs and dissociates hydrogen.The results reveal that Ni_(x)Zn_(y)Ti_(1)(Ni_(0.5)Zn_(0.5)Ti_(1))shows excellent catalytic performance under mild conditions(70℃and 6 bar).These findings provide a rational strategy for the development of highly active non-noble-metal hydrogenation catalysts.

One-step synthesis of c-caprolactam via the liquid phase catalytic nitrosation of cyclohexane in the presence of concentrated sulfuric acid

A simple and efficient approach for the synthesis of e-caprolactam via the liquid phase nitrosation of cyclohexane and nitrosyl sulfuric acid in the presence of concentrated sulfuric acid has been developed. A series of novel A1VPO composites were prepared by an impregnation method and the composites were then employed to catalyze the nitrosation reaction of cyclohexane and nitrosyl sulfuric acid. Compared to the reaction using fuming sulfuric acid, the selectivity for the desired product was significantly improved using this one-step catalytic process. This method affords a shortcut to prepare ecaprolactam and its analogs from cyclohexane.