Intrinsic kinetics of catalytic hydrogenation of 2-nitro-4-acetylamino anisole to 2-amino-4-acetylamino anisole over Raney nickel catalyst

The catalytic hydrogenation of 2-nitro-4-acetylamino anisole(NMA)is a less-polluting and efficient method to produce 2-amino-4-acetamino anisole(AMA).However,the kinetics of catalytic hydrogenation of NMA to AMA remains obscure.In this work,the kinetic models including power-law model and Langmuir-Hinshelwood-Hougen-Watson(LHHW)model of NMA hydrogenation to AMA catalyzed by Raney nickel catalyst were investigated.All experiments were carried out under the elimination of mass transfer resistance within the temperature range of 70–100°C and the hydrogen pressure of 0.8–1.5 MPa.The reaction was found to follow 0.52-order kinetics with respect to the NMA concentration and 1.10-order kinetics in terms of hydrogen pressure.Based on the LHHW model,the dual-site dissociation adsorption of hydrogen was analyzed to be the rate determining step.The research of intrinsic kinetics of NMA to AMA provides the guidance for the reactor design and inspires the catalyst modification.

RuRh Bimetallic Nanoparticles Stabilized by 15-membered Macrocycles-terminated Poly(propylene imine) Dendrimer:Preparation and Catalytic Hydrogenation of Nitrile–Butadiene Rubber

A new fourth-generation poly(propylene imine) dendrimer(G4-M) containing 32 triolefinic 15-membered macrocycles on the surfaces has been synthesized. The bimetallic Ru Rh dendrimer-stabilized nanoparticles(DSNs) were first prepared within G4-M by a co-complexation route. The new G4-M dendrimer has been characterized by 1H nuclear magnetic resonance, infrared radiation, and elemental analysis.The dendrimer-stabilized bimetallic ions and reduction courses were analyzed by UV-vis spectroscopy. Highresolution transmission electron microscopy and energy dispersive spectrometer were used to characterize the bimetallic nanoparticle size, size distribution, and particle morphology. The Ru Rh bimetallic DSNs showed high catalytic activity for the hydrogenation of nitrile-butadiene rubber.

Catalytic Hydrogenation of Nitrobenzene to Aniline by Ag/γ-Fe_2O_3

The Ag/γ-Fe_2O_3 nanocomposite was synthesized by solvothermal reduction method via using ferric nitrate and silver nitrate as raw materials, and ethylene glycol as the reducing agent. The composite was characterized by X-ray powder diffraction, scanning electron microscope, transmission electron microscope, and energy dispersive X-ray. The prepared Ag/γ-Fe_2O_3 was used for the catalytic hydrogenation of nitrobenzene to aniline by hydrazine hydrate. The factors such as the silver content in the catalyst, reaction time, reaction temperature and the regeneration of catalyst were investigated. The results showed that the yield of aniline reached 100% by utilizing the 1%wt（nitrobenzene） Ag/γ-Fe_2O_3 for the catalytic hydrogenation of nitrobenzene for 3 h to obtain aniline at 78 ℃, hydrazine hydrate as the hydrogen source, while the silver content in the catalyst was 3%mol.

Catalytic Hydrogenation of Diacetyl Monoxime to Tetramethylpyrazine with the Soluble Transition Metal Catalysts

Catalytic hydrogenation of diacetyl monoxime to tetramethylpyrazine, by the homogeneous catalysts generated in situ from some transition metal chlorides with triphenylphosphine in ethanol under H-2 pressure of 0.6 similar to 4.6 MPa at 100 similar to 150 degrees C, has been studied. The optimum H-2 partial pressure was observed at about 1.3 MPa. The maximum conversion of diacetyl monoxime and yield of tetramethylpyrazine were 97% and 90%, respectively.

STUDIES ON THE SYNTHESIS OF BAIMUXINOL BY CATALYTIC HYDROGENATION OF DEHYDROBAIMUXINOL

Baimuxinol, a 4-hydroxymethyl agarofuran isolated from Aquilaria Sinensis, was synthsizd. The stereoselectivity of catalytic hydrogenation of dehydrobaimuxino and its derivatives was studied.

Hierarchical ZrO_(2)@N-doped carbon nano-networks anchored ultrafine Pd nanoparticles for highly efficient catalytic hydrogenation

Carbon supported metal catalysts have received considerable interest due to their widespread applications in heterogeneous catalysis.However,the controllable synthesis of carbon support with defined morphology and composition still represents great challenging.Herein,we reported the synthesis of a well-defined hierarchically nanosized H-ZrO_(2)/NC(nitrogen-doped carbon)network via an inheritable carbonization strategy.When immobilizing the palladium clusters into the support,the N-doped sites and oxygen vacancy of the carbon composite can effectively stabilize and activate Pd through strong metal-support interaction which was also confirmed by density functional theory(DFT)calculations.Moreover,the hierarchically nanosized network can contribute to the exposure of active sites and facilitate the mass transfer during the catalytic process.As a result,benefiting from the hierarchical structure,composition and hydrolytic nature,Pd@H-ZrO_(2)/NC exhibited excellent catalytic activity and stability towards the hydrogenation of furfural in mild reaction conditions,as well as good universality toward the hydrogenation of a series of unsaturated hydrocarbons.

Novel hollow microsphere with porous carbon shell embedded with Cu/Co bimetal nanoparticles:Facile large-scale preparation and catalytic hydrogenation performance

Non-noble bimetals have attracted extensive attention for their natural aboundance and low cost,but it remains a big challenge to design and synthesize novel supported non-noble bimetal nanocatalyst in a controllable and high-efficient manner.Herein,a novel hollow spherical supported non-noble bimetal nanocatalyst with porous carbon shell as the continuous matrix and Cu/Co bimetal nanoparticles as the dispersion phase is successfully fabricated by a convenient strategy involving spray drying and subsequent heat treatment.The morphology and microstructure depend catalyst activity of the hollow spherical supported catalyst has been studied systematically.It is found that the heating temperature plays a critical role in determining the microstructure and catalytic performance of the products.With an optimal heating temperature of 600°C,the corresponding product exhibits the highest normalized reaction rate constant(k_(n))of 25.4 s^(-1)g^(-1)for catalytic reduction of 4-notrophenol,which can be attributed to the suitable synergism of the well-defined bimetal structure,combined effect of the two metallic phases and the metal-support interaction.This work provides an additional strategy for the simultaneous formation of both the support and the active loading phase of supported non-noble bimetal nanocatalyst,and may shed some light on the high-efficiency synthesis of other supported heterostructure with various compositions and properties.

Catalytic hydrogenation of insoluble organic matter of CS_(2)/Acetone from coal over mesoporous HZSM-5 supported Ni and Ru

Four supported catalysts,nickel and ruthenium on a HZSM-5 support,were prepared by equal volume impregnation and in-situ decomposition of carbonyl nickel.The properties of catalysts were investigated by catalytic hydro-conversion of 2,2′-dinaphthyl ether as the model compound and extraction residue of Naomaohu lignite as the sample under an initial H2 pressure of 5 MPa and temperature at 150℃.According to the catalytic hydroconversion results of the model compound,Ni−Ru/HZSM5 exhibited the best catalytic performance.It not only activated H2 into H…H,but also further heterolytically split H…H into immobile H‒attached on the acidic centers of Ni−Ru/HZSM-5 and relatively mobile H+.Catalytic hydro-conversion of the extraction residue from Naomaohu lignite was further examined over the optimized catalyst,Ni−Ru/HZSM-5.Detailed molecular compositions of products from the extraction residue with and without hydrogenation were characterized by Fourier transform infrared spectroscopy and gas chromatography/mass spectrometry.The analytical results showed that the oxygencontaining functional groups in products of hydrogenated extraction residue were obviously reduced after the catalytic treatment.The relative content of oxygenates in the product with catalytic treatment was 18.57%lower than that in the product without catalytic treatment.

Asymmetric catalytic hydrogenation of imines and enamines in natural product synthesis

Asymmetric catalytic hydrogenations of imines and enamines with chiral transition-metal complexes bearing chiral ligands are among the most green and powerful approaches for the elaboration of chiral amine structures in organic synthesis.This review focuses on recent applications of asymmetric hydrogenations of imine and enamine substrates in the total syntheses of natural products.These applications include diverse processes involving asymmetric transfer hydrogenation(ATH)and asymmetric hydrogenation(AH)to form key chiral amine motifs in natural products with good efficiency and high-level enantiocontrol.

Selective hydrogenation of glucose to sorbitol with tannic acid-based porous carbon sphere supported Ni-Ru bimetallic catalysts

Ni-Ru bimetallic porous carbon sphere(Ni-Ru@PCS) catalysts were synthesized via formaldehyde-assisted, metal-coordinated crosslinking sol-gel chemistry, in which biomass-derived tannic acid and F127 surfactant were used as carbon precursor and soft template, respectively, and Ni2+and Ru3+were used as cross-linkers. In the developed method, Ni-Ru particles became uniformly dispersed in the carbon skeleton due to strong coordination bonds between metal ions(Ni2+and Ru^(3+)) and tannic acid molecules and bimetal interactions. The as-synthesized Ni-Ru10:1@PCS catalyst with a loading Ni:Ru mole ratio of 10:1 was applied for the selective hydrogenation of glucose to sorbitol, and provided 99% glucose conversion with a sorbitol selectivity of 100% at 140℃ in 150 min reaction time and exhibited good stability and recyclability in which sorbitol yield remained at 98% after 4 cycles with little or no metal agglomeration. The catalyst was applied to glucose solutions as high as 20 wt% with 97% sorbitol yields being obtained at 140℃ in 20 h. The developed bimetallic porous carbon sphere catalysts take advantage of sustainably-derived materials in their structure and are applicable to related biomass conversion reactions.

CATALYTIC PERFORMANCE OF MIXED-BIMETALLIC RUTHENIUM CARBONYL CLUSTERDERIVED CATALYSTS IN CO HYDROGENATION

The bimetallic catalysts prepared from SiO_2-supported Ru-Co,Ru- Fe and Ru-Mo carbonyl clusters exhibited high yields and selectivities towards oxygenates such as C_1-C_5 from CO+H_2,in contrast to the catalysts prepared from homometallic and bimetallic Ru,Ru-Ni,Ru-Rh,Ru-Mn,and Ru- Cr carbonyl clusters.The FTIR investigation revealed that the 1584 cm^(-1) species plays an important role in the formation of oxygenates in CO hydrogenation,which is possibly assigned to surface formyl species.

Layer-structure adjustable MoS_(2) catalysts for the slurry-phase hydrogenation of polycyclic aromatic hydrocarbons

Slurry-phase hydrogenation technology is the frontier topic in the efficient conversion of heavy oils into light fractions around the world.Developing highly active dispersed MoS_(2) catalysts is the major obstacle to realize the industrial application of upgrading heavy oils.In this work,both top-down ball-milling method and bottom-up hydrothermal method were designed to synthesize MoS_(2) catalysts with controllable layer structures.The stacking layers and lateral sizes for micro-scaled MoS_(2) catalysts by ball-milling method can be reduced to their limits and stabilize at 6~8 layers and lateral size of ca.30 nm.The more flexible bottom-up hydrothermal method can construct MoS_(2) catalysts with much smaller lateral sizes and fewer stacking layers,especially,MoS_(2) catalyst fabricated with ammonium tetrathiomolybdate as Mo and S precursor possesses average stacking layers of 2 and lateral size of 5 ~ 10 nm.Polycyclic aromatic hydrocarbons anthracene,phenanthrene and naphthalene were used as model compounds of heavy oils to investigate the catalytic hydrogenation performance of designed MoS_(2) catalysts.The catalytic activities of MoS_(2) catalysts can be well correlated with their stacking layers and lateral size.The edges of top and bottom S-Mo-S atomic layers for MoS_(2) sheets,named rim sites,are positively correlated with the exposure of active sites for catalytic hydrogenation of PAHs.The highest catalytic activity of MoS_(2) catalyst results from its layer structures of 100% rim sites and the smallest lateral size of5 ~ 10 nm,which is beneficial to expose maximum active sites for catalytic hydrogenation reactions.This work can guide us to design the highly active hydrogenation catalysts,and promote the industrial application of upgrading heavy oils.

Carbon coated LaFe_(0.92)Pd_(0.08)O_(3) composites for catalytic transfer hydrogenation:Balance in the ability of substrates adsorption and conversion

Catalytic transfer hydrogenation(CTH)is a green and efficient pathway for selective hydrogenation of unsaturated aldehydes and ketones.However,managing the abilities of solid catalysts to adsorb substrates and to convert them into desired products is a challenging task.Herein,we report the synthesis of carbon coated LaFe_(0.92)Pd_(0.08)O_(3) composites(LFPO-8@C)for CTH of benzaldehyde(BzH)into benzyl alcohol(BzOH),using isopropanol(IPA)as hydrogen source.The coating with carbon improves the ability to adsorb/transfer reactants from solution to active sites,and the doping of Pd2+at Fe3+site strengthens the ability of LaFeO_(3) to convert BzH into BzOH.A balanced point between them(i.e.,abilities to adsorb BzH and to convert BzH into BzOH)is obtained at LFPO-8@C,which exhibits a BzOH formation rate of 3.88 mmol·gcat^(-1)·h^(-1) at 180℃ for 3 h,which is 1.50 and 2.72 times faster than those of LFPO-8 and LaFeO_(3)@C.A reaction mechanism is proposed,in which the acidic sites(e.g.,Fe^(4+),oxygen vacancy)are used for the activation of C=O bond of BzH and O-H bond of IPA,and the basic sites(e.g.,lattice oxygen)for the activation ofα-H(O-H)bond of IPA.

An efficient Approach to Modify the Catalyst Activity for the Hydrogenation of Nitrobenzene

The addition of a suitable amount of PPh3 to PdCl2 or PdCl2(PhCN)(2) in situ can considerably increase the catalytic activity in the hydrogenation of nitrobenzene, while the catalytic activities of PdCl2 (reduced)+PPh3, PdCl2(PPh3)(2) and Pd(PPh3)(4) are very poor. The poisoning of catalyst by mercury indicates that the catalytically active species are composed of Pd(0) colloidal particles. Transmission electron micrographs show that the size of nanometric Pd(0) particles of PdCl2 with PPh3 added in situ is smaller than that of PhCl2(PPh3) or PdCl2 (reduced)+PPh3. A synergic effect of bimetallic catalysts such as PdCl2+nPPh(3)+NiCl2 (n= 0.5, 1) and PdCl2(PhCN)(2)+PPh3+FeCl3 gives rise to a further increase in the catalytic activity.

Synthesis of New Ligand 1,2-Bis{di[(R,R)-1,3,2-oxzaphosphlidine]phosphino}ethane with C_2-symmetric Axis and Application in Rh-catalyzed Asymmetric Hydrogenation

New ligand 1,2-bis{di[（R,R）-1,3,2-oxzaphosphlidine]phosphino}ethane [（R,R）-BDOPPEs 1,2,3 and 4] with C2-symmetric axis and bearing nitrogen and oxygen were synthesized from readily available optically active amino alcohols.Rh complexes with these ligands were highly enantioselective catalysts for asymmetric hydrogenation of N-benzoyldehydroamino acid derivatives and α-functionalized ketones in 99%e.e.and 98%e.e.,respectively.This new class of（R,R）-BDOPPEs 1,2,3 and 4 gave much more effectivity and enantionselectivity than their corresponding non-C2-asymmetric aminophosphine phosphinite.

Synthesis of ternary magnetic nanoparticles for enhanced catalytic conversion of biomass-derived methyl levulinate into γ-valerolactone

Conversion of levulinic acid and its esters into versatile y-valerolactone(GVL)is a pivotal and challenging step in biorefineries,limited by high catalyst cost,the use of hydrogen atmosphere,or tedious catalyst preparation and recycling process.Here we have successfully synthesized a ternary magnetic nanoparticle catalyst(Al_(2)O_(3)-ZrO_(2)/Fe_(3)O_(4)(5)),over which biomass-derived methyl levulinate(ML)can be quantitively converted to GVL with an extremely high selectivity of>99%and yield of-98%in the absence of molecular hydrogen.Al_(2)O_(3)-ZrO_(2)/Fe_(3)O_(4)(5)incorporates simultaneously inexpensive alumina and zirconia onto magnetite support by a facile coprecipitation method,giving rise to a core-shell structure,welldistributed acid-base sites,and strong magnetism,as evidenced by the X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM),transmission electron microscopy(TEM),high-angle annular dark-field scanning-TEM(HAADF-STEM),SEM-energy dispersive Xray spectroscopy(SEM-EDX),temperature-programmed desorption of ammonia(NH3-TPD),temperature-programmed desorption of carbon dioxide(CO_(2)-TPD),pyridine-adsorption infrared spectra(Py-IR),and vibrating sample magnetometry(VSM).Such characteristics enable it to be highly active and easily recycled by a magnet for at least five cycles with a slight loss of its catalytic activity,avoiding a time-consuming and energy-intensive reactivation process.It is found that there was a synergistic effect among the metal oxides,and the high efficiency and selectivity originating from such synergism are evidenced by kinetic studies.Furthermore,a reaction mechanism regarding the hydrogenation of ML to GVL is proposed by these findings,coupled with gas chromatography-mass spectrometry(GC-MS)analysis.Accordingly,this readily synthesized and recovered magnetic nanocatalyst for conversion of biomassderived ML into GVL can provide an eco-friendly and safe way for biomass valorization.

Reductive Desulfurization of Thioamides to Amines by Catalytic Hydrogen Transfer Reaction

Introduction Reductive desulfurization of thioamides to amines is one of the methods to prepare amines and is generally achieved by a) Zn in acid, b) sodium or aluminum amal- gams, c) lithium alumminium hydride, d) Raney Ni and e) electrolytic reduction. These methods are not very convenient to be operated and some need more complex instrument. Here is reported the reductive desulfurization of thioamides to amines by catalytic hydrogen transfer reaction(CHT).

Microemulsion-mediated hydrothermal synthesis of flower- like MoS2 nanomaterials with enhanced catalytic activities for anthracene hydrogenation

Flower-like intercalated MoS2 nanomaterials have been successfully synthesized via a microemulsion- mediated hydrotherrnal （MMH） method, and characterized by X-ray diffraction, Raman spectroscopy, element analysis, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy in detail. Their catalytic performance for anthracene hydrogenation was evaluated using a slurry-bed batch reactor with an initial hydrogen pressure of 80 bar at 350 ℃ for 4 h. The intercalated MoS2 nanoflowers synthesized from Na2MoO4 （MoS2-S） and H2MoO4 （MoS2-A） as molybde- num precursors have diameters of about 150 and 50 nm, respectively. MoS2 nanosheets on MoS2-S and MoS2-A possess stacking layer numbers of 5-10 and 2-5, and slab lengths of about 15 and 10 nm, respectively. The interlayer distances of MoS2-S and MoS2-A are both enlarged from 0.62 nm to about 0.95 nm due to the intercalation ofNH4＋ and surfactant molecules. The MoS2 nanoflowers have high catalytic activities for anthracene hydrogenation. The selectivity for octahydroanthracene, a deeply hydrogenated product, over MoS2-A is 89.8%, which is 31.0 times higher than that over commercial bulk MoS2. Fully hydrogenated product （perhydroanthracene） was also detected over MoS2 nanoflowers with a selectivity of 3.7%. The enhanced hydrogenation activities of MoS2 nanoflowers can be ascribed to the high exposure of catalytic active sites, resulting from the smaller particle size, fewer stacking layer, shorter slab length and enlarged interlayer distance of MoS2 nanoflowers compared with commercial bulk MoS2. In addition, a possible growth mechanism of MoS2 nanoflowers synthesized via the MMH method was proposed.

Novel Method for Selective Debenzylation Under Maintenance of Fluoro Atom Substituted on β-Amino Acids

tert-Butyl （R）-3-amino-3-（3-fluorophenyl）propanoate（5） was prepared with conventional debenzylation method. However, the tert-butyl （R）-3-[（S）-1-phenylethyl-amino]-3-（3-fluorophenyl） propanoate（6） and tert-butyl （R）-3-amino-3-phenylpropanoate（7） were generated as the byproducts under the general catalytic hydrogenation Pd（OH）2/C-H2 conditions. So a series of experiments was performed to optimize the reaction conditions so that product 5 could be obtained with high purity and yield. Finally an effective catalytic system, Pd/C-HCOOH-CH3OH, was discovered.

Catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol with formic acid as hydrogen donor over CuCs-MCM catalyst

Catalytic transfer hydroge nation(CTH)of furfural(FF)to furfu ryl alcohol(FFA)has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6%FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.