An 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 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.
This 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 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 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 AbstractAchieving the removal of the toxic nitric oxide (NO) gas efficiently and cheaply has always been a challenge. Herein, we systematically investigate the reduction mechanisms of NO on the surface of the Fe–PCs (PCs?=?phthalocyanines) using density functional theory calculations. The isolated iron atom not only plays the role of an adsorption and activation site for the NO molecule but also works as an electron transfer medium in the whole reaction process. The results indicate that the catalytic reduction of NO to N2 takes place through a continuous two-step pathway. The first step involves the reduction of NO to N2O through a competitive Langmuir–Hinshelwood and Eley–Rideal mechanisms with the energy barrier of 1.19 eV and 0.60 eV, respectively. The second step involves the reduction of N2O to N2 with an energy barrier of 0.91 eV. These reaction pathways are favorable thermodynamically, thus the Fe–PCs catalyst is a promising candidate for the abatement of NO gases.
Graphic AbstractCuO–CeO2 (Cu–Ce) catalyst with a CuO/CeO2 mass ratio of 1 prepared by a sol–gel method is used in the CO catalytic oxidation reaction in the actual industrial sulfur-containing atmosphere. At a reaction temperature of 200 °C, the catalyst exhibits quite different stability under sulfur-containing and sulfur-free conditions. When 30 ppm SO2 was added to the feed gas, the Cu–Ce catalyst had an initial CO conversion rate of 100%, gradually decreasing after 26 h, and this catalyst completely deactivated at about 50 h. However, the CO conversion rate of the catalyst under sulfur-free conditions could be nearly maintained at 100% within the measured time range (60 h). The results of IR, Raman, and XPS characterizations proved that the accumulation of cerium sulfate on the Cu–Ce catalyst would cover the active sites of the catalyst, eventually leading to the complete deactivation of the catalyst, which provides favorable evidence for the actual industrial anti-sulfur application.
Graphical 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 AbstractThe paper presents a short review of strategies used to develop coke resistant, nickel-based, catalysts for autothermal reforming of ethanol to hydrogen. Autothermal reforming of ethanol can be used in conjunction with pronton-exchange membrane fuel cells (PEMFCs) in the transportation sector, stationary and portable applications to replace the use of fossil fuels. Nickel-based catalysts are used in commercial processes for their high carbon–carbon bond cleavage and low cost compared to noble metals. However, the use of nickel-based catalysts is challenged by rapid deactivation caused by coke formation. A considerable effort is expended on innovating strategies to develop coke resistant nickel-based catalysts. The strategies reviewed in this paper are (i) the use of catalysts’ preparation methods targeting high dispersion of nickel nanoparticles smaller than the critical size of 10 nm (nm); (ii) modifying commonly used acidic supports (alumina, silica et cetera) to passivate the acidity to inhibit the production of coke precursor-ethylene; (iii) the addition of promoters and second active metals to promote supports and the active phase; (iv) controlling operating conditions to inhibit coke formation and the use of precursors with well-defined structures to stabilize highly dispersed nickel nanoparticles.
Graphical AbstractThis work addresses the reduction of NOx by H2 under O2-rich conditions using Al2O3/SiO2-supported Pt catalysts with different loads of WOx promotor. The samples were thoroughly characterised by N2 physisorption, temperature-programmed desorption of CO, scanning electron microscopy, X-ray diffraction, laser raman spectroscopy, X-ray photoelectron spectroscopy and diffuse reflectance infrared fourier transform spectroscopy with probe molecule CO. The catalytic studies of the samples without WOx showed pronounced NOx conversion below 200 °C, whereas highest efficiency was related to small Pt particles. The introduction of WOx provided increasing deNOx activity as well as N2 selectivity. This promoting effect was referred to an additional reaction path at the Pt-WOx/Al2O3/SiO2 interface, whereas an electronic activation of Pt by strong metal support interaction was excluded.
Graphic AbstractIn 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 AbstractIn this study, we describe the synthetic of uranyl nitrate ion functionalized MOFs linked by carboxyl, which displays block shape crystals structure. The as-prepared uranyl-MOF has been efficiently utilized as heterogeneous catalyst for selective aerobic oxidation of sulfides under visible-light irradiation. Photochemistry of extended MOFs including uranyl nitrate ion has been examined. The sulfoxidation reaction proceeds with good yields for a large variety of different sulfides. This process is carried out under visible light conditions, methanol as single solvent, and the uranyl-MOF material can be recycled up to five times. Sulfoxidation reaction mainly proceeds through an electron and energy transfer mechanism of oxygen in uranyl nitrate ion.
Graphic AbstractIn this study, we describe the synthetic of uranyl nitrate ion functionalized MOFs. The as-prepared uranyl-MOF was efficiently utilized as heterogeneous catalyst for selective aerobic oxidation of sulfides under visible-light irradiation. Photochemistry of extended MOFs including uranyl nitrate ion has been examined.
Solid 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 AbstractIn 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 AbstractIn this study, graphene oxide used as a stable support to adsorb and stabilize palladium nanoparticles for preparing a heterogeneous nanocatalyst. In order to increase the palladium adsorption, the surface of graphene oxide was functionalized with β-Cyclodextrin and cyanoguanidine compounds. The prepared nanocatalyst was defined by various characterization techniques such as FT-IR, XRD, TEM, SEM–EDX, ICP and UV–Vis. The catalytic efficiency of the synthesized organic–inorganic nanocomposite investigated by focusing on the Suzuki–Miyaura binding reaction and reduction of 4-nitrophenol to 4-aminophenol, which the nanocatalyst work is easy, affordable, and environmentally safe. The performed reaction showed high yields of biphenyl compounds through the Suzuki–Miyaura reaction and confirms very good conversion of 4-nitrophenol to its reduced form. Also, the proposed nanocatalyst presented significant catalytic efficiency (yield: 98% to 91%) after using five times.
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 AbstractIn 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 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 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 Abstract