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Research Article
Exploring the Influence of Transition Metal Incorporation on the Performance of Cerium Vanadates in 1-Butene Oxidative Dehydrogenation
Abstract: Various transition metals; Cr, Mn, Fe and Co were substituted in cerium site in CeVO4 by a simple pH controlled precipitation followed by the hydrothermal treatment and investigated for oxidative dehydrogenation of 1-butene (ODH1B) using oxygen as oxidant. Phyisco-chemical methods like Powder X-Ray Diffraction, SEM, TEM and X-Ray photoelectron spectroscopy were employed to understand the structural, morphological and surface features of the catalyst. The formation of CeO2 crystallites on the surface of CeVO4 was evidenced by PXRD and Raman spectroscopy studies. The surface ratio of Ce4+/Ce3+ was calculated from core X-ray photoelectron spectra of pure CeVO4 and with ‘Mn’ substitution. Catalytic activity towards ODH of 1-butene for all the transition metal substituted CeVO4 were carried at optimized reaction conditions in which the ‘Mn’ substituted catalyst gave a better activity. Further activity studies were carried out to optimize the manganese loading and for the optimized catalyst composition 70% selectivity towards butadiene was achieved and the result was compared with Manganese impregnated CeVO4.
Keywords: Vanadates; Cerium; Oxidative Dehydrogenation; 1-Butene; Butadiene
Publication details: Received: 01st April 2019; Accepted: 24th April 2019; Published: 04th May 2019
1. Introduction
1, 3-butadiene (BD) is one of the important platform chemical which is employed in the production of many fine chemicals and commercial end products. The potential of BD to form rubber like polymers was well identified and it is an important building block chemical which is used to synthesize a variety of polymers like SBR (styrene-butadiene rubber), polybutadiene (PB), Styrene butadiene latex, Acrylonitrile-butadiene-styrene (ABS) resins, adiponitrile and nitrile rubber. Among this the SBR finds more usage as these are used for the manufacture of tyres and along with that it is also used in the production of adhesives, sealants, coatings, and other rubber articles such as shoe soles, etc.[1-2] In the early 20th century, BD was synthesized by Lebedev process,[3-4, 5] aldol process and Reppe process.[6] Due to the supply demand factors and operational costs these routes were abandoned. The emergence of fossil fuels fuelled many pathways as it was a remarkable source for many of the platform chemicals and fine chemicals. Due to the invention of shale gas and the ethane only steam cracking process which has lower operating costs and increased selectivity towards ethene, the production of BD by naphtha cracking does not satisfy the demands of the growing BD market. Due to these restrictions on the availability of BD, high BD prices are likely to occur in near future.[7] The dehydrogenation of butane and butene (Eq.(1)) is another pathway for the production of BD. The dehydrogenation process is highly endothermic and requires high temperature for a reasonable conversion of butane which results in the coke formation and low yield of BD. Oxidative dehydrogenation (ODH) overcomes all the drawbacks of dehydrogenation where the thermodynamic limitations can be reduced by oxidizing the hydrogen formed using an oxidant (Eq. (2)) and coke is also removed by oxidizing it to COx.
C4H8→ C4H6 + H2 ΔH° = 110 kJ mol-1 [8] (1)
C4H8 + 1/2 O2→ C4H6 + H2O ΔH° = -132 kJ mol-1 [9] (2)
The exothermic oxidation of hydrogen to water helps in partially covering the heat requirements of the endothermic dehydrogenation reaction. Butenes which are obtained from refining and naphtha cracking units serve as the starting materials for conversion into butadiene through a single-stage process. Oxo-D process of Petro-Tex (1965) and OXD process of Phillips was developed wherein steam was used in the process with steam/butene molar ratio of 12/1. Among the materials investigated for ODH of 1-butene to 1,3-butadiene bismuth molybdates are the widely studied oxide systems[10-12] and a few noble metal based systems[13-15] are also been reported till date in open literature. Bismuth molybdates are extensively studied systems but in pure form it exhibits low performance in ODH reaction. To improve catalytic performance, metals like Co, Ni, Fe, La, V, Ce was incorporated and investigated.[16-21] In all these processes steam or CO2 was employed as diluent to increase the selectivity of BD.
Rare earth vanadates are an important class of inorganic materials and owing to their outstanding optical, catalytic, electrical and magnetic properties they have a wide applications as sensors, catalysts and heat-resistant materials.[22-23] Among these rare earth vanadates, CeVO4 is widely studied as these possess a diverse potential applications such as oxidation catalysts, luminescent materials, gas sensors and electrodes. Vanadium based oxides are known for catalyst using several oxidation reactions.[24] Even though unsupported vanadia is an active catalyst deactivates fast due to which vanadium oxides are generally supported on oxide supports. Ceria shows a promoting effect among various supports like ZrO2, TiO2, Al2O3, SiO2, CeO2, and Nb2O5.[25-27] As a consequence of this much efforts was made in studying the characteristics of vanadia and/or ceria catalysts. During in situ spectroscopic studies of V2O5/CeO2 catalysts it was observed that, there was formation of cerium orthovanadates (CeVO4) upon activation and its formation increases proportionally when vanadia loading increases on the CeO2 support. The product distribution remained similar at certain vanadia coverage for both V2O5/CeO2 and for pure CeVO4. This observation emphasize that there may be similar active site on both catalysts.[28-31]
In the present study, a series of transition metal incorporated cerium vanadates (CeMVO4; M=Cr, Mn, Fe and Co) were synthesized by pH controlled coprecipitation method. Catalytic activity towards ODH of 1-butene for all the prepared catalysts were carried out at optimized reaction conditions in which the ‘Mn’ substituted catalyst gave a better activity. Manganese loading was optimized for the reaction; further the relationship between manganese content and catalytic activity was investigated through detailed characterization studies.
2. Experimental Section
2.1. Catalyst Preparation
CeVO4 was prepared by a pH modified hydrothermal route. Cerium (III) nitrate (Alfa Aesar), Ammonium metavanadate (Merck), Manganese (II) nitrate (Alfa Aesar), Chromium(III) nitrate (Alfa Aesar), Iron(II) nitrate (Alfa Aesar), Cobalt (II) nitrate (Alfa Aesar) were used as metal precursors, Nitric acid (Merck) for stabilization and NaOH (Merck) for precipitation. Ammonium metavanadate was dissolved in 50 mL of warm distilled water under vigorous stirring and to this solution dilute HNO3 was added to reduce the pH to 1.8. After maintaining the pH cerium nitrate was added to this solution. After homogenizing the metal salts, NaOH (1 M) was added drop wise to precipitate cerium and vanadium ions as CeVO4. This solution with precipitate was transferred to teflon lined autoclave and placed in oven for 24 hours which was maintained at 180 °C. After cooling, the precipitate was centrifuged and washed several times to remove excess base. This precipitate was dried in oven for 12 hours after which it was calcined at 600 °C. By this method during homogenizing metal ions other transitional metals like Cr, Mn, Fe and Co were added. CeVO4 prepared with various heteroatoms were prepared and denoted as given in table 1.
2.2. Catalyst characterization
Powder X-ray diffraction (PXRD) data of all the synthesized materials were collected in a PANanalytical X’pert Pro dual goniometer diffractometer. An X’celerator solid state detector with a step size of 0.008° and a time per step of 45.72 s was used. The X-ray radiation source used was Cu-Kα (1.54 Å) with a Ni filter and data collection was carried out using a flat holder in Bragg-Brentango geometry. Nitrogen adsorption-desorption isotherms for the materials were collected from Quantachrome Quadrasorb SI. The Brunauer-Emmett-Teller (BET) model at relative pressure of P/P0 = 0.05 - 0.3 was used to calculate the surface area. An FEI TECNAI F30 electron microscope operating at 300 kV was used for recording high resolution transmission electron microscopy (HRTEM) images of all materials. Samples were powdered and dispersed in isopropanol before depositing onto a holey carbon grid. Thermal analysis was done using a METTLER-TOLEDO TGA/SDTA851e instrument. Raman spectra were recorded using a Horiba JY LabRAMHR800 Raman spectrometer coupled with a microscope in reflectance mode with a 514 nm and 635 nm excitation laser sources and a spectral resolution of 0.3 cm-1. The sample was pelletized into small discs for analysis. XPS of our samples were analyzed in a custom built near-ambient pressure photoelectron spectrometer (NAPPES) (Prevac, Poland). This instrument has a monochromatic Al Kα X-ray source (VG Scienta, MX 650), a dual anode (Al Kα, Mg Kα) source and a Helium UV discharge lamp. The analysis chamber is equipped with a differentially pumped high pressure electron analyzer (VG Scienta, R3000 HP). The analyzer aperture cone is of 0.8 mm and in this setup XPS can be performed up to 1mbar.[32]
2.3. Catalytic Activity Tests
The catalytic activity of all the materials prepared were tested using a fixed bed reactor (FBR) having two furnace zones. An inconel reactor tube with 8 mm internal diameter and 480 mm length was used to pack the catalyst. The temperature on the wall of the reactor and in the catalyst bed was measured using a K-type coaxially centered thermocouple. The catalyst was pelletized and sieved through the mesh size of 1.6-1.7 mm. The catalyst charge was 1 cm3 of sieved materials and was placed in the middle of the reactor using glass wool. On the top and bottom of the catalyst bed the reactor was filled with inert ceramic beads which do not possess any catalytic activity. The catalyst tests were conducted at different temperatures and with various flow rates of oxidant and substrate. The gases flow was controlled using a Brook's make Mass Flow Controller (5890E series) of respective gases. The liquid and gaseous products were separated in a gas-liquid separator where the gaseous products were analyzed by online GC. The gaseous sample was analyzed by Thermofischer 1110 Gas chromatography instrument. In a typical online GC analysis the hydrocarbons were eluted by Restek Alumina plot-Q column followed by detection in FID detector and the permanent gases were eluted by Porapak Q and Molecular Sieves column connected in series followed by detection in TCD. A combined gas chromatograph from dual channel analysis reference to response from calibration mixture gave the concentrations in the reaction mixture.
Conversion is defined as the fraction of reactant transformed and given by the relation:
1-butene conversion (mol %) = 100× (1Bin-1Bout)/1Bin
Selectivity has been determined from the peak area as,[14]
SelectivityBD (%) = 100 × areaBD / (sum of all areas)
It is calculated for each product based on its formation.
Reaction yield or partial conversion for a given product is therefore,
YieldBD= (conversionBD × selectivityBD)/100
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3. Results and Discussions
3.1. Powder XRD Patterns
PXRD patterns of all the catalysts synthesized are shown in Fig. 1. In the PXRD pattern of CeVO4 the peaks of tetragonal phase of CeVO4 (JCPDS. No. 12-0757) were predominant with additional peaks of cubic CeO2 (JCPDS. No.78-0694) as an impure phase. In CeVO4 when the transition elements Cr, Mn, Fe and Co was incorporated in cerium site there was an increase in the intensity of the peaks corresponding to CeO2 (Fig. 1a). In case of 'Co' incorporated catalyst the peaks corresponding to ceria phase were predominant which is mainly due to the blocking of ceria which is agglomerated on the surface of the catalyst. Based on the catalytic activity of CeVO4 with three different molar ratios of 'Mn' was incorporated and the peaks corresponding to CeO2 increased as the loading of the 'Mn' increased (Fig. 1b). In all the catalysts peaks corresponding to polymeric V2O5 were not found.
S.No | Catalyst (molar ratio) | Code | Surface area (m2/g) |
1 | CeVO4 (1:1) | CV | 6.7 |
2 | CeCrVO4 (0.8:0.2:1) | CCrV | 5.9 |
3 | CeMnVO4 (0.8:0.2:1) | CMV1 | 5.7 |
4 | CeMnVO4 (0.88:0.12:1) | CMV2 | 6.2 |
5 | CeMnVO4(0.94:0.06:1) | CMV3 | 6.3 |
6 | CeFeVO4 (0.8:0.2:1) | CFV | 4.8 |
7 | CeCoVO4(0.8:0.2:1) | CCV | 4.5 |
3.2. Surface Area Analysis
Surface area of all the catalysts were calculated by using Brunauer-Emmett-Teller (BET) equation and the results are shown in Table. 1. The surface area of all the samples were low which are characteristic for these type of materials.[33] The low surface area of these samples were due to the crystal growth and agglomeration of particles during calcination at 600 °C.
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3.3. Transmission Electron Microscopy (TEM)
TEM images shown in Fig. 2 depict the morphology of the crystallites of CMV2 which were mostly cylindrical and spherical structures both measuring 20-50 nm. In HRTEM it was observed that there was a homogeneous distribution of CeO2 over the CeVO4 matrix and separate clusters of CeO2 were not perceived. In addition to that the lattice fringes of MnO2 or polymeric V2O5 species were not observed. The lattice fringes of both CeVO4 and CeO2 were detected and these d-spacing matched well with the value obtained from PXRD pattern.
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3.4. Raman Spectroscopy
Raman spectra of all the catalysts are shown in Fig. 3. In the case of CeVO4 bands at 223, 258, 368, 460, 783, 796 and 858 cm-1 were observed. The Raman band at 858 cm-1 corresponds to symmetric stretching of vanadate species (A1g), peaks at 796 and 783 cm-1 corresponds to the antisymmetric stretching of vanadates (Eg and B2g) and 460 and 368 cm-1 to deformations of B2g and B1g.[34-36] The peak corresponding to vibrational mode of the cubic fluorite (F2g) CeO2 lattice[37] at 460 cm-1 increases as transition metals were incorporated in the CeVO4 lattice. In addition, the incorporation of transition metals in 'Ce' site decreased the intensity of peaks corresponding to CeVO4. Raman band corresponding to VOx species from polymeric V2O5 at 995 cm-1 were not observed on the spectra of any of the samples taken for the study. In case of manganese incorporated CeVO4 at higher loadings of manganese the bands corresponding to Mn-O stretching vibration of MnO2 was observed at 578 cm-1.[38]
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3.5. X-ray photoelectron Spectroscopy (XPS)
To explore the electronic and surface properties of CV and CMV2, both the catalysts were subjected to XPS analysis. O 1s spectra of CV and CMV2 are shown in Fig. 4 in which a prominent peak at 529.1 eV was observed which corresponds to the lattice oxygen of the CeVO4 and CeO2.[36-39, 40] In case of CMV2 the O 1s peak was slightly broad due to the surface hydroxyl impurities at 530.1 eV. V 2p spectra are shown in Fig. 5 in which two peaks corresponding to V 2p3/2 (516.4 eV) and V 2p1/2(524.1 eV) were observed.[39-41]
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To understand the changes in surface Ce4+/Ce3+ ratio in CV after substituting 'Mn' the Ce 3d core level spectra was taken (Fig. 6). The curve fitting were carried out by using CASA software and Shirley background subtraction was employed for background removal. In Ce 3d core level the peaks resulting from Ce4+ at 900.8 eV (u), 907.2 eV (u″) and 916.7 eV (u′′′), 882.4 eV (ν), 888.8eV (ν″) and 898.1 eV (ν′′′) and four peaks corresponding to Ce3+ at 903.7 eV (u′), 884.7 eV (ν′), 899.2 eV (uo) and 880.1 eV (νo)[37,40] were observed in both CV and CMV2.
Catalyst | Peak areaa(%) | |
Ce3+ | Ce4+ | |
CV | 43 | 57 |
CMV2 | 30 | 70 |
a - calculated from area under the curve after curve fitting |
Due to the activation in CeVO4 surface the concentration of Ce4+ was slightly higher than expected (Table. 2). After 'Mn' substitution, as observed in PXRD in XPS also it was evident that the ratio of Ce4+ also increased. This increase in ratio of Ce4+ helps in increasing the selectivity of BD which will be discussed in catalytic activity discussion. In CMV2 catalyst the spectra of Mn 2p was recorded (Fig. 7) in which low intense and broad peaks corresponding to 2p3/2 (Mn3+-641.3 and Mn4+-642.6 eV) and 2p1/2(653 eV) were observed.[42-43]
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4. Catalytic Activity
4.1. Effect of Transition Metal Substitution in CeVO4
To understand the role of transition metals substitution in CeVO4 for ODH of 1-butene to 1, 3-butadiene, 'Cr, Mn, Fe, Co' was substituted in 'Ce' site (Fig. 7). All the catalysts were tested with the reactant flow 6000 h-1 (Ar:1-butene:O2 - 8:1:1), at 400 °C and atmospheric pressure. With CeVO4 37% conversion of 1-butene and 41% selectivity towards 1,3-butadiene was obtained. Among the first row transition metals Cr, Mn, Fe, Co are known to be catalytically active for oxidative dehydrogenation reactions. In order to investigate their role in enhancing the activity of CeVO4 towards ODH of 1-butene to 1,3-butadiene 0.2 molar ratio of these metals were substituted in the 'Ce' site. Among the four transition metals substituted CeVO4, Manganese substituted catalyst showed an increased conversion and selectivity when compared to other metal substituted catalyst. In case of CMV1 1-butene conversion of 54% and 44% selectivity towards 1,3-butadiene was obtained. FCV which contains 'Fe' substitution showed a similar selectivity as CMV1 but the conversion of 1-butene was lower than that of CV. Based on the catalytic activity, it was found that 'Mn' substituted catalyst is better when compared to other three catalyst and further studies were made to optimize the reaction parameters and manganese loading.
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Fig. 8. Effect of manganese loading on ODH of 1-butene (Reaction conditions: Total reactant flow 6000 h-1 (Ar:1-butene:O2 - 8:1:1), at 350-450 °C and atmospheric pressure)
4.2. Effect of Manganese Loading
To optimize the amount of manganese loading in CeVO4 three molar ratios (0.2,0.12,0.06-CMV1, CMV2, CMV3 respectively) of manganese substituted CeVO4 was prepared and investigated for ODH of 1-butene (Fig. 8). All the catalysts were tested with the reactant flow 6000 h-1 (Ar:1-butene:O2 - 8:1:1), temperature range between 350-450 °C and atmospheric pressure. As the loading of manganese increased the conversion of 1-butene increased (at 400 °C) which is due to the increase of active redox sites of 'Mn' for reaction. Initially the selectivity towards 1,3-butadiene increased when the manganese loading was increased from 0.06 to 0.12 molar ratio and when the loading was further increased the selectivity towards 1,3-butadiene drastically decreased. This trend was also observed in other two temperatures (350 and 450 °C). At 400 °C with CMV2 as the catalyst a nominal conversion of 1-butene (50.5%) and 70% selectivity towards 1,3-butadiene was obtained. The product distribution at all temperatures for CMV2 is shown in Fig. 9, in which as the temperature increases the selectivity towards BD increases proportionally as conversion increases. The selectivity for 1,3-butadiene decreases with increase in temperature above 400 °C which is due to the total oxidation of 1-butene to CO2 at higher temperatures which was evident from the increase in the selectivity of CO2. Based on these studies it was observed that the optimized condition for increased activity for ODH of 1-butene using CMV as catalyst is 0.12 molar ratio loading of Mn and temperature 400 °C with 6000 h-1 total flow of reactants.
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4.3. Effect of Method of Preparation
In order to emphasize the effect of method of preparation of CMV2, Mn impregnated CeVO4 (Mn-imp CeVO4) was prepared with the same loading of Mn that was substituted in CeVO4. Both the catalysts were tested at same reaction conditions, the reactant flow 6000 h-1 (Ar:1-butene:O2 - 8:1:1), at 400 °C and at atmospheric pressure. When CMV2 catalyst was employed the selectivity towards BD was higher than the combustion products like CO2 and H2 (Fig. 10). As the ‘Mn’ impregnated CeVO4 was utilized the selectivity towards total combustion products was higher than CMV2 catalyst. As shown in Fig. 10, it is evident that the hydrogen selectivity from 1% in CMV2 increases to 25% in case of Mn-imp CeVO4. This difference in activity is due to the formation of more CeO2 crystallites on the surface of the CMV2 catalyst when compared to Mn-impregnated CeVO4. The synergistic interaction of MnOx and CeO2 enables the formation of a —Mn—O—Ce— bond which greatly reduce the oxygen vacancies formed on the surface of the catalyst.[44] When the oxygen vacancies are reduced the over oxidation of hydrocarbons are minimized which in turn increases the selectivity towards desired dehydrogenated products. This nature of CMV2 helps in achieving an increased selectivity towards 1,3-butadiene with a nominal conversion of 1-butene.
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4.4. Spent Catalyst - TGA Analysis
To investigate the amount of coke deposited on the spent catalyst the catalyst after reaction was subjected to TGA analysis from room temperature to 800 °C in presence of air (Fig. 11). FCV showed a highest weight loss of 2.5% when compared to all other catalysts that was studied. CMV catalysts showed lower weight loss when compared to all the other transition metal substituted CeVO4 which supports the activity profile where the selectivity towards CO2 was low. The CMV catalysts showed a weight gain which is likely due to the oxidation of Ce3+ which also suggests that there was very less coke deposition on these catalysts which was not even detectable. This supports the superior activity performance of the CMV4 catalyst when compared to other transition metal containing CeVO4. Spent catalyst PXRD was also taken in which the CeVO4 phase was intact with slight increase in the intensity of peaks corresponding to CeO2.
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5. Conclusions
CeVO4 with various transition metals substituted in ‘Ce’ site were prepared by simple pH controlled precipitation followed by hydrothermal treatment. From PXRD it was evident that due to substitution, CeO2 was formed on the surface of CeVO4 which was very less in pure CeVO4. Raman bands and transmission electron microscopy also support the information obtained from the PXRD pattern. From X-ray photoelectron spectroscopy the surface ratio of Ce4+/Ce3+ was calculated for CeVO4 and ‘Mn’ substituted CeVO4 in which the ratio of Ce4+ is higher after incorporation of manganese. The CeVO4 with ‘Mn’ showed a superior catalytic activity for ODH of 1-butene to 1,3-butadiene when compared to other transition metal substituted CeVO4. From the optimization studies it was found that catalyst with 0.12 molar ratio of manganese gives a better selectivity (70 %) towards 1,3-butadiene at 400 °C. In this study a better activity was obtained compared to other catalysts reported for ODH of 1-butene and the improved selectivity in this process is achieved without usage of steam.
Acknowledgements
Conflicts of Interest
References
-
White W.C. Butadiene Production Process Overview. Chem. Biol. Interact., 2007, 166, 10-14. [CrossRef]
-
Whitby G. S. Synthetic Rubber, John Wiley & Sons, New York, 1954, Chapter 2. [CrossRef]
-
Makshina E. V.; Dusselier M.; Janssens W.; Degreve J.; Jacobsa P. A.; Sels B.F. Review of Old Chemistry and New Catalytic Advances in the on-Purpose Synthesis of Butadiene. Chem. Soc. Rev., 2014, 43, 7917-7953. [CrossRef]
-
Dumez F. J.; Froment G. F. Dehydrogenation of 1-Butene into Butadiene. Kinetics, Catalyst Coking, and Reactor Design. Ind. Eng. Chem. Proc. Dd., 1976, 15, 291−301. [CrossRef]
-
Jung J. C.; Lee H.; Kim H.; Chung Y. M.; Kim T. J.; Lee S. J.; Oh S. H.; Kim Y. S.; Song A. Synergistic Effect of α-Bi2Mo3O12 and γ-Bi2MoO6 Catalysts in the Oxidative Dehydrogenation of C4 Raffinate-3 to 1,3-Butadiene. J. Mol. Catal. A, 2007, 271, 261-265. [CrossRef]
-
Soares A. P. V.; Dimitrov L. D.; de Oliveira M. C. R. A.; Hilaire L.; Portela M. F.; Grasselli R. K. Synergy Effects Between β and γ Phases of Bismuth Molybdates in the Selective Catalytic Oxidation of 1-Butene. Appl. Catal. A, 2003, 253, 191-200. [CrossRef]
-
Batist Ph. A.; van de Moesdijk C. G. M.; Matsuura I.; Schuit G. C. A. The Catalytic Oxidation of 1-Butene over Bismuth Molybdates: Promoters for the Bi2O3·3MoO3 Catalyst. J. Catal., 1971, 20, 40-57. [CrossRef]
-
Furukawa S.; Endo M.; Komatsu T. Bifunctional Catalytic System Effective for Oxidative Dehydrogenation of 1-Butene and n-Butane Using Pd-Based Intermetallic Compounds. ACS Catal., 2014, 4, 3533-3542. [CrossRef]
-
She Y.; Han J.; Ma Y. H. Palladium Membrane Reactor for the Dehydrogenation of Ethylbenzene to Styrene. Catal. Today, 2001, 67, 43-53. [CrossRef]
-
Fujimoto K.; Kunugi T. Oxidative Dehydrogenation of Ethylbenzene Over Modified Palladium Catalysts. Ind. Eng. Chem. Prod. Rd., 1981, 20, 319-323. [CrossRef]
-
Jung J. C.; Lee H.; Seo J. G.; Park S.; Chung Y. M; Kim T. J.; Lee S. J.; Oh S. H.; Kim Y. S.; Song I. K. Oxidative Dehydrogenation of n-Butene to 1,3-Butadiene over Multicomponent Bismuth Molybdate (MII9Fe3Bi1Mo12O51) Catalysts: Effect of Divalent Metal (MII). Catal. Today, 2009, 141, 325-329. [CrossRef]
-
Park J. H.; Noh H.; Park J. W.; Row K.; Jung K. D.; Shin C. H. Effects of Iron Content on Bismuth Molybdate for the Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene. Appl. Catal. A, 2012, 431- 432, 137-143. [CrossRef]
-
Park J. H.; Row K.; Shin C. H. Oxidative Dehydrogenation of 1-Butene to 1,3-Butadiene over BiFe0.65NixMo Oxide Catalysts: Effect of Nickel Content. Catal. Comm., 2013, 31, 76-80. [CrossRef]
-
Wan C.; Cheng D. G.; Chen F.; Zhan X. Characterization and Kinetic Study of BiMoLax Oxide Catalysts for Oxidative Dehydrogenation of 1-Butene to 1,3-Butadiene. Chem. Eng. Sci., 2015, 135, 553-558. [CrossRef]
-
Park J. H.; Shin C. H. Influence of the Catalyst Composition in the Oxidative Dehydrogenation of 1-Butene over BiVxMo1−x Oxide Catalysts. Appl. Catal. A, 2015, 495, 1-7. [CrossRef]
-
Wan C.; Cheng D. G.; Chen F.; Zhan X. The Role of Active Phase in Ce Modified BiMo Catalysts for Oxidative Dehydrogenation of 1-Butene. Catal. Today, 2016, 264, 180-184. [CrossRef]
-
Duan X.; Lieber C M. General Synthesis of Compound Semiconductor Nanowires. Adv. Mater., 2000, 12, 298-302. [CrossRef]
-
Weckhuysen B. M.; Keller D. E. Chemistry, Spectroscopy and the Role of Supported Vanadium Oxides in Heterogeneous Catalysis. Catal. Today, 2003, 78, 25-46. [CrossRef]
-
Khodakov A.; Olthof B.; Bell A. T. Structure and Catalytic Properties of Supported Vanadium Oxides: Support Effects on Oxidative Dehydrogenation Reactions. J. Catal., 1999, 181, 205-216. [CrossRef]
-
Banares M. A.; Martinez-Huerta M. V.; Gao X.; Fierro J. L. G.; Wachs I. E. Dynamic Behavior of Supported Vanadia Catalysts in the Selective Oxidation of Ethane: In situ Raman, UV–Vis DRS and Reactivity Studies. Catal. Today, 2000, 61, 295-301. [CrossRef]
-
Wachs I. E. Recent Conceptual Advances in the Catalysis Science of Mixed Metal Oxide Catalytic Materials. Catal. Today, 2005, 100, 79-94. [CrossRef]
-
Daniell W.; Ponchel A.; Kuba S.; Anderle F.; Weingand T.; Gregory D. H.; Knozinger H. Characterization and Catalytic Behavior of VOx - CeO2 Catalysts for the Oxidative Dehydrogenation of Propane. Top. Catal., 2002, 20, 65-74. [CrossRef]
-
Reddy B. M.; Khan A.; Yamada Y.; Kobayashi T.; Loridant S.; Volta J. C. Structural Characterization of CeO2−TiO2 and V2O5/CeO2−TiO2 Catalysts by Raman and XPS Techniques. J. Phys. Chem. B, 2003, 107, 5162-5167. [CrossRef]
-
Martinez-Huerta M. V.; Coronado J. M.; Fernandez-Garcia M.; Iglesias-Juez A.; Deo G.; Fierro J. L. G.; Banares M. A. Nature of the Vanadia–Ceria Interface in V5+/CeO2 Catalysts and its Relevance for the Solid-State Reaction Toward CeVO4 and Catalytic Properties. J.Catal., 2004, 225, 240-248. [CrossRef]
-
Da Silva J. L. F.; Ganduglia-Pirovano M. V.; Sauer J. Hybrid Functionals Applied to Rare-Earth Oxides: The Example of Ceria. Phys. Rev. B, 2007, 76, 125117. [CrossRef]
-
Roy K.; Vinod C. P.; Gopinath C. S. Design and Performance Aspects of a Custom-Built Ambient Pressure Photoelectron Spectrometer toward Bridging the Pressure Gap: Oxidation of Cu, Ag, and Au Surfaces at 1 mbar O-2 Pressure. J. Phys. Chem. C, 2013, 117, 4717-4726. [CrossRef]
-
Gillot S.; Dacquin J. P.; Dujardin C.; Granger P. High Intrinsic Catalytic Activity of CeVO4-Based Catalysts for Ammonia-SCR: Influence of pH During Hydrothermal Synthesis. Top Catal., 2016, 59, 987-995. [CrossRef]
-
Luo F.; Jia C. J.; Liu R.; Sun L. D.; Yan C. H. Nanorods-Assembled CeVO4 Hollow Spheres as Active Catalyst for Oxidative Dehydrogenation of Propane. Mater. Res. Bull., 2013, 48, 1122-1127. [CrossRef]
-
Santos C. C.; Silva E. N.; Ayala A. P.; Guedes T.; Pizani P. S.; Loong C. K.; Boatner L. A. J. Raman Investigations of Rare Earth Orthovanadates. Appl. Phys., 2007, 101, 053511. [CrossRef]
-
Hirata T.; Watanabe A. A Comparison Between the Raman Spectra of Ce1−xCaxVO4−0.5x (0≤x≤0.41) and Ce1−xBixVO4(0≤x≤0.68). J. of Solid State Chem., 2001, 158, 264-267. [CrossRef]
-
Venugopal A. K.; Venugopalan A. T.; Kaliyappan P.; Raja T. Oxidative Dehydrogenation of Ethyl Benzene to Styrene over Hydrotalcite Derived Cerium Containing Mixed Metal Oxides. Green Chem., 2013, 15, 3259-3267. [CrossRef]
-
Lee H.; Kang J.; Cho M. S.; Choi J. B.; Lee Y. MnO2/Graphene Composite Electrodes for Super Capacitors: the Effect of Graphene Intercalation on Capacitance. J. Mater. Chem., 2011, 21, 18215-18219. [CrossRef]
-
Hou J.; Huang H.; Han Z.; Pan H. The Role of Oxygen Adsorption and Gas Sensing Mechanism for Cerium Vanadate (CeVO4) Nanorods. RSC Adv., 2016, 6, 14552-14558. [CrossRef]
-
Ju P.; Yu Y.; Wang M.; Zhao Y.; Zhang D.; Sun C.; Han X. Synthesis of EDTA-Assisted CeVO4 Nanorods as Robust Peroxidase Mimics towards Colorimetric Detection of H2O2. J. Mater. Chem. B, 2016, 4, 6316-6325. [CrossRef]
-
Pfau A.; Schierbaum K. D. The Electronic Structure of Stoichiometric and Reduced CeO2 Surfaces: an XPS, UPS and HREELS Study. Surf. Sci., 1994, 321, 71-80. [CrossRef]
-
Choudhary T. V.; Banerjee S.; Choudhary V. R. Catalysts for Combustion of Methane and Lower Alkanes. Appl. Catal. A, 2002, 234, 1-23. [CrossRef]
-
Yoon J.S.; Lim Y.S.; Choi B.H.; Hwang H.J. Catalytic Activity of Perovskite-Type Doped La0. 08Sr0. 92Ti1− xMxO3− δ (M= Mn, Fe, and Co) Oxides for Methane Oxidation. Int. J. Hydrogen Energy, 2014, 39, 7955-7962. [CrossRef]
-
Zhang P.; Lu H.; Zhou Y.; Zhang L.; Wu Z.; Yang S.; Shi H.; Zhu Q.; Chen Y.; Dai S. Mesoporous MnCeOx Solid Solutions for Low Temperature and Selective Oxidation of Hydrocarbons. Nature Comm., Article. No. 8446, 2015. [CrossRef]
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