Project description:The reduction of nitroarenes to anilines as well as azobenzenes to hydrazobenzenes using a single base-metal catalyst is reported. The hydrogenation reactions are performed with an air-and moisture-stable manganese catalyst and proceed under relatively mild reaction conditions. The transformation tolerates a broad range of functional groups, affording aniline derivatives and hydrazobenzenes in high yields. Mechanistic studies suggest that the reaction proceeds via a bifunctional activation involving metal-ligand cooperative catalysis.
Project description:Hydrogenation reactions are fundamental functional group transformations in chemical synthesis. Here, we introduce an electrochemical method for the hydrogenation of ketones and aldehydes by in situ formation of a Mn-H species. We utilise protons and electric current as surrogate for H2 and a base-metal complex to form selectively the alcohols. The method is chemoselective for the hydrogenation of C=O bonds over C=C bonds. Mechanistic studies revealed initial 3 e- reduction of the catalyst forming the steady state species [Mn2 (H-1 L)(CO)6 ]- . Subsequently, we assume protonation, reduction and internal proton shift forming the hydride species. Finally, the transfer of the hydride and a proton to the ketone yields the alcohol and the steady state species is regenerated via reduction. The interplay of two manganese centres and the internal proton relay represent the key features for ketone and aldehyde reduction as the respective mononuclear complex and the complex without the proton relay are barely active.
Project description:Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.
Project description:The control of product distribution in a multistep catalytic selective hydrogenation reaction is challenging. For instance, the deep hydrogenation of dimethyl oxalate (DMO) is inclined to proceed over Cu/SiO2 catalysts because of inevitable coexistence of Cu+ and Cu0, leading to hard acquisition of the preliminary hydrogenation product, methyl glycolate (MG). Here, the oriented DMO hydrogenation into MG is achieved over the sputtering (SP) Cu/SiO2 catalysts with a selectivity of more than 87% via freezing Cu in a zero-valence state. Our density functional theory calculation results revealed that Cu0 is the active site of the preliminary hydrogenation step, selectively converting DMO to MG via •H addition, while Cu+ is a key factor for deep hydrogenation. The prominent Coster-Kronig transition enhancement is observed over SP-Cu/SiO2 from Auger spectra, indicating that the electron density of inner shells in Cu atoms is enhanced by high-energy argon plasma bombardment during the SP process. Thus, the "penetration effect" of outermost electrons could also be enhanced, making these Cu nanoparticles exhibit high oxidation resistance ability and present noble metal-like behaviors as Au or Ag. Therefore, the regulation of Cu chemical properties by changing the electron structure is a feasible strategy to control the hydrogenation products, inspiring the rational design of selective hydrogenation catalysts.
Project description:Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.
Project description:We report nuclear spin hyperpolarization of various alkenes achieved in alkyne hydrogenations with parahydrogen over a metal-free hydroborane catalyst (HCAT). Being an intramolecular frustrated Lewis pair aminoborane, HCAT utilizes a non-pairwise mechanism of H2 transfer to alkynes that normally prevents parahydrogen-induced polarization (PHIP) from being observed. Nevertheless, the specific spin dynamics in catalytic intermediates leads to the hyperpolarization of predominantly one hydrogen in alkene. PHIP enabled the detection of important HCAT-alkyne-H2 intermediates through substantial 1 H, 11 B and 15 N signal enhancement and allowed advanced characterization of the catalytic process.
Project description:Hydrogenation of CO2 to form methanol utilizing green hydrogen is a promising route to realizing carbon neutrality. However, the development of catalyst with high activity and selectivity to methanol from the CO2 hydrogenation is still a challenge due to the chemical inertness of CO2 and its characteristics of multi-path conversion. Herein, a series of highly active carbon-confining molybdenum sulfide (MoS2@C) catalysts were prepared by the in-situ pyrolysis method. In comparison with the bulk MoS2 and MoS2/C, the stronger interaction between MoS2 and the carbon layer was clearly generated. Under the optimized reaction conditions, MoS2@C showed better catalytic performance and long-term stability. The MoS2@C catalyst could sustain around 32.4% conversion of CO2 with 94.8% selectivity of MeOH for at least 150 h.
Project description:Palladium promotion and deposition on monoclinic zirconia are effective strategies to boost the performance of bulk In2O3 in CO2-to-methanol and could unlock superior reactivity if well integrated into a single catalytic system. However, harnessing synergic effects of the individual components is crucial and very challenging as it requires precise control over their assembly. Herein, we present ternary Pd-In2O3-ZrO2 catalysts prepared by flame spray pyrolysis (FSP) with remarkable methanol productivity and improved metal utilization, surpassing their binary counterparts. Unlike established impregnation and co-precipitation methods, FSP produces materials combining low-nuclearity palladium species associated with In2O3 monolayers highly dispersed on the ZrO2 carrier, whose surface partially transforms from a tetragonal into a monoclinic-like structure upon reaction. A pioneering protocol developed to quantify oxygen vacancies using in situ electron paramagnetic resonance spectroscopy reveals their enhanced generation because of this unique catalyst architecture, thereby rationalizing its high and sustained methanol productivity. Assembling multicomponent catalysts to harness synergic effects is challenging. Now, flame spray pyrolysis permits the synthesis of ternary Pd-In2O3-ZrO2 catalysts with an optimal architecture and an enriched density of oxygen vacancies for maximal performance in CO2-based methanol synthesis.
Project description:Phenylacetylene is a detrimental impurity in the polymerisation of styrene, capable of poisoning catalysts even at ppm levels and significantly degrading the quality of polystyrene. The semi-hydrogenation of phenylacetylene to styrene instead of ethylbenzene is, therefore, an important industrial process. We report a novel cerium(iv)-based metal-organic framework (denoted as Ce-bptc), which comprises {Ce6} clusters bridged by biphenyl-3,3',5,5'-tetracarboxylate linkers. Ce-bptc serves as an ideal support for palladium nanoparticles and the Pd@Ce-bptc catalyst demonstrates excellent catalytic performance for semi-hydrogenation of phenylacetylene, achieving a selectivity of 93% towards styrene on full conversion under ambient conditions with excellent reusability. In situ synchrotron X-ray powder diffraction and electron paramagnetic resonance spectroscopy reveal the binding domains of phenylacetylene within Ce-bptc, and details of the reaction mechanism are discussed.