Ceria Promoted Cu-Ni/SiO2 Catalyst for Selective Hydrodeoxygenation of Vanillin.

A ceria (CeO2) promoted Cu-Ni bimetallic catalyst supported on SiO2 (Cu-Ni/CeO2-SiO2) was prepared and evaluated for catalytic hydrodeoxygenation (HDO) of vanillin. Silica supported monometallic Cu and Ni catalysts and bimetallic Cu-Ni catalyst (Cu/SiO2, Ni/SiO2, and Cu-Ni/SiO2), without a ceria promoter, were also synthesized and tested for the same application. The highest conversion of vanillin was achieved with the Cu-Ni/CeO2-SiO2 catalyst. Vanillyl alcohol was the sole product in the initial 2 h, followed by the formation of 2-methoxy-4-methylphenol, which was observed. Characterization of the synthesized catalysts revealed the presence of overlapping crystalline phases of CuO, NiO, and CeO2 on the Cu-Ni/CeO2-SiO2 surface. We extended our study to find out the results of using CeO2 as the support of the Cu-Ni bimetallic catalyst (Cu-Ni/CeO2). Partial incorporation of Cu and Ni cations into the ceria lattice took place, leading to the decrease of specific surface area and a concomitant compromise in the conversion. In the case of the Cu-Ni/CeO2-SiO2 catalyst, the higher conversion was accredited to the facile formation of Cu+ active centers by the synergistic interaction between Ce+4/Ce+3 and Cu+2/Cu+ redox couples and the incorporation of oxygen vacancies on the catalyst surface.

Design and Catalytic Application of Functional Porous Organic Polymers: Opportunities and Challenges.

This review article encompasses the progress and conventional overview of current research activities of porous organic polymers (POPs), especially in catalysis, as they have garnered colossal interest in the scientific fraternity due to their intriguing characteristic features. Various synthetic strategies with possible modification of functionality of POPs have been used to improve the catalytic efficiency towards value-added chemicals production. Accordingly, this review article is mainly focused on the design, development of various functionalized POPs by employing Friedel-Crafts alkylation, FeCl3 assisted oxidative polymerisation and polymerisation in nonaqueous medium, and a comprehensive understanding in potential catalytic applications namely, acetalization, hydrodeoxygenation (HDO), hydrogenation, coupling, photocatalytic hydrogen evolution and biomass conversion towards the production of value-added chemicals in biodiesel and chemical industries.

Nanostructured Nickel/Silica Catalysts for Continuous Flow Conversion of Levulinic Acid to γ-Valerolactone.

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.

Nanowire Morphology of Mono- and Bidoped α-MnO2 Catalysts for Remarkable Enhancement in Soot Oxidation.

In the present work, nanowire morphologies of α-MnO2, cobalt monodoped α-MnO2, Cu and Co bidoped α-MnO2, and Ni and Co bidoped α-MnO2 samples were prepared by a facile hydrothermal synthesis. The structural, morphological, surface, and redox properties of all the as-prepared samples were investigated by various characterization techniques, namely, scanning electron microscopy (SEM), transmission and high resolution electron microscopy (TEM and HR-TEM), powder X-ray diffraction (XRD), N2 sorption surface area measurements, X-ray photoelectron spectroscopy (XPS), hydrogen-temperature-programmed reduction (H2-TPR), and oxygen-temperature-programmed desorption (O2-TPD). The soot oxidation performance was found to be significantly improved via metal mono- and bidoping. In particular, Cu and Co bidoped α-MnO2 nanowires showed a remarkable improvement in soot oxidation performance, with its T50 (50% soot conversion) values of 279 and 431 °C under tight and loose contact conditions, respectively. The soot combustion activation energy for the Cu and Co bidoped MnO2 nanowires is 121 kJ/mol. The increased oxygen vacancies, greater number of active sites, facile redox behavior, and strong synergistic interaction were the key factors for the excellent catalytic activity. The longevity of Cu and Co bidoped α-MnO2 nanowires was analyzed, and it was found that the Cu/Co bidoped α-MnO2 nanowires were highly stable after five successive cycles and showed an insignificant decrease in soot oxidation activity. Furthermore, the HR-TEM analysis of a spent catalyst after five cycles indicated that the (310) crystal plane of α-MnO2 interacts with the soot particles; therefore, we can assume that more-reactive exposed surfaces positively affect the reaction of soot oxidation. Thus, the Cu and Co bidoped α-MnO2 nanowires provide promise as a highly effective alternative to precious metal based automotive catalysts.

Novelty of Dynamic Process in the Synthesis of Biocompatible Silica Nanotubes by Biomimetic Glycyldodecylamide as a Soft Template.

A dynamic process in the synthesis of silica nanotubes (SNTs) by utilizing glycyldodecylamide (GDA) as a soft template was thoroughly investigated. The morphological evolution from GDA to SNTs was deeply explored to elucidate the formation mechanism for optimizing the synthesis procedure. Various analytical tools, namely, XRD, FTIR, SEM, TEM, Z-potential, and N2 adsorption/desorption isotherms, were employed during the synthesis procedure. The interactive structure of GDA was also investigated using TEM-EDX as a function of aging time. These studies revealed the stepwise morphology of nanograin, nanofiber, curved plate, and nanotube in the ethanol/water solution when aged at room temperature. The supramolecular GDA molded the vesicle type nanostructure which was surrounded by silica and facilitated the formation of uniform SNTs. The stimulus for GDA to be curved into a vesicle was the intermolecular hydrogen bonding between adjacent amide groups of the template molecules. This was illustrated by FTIR spectra of GDA-silica intermediate by detecting the transition of amide I peak from 1678 to 1635 cm-1. The effect of hydrogen bonding became stronger when the sample was aged.

MnO(x) Nanoparticle-Dispersed CeO2 Nanocubes: A Remarkable Heteronanostructured System with Unusual Structural Characteristics and Superior Catalytic Performance.

Understanding the interface-induced effects of heteronanostructured catalysts remains a significant challenge due to their structural complexity, but it is crucial for developing novel applied catalytic materials. This work reports a systematic characterization and catalytic evaluation of MnOx nanoparticle-dispersed CeO2 nanocubes for two important industrial applications, namely, diesel soot oxidation and continuous-flow benzylamine oxidation. The X-ray diffraction and Raman studies reveal an unusual lattice expansion in CeO2 after the addition of MnOx. This interesting observation is due to conversion of smaller sized Ce(4+) (0.097 nm) to larger sized Ce(3+) (0.114 nm) in cerium oxide led by the strong interaction between MnOx and CeO2 at their interface. Another striking observation noticed from transmission electron microscopy, high angle annular dark-field scanning transmission electron microscopy, and electron energy loss spectroscopy studies is that the MnOx species are well-dispersed along the edges of the CeO2 nanocubes. This remarkable decoration leads to an enhanced reducible nature of the cerium oxide at the MnOx/CeO2 interface. It was found that MnOx/CeO2 heteronanostructures efficiently catalyze soot oxidation at lower temperatures (50% soot conversion, T50 ∼660 K) compared with that of bare CeO2 nanocubes (T50 ∼723 K). Importantly, the MnOx/CeO2 heteronanostructures exhibit a noticeable steady performance in the oxidation of benzylamine with a high selectivity of the dibenzylimine product (∼94-98%) compared with that of CeO2 nanocubes (∼69-91%). The existence of a strong synergistic effect at the interface sites between the CeO2 and MnOx components is a key factor for outstanding catalytic efficiency of the MnOx/CeO2 heteronanostructures.

Selective hydrogenation of butadiene over TiO2 supported copper, gold and gold-copper catalysts prepared by deposition-precipitation.

Oxide supported copper and gold catalysts are active for the selective hydrogenation of polyunsaturated hydrocarbons but their low activity compared to palladium catalysts and the deactivation of copper catalysts limit their use. There are only a very limited number of studies concerned with the use of bimetallic Au-Cu catalysts for selective hydrogenation reactions and the aim of this work was to prepare TiO2-supported monometallic Au and Cu and bimetallic AuCu (Cu/Au atomic ratio of 1 and 3) catalysts and to evaluate their catalytic performance in the selective hydrogenation of butadiene. Small gold, copper and gold-copper nanoparticles (average particle size < 2 nm) were obtained on TiO2 using the preparation method of deposition-precipitation with urea followed by reduction under H2 at 300 °C. Very small clusters were observed for Cu/TiO2 (∼1 nm) which might result from O2 induced copper redispersion, as also supported by the XPS analyses. The alloying of copper with gold was found to inhibit its redispersion and also limits its reoxidation, as attested by XPS. The bimetallic character of the AuCu nanoparticles was confirmed by XPS and EDX-HAADF. Cu/TiO2 was initially more active than Au/TiO2 in the selective hydrogenation of butadiene at 75 °C but it deactivated rapidly during the first hours of reaction whereas the gold catalyst was very stable up to 20 hours of reaction. The bimetallic AuCu/TiO2 catalysts displayed an activation period during the first hours of the reaction, which was very pronounced for the sample containing a higher Cu/Au atomic ratio. This initial gain in activity was tentatively assigned to copper segregation at the surface of the bimetallic nanoparticles, induced by the reactants. When the AuCu/TiO2 catalysts were pre-exposed to air at 75 °C before butadiene hydrogenation, surface copper segregation occurred, leading to higher initial activity and the suppression of the activation period. Under the same conditions, Cu/TiO2 totally lost its activity, probably due to irreversible copper oxidation.

Structural characterization and oxidative dehydrogenation activity of V2O5/Ce(x)Zr(1-x)O2/SiO2 catalysts.

The thermal stability of a nanosized Ce(x)Zr(1-x)O2 solid solution on a silica surface and the dispersion behavior of V2O5 over Ce(x)Zr(1-x)O2/SiO2 have been investigated using XRD, Raman spectroscopy, XPS, HREM, and BET surface area techniques. Oxidative dehydrogenation of ethylbenzene to styrene was performed as a test reaction to assess the usefulness of the VOx/Ce(x)Zr(1-x)O2/SiO2 catalyst. Ce(x)Zr(1-x)O2/SiO2 (1:1:2 mol ratio based on oxides) was synthesized through a soft-chemical route from ultrahigh dilute solutions by adopting a deposition coprecipitation technique. A theoretical monolayer equivalent to 10 wt % V2O5 was impregnated over the calcined Ce(x)Zr(1-x)O2/SiO2 sample (773 K) by an aqueous wet impregnation technique. The prepared V2O5/Ce(x)Zr(1-x)O2/SiO2 sample was subjected to thermal treatments from 773 to 1073 K. The XRD measurements indicate the presence of cubic Ce0.75Zr0.25O2 in the case of Ce(x)Zr(1-x)O2/SiO2, while cubic Ce0.5Zr0.5O2 and tetragonal Ce0.16Zr0.84O2 in the case of V2O5/Ce(x)Zr(1-x)O2/SiO2 when calcined at various temperatures. Dispersed vanadium oxide induces more incorporation of zirconium into the ceria lattice, thereby decreasing its lattice size and also accelerating the crystallization of Ce-Zr-O solid solutions at higher calcination temperatures. Further, it interacts selectively with the ceria portion of the composite oxide to form CeVO4. The RS measurements provide good evidence about the dispersed form of vanadium oxide and the CeVO4 compound. The HREM studies show the presence of small Ce-Zr-oxide particles of approximately 5 nm size over the surface of amorphous silica and corroborate with the results obtained from other techniques. The catalytic activity studies reveal the ability of vanadium oxide supported on Ce(x)Zr(1-x)O2/SiO2 to efficiently catalyze the ODH of ethylbenzene at normal atmospheric pressure. The remarkable ability of Ce(x)Zr(1-x)O2 to prevent the deactivation of supported vanadium oxide leading to stable activity in the time-on-stream experiments and high selectivity to styrene are other important observations.

Structural characterization of CeO(2)-ZrO(2)/TiO(2) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) mixed oxide catalysts by XRD, Raman spectroscopy, HREM, and other techniques.

Structural characteristics of CeO(2)-ZrO(2)/TiO(2) (CZ/T) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) (V/CZ/T) mixed oxide catalysts have been investigated using X-ray diffraction (XRD), BET surface area, Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques. The CeO(2)-ZrO(2) (1:1 mole ratio) solid solution was deposited over a finely powdered TiO(2) support by a deposition precipitation method. A nominal 5 wt % V(2)O(5) was impregnated over the calcined (773 K) CZ/T mixed oxide carrier by a wet impregnation technique. The obtained CZ/T and V/CZ/T samples were further subjected to thermal treatments from 773 to 1073 K to understand the dispersion and temperature stability of these materials. In the case of CZ/T samples, the XRD results suggest the formation of different cubic and tetragonal Ce-Zr-oxide phases, Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), Ce(0.5)Zr(0.5)O(2), and Ce(0.16)Zr(0.84)O(2) in varying proportions depending on the treatment temperature. With increasing calcination temperature from 773 to 1073 K, the intensity of the lines pertaining to cubic Ce(0.6)Zr(0.4)O(2) and Ce(0.5)Zr(0.5)O(2) phases increased at the expense of cubic Ce(0.75)Zr(0.25)O(2), indicating more incorporation of zirconia into the ceria lattice. The TiO(2) was mainly in the anatase form whose crystallite size also increased with increasing treatment temperature. A better crystallization and more incorporation of zirconia into the ceria lattice was noted when CZ/T was impregnated with V(2)O(5). However, no crystalline V(2)O(5) could be seen from both XRD and RS measurements. In particular, a preferential formation of CeVO(4) compound and an intense tetragonal Ce(0.16)Zr(0.84)O(2) phase were noted beyond 873 K. The HREM results indicate, in the case of CZ/T samples, a well-dispersed Ce-Zr-oxide of the size approximately 5 nm over the bigger crystals ( approximately 40 nm) of TiO(2) when treated at 873 K. The exact structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic fluorite geometry and the TiO(2) is in anatase form. A better crystallization of Ce-Zr-oxides ( approximately 8 nm) over the surface of bigger crystals of TiO(2) was noted at 1073 K. A further enhancement in the crystallite size and zirconia-rich tetragonal phase was noted in the case of V/CZ/T samples. Further, the structure of CeVO(4) formed was also clearly identified in conformity with XRD and RS results.

Structural characterization of nanosized CeO(2)-SiO(2), CeO(2)-TiO(2), and CeO(2)-ZrO(2) catalysts by XRD, Raman, and HREM techniques.

Structural characteristics of nanosized ceria-silica, ceria-titania, and ceria-zirconia mixed oxide catalysts have been investigated using X-ray diffraction (XRD), Raman spectroscopy, BET surface area, thermogravimetry, and high-resolution transmission electron microscopy (HREM). The effect of support oxides on the crystal modification of ceria cubic lattice was mainly focused. The investigated oxides were obtained by soft chemical routes with ultrahighly dilute solutions and were subjected to thermal treatments from 773 to 1073 K. The XRD results suggest that the CeO(2)-SiO(2) sample primarily consists of nanocrystalline CeO(2) on the amorphous SiO(2) surface. Both crystalline CeO(2) and TiO(2) anatase phases were noted in the case of CeO(2)-TiO(2) sample. Formation of cubic Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) (at 1073 K) were observed in the case of the CeO(2)-ZrO(2) sample. Raman measurements disclose the fluorite structure of ceria and the presence of oxygen vacancies/Ce(3+). The HREM results reveal well-dispersed CeO(2) nanocrystals over the amorphous SiO(2) matrix in the cases of CeO(2)-SiO(2), isolated CeO(2), and TiO(2) (anatase) nanocrystals, some overlapping regions in the case of CeO(2)-TiO(2), and nanosized CeO(2) and Ce-Zr oxides in the case of CeO(2)-ZrO(2) sample. The exact structural features of these crystals as determined by digital diffraction analysis of HREM experimental images reveal that the CeO(2) is mainly in cubic fluorite geometry. The oxygen storage capacity (OSC) as determined by thermogravimetry reveals that the OSC of the mixed oxide systems is more than that of pure CeO(2) and is system dependent.

Surface stabilized nanosized Ce(x)Zr(1-x)O(2) solid solutions over SiO(2): characterization by XRD, Raman, and HREM techniques.

Ce(x)Zr(1)(-)(x)O(2) solid solutions deposited over silica surface were investigated by X-ray diffraction (XRD), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques in order to understand the role of silica support and the temperature stability of these composite oxides. For the purpose of comparison, an unsupported Ce(x)Zr(1)(-)(x)O(2) was also synthesized and subjected to characterization by various techniques. The Ce(x)Zr(1)(-)(x)O(2)/SiO(2) (CZ/S) (1:1:2 mole ratio based on oxides) was synthesized by depositing Ce(x)Zr(1)(-)(x)O(2) solid solution over a colloidal SiO(2) support by a deposition precipitation method and unsupported Ce(x)Zr(1)(-)(x)O(2) (CZ) (1:1 mole ratio based on oxides) was prepared by a coprecipitation procedure, and the obtained catalysts were subjected to thermal treatments from 773 to 1073 K. The XRD measurements disclose the presence of cubic phases with the composition Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) in CZ samples, while CZ/S samples possess Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), and Ce(0.5)Zr(0.5)O(2) in different proportions. The crystallinity of these phases increased with increasing calcination temperature. The cell a parameter estimations indicate contraction of ceria lattice due to the incorporation of zirconium cations into the CeO(2) unit cell. Raman measurements indicate the presence of oxygen vacancies, lattice defects, and displacement of oxygen ions from their normal lattice positions in both the series of samples. The HREM results reveal, in the case of CZ/S samples, a well-dispersed nanosized Ce-Zr-oxides over the surface of amorphous SiO(2). The structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic geometry and exhibit high thermal stability. Oxygen storage capacity measurements by a thermogravimetric method reveal a substantial enhancement in the oxygen vacancy concentration of CZ/S sample over the unsupported CZ sample.