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In this study nanostructured MoO3 and WO3 promoted SnO2 solid acid catalysts were explored for the production of glycerol carbonate via carbonylation of bioglycerol with urea. The investigated reference SnO2 and promoted catalysts were synthesized by fusion and wet-impregnation methods, respectively. The physicochemical properties of the prepared catalysts were thoroughly analyzed by XRD, Raman, BET surface area, TEM, FTIR, pyridine adsorbed FTIR, NH3-TPD, and XPS techniques. It was found from the characterization studies that integration of SnO2 with MoO3 and WO3 promoters leads to remarkable structural, textural, and acidic properties. Especially, a high quantity of acidic sites were observed over the MoO3/SnO2 catalyst (~ 81.45 μmol g−1) followed by WO3/SnO2 (61.81 μmol g−1) and pure SnO2 (46.47 μmol g−1), which played a key role in the carbonylation of bioglycerol with urea. The BET specific surface area and oxygen vacancies of SnO2 were significantly enhanced after the addition of MoO3 and WO3 promoters. TEM images revealed the formation of nanosized particles with a diameter of around 5–25 nm for the synthesized catalysts. The MoO3/SnO2 catalyst exhibited a high conversion and selectivity towards glycerol carbonate in comparison to other catalysts. The observed better performance is attributed to unique properties of MoO3/SnO2 catalyst including smaller crystallite size, high specific surface area, abundant oxygen vacancies, and more number of acidic sites. This catalyst also exhibited remarkable stability with no significant loss of activity in the recycling experiments. Nanostructured MoO3/SnO2 solid acid catalyst exhibited an excellent catalytic activity and a high selectivity to glycerol carbonate in the carbonylation of bioglycerol with urea under solvent-free and mild conditions.

This work reports the synthesis of mesoporous Ce1-x-ZrxO2-δ (x = 0.5 and 0.8) mixed oxides with distinct Ce/Zr mole ratio by inverse micelle template method and their catalytic exploration for epoxidation of styrene in isopropanol solvent using TBHP as the oxidant. Among various catalysts investigated, the Ce0.8Zr0.2O2 combination catalyst exhibited best catalytic activity with ~ 98% conversion and ~ 90% selectivity to styrene epoxide. The synthesized Ce–Zr mixed oxide catalysts were characterized by various state-of-the-art techniques. Characterization studies revealed that Ce/Zr mole ratio has an imperative influence on the physicochemical properties such as surface area, oxygen vacancy concentration, and redox nature. Interestingly, catalytic efficiency was significantly improved with the increase of Ce and decrease of Zr content in the Ce–Zr mixed oxides. Catalytic efficiency and distribution of the products for styrene oxidation under various conditions such as reaction time, solvent, temperature, and styrene to TBHP mole ratio were also evaluated. Reusability of the highly active Ce0.8Zr0.2O2 mixed oxide catalyst was also demonstrated.

Shape-controlled metal nanomaterials are considered as a unique class of catalysts because of their synergistic size- and shape-dependent catalytic properties. This work reports the synthesis of a novel size- and shape-controlled catalyst, consisting of highly dispersed MnOx nanoparticles (average particle size of 4.5 nm) on shape-controlled SiO2 nanospheres (250–300 nm) for selective cyclohexene oxidation using air as the oxidant under solvent- and base-free conditions. The MnOx/SiO2 catalyst exhibited an excellent cyclohexene conversion (~ 92%) with a high selectivity (~ 96%) to the allylic products (2-cyclohexene-ol and 2-cyclohexene-one) under mild conditions, outperforming various SiO2 supported CoOx, FeOx, and CuOx catalysts. The better performance of shape-controlled MnOx/SiO2 nanocatalyst is due to high redox nature of Mn, uniform dispersion of smaller sized MnOx nanoparticles, and synergetic interaction between MnOx and SiO2 spheres, as evidenced by XPS and TEM studies. Further, the MnOx/SiO2 catalyst could be reused at least 5 times for selective cyclohexene oxidation with a negligible loss in its catalytic performance, indicating the excellent stability of shape-controlled metal nanocatalysts in organic synthesis under economically viable and mild conditions. Shape-controlled MnOx/SiO2 nanocatalyst shows an excellent catalytic activity and a high selectivity to allylic products in the oxidation of cyclohexene under mild conditions

A series of Ce1 − x–ZrxO2 − δ (x = 0.2, 0.5, and 0.8) mixed oxides were prepared by coprecipitation method and explored for selective oxidation of vanillyl alcohol employing O2 and acetonitrile as the oxidant and solvent, respectively under base-free conditions. To ascertain the key factors responsible for vanillyl alcohol oxidation, the physicochemical properties of the synthesized catalysts were investigated by various characterization techniques namely, XRD, BET surface area, Raman, XPS, and H2-TPR. It was observed from this exercise that the catalytic activity dependents on the Ce:Zr mole ratio, which is related to the degree of reducibility of the catalyst. Interestingly, the catalytic activity is enhanced with the increase of Ce content in the Ce–Zr mixed oxide. Among the investigated catalysts, the Ce0.8Zr0.2O2 combination exhibited a high catalytic activity with ~ 98% conversion and ~ 99% selectivity to vanillin. Smaller crystallite size, large BET surface area, more number of oxygen vacancies, improved redox properties, and strong synergetic interaction are found to be the key factors to promote the oxidation ability of Ce0.8Zr0.2O2 catalysts towards vanillyl alcohol oxidation. Further, the influence of reaction parameters such as time, solvent, temperature, and oxygen pressure were also studied to optimize the catalytic process for vanillyl alcohol oxidation. As revealed by these studies, the high activity of Ce0.8Zr0.2O2 catalyst could be retained up to five cycles without appreciable loss in the activity and selectivity. Nanosized Ce0.8Zr0.2O2 catalyst exhibited an excellent catalytic activity and superior selectivity to vanillin in the liquid phase oxidation of vanillyl alcohol under ecofriendly conditions

Selective allylic oxidation of cyclohexene was investigated over nanostructured CeO2/SiO2 and CeO2–Sm2O3/SiO2 catalysts synthesized by a feasible deposition precipitation method. The CeO2–Sm2O3/SiO2 catalyst showed excellent catalytic efficiency with ~89 % cyclohexene conversion and ~90 % selectivity for allylic products (i.e., 2-cyclohexen-1-ol and 2-cyclohexene-1-one), while only ~50 and ~35 % cyclohexene conversion was observed, respectively, over CeO2/SiO2 and CeO2 catalysts. Systematic characterization of the designed catalysts was undertaken to correlate their catalytic activity with the physicochemical properties using X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) surface area measurements, Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and NH3-temperature programmed desorption (TPD) techniques. The results revealed that doping of Sm3+ into the ceria lattice and simultaneous dispersion of resultant Ce–Sm mixed oxides on the silica surface led to improved structural, acidic, and catalytic properties. The better catalytic efficiency of CeO2–Sm2O3/SiO2 was due to high specific surface area, more structural defects, and high concentration of strong acid sites, stimulated by synergistic interaction between various oxides in the catalyst. The cyclohexene conversion and selectivity for allylic products depended on the reaction temperature, nature of solvent, molar ratio of cyclohexene to oxidant, and reaction time. Possible reaction pathways are proposed for selective allylic oxidation of cyclohexene towards 2-cyclohexen-1-ol and 2-cyclohexene-1-one products. SiO2-supported CeO2–Sm2O3 nanocatalyst exhibited outstanding catalytic performance with superior selectivity for allylic products in liquid-phase selective oxidation of cyclohexene under mild reaction conditions.

The oxidation of cyclohexene was studied using nanostructured CeO2, CeO2/SiO2, CeO2-Sm2O3, and CeO2-Sm2O3/SiO2 catalysts. The CeO2-Sm2O3/SiO2 catalyst shows ~ 96% cyclohexene conversion and ~ 91% selectivity to allylic products, namely, 2-cyclohexen-1-one (~ 53%) and 2-cyclohexen-1-ol (~ 38%) owing to favorable redox (oxygen vacancies) and acid sites stimulated by synergistic interactions of dopant (Sm) and support (SiO2) with CeO2. In contrast, only ~ 40, ~ 55, and ~ 78% of cyclohexene conversions were observed, respectively, over CeO2, CeO2/SiO2, and CeO2-Sm2O3 catalysts. With the increase of reaction time, temperature, and molar ratio of cyclohexene/oxidant, the conversion of cyclohexene and the selectivity of 2-cyclohexen-1-one are increased considerably.

We have synthesized CuO nanostructures with flake, dandelion-microsphere, and short-ribbon shapes using solution-phase methods and have evaluated their structure–performance relationship in the heterogeneous catalysis of liquid-phase oxidative coupling reactions. The formation of nanostructures and the morphological evolution were confirmed by transmission electron microscopy, scanning electron microscopy, X-ray diffraction analysis, X-ray photoelectron spectroscopy, Raman spectroscopy, energy-dispersive X-ray spectroscopy, elemental mapping analysis, and Fourier transform infrared spectroscopy. CuO nanostructures with different morphologies were tested for the catalytic oxidative coupling of aromatic amines to imines under solvent-free conditions. We found that the flake-shaped CuO nanostructures exhibited superior catalytic efficiency compared to that of the dandelion- and short-ribbon-shaped CuO nanostructures. We also performed extensive density functional theory (DFT) calculations to gain atomic-level insight into the intriguing reactivity trends observed for the different CuO nanostructures. Our DFT calculations provided for the first time a detailed and comprehensive view of the oxidative coupling reaction of benzylamine over CuO, which yields N-benzylidene-1-phenylmethanamine as the major product. CuO(111) is identified as the reactive surface; the specific arrangement of coordinatively unsaturated Cu and O sites on the most stable CuO(111) surface allows N–H and C–H bond-activation reactions to proceed with low-energy barriers. The high catalytic activity of the flake-shaped CuO nanostructure can be attributed to the greatest exposure of the active CuO(111) facets. Our finding sheds light on the prospective utility of inexpensive CuO nanostructured catalysts with different morphologies in performing solvent-free oxidative coupling of aromatic amines to obtain biologically and pharmaceutically important imine derivatives with high selectivity.

This article represents a comparative study of a series of doped ceria catalysts towards environmental applications like CO and soot oxidation catalysis. Transition and rare earth metals of varying size and reducibility property have been selected namely, zirconium (Zr), hafnium (Hf), iron (Fe), manganese (Mn), praseodymium (Pr), and lanthanum (La) as dopants. A facile coprecipitation approach has been used to incorporate the dopants into ceria lattice.The formation of homogeneous solid solutions and their respective physicochemical properties have been confirmed by employing XRD analysis, BET surface area measurements, TEM, Raman, UV-DRS, XPS, and TPR techniques. All the doped CeO2 samples exhibited smaller crystallite size, larger BET surface area, and higher amounts of oxygen vacancies than that of pure CeO2. CO oxidation has been performed in the presence of oxygen under atmospheric pressure, and 300–850 K temperature range in a fixed bed microreactor. Soot oxidation was carried out in presence of air using a thermo gravimetric analyzer within a much wider temperature window of 300–1273 K. The physicochemical properties of the doped ceria materials have been comparatively analyzed to correlate the influence of dopants with their improved behaviour in both the oxidation reactions. Vital role of ‘lattice oxygen’ in CO oxidation and ‘active oxygen species’ in soot oxidation on the catalyst surface has been considered, assuming that Mars and van Krevelen mechanism and active oxygen mechanism play the key role in CO and soot oxidation, respectively. The O 1s XP spectra confirmed that Mn doped ceria (denoted as CM) exhibited most loosely bound lattice oxygen and highest concentration of surface adsorbed oxygen species compared to other materials. Accordingly, a superior CO and soot oxidation activity have been observed for manganese doped ceria. Significant lowering of T50 (390 K and 669 K for CO and soot oxidation respectively) temperature have been observed in both the oxidation reactions; which is primarily attributed to the considerable lowering of lattice oxygen binding energy and higher concentration of surface adsorbed oxygen species.

The current transition from petrochemical resources to biomass-derived platform molecules is in great demand for the development of synergies, scientific innovations and breakthroughs, and steep changes in the infrastructure of chemical industries. This article is focused on new opportunities for the production of biofuel additives from bioglycerol, which is obtained as waste and/or by-product from the current biodiesel industries. Here, we summarize the recent relevant processes for the production of biofuel additives from bioglycerol over various acid catalysts in two different pathways: (i) the esterification of bioglycerol with acetic acid, levulinic acid and other acids, and (ii) the acetalization of bioglycerol with acetone, furfural, benzaldehyde and other carbonyl compounds. It is evident that the synthesis of biofuel additives through esterfication and acetalization of bioglycerol is an important research area with imperative prospects for industrial applications.

Ceria is the hub of constant and diverse research interest due to its wide industrial applications. In the present work, we have developed Mn-doped CeO 2 catalysts for vanillyl alcohol oxidation. Accordingly, we synthesized nanostructured Mn-doped CeO 2 catalysts with various concentration of MnO x by an economical coprecipitation method and characterized using XRD, ICP-OES, BET surface area, Raman spectroscopy, TEM, XPS, and H 2 -TPR techniques. XRD and TEM results confirmed formation of nanocrystalline solid solutions with the incorporation of Mn into ceria lattice. ICP-OES analysis confirmed actual amount of MnO x loadings in the respective catalysts. The BET surface area of CeO 2 significantly enhanced after the incorporation of MnO x dopant. Raman results disclosed that the incorporation of MnO x into ceria lattice greatly enhances the oxygen vacancies, which are responsible for the improved catalytic activity. XPS analysis revealed that Ce and Mn exist in +3, +4 and +2, +3, +4 oxidation st a tes, respectively, on the surface of the samples. H 2 -TPR results showed pronounced enhancement in the reduction of CeO 2 by MnO x doping. Catalytic activity studies confirmed that among all the catalysts, the Ce 0.7 Mn 0.3 O 2−δ showed superior activity for vanillyl alcohol oxidation with 89% conversion and 95% selectivity, which could be attributed to higher concentration of oxygen vacancies, a high BET surface area, low temperature reducibility, and facile synergetic interaction between CeO 2 and MnO x .

This work investigates the structure-activity properties of CuOx-decorated CeO2 nanocubes with a meticulous scrutiny on the role of the CuOx/CeO2 nanointerface in the catalytic oxidation of diesel soot, a critical environmental problem all over the world. For this, a systematic characterization of the materials has been undertaken using transmission electron microscopy (TEM), transmission electron microscopy-energy-dispersive X-ray spectroscopy (TEM-EDS), high-angle annular dark-field-scanning transmission electron microscopy (HAADF-STEM), scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS), X-ray diffraction (XRD), Raman, N2 adsorption-desorption, and X-ray photoelectron spectroscopy (XPS) techniques. The TEM images show the formation of nanosized CeO2 cubes (∼25 nm) and CuOx nanoparticles (∼8.5 nm). The TEM-EDS elemental mapping images reveal the uniform decoration of CuOx nanoparticles on CeO2 nanocubes. The XPS and Raman studies show that the decoration of CuOx on CeO2 nanocubes leads to improved structural defects, such as higher concentrations of Ce(3+) ions and abundant oxygen vacancies. It was found that CuOx-decorated CeO2 nanocubes efficiently catalyze soot oxidation at a much lower temperature (T50 = 646 K, temperature at which 50% soot conversion is achieved) compared to that of pristine CeO2 nanocubes (T50 = 725 K) under tight contact conditions. Similarly, a huge 91 K difference in the T50 values of CuOx/CeO2 (T50 = 744 K) and pristine CeO2 (T50 = 835 K) was found in the loose-contact soot oxidation studies. The superior catalytic performance of CuOx-decorated CeO2 nanocubes is mainly attributed to the improved redox efficiency of CeO2 at the nanointerface sites of CuOx-CeO2, as evidenced by Ce M5,4 EELS analysis, supported by XRD, Raman, and XPS studies, a clear proof for the role of nanointerfaces in the performance of heterostructured nanocatalysts.

Designing Au nanocatalysts supported on nanosized metal oxides has drawn much attention due to remarkable nanoscale influenced metal-support interactions and their favorable role in heterogeneous catalysis. This work reports development of Au nanocatalysts dispersed on nanosized CeO2 and CeO2-ZrO2 supports for solvent- and base-free oxidative coupling of benzylamines into N-benzylbenzaldimines using O2 as a green oxidant. The physicochemical characterization of nanocatalysts has been undertaken using HRTEM, UV–vis DRS, XRD, Raman, BET, TG-DTA, AAS, and XPS techniques. HRTEM images reveal the formation of nanosized CeO2 and CeO2-ZrO2 supports with an average diameter of ∼10 and 7 nm, respectively. HRTEM images also indicated that Au/CeO2-ZrO2 catalyst has smaller Au nanoparticles (∼2.1 nm) compared with that of Au/CeO2 catalyst (∼3.7 nm). Raman and XPS studies showed that the addition of ZrO2 to CeO2 leads to abundant oxygen vacancies and higher concentration of Ce3+, respectively. The Au/CeO2-ZrO2 catalyst exhibited a higher efficiency in benzylamine conversion (∼95%) followed by Au/CeO2 (∼78%), CeO2-ZrO2 (∼51%), and CeO2 (∼39%). The Au/CeO2-ZrO2 catalyst was also found to effective for oxidative coupling of various benzylamines, and moderate to good product yields were obtained. The presence of smaller Au particles (2.1 nm) and improved surface-defect properties of nanoscale CeO2-ZrO2 support are found to be key factors for high performance of Au/CeO2-ZrO2 catalyst. Additionally, the reaction temperature is one of the important factors for the performance of catalysts. Remarkably, ∼99.6–99.9% selectivity for N-benzylbenzaldimines was found in the amine oxidation, which highlights the significance of present work in the selective oxidation catalysis.

The development of promising solid acid catalysts alternative to hazardous liquid acids is essential towards a sustainable chemical industry. This work reports the synthesis of nanostructured CeO2–MoO3/SiO2 and CeO2–WO3/SiO2 solid acids, along with CeO2–MoO3, CeO2–WO3 and CeO2 for continuous-flow oxidative coupling of benzylamine using O2 as a green oxidant. A systematic physicochemical characterization has been undertaken using XRD, Raman, N2 adsorption–desorption, TEM, NH3-TPD, and XPS techniques. It was found that the dispersion of CeO2–MoO3 and CeO2–WO3 species on the SiO2 support leads to remarkable structural and acidic properties, due to the synergetic effect of the respective components. TEM analysis reveals the presence of highly dispersed WO3 (0.8–1.2 nm) and MoO3 (0.8–1 nm) nanoparticles in the synthesized catalysts. Among the various catalysts developed, the CeO2–MoO3/SiO2 sample exhibited higher BET surface area (248 m2 g−1), abundant oxygen vacancy defects, and large amounts of strong acidic sites. Owing to improved properties, the CeO2–MoO3/SiO2 solid-acid showed a superior catalytic performance in the continuous-flow oxidative coupling of benzylamine: the obtained benzylamine conversions for 1 h are ∼11.8, 55, 70, 76, and 96%, respectively, for CeO2, CeO2–WO3, CeO2–WO3/SiO2, CeO2–MoO3, and CeO2–MoO3/SiO2 catalysts. Importantly, the CeO2–MoO3/SiO2 solid acid exhibited a remarkable steady performance in terms of benzylamine conversion (∼88–96%) and selectivity of N-benzylbenzaldimine product (∼96–97.8%) up to 6 h. The outstanding catalytic performance of CeO2–MoO3/SiO2 solid acid coupled with the application of continuous-flow synthesis, economical benefits of the respective oxides, and eco-friendly oxidant is expected to bring new opportunities in the design of industrially-favourable chemical processes.

Selective transformation of levulinic acid (LA) to γ-valerolactone (GVL) using novel heterogeneous catalysts is one of the promising strategies for viable biomass processing. In this framework, we developed a continuous flow process for the selective hydrogenation of LA to GVL using several nanostructured Ni/SiO2 catalysts. The structural, textural, acidic, and redox properties of Ni/SiO2 catalysts, tuned by selectively varying the Ni amount from 5 to 40 wt %, were critically investigated using numerous materials characterization techniques. Electron microscopy images showed the formation of uniformly dispersed Ni nanoparticles on the SiO2 support, up to 30% Ni loading (average particle size is 9.2 nm), followed by a drastic increase in the particles size (21.3 nm) for 40% Ni-loaded catalyst. The fine dispersion of Ni particles has elicited a synergistic metal-support interaction, especially in 30% Ni/SiO2 catalyst, resulting in enhanced acidic and redox properties. Among the various catalysts tested, the 30% Ni/SiO2 catalyst showed the best performance with a remarkable 98% selectivity of GVL at complete conversion of LA for 2 h reaction time. Interestingly, this catalyst showed a steady selectivity to GVL (>97%), with a 54.5% conversion of LA during 20 h time-on-stream. The best performance of 30% Ni/SiO2 catalyst was attributed to well-balanced catalytic properties, such as ample amounts of strong acidic sites and abundant active metal sites. The obtained results show a great potential of applying earth-abundant nickel/silica catalysts for upgrading biomass platform molecules into value-added chemicals and high-energy-density fuels. ispartof: ACS OMEGA vol:3 issue:12 pages:16839-16849 ispartof: location:United States status: published

This work demonstrates that MoOx/CeO2–ZrO2 solid acid acts as a promising catalyst in the solvent-free oxidative-coupling of benzylamine into dibenzylimine with O2 as the oxidant. The benzylamine conversions were found to be ~27, 51, 74, and 99 % for CeO2, CeO2–ZrO2, MoOx/CeO2, and MoOx/CeO2–ZrO2 catalysts, respectively. The MoOx/CeO2–ZrO2 catalyst also efficiently converts various substituted- and secondary-benzylamines under solvent-free conditions with O2 resulting in moderate to excellent yields. Remarkably, a high selectivity of ~99.6–99.9 % towards the dibenzylimine product was found for all reaction conditions. The outstanding performance of MoOx/CeO2–ZrO2 catalyst was attributed to high specific surface area, improved structural defects, and superior acid properties. The MoOx/CeO2–ZrO2 catalyst show an outstanding performance in the oxidation of benzylamine and its derivatives, which is attributed to abundant acidic sites, large number of oxygen vacancies, and superior BET surface area.

The influence of dopant size and valence state on the reduction properties, oxygen defects, and lattice strain in doped ceria has been studied fastidiously. This is of particular importance in environmental application, such as soot and CO oxidation. Herein, isovalent (Zr 4+ ) and aliovalent (La 3+ , Eu 3+ , and Sm 3+ ) metal ions doped ceria catalysts were synthesized by coprecipitation method with aqueous ammonia as the precipitant. The interplay of dopant size and valence in the ceria lattice is experimentally analysed in detail at the structural and electronic level by XRD, BET, TEM, Raman, TPR, and XPS techniques, and finally evaluated for soot and CO oxidation reactions. According to the analysis results, the size or the valence of the dopant or both together positively influence the ceria properties. The isovalent substituent (Zr 4+ ), which is different in size with respect to ceria, enhanced the ceria intrinsic activity by decreasing its reduction temperature and oxygen vacancy formation energy, thereby increased the activity. Whereas, aliovalent dopants (La 3+ , Eu 3+ , and Sm 3+ ) having different in size and valence compared to pure ceria further improved the structural and catalytic properties of bare ceria by inducing additional oxygen vacancies. The observed activity of doped materials towards soot and CO oxidation reactions is as follows: aliovalent doped ceria > isovalent doped ceria > ceria. The marked influence of isovalent and aliovalent dopants on the ceria properties are highlighted in this study.

The development of noble-metal-free catalysts is currently a topic of paramount research investigation in the chemical industry. In this work, a promising CeO2–MoO3/SiO2 catalyst was synthesized for the oxidation of a wide variety of benzylamines with O2 as the oxidant under solvent-free conditions. For comparison, the efficiency of CeO2 and CeO2–MoO3 catalysts were also studied for the oxidation of benzylamine under identical conditions. The physicochemical properties of the catalysts were thoroughly analysed using X-ray diffraction, Raman spectroscopy, Barrett–Joyner–Halenda pore size distribution, Brunauer–Emmet–Teller (BET) surface area, Fourier-transform infrared spectroscopy, ammonia-temperature programmed desorption (NH3-TPD), and X-ray photoelectron spectroscopy techniques. Characterization studies revealed that the CeO2–MoO3/SiO2 catalyst shows favourable structural, textural and acidic properties, which are due to strong interaction between the Ce–Mo mixed oxide and the SiO2. In particular, the CeO2–MoO3/SiO2 sample exhibits smaller crystallite size and highest BET surface area compared with the CeO2–MoO3 and bare CeO2. Raman analysis revealed that the CeO2–MoO3/SiO2 sample exhibits greater number of oxygen vacancy defects. The NH3-TPD studies indicated that the CeO2–MoO3/SiO2 sample has large amount of acidic sites. Owing to the beneficial properties, the CeO2–MoO3/SiO2 sample exhibited an outstanding catalytic performance for the aerobic oxidation of various benzylamines. The achieved benzylamine conversions are ~16, 65 and 98 %, respectively, for CeO2, CeO2–MoO3 and CeO2–MoO3/SiO2 samples. Despite the nature of the catalyst used and the reaction conditions employed, almost ~100 % selectivity for the dibenzylimine product was found in the present study. Remarkably, the CeO2–MoO3/SiO2 catalyst can be repeatedly used up to 5 cycles without any considerable variation in the benzylamine conversion and imine product selectivity. The CeO2–MoO3/SiO2 catalyst showed an outstanding efficiency in the oxidation of benzylamine, which is attributed to abundant acidic sites, large number of oxygen vacancies, and superior BET surface area.

The hydrodesulfurization reaction of thiophene has been investigated over graphene-like few-layer MoS2 as well as over Co- and Ni-nanoparticle-covered few-layer MoS2. Conversion of thiophene to n-butane over few-layer MoS2 is superior to that over bulk MoS2; the percent conversion is approximately 64 % at 450 °C. However, over few-layer MoS2 covered with Co or Ni nanoparticles the conversion increases to approximately 98 % at around 375 °C as a result of the smaller nanoparticles being more effective.

Few-layer graphene-like sheets of MoS2, WS2, MoSe2 and WSe2 were prepared by employing two methods. The first method uses microwave synthesis in ethylene glycol or water medium and the second method involves laser irradiation of the bulk samples dispersed in dimethylformamide. The few-layer dichalcogenide samples were characterized by various microscopic and spectroscopic techniques. These graphene mimics show room-temperature ferromagnetism and exchange bias besides magnetoresistance at room temperature. We have deposited nanoparticles of gold, silver, and platinum on few-layer WS2 and characterized the nanocomposites. Nanocomposites of MoS2 with reduced graphene oxide show increase in resistivity with increasing amount of MoS2. The polyaniline MoS2 composite prepared by in situ polymerization of aniline in the presence of few-layer MoS2 shows evidence of polaronic character.

Graphene has been decorated by nanoparticles of noble metals and other inorganic materials. In the present study, we have decorated graphene-like MoS2 and MoSe2, containing 3–5 layers, with Au, Ag and Pt nanoparticles. We have characterized these nanocomposites using X-ray diffraction, electron microscopy and absorption spectroscopy. The studies reveal that the surfaces of the layered inorganic materials get uniformly coated with the noble metal nanoparticles. There are indications that the interaction of the metal particles with these layered materials is rather weak.

Graphene analogues of TaS2 and TiS2 (3-4 layers), prepared by Li intercalation followed by exfoliation in water, were characterized. Nanocomposites of CdS with few-layer TiS2 and TaS2 were employed for the visible-light-induced H2 evolution reaction (HER). Benzyl alcohol was used as the sacrificial electron donor, which was oxidized to benzaldehyde during the reaction. Few-layer TiS2 is a semiconductor with a band gap of 0.7 eV, and its nanocomposite with CdS showed an activity of 1000 μmol h(-1) g(-1). The nanocomposite of few-layer TaS2, in contrast, gave rise to higher activity of 2320 μmol h(-1) g(-1), which was attributed to the metallic nature of few-layer TaS2. The amount of hydrogen evolved after 20 and 16 h for the CdS/TiS2 and CdS/TaS2 nanocomposites was 14,833 and 28,132 μmol, respectively, with turnover frequencies of 0.24 and 0.57 h(-1), respectively.