Vanadia supported on nickel manganese oxide nanocatalysts for the catalytic oxidation of aromatic alcohols
© Adil et al.; licensee Springer. 2015
Received: 14 December 2014
Accepted: 10 January 2015
Published: 6 February 2015
Vanadia nanoparticles supported on nickel manganese mixed oxides were synthesized by co-precipitation method. The catalytic properties of these materials were investigated for the oxidation of benzyl alcohol using molecular oxygen as oxidant. It was observed that the calcination temperature and the size of particles play an important role in the catalytic process. The catalyst was evaluated for its oxidation property against aliphatic and aromatic alcohols, which was found to display selectivity towards aromatic alcohols. The samples were characterized by employing scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller analysis, thermogravimetric analysis, and X-ray photoelectron spectroscopy.
Catalysis, which is largely a surface phenomenon, is an area of research that has been a widely studied subject by scientists and technologists [1-4]. However, the zeal for finding a better performing catalyst for various processes including CO oxidation , Fischer-Tropsch synthesis , MOFs for biomimetic catalysis , fuel cell reactions , and selective hydrogenolysis of aryl ethers  still is an ongoing process. Among several elements that are being tested and tried for catalysis, vanadium oxide and other compounds containing vanadium have attracted significant attention as catalyst for many oxidation reactions [10-14]. Apart from this, vanadium oxide has also been explored for various other applications including pseudocapacitors  and cathode material  in various conversion reactions of alkanes to alkenes, organic acids, and the synthesis of light olefins by means of oxidative dehydrogenation (ODH) [17-22]. Furthermore, the catalytic oxidation properties of vanadium-based catalysts have also been extensively exploited for several other reactions such as conversion of propane to COx/H2 , propane partial oxidation , oxidation of SO2 , formaldehyde to formic acid , oxidation of α-hydroxy ketones, α-hydroxy esters , aerobic oxidative cleavage of secondary-tertiary glycols , and oxidative dehydrogenation of ethane . In some cases, it has also been used as support material for other catalysts, e.g., Pt nanoparticles, supported by vanadia-decorated carbon nanotubes for methanol electro-oxidation reaction . Notably, vanadium has displayed excellent catalytic activities in all forms, whether it has been employed as a supported active phase or in the form of mixed oxides prepared in combination with other ions; it displayed efficient catalytic properties as an oxidation catalyst.
Recently, mixed metal oxides (MMO) have attracted significant attention as solid catalysts, due to their low cost, easy regeneration, selective action, and excellent acid–base redox properties . Among various MMO, manganese-based MMO have attracted much attention due to their higher catalytic performances . Several catalytic reactions using manganese-oxide-based MMO have been reported. Examples include the catalytic reaction of hydrogen production via autothermal reforming of ethanol , steam reforming of tar from biomass pyrolysis , methane combustion at low temperature , and enhanced glucose electrooxidation  carried out using nickel manganese MMO. Our group has been involved in the synthesis of various MMOs  and evaluated their catalytic performance for several organic transformations . In this study, to exploit the excellent catalytic activity of vanadium oxide, we report the synthesis of heterogeneous catalysts based on vanadium oxide nanoparticles supported on nickel manganese oxide MMO. The as-prepared catalysts were characterized using various spectroscopic and microscopic techniques including transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), and thermogravimetric analysis (TGA), and their catalytic activities were evaluated for the oxidation of various aromatic alcohols.
Preparation of vanadium oxide supported on nickel manganese oxide by deposition method
Ninety-five milliliters of 0.2 M solutions of nickel nitrate and manganese nitrate were mixed in a round-bottomed flask, followed by addition of 10 mL of 0.2 M solution of vanadium chloride. The resulting solution was heated to 80°C under stirring using a mechanical stirrer. A 1 M solution of NaHCO3 was added dropwise until the solution attained a pH 9. The solution was continuously stirred at the same temperature for about 3 h and left on stirring over night at room temperature. The solution was filtered using a Buchner funnel under vacuum and then dried at 70°C overnight. The product obtained was characterized using SEM, TEM, EDAX, XRD, XPS, Brunauer-Emmett-Teller (BET), and TGA. The resulting powder was then calcined at different temperatures and evaluated for its oxidation activity for the oxidation of benzyl alcohol as a model precursor.
In a typical reaction, 300 mg of catalyst was loaded in a glass flask pre-charged with 0.2 mL (2 mmol) benzyl alcohol mixed with 10 mL toluene as a solvent; the mixture was then refluxed at 100°C, and oxygen was bubbled at a flow rate of 20 mL min−1 into the mixture under vigorous stirring. After reaction, the solid catalyst was separated by centrifugation, and the liquid samples were analyzed by gas chromatography to evaluate the conversion of the desired product using an Agilent 7890A GC (Agilent Technologies, Inc., Santa Clara, CA, USA), equipped with a flame ionization detector (FID) and a 19019S-001 HP-PONA column.
SEM and elemental analysis (energy-dispersive X-ray analysis (EDX)) were carried out using a Jeol SEM model JSM 6360A (JEOL Ltd., Akishima-shi, Japan). This was used to determine the morphology of nanoparticles and its elemental composition. TEM was carried out using a Jeol TEM model JEM-1101 (JEOL Ltd., Akishima-shi, Japan), which was used to determine the shape and size of nanoparticles. Powder X-ray diffraction studies were carried out using an Altima IV (Make: Rigaku, Shibuya-ku, Japan) X-ray diffractometer. Fourier transform infrared spectroscopy (FT-IR) spectra were recorded as KBr pellets using a PerkinElmer 1000 FT-IR spectrophotometer (PerkinElmer, Waltham, MA, USA). BET surface area was measured on a NOVA 4200e surface area and pore size analyzer (Quantachrome Instruments, FL, USA). Thermogravimetric analysis was carried out using PerkinElmer Thermogravimetric Analyzer 7 (PerkinElmer, Waltham, MA, USA). XPS was measured on a PHI 5600 Multi-Technique XPS (Physical Electronics, Lake Drive East, Chanhassen, MN, USA) using monochromatized Al Kα at 1486.6 eV. Peak fitting was performed with CASA XPS Version 2.3.14 software.
Results and discussion
Textural and structural properties of vanadium-oxide-doped nickel manganese oxide
Calcination temperature (°C)
Binding energies of transition metal compounds calculated from the maxima in the XPS spectra
BE 1 (2p 1/2 ) (eV)
BE 2 (2p 3/2 ) (eV)
ΔE (BE 1 -BE 2 ) (eV)
From the above results, it can be concluded the oxidation property of the mixed metal oxides used is not related to the redox properties of the transition metals used but could be a surface phenomenon.
Evaluation of catalytic properties
Optimization of percentage of Vanadium oxide nanoparticles and calcination temperature
In order to ascertain the percentage composition of vanadium oxide nanoparticles to be supported on the nickel-manganese-mixed oxide for the best catalytic performance as an oxidation catalyst, a series of catalysts with varying percentages of vanadium oxide nanoparticles were synthesized and evaluated for their catalytic property, monitoring the oxidation of benzyl alcohol to benzaldehyde as a model reaction. The reaction was carried out at 100°C, while passing molecular O2 gas as a source of oxygen. During the study, a trend of steady increase in performance of the synthesized catalyst was observed with the increase in the composition percentage of vanadium oxide, which explains the influence of vanadium oxide nanoparticles on the catalytic performance. The catalyst with 1% and 3% vanadium oxide yielded 65.77% and 74.27% conversion product, respectively, within 75 min, while the catalyst with 5% vanadium oxide nanoparticles yielded 100% conversion product within the same time. In order to understand the effect of presence of vanadium oxide nanoparticles, a similar reaction was carried out in the presence of the catalyst without the vanadium oxide nanoparticles (i.e., NiMnO) which yielded a 52.56% conversion product. This indicated that vanadium oxide acts as a promoter for the selective catalytic oxidation.
Effect of calcination temperature on the catalytic properties
Temperature ( °C)
Optimization of source of oxygen
Effect of different sources of oxygen on the catalytic properties
Catalytic performance on different substrates of benzyl alcohol
We have synthesized vanadia-supported nickel manganese mixed oxide catalyst using facile sol–gel chemistry. Nanovanadia-supported nickel manganese oxide shows high activity and stability for the oxidation of benzyl alcohol using molecular oxygen as a source of oxygen. A synergistic effect between optimum calcination temperatures and the chemical kinetics of the reaction was observed, and it was confirmed that calcination temperature plays an important role forming an active and durable catalyst. It can be believed that this catalyst can be further used for the evaluation of its oxidative property for the synthesis of other important aromatic and aliphatic aldehydes.
This project was supported by King Saud University, Deanship of Scientific Research, College of Science, Research Center.
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