In this research, four cholines supported on core–shell iron oxides, Fe2O3@MgO@Ch.OAc (choline acetate), Fe2O3@MgO@Ch.OH (choline hydroxide), Fe3O4@Ch.OAc, Fe3O4@Ch.OH, were synthesized. The synthesized catalysts were tested in 1,2,3-triazoles synthesis by the reaction of nitromethane, aldehyde, and benzyl azide in EtOH as a green solvent. Among four synthesized heterogeneous catalysts, the Fe2O3@MgO@ch.OAc showed superior catalytic activity for the reaction and afforded the desired triazoles in good isolated yields under mild reaction conditions.
Graphic AbstractAn efficient solvent-free catalyst system for hydrosilylation of aldehydes and ketones was developed based on iron pre-catalyst Fe2(CO)9/C6H4-o-(NCH2PPh2)2BH. The reactions were tolerant of many functional groups and the corresponding alcohols were isolated in good to excellent yields following basic hydrolysis of the reaction products. The reaction is likely catalyzed by an in situ generated pincer ligated iron hydride complex.
Graphic AbstractBenzyl alcohol can be oxidized selectively to benzaldehyde over platinum-based catalysts using either oxygen (O2, supplied in the form of synthetic air) or the more powerful hydrogen peroxide (H2O2) as the oxidant. Here we compare these oxidants in the aqueous phase oxidation of benzyl alcohol in a batch reactor at 363.15 K or 393.15 K over monodisperse Pt and Pt–Ni nanostructures synthesized with molybdenum hexacarbonyl (Mo(CO)6) as a reductant. The initial catalytic activity of either Pt or a Pt–Ni alloy anchored on titania support (TiO2) is much higher when using H2O2 than when using O2 (supplied in the form of synthetic air). However, the high initial activity using H2O2 is accompanied by a strong decrease in the activity over Pt. Alloying Pt with Ni results in a reduction in the activity in the benzyl alcohol oxidation when using O2 but enhances the initial activity when using H2O2. The results are rationalized based on a change in the relative surface concentration of oxygen-containing species upon changing the oxidant or alloying Pt with Ni.
Graphic AbstractThe magic number clusters Au102(p-MBA)44 and Au144(p-MBA)60 were synthesized and tested for their ability to catalyze the reduction of 4-nitrophenol. Kinetic and thermodynamic analyses demonstrate that both clusters are effective catalysts with activation energies less than 10 kJ/mol and turnover frequencies approaching 103 h–1 per surface gold atom.
Graphic AbstractA monolithic complexed catalyst composed of a piece of Co foam decorated with Ru nanosheets has been fabricated. This catalyst has demonstrated excellent performance in catalyzing NaBH4 hydrolysis under alkaline conditions. Most importantly, the bulky size of the developed catalyst provides convenience to control the start and stop of hydrogen production by manipulating the attachment and detachment between the catalyst and NaBH4 solution. These features endow this catalyst with great potential for on-site hydrogen supply.
Graphic AbstractThe statistical selectivity models were developed for four different Fischer–Tropsch synthesis product range, including methane (CH4), light olefins (C2=C4), light paraffins (C2–C4), and long-chain hydrocarbons (C5+), based on the experimental data obtained over thirteen γ-Al2O3 supported cobalt-based catalysts with different cobalt particle and pore sizes. The input variables consist of cobalt metal particle size and catalyst pore size. The cubic and quadratic polynomial equations were fitted to the experimental data, however, the mathematical models were subjected to model reduction for the enhancement of model adequacy, which was investigated through ANOVA. The multi-objective optimization revealed that the maximum C5+?selectivity (84.150%) could be achieved at the cobalt particle size and pore sizes of 14.764 and 23.129 nm, respectively, while keeping the selectivity to other hydrocarbon products minimum.
Graphic AbstractNi–Mo2C and Ni–WC were evaluated in dry reforming of methane employing different CH4/CO2 ratios. Ni–Mo2C remained active under an excess of CH4, but deactivation occurred under an excess of CO2. Ni–WC was resistant to excess of CO2 but showed carbon deposition under excess of CH4.
Graphic AbstractThis work proposed a new path to synthesize Ni-phyllosilicate through the reaction of nickel hydroxide and silica sol on the surface of Ni-foam to form the monolithic Ni-phyllosilicate/Ni-foam catalyst. Ni-phyllosilicate could reprint the morphology of nickel hydroxid and firmly anchor on the framework of Ni-foam, which obtained fine Ni particles of 2.8 nm after reduction in H2 at 650 °C, resulting in high catalytic activity for CO2 methanation. In addition, the Ni-phyllosilicate/Ni-foam catalyst showed high long-term stability in a 100 h-lifetime test owing to the combined effects of surface confinement of Ni-phyllosilicate, firm anchoring between Ni-phyllosilicate and Ni-foam, as well as the high heat transfer property of Ni-foam.
Graphical AbstractZSM-48 and ZSM-22 zeolites with similar Si/Al ratio were synthesized and modified by alkali treatment. Moreover, n-dodecane hydroisomerization performance of Pt supported ZSM-22 and ZSM-48 were investigated. The catalytic results showed that the activity and the isomers selectivity of n-dodecane hydroisomerization could be improved by alkali treatment. The isomers distributions were distinct for Pt/ZSM-48 and Pt/ZSM-22. Mono-branched isomers near the end of the chains were more prone to be generated on Pt/ZSM-22 catalyst, which suggested “pore-mouth” catalysis model dominating the hydroisomerization catalysis. However, di-branched isomers and mono-branched isomers with methyl near the middle of the carbon chains were favorable to be formed over Pt/ZSM-48 catalyst according to the “key-lock” catalysis model. Moreover, more central-branched isomers were formed at high reaction temperature (>?320 °C) especially for Pt/ HZSM-22.
Graphic AbstractBeta-zeolite supported ruthenium catalysts for reductive amination of 5-hydroxymethyl-2-furaldehyde (HMF) with an aqueous solution of ammonia (NH3 aq.) and molecular hydrogen (H2) are examined to synthesize the corresponding primary amine of 5-aminomethyl-2-furylmethanol (FAA). Various SiO2/Al2O3 (Si/2Al) ratios of the beta-zeolite support were used to prepare the Ru-based catalysts. It was observed that the Si/2Al ratio was contributed to the catalytic activity, and the Si/2Al?=?150 of beta-zeolite was found to be the most active for Ru catalyzed reductive amination of HMF, affording ca. 70% yield. Characterization techniques were taken to analysis the factors that influence the reactivity of catalysts, and which revealed that not only the ruthenium nanoparticle size but also the ratio of RuO2 against metallic Ru species were crucial factors for the reactivity of reductive amination of HMF to FAA.
Graphical AbstractIn order to further improve the catalytic activity and stability of heterogeneous acid catalysts, a polystyrene microspheres modified sulfonic acid-based catalyst (PS-SO3H) was prepared. PS-SO3H was characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscope, transmission electron microscope, N2 adsorption–desorption, and X-ray photoelectron spectroscopy. Catalytic efficiency was determined using the reaction of furfuryl alcoholysis to ethyl levulinate (EL). The obtained results showed that PS-SO3H had excellent catalytic performance, with EL yield of 94.7%. In addition, PS-SO3H was easily separated from the reaction system and recycled multiple times without significant reduction in activity. High catalytic activity stemmed from the effect of Brønsted acid sites and appropriate structural properties.
Graphical Abstract0D/2D Pt-C3N4/CdS heterojunction photocatalyst were fabricated with CdS quantum dots interspersed on g-C3N4 nanosheets via successive ionic layer absorption process. The obtained Pt-C3N4/CdS Z-scheme heterojunction with Pt cocatalyst deposited on g-C3N4 nanosheets exhibited H2 production rate of 35.3 mmol g?1 h?1, which is 3.1 times higher than that of Pt-CdS/C3N4. The enhanced photocatalytic activity are attributed to the Z-scheme charge carrier transfer mechanism with stronger redox ability. The photocatalytic mechanism of the CdS/g-C3N4 composite is investigated and demonstrated in this work. It may provide unique insights to design 0D/2D Z-scheme heterojunction photocatalyst systems using a facile method for highly efficient H2 production.
Graphic AbstractSchematic illustration of charge transfer modulated by the metal cocatalyst selective deposition on heterojunction-type II (a) and direct Z-Scheme mechanisms (b) over the C3N4/CdS heterostructure composites under visible light irradiation.
In this paper, we have produced carboxylic acids by the oxidation of various alcohols in the presence of CO2 using SBA-15/IL supported Cu(II) (SBA-15/IL/Cu(II)) as nanocatalyst. The obtained products showed to have excellent yields by taking into account of SBA-15/IL/Cu(II) nanocatalyst. In addition, the analysis of EDX, SEM, TGA, TEM, XPS, and FT-IR showed the heterogeneous structure of SBA-15/IL/Cu (II) catalyst. It is determined that, after using SBA-15 excess, the catalytic stability of the system was enhanced. Moreover, hot filtration provided a full vision in the heterogeneous catalyst nature. The recycling as well as reuse of the catalyst were studied in cases of coupling reactions many times. Moreover, we have studied the mechanism of the coupling reactions.
Graphic AbstractMicro-mesoporous aluminosilicates based on ZSM-5 zeolite, obtained by a dual template method, as well as in the presence of a dual-functional template (i.e. a Gemini-type surfactant), were tested in the oxidation of furfural with hydrogen peroxide. Even substantial changes in acidity and porosity of the catalysts result in minor variations of selectivity towards the desired products. Application of the synthesized zeolite-based materials in the oxidation of furfural with hydrogen peroxide leads to formation of 2(5H)-furanone (yield up to 28.5%) and succinic acid (up to 19.5%) as the main C4 reaction products. The kinetic model developed previously to treat the results for oxidation of furfural over sulfated zirconia was able to describe the data also for micro-mesoporous aluminosilicates.
Graphical AbstractRegularly dispersed Pt particles on SBA-15 supported catalysts were synthesized with a Pt loading of 5 wt% by a sol-immobilisation method, wherein various Pt particle sizes within 1–5 nm were finely controlled via the adjustment of the addition amount of polyvinyl alcohol (PVA). A high PVA/Pt ratio of the initial solution tended to generate small Pt particles on the SBA-15 support due to intense protection against Pt particle aggregation. In addition, the effect of Pt particle size on naphthalene hydrogenation was investigated in terms of catalytic performance. Compared with the performance of other catalysts with Pt particle sizes greater or less than 3.5 nm, Pt nanoparticles with sizes centered at 3.5 nm exhibited excellent catalytic performance towards decalin. This excellent catalytic performance was mainly attributed to a suitable ratio of the edge sites to flat sites on these Pt nanoparticles, benefitting the rapid adsorption of naphthalene and dissociation of hydrogen.
Graphical AbstractThe Pt/SBA-15 catalysts were prepared by sol-immobilisation method. The highest performance was attributed to the Pt-nanoparticles with suitable flat/edge sites ratio.
In this work, density functional theory is used to study the mechanism of propane dehydrogenation over non-metallic C3N catalyst. The structure, electrostatic potential and density of state of C3N are introduced, as well as the adsorption of reactants on catalyst is studied. The propane dehydrogenation reaction is divided into the first dehydrogenation and the second dehydrogenation (deep dehydrogenation). We explore the possible dehydrogenation pathways in two-step dehydrogenation. The rate control step of the first dehydrogenation is the removal of methylene hydrogen atom from propane, and its energy barrier is 47.79 kcal/mol, which reflected the catalytic activity of the catalyst. The rate control step of deep dehydrogenation is the process of removing the first hydrogen atom of the product propylene to produce the by-product. The energy barrier is 72.80 kcal/mol, which is much larger than that of the first step of dehydrogenation, reflecting the excellent selectivity of the catalyst.
Graphic AbstractSolid base metal oxide catalysts such as MgO offer utility in a wide variety of syntheses from pharmaceuticals to fuels. The (111) facet of MgO shows enhanced, unique properties relative to the other facets. Carbon coatings have emerged as a promising modification to impart metal oxide catalyst stability. Here, we report the synthesis, characterization, and catalytic properties of commercial MgO, MgO(111), and carbon coated derivatives thereof for 2-pentanone condensation. The dimer and trimer products of this reaction can be used as precursors for biofuels upon oxygen removal and thus have relevance in environmental sustainability. MgO(111) maintained impressive selectivity towards the dimer product after carbon coating, whereas the other catalysts experienced a decrease in conversion and selectivity as a consequence of the carbon coating. Our findings highlight the catalytic efficacy of MgO(111), provide insight into carbon coating for catalyst stability, and pave the way for continued mechanistic investigations.
Graphical AbstractLignocellulosic biofuels are the most promising sustainable fuels for supplementing shrinking fossil resources. In this work, acid-modified vermiculite (AVM)-supported Pd–Ni bimetallic catalyst (Pd–Ni/AVM) was investigated for the hydrodeoxygenation of bio-oil and its model compounds to assess its reactivity. Pd–Ni/AVM was found to efficiently hydrodeoxygenate the investigated model compound (phenol). The phenol conversion reached 94% at 0.5% of Ni loading and temperatures beyond 513 K. Using these parameters, the phenolic hydroxyl group was removed, and the C?=?C bonds were saturated. This catalyst was also efficient in the hydrodeoxygenation of bio-oil. H2-TPR experiments elucidated the synergistic effects between the active component and the carrier, which were considered the main reason for the catalytic activity. Strong influences of the Ni loading and temperature on the hydrogenation of phenol were also observed when the Pd loading was fixed at 1 wt%.
Graphic AbstractLaBO3 (B?=?Fe, Mn, and FeMn) perovskite-type oxides were prepared by sol–gel method and then used as catalysts in CO hydrogenation for light olefins. The catalysts were characterized using XRD, H2-TPR, SEM, CO (CO2)-TPD, and XPS. The results showed that the lattice oxygen migration and oxygen vacancies promoted oxygen mobility by doping Mn2+ at the B site, Moreover, the presence of manganese as a promoter in the catalyst increased olefin selectivity compared with the olefin selectivity of the catalyst containing iron at the B-site and exhibited resistance to carbon deposition; while reducing the metal elements. In CO hydrogenation, potassium-promoted LaFeMnO3 catalysts afforded high catalytic activity and C2=–C4= selectivity. An O/P value of 5.0 and a C2=–C4= fraction of 54% were achieved for all hydrocarbons with low methane selectivity.
Graphic AbstractCO2 hydrogenation to CH3OH via heterogeneous catalysis is one of the most promising and available approaches for mitigation of anthropogenic CO2 issues. In this work, thermodynamic equilibria of CO2 to methanol were compared with experimental results at given conditions using a commercial Cu/ZnO/Al2O3 catalyst for CO hydrogenation to methanol. It was found that, the high pressure, low temperature, and high H2/CO2 ratio are favorable to methanol synthesis from CO2. Furthermore, the kinetic data were measured with an isothermal integral reactor under temperature between 160 and 240 °C, lower than that for CO hydrogenation to methanol reaction. Based on the single-active site and dual-active site LH mechanisms, both kinetic models can achieve full illustration of the influence of the operating conditions and the mechanisms. According to comparative analysis of the error variances of model correlations and the adsorbate coverages on the active sites, the dual-site mechanism identified to be superior to the single-site one for methanol synthesis from CO2 feedstock. Overall, this paper provides fundamental understanding of the thermodynamic and kinetic aspects of a central route for CO2 Valorisation.
Graphical Abstract