Optimizing Reflux Synthesis Method of Mo-V-Te-Nb mixed oxide Catalysts for Light Alkane Selective Oxidation

[EN] The investigation here presented studies the effect of the synthesis temperature (from 80 to 110 degrees C) and the time (from 1 to 4 days) employed to precipitate catalyst precursors by reflux method, on the physic-chemical and the catalytic properties of the resulting Mo-V-Te-Nb mixed oxide catalysts for both propane partial oxidation into acrylic acid and ethane oxidative dehydrogenation (ODH) to ethylene. The insight obtained has allowed an important optimization of the not commonly used reflux method to prepare Mo-V-Te-Nb oxide materials with competitive catalytic performance. The yields achieved overcome those from optimized catalysts prepared by conventional hydrothermal method, and approach those reached with catalysts prepared using the "slurry method". The optimum rise for the synthesis temperature is found as a key factor for the reflux method. It allows access to an increased vanadium content into the reflux precipitate, which favors the formation of a pseudo-amorphous Mo-V-Te-Nb oxometallate. This precipitate behaves as a precursor for the crystallization, during the solid-state activation step at high-temperature (600 degrees C/N-2), of the structure type (TeO)(2)M20O56 (M = Mo, V, Nb), key for the selective conversion of propane or ethane. On the other hand, for the optimum temperature of synthesis, i.e. 110 degrees C, higher synthesis time of the precursor leads to smaller crystal sizes in the final catalyst (higher specific surface areas) and lowers the average oxidation state of vanadium from V+5 to V+4, which significantly enhances the catalytic behavior.Authors gratefully acknowledge the funds from DGICYT (Spain) by the project RTI2018-099668-B-C21, as well as the funds from Comunidad de Madrid by the project 2017-T1/IND-6025 within the program "Atraccion y Retencion de Talento Investigador" of the V PRICIT.Massó Ramírez, A.; Ivars-Barceló, F.; López Nieto, JM. (2020). Optimizing Reflux Synthesis Method of Mo-V-Te-Nb mixed oxide Catalysts for Light Alkane Selective Oxidation. Catalysis Today. 356:322-329. https://doi.org/10.1016/j.cattod.2019.10.030S322329356Grasselli, R. K., Burrington, J. D., Buttrey, D. J., DeSanto Jr., P., Lugmair, C. G., Volpe Jr., A. F., & Weingand, T. (2003). Topics in Catalysis, 23(1/4), 5-22. doi:10.1023/a:1024859917786Chieregato, A., López Nieto, J. M., & Cavani, F. (2015). Mixed-oxide catalysts with vanadium as the key element for gas-phase reactions. Coordination Chemistry Reviews, 301-302, 3-23. doi:10.1016/j.ccr.2014.12.003Védrine, J. C., & Fechete, I. (2016). Heterogeneous partial oxidation catalysis on metal oxides. Comptes Rendus Chimie, 19(10), 1203-1225. doi:10.1016/j.crci.2015.09.021Sprung, C., Yablonsky, G., Schlögl, R., & Trunschke, A. (2018). Constructing A Rational Kinetic Model of the Selective Propane Oxidation Over A Mixed Metal Oxide Catalyst. Catalysts, 8(8), 330. doi:10.3390/catal8080330Grasselli, R. K. (2014). Site isolation and phase cooperation: Two important concepts in selective oxidation catalysis: A retrospective. Catalysis Today, 238, 10-27. doi:10.1016/j.cattod.2014.05.036López Nieto, J. M., Solsona, B., Concepción, P., Ivars, F., Dejoz, A., & Vázquez, M. I. (2010). Reaction products and pathways in the selective oxidation of C2–C4 alkanes on MoVTeNb mixed oxide catalysts. Catalysis Today, 157(1-4), 291-296. doi:10.1016/j.cattod.2010.01.046Ushikubo, T., Oshima, K., Kayou, A., & Hatano, M. (1997). Ammoxidation of propane over Mo-V-Nb-Te mixed oxide catalysts. Spillover and Migration of Surface Species on Catalysts, Proceedings of the 4th International Conference on Spillover, 473-480. doi:10.1016/s0167-2991(97)80871-3Tsuji, H., & Koyasu, Y. (2002). Synthesis of MoVNbTe(Sb)Ox Composite Oxide Catalysts via Reduction of Polyoxometalates in an Aqueous Medium. Journal of the American Chemical Society, 124(20), 5608-5609. doi:10.1021/ja0122344BOTELLA, P. (2004). Selective oxidative dehydrogenation of ethane on MoVTeNbO mixed metal oxide catalysts. Journal of Catalysis, 225(2), 428-438. doi:10.1016/j.jcat.2004.04.024J.M. López Nieto, P. Botella, M.I. Vázquez, A. Dejoz, Method for the oxidative dehydrogenation of ethane, US Patent 7,319,179 B2 (2008). J.M. López Nieto, P. Botella, M.I. Vázquez, A. Dejoz, Method for the oxidative dehydrogenation of ethane, EP 1,479,438 A1 (2004), assigned to CSIC and UPV.Dubois, J.-L. (2005). Selective oxidation of hydrocarbons and the global warming problem. Catalysis Today, 99(1-2), 5-14. doi:10.1016/j.cattod.2004.09.019Gaffney, A. M., & Mason, O. M. (2017). Ethylene production via Oxidative Dehydrogenation of Ethane using M1 catalyst. Catalysis Today, 285, 159-165. doi:10.1016/j.cattod.2017.01.020Botella, P., García-González, E., López Nieto, J. M., & González-Calbet, J. M. (2005). MoVTeNbO multifunctional catalysts: Correlation between constituent crystalline phases and catalytic performance. Solid State Sciences, 7(5), 507-519. doi:10.1016/j.solidstatesciences.2005.01.012CELAYASANFIZ, A., HANSEN, T., SAKTHIVEL, A., TRUNSCHKE, A., SCHLOGL, R., KNOESTER, A., … HAMID, S. (2008). How important is the (001) plane of M1 for selective oxidation of propane to acrylic acid? Journal of Catalysis, 258(1), 35-43. doi:10.1016/j.jcat.2008.05.028Nguyen, T. T., Deniau, B., Baca, M., & Millet, J.-M. M. (2016). Influence of Nb Content on the Structure, Cationic and Valence Distribution and Catalytic Properties of MoVTe(Sb)NbO M1 Phase Used as Catalysts for the Oxidation of Light Alkanes. Topics in Catalysis, 59(17-18), 1496-1505. doi:10.1007/s11244-016-0667-yBotella, P., López Nieto, J. M., Solsona, B., Mifsud, A., & Márquez, F. (2002). The Preparation, Characterization, and Catalytic Behavior of MoVTeNbO Catalysts Prepared by Hydrothermal Synthesis. Journal of Catalysis, 209(2), 445-455. doi:10.1006/jcat.2002.3648Vitry, D. (2003). Mo-V-Te-(Nb)-O mixed metal oxides prepared by hydrothermal synthesis for catalytic selective oxidations of propane and propene to acrylic acid. Applied Catalysis A: General, 251(2), 411-424. doi:10.1016/s0926-860x(03)00381-8Celaya Sanfiz, A., Hansen, T. W., Girgsdies, F., Timpe, O., Rödel, E., Ressler, T., … Schlögl, R. (2008). Preparation of Phase-Pure M1 MoVTeNb Oxide Catalysts by Hydrothermal Synthesis—Influence of Reaction Parameters on Structure and Morphology. Topics in Catalysis, 50(1-4), 19-32. doi:10.1007/s11244-008-9106-zBeato, P., Blume, A., Girgsdies, F., Jentoft, R. E., Schlögl, R., Timpe, O., … Mohd Salim, L. (2006). Analysis of structural transformations during the synthesis of a MoVTeNb mixed oxide catalyst. Applied Catalysis A: General, 307(1), 137-147. doi:10.1016/j.apcata.2006.03.014HIBST, H., ROSOWSKI, F., & COX, G. (2006). New Cs-containing Mo–V4+ based oxides with the structure of the M1 phase—Base for new catalysts for the direct alkane activation. Catalysis Today, 117(1-3), 234-241. doi:10.1016/j.cattod.2006.05.045Sanfiz, A. C., Hansen, T. W., Teschner, D., Schnörch, P., Girgsdies, F., Trunschke, A., … Hamid, S. B. A. (2010). Dynamics of the MoVTeNb Oxide M1 Phase in Propane Oxidation. The Journal of Physical Chemistry C, 114(4), 1912-1921. doi:10.1021/jp909352uKardash, T. Y., Lazareva, E. V., Svintsitskiy, D. A., Ishchenko, A. V., Bondareva, V. M., & Neder, R. B. (2018). The evolution of the M1 local structure during preparation of VMoNbTeO catalysts for ethane oxidative dehydrogenation to ethylene. RSC Advances, 8(63), 35903-35916. doi:10.1039/c8ra06424eConcepción, P., Hernández, S., & Nieto, J. M. L. (2011). On the nature of active sites in MoVTeO and MoVTeNbO catalysts: The influence of catalyst activation temperature. Applied Catalysis A: General, 391(1-2), 92-101. doi:10.1016/j.apcata.2010.05.011Baca, M., & Millet, J.-M. M. (2005). Bulk oxidation state of the different cationic elements in the MoVTe(Sb)NbO catalysts for oxidation or ammoxidation of propane. Applied Catalysis A: General, 279(1-2), 67-77. doi:10.1016/j.apcata.2004.10.014Lwin, S., Diao, W., Baroi, C., Gaffney, A., & Fushimi, R. (2017). Characterization of MoVTeNbOx Catalysts during Oxidation Reactions Using In Situ/Operando Techniques: A Review. Catalysts, 7(12), 109. doi:10.3390/catal7040109Ramli, I., Botella, P., Ivars, F., Pei Meng, W., Zawawi, S. M. M., Ahangar, H. A., … Nieto, J. M. L. (2011). Reflux method as a novel route for the synthesis of MoVTeNbOx catalysts for selective oxidation of propane to acrylic acid. Journal of Molecular Catalysis A: Chemical, 342-343, 50-57. doi:10.1016/j.molcata.2011.04.009BOTELLA, P., DEJOZ, A., LOPEZNIETO, J., CONCEPCION, P., & VAZQUEZ, M. (2006). Selective oxidative dehydrogenation of ethane over MoVSbO mixed oxide catalysts. Applied Catalysis A: General, 298, 16-23. doi:10.1016/j.apcata.2005.09.018Leclaire, A., Borel, M. M., Chardon, J., & Raveau, B. (1995). A mixed valent Keggin polyoxometallate involving molybdenum and tungsten. Materials Research Bulletin, 30(9), 1075-1080. doi:10.1016/0025-5408(95)00103-4Corella-Ochoa, M. N., Miras, H. N., Kidd, A., Long, D.-L., & Cronin, L. (2011). Assembly of a family of mixed metal {Mo : V} polyoxometalates templated by TeO32−: {Mo12V12Te3}, {Mo12V12Te2} and {Mo17V8Te}. Chemical Communications, 47(31), 8799. doi:10.1039/c1cc12782aBotella, P., López Nieto, J. M., & Solsona, B. (2002). Catalysis Letters, 78(1/4), 383-387. doi:10.1023/a:1014973005107Mestl, G. (2002). In situ Raman spectroscopy for the characterization of MoVW mixed oxide catalysts. Journal of Raman Spectroscopy, 33(5), 333-347. doi:10.1002/jrs.843Dieterle, M., & Mestl, G. (2002). Raman spectroscopy of molybdenum oxides. Physical Chemistry Chemical Physics, 4(5), 822-826. doi:10.1039/b107046kKnoezinger, H., & Jeziorowski, H. (1978). Raman spectra of molybdenum oxide supported on the surface of aluminas. The Journal of Physical Chemistry, 82(18), 2002-2005. doi:10.1021/j100507a011SOLSONA, B., VAZQUEZ, M., IVARS, F., DEJOZ, A., CONCEPCION, P., & LOPEZNIETO, J. (2007). Selective oxidation of propane and ethane on diluted Mo–V–Nb–Te mixed-oxide catalysts. Journal of Catalysis, 252(2), 271-280. doi:10.1016/j.jcat.2007.09.019Nguyen, T. T., Burel, L., Nguyen, D. L., Pham-Huu, C., & Millet, J. M. M. (2012). Catalytic performance of MoVTeNbO catalyst supported on SiC foam in oxidative dehydrogenation of ethane and ammoxidation of propane. Applied Catalysis A: General, 433-434, 41-48. doi:10.1016/j.apcata.2012.04.03

Complete arsenic removal from water using biocatalytic systems based on anaerobic films grown on carbon fibers

[EN] Arsenic is a hazardous metalloid with potentially negative impacts on both the environment and human health. Current methods of arsenic remediation are expensive and can cause secondary contamination. In this paper we explore the potential of using bioelectrochemical systems (a group of environmentally friendly bio-based technologies with great potential for bioremediation and waste valorisation) for arsenic removal. Previous studies have reported that the spontaneous oxidation of As(III) to As(V) was completely realized in bioelectrochemical systems, however, any of the them succeeded in removing the total arsenic concentration. This study demonstrates that not only it is possible to oxidize As(III) to As(V), but also the total elimination of arsenic can be achieved as the result of intracellular accumulation.SIThis research was possible thanks to the financial support by "Consejeria de Educacion de la Junta de Castilla y Leon" (ref: LE320P18), a project co-financed by FEDER funds. R. M. Alonso thanks the University of Leon for his predoctoral contract. F. Ivars-Barcelo acknowledges the& Spanish "Agencia Estatal de Investigacion" for the Ramon y Cajal excellence grant (Ref.: RYC2020-029470-I/AEI/10.13039/501100011033)

Relationship between bulk phase, near surface and outermost atomic layer of VPO catalysts and their catalytic performance in the oxidative dehydrogenation of ethane

A set of vanadium phosphorous oxide (VPO) catalysts, mainly consisting of (VO)₂P₂O₇, VO(PO₃)₂ or VOPO₄∙2H₂O bulk crystalline phases, has been investigated for the oxidative dehydrogenation (ODH) of ethane to ethylene, a key potential reaction for a sustainable industrial and socioeconomic development. The catalytic performance on these VPO catalysts has been explained on the basis of the main crystalline phases and the corresponding suface features found by XPS and LEISS at 400 ˚C, i.e. within the temperature range used for ODH reaction. The catalysts based on (VO)₂P₂O₇ phase presented the highest catalytic activity and productivity to ethylene. Nevertheless, the catalysts consisting of VO(PO₃)₂ structure showed higher selectivity to ethylene, reaching 90% selectivity at ca. 10% ethane conversion. To the best of our knowledge, this is the highest selectivity reported on a vanadium phosphorous oxide at similar conversions for the ethane ODH. In general, catalysts consisting of crystalline phases with vanadium present as V⁴⁺, i.e. (VO)₂P₂O₇ and VO(PO₃)₂, were found to be significantly more selective to ethylene than those containing V⁵⁺ phases. The surface analysis by XPS showed an inverse correlation between the mean oxidation state of vanadium near surface and the selectivity to ethylene. The lower averaged oxidation states of vanadium appear to be favoured by the presence of V³⁺ species near the surface, which was only found in the catalysts containing V⁴⁺ phases. Among those catalysts the one based on VO(PO₃)₂ phase shows the highest selectivity, which could be related to the most isolated scenario of V species (the lowest V content relative to P) found at the outermost surface by low energy ion scattering spectroscopy (LEISS), a "true" surface technique only sensitive to the outermost atomic layer

Mechanochemical Preparation of Magnetically Separable Fe and Cu-Based Bimetallic Nanocatalysts for Vanillin Production

A highly sustainable method for the preparation of supported iron oxide and copper nanoparticles (NPs) on a biomass-derived carbon by solvent-free mechanochemical process is reported. In-situ mechanochemically obtained extracts from orange peel could behave as a green reducing agent, allowing the formation of Cu metal nanoparticles as well as generating a magnetic phase (magnetite) in the systems via partial Fe3+ reduction. At the same time, orange peel residues also served as template and carbon source, adding oxygen functionalities, which were found to benefit the catalytic performance of mechanochemically synthesized nanomaterials. The series of magnetic Cu-Fe@OP were tested in the oxidation of trans-ferulic acid towards vanillin, remarkably revealing a maximum vanillin yield of 82% for the sample treated at 200 °C

Oxidación selectiva de hidrocarburos ligeros sobre catalizadores basados en óxidos metálicos mixtos

La presente tesis doctoral muestra un estudio sobre la síntesis y caracterización de bronces basados en óxidos metálicos de Mo y V, para ser empelados como catalizadores en reacciones de oxidación parcial de hidrocarburos de cadena corta (C2-C4), en especial para la oxidación de propano a ácido acrílico. Mediante síntesis hidrotermal se han preparado óxidos ternarios Mo-V-X (X= diferentes metales), obteniendo catalizadores activos y selectivos en la oxidación de propano a ácido acrílico únicamente en el caso de los materiales con Sb ó Te. Posteriormente, se ha estudiado la influencia de parámetros de síntesis y la incorporación de promotores en las propiedades catalíticas de estos materiales. Cabe destacar que tanto presencia de agentes reductores y/o la incorporación de promotores en el gel de síntesis (niobio o metales alcalinos), como las características de los procedimientos de activación o la modificación de los catalizadores mediante tratamientos post-síntesis (incorporación selectiva de promotores o tratamiento con disoluciones acuosas de agua oxigenada), pueden mejorar sustancialmente las propiedades catalíticas de estos materiales. Las propiedades químico-físicas de los materiales obtenidos se han determinado mediante el empleo combinado de diversas técnicas espectroscópicas (XPS, EPR y XAS), DRX, microscopía electrónica (SEM/TEM), análisis de las características ácidas (TPD-NH3), etc. Comparando los resultados catalíticos y de caracterización se ha conseguido establecer aspectos clave de la síntesis y modificación de estos materiales, lo cual nos ha permitido desarrollar nuevos materiales que, aún manteniendo la misma estructura cristalina básica, presentan mejoras sustanciales en las propiedades catalíticas. Así, se han conseguido obtener catalizadores con rendimientos catalíticos muy superiores a los obtenidos con los catalizadores ternarios de partida, tanto para la oxidación de propano a ácido acrílico como para la deshidrogenación oxidativa de etano.Ivars Barceló, F. (2010). Oxidación selectiva de hidrocarburos ligeros sobre catalizadores basados en óxidos metálicos mixtos [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/11074Palanci

Modeling and Thermodynamic Studies of γ‐Valerolactone Production from Bio‐derived Methyl Levulinate

Abstract The exploitation of biomass to reduce the dependency on fossil fuels represents a challenge that needs to be solved as soon as possible. Nowadays, one of the most fashionable processes is γ‐valerolactone (GVL) production from bio‐derived methyl levulinate (ML). Deep understanding of the thermodynamic aspects involved in this process is key for a successful outcome, but detailed studies are missing in the existing literature. A thermodynamic study of the reaction of γ‐valerolactone (GVL) production from bio‐derived methyl levulinate (ML) is performed by the Gibbs free energy minimization method. The effect of various reaction conditions (temperature, concentration, flow rate) and the implication of possible intermediates and byproducts are assessed. Conversion and selectivity are calculated from the simulation of the ML hydrogenation using isopropanol as the hydrogen donor under continuous flow conditions. Significant increases in GVL selectivity can be achieved under dry conditions, keeping the high conversion. Comparison between theoretical and experimental results from a previous article discloses the effect of using 5%RuTiO2 catalysts, which increases the selectivity from 3–40% to 41–98%. Enthalpy and Gibbs free energy of the reactions at issue are also calculated from models using Barin equations according to Aspen Physical Property System parameters

Novel Applications of Microbial Fuel Cells in Sensors and Biosensors

A microbial fuel cell (MFC) is a type of bio-electrochemical system with novel features, such as electricity generation, wastewater treatment, and biosensor applications. In recent years, progressive trends in MFC research on its chemical, electrochemical, and microbiological aspects has resulted in its noticeable applications in the field of sensing. This review was consequently aimed to provide an overview of the most interesting new applications of MFCs in sensors, such as providing the required electrical current and power for remote sensors (energy supply device for sensors) and detection of pollutants, biochemical oxygen demand (BOD), and specific DNA strands by MFCs without an external analytical device (self-powered biosensors). Moreover, in this review, procedures of MFC operation as a power supply for pH, temperature, and organic loading rate (OLR) sensors, and also self-powered biosensors of toxicity, pollutants, and BOD have been discussed

Influence of gel composition in the synthesis of MoVTeNb catalysts over their catalytic performance in partial propane and propylene oxidation

[EN] MoVTeNb mixed oxides catalysts have been prepared by a slurry method with different molar compositions (Mo/Te ratio from 2 to 6 and Nb/(V + Nb) ratio from 0 to 0.7) in the synthesis gel leading to different crystalline phases distribution and catalytic behaviour in the partial oxidation of both propane and propylene to acrylic acid. Chemical analysis indicates that the composition of samples before and after the heat-treatment changes, especially the Te-content, since a significant amount of Te is lost during the heat-treatment step when the amount of oxalate (from niobium oxalate) increases in the synthesis gel. Thus, the nature of the crystalline phases and the catalytic performance of heat-treated materials will be related to the final chemical composition. On the other hand, only the catalysts presenting Te(2)M(20)O(57) (M = Mo, V, Nb) crystalline structure, the so-called M1 phase, were active and selective in the partial oxidation of propane to acrylic acid. Moreover, all catalysts were active and relatively selective to the formation of O-containing products, i.e. acrolein and/or acrylic acid, during the partial propylene oxidation although the more active ones were those presenting M1 phase. (C) 2009 Elsevier B.V. All rights reserved.Financial support from DGICYT in Spain (Project CTQ2006- 09358/BQU) and the European Union through the FP6 Integrated Project (TOPCOMBI, NMP2-CT2005-515792) is gratefully acknowledgedIvars Barceló, F.; Solsona Espriu, BE.; Hernández Morejudo, S.; López Nieto, JM. (2010). Influence of gel composition in the synthesis of MoVTeNb catalysts over their catalytic performance in partial propane and propylene oxidation. Catalysis Today. 149(3-4):260-266. doi:10.1016/j.cattod.2009.09.018S2602661493-

Selective propane oxidation over MoVSbO catalysts. On the preparation, characterization and catalytic behavior of M1 phase

Nb-free (SbO)(2)M(20)O(56) catalysts (M = Mo, V) presenting pure M1 phase have been prepared by a post-synthesis treatment with hydrogen peroxide of a heat-treated MoVSbO mixed metal oxide catalyst previously prepared by hydrothermal method. The characterization of catalysts and their results for propane oxidation suggest that the optimization in the preparation of the M1 phase depends strongly on the washing procedure. The optimal removing of Sb species formed during post-synthesis treatment can explain the improvement in the catalytic activity; while the better selectivity to acrylic acid of the catalysts obtained by post-synthesis treatment can be explained by the elimination of M2 phase and the modification of the M1 phase crystals surface. The importance of M1 phase in the catalytic performance during the selective propane oxidation over Nb-free Mo-V-Sb based catalysts is also discussed. (C) 2008 Elsevier Inc. All rights reserved.The authors thank the Spanish CICYT for financial support (Projects NAN2004-09267-CO3-02 and CTQ2006-09358/BQU) and the technical support of the Microscopy Department of Universidad Politecnica de Valencia (Spain).Ivars Barceló, F.; Solsona Espriu, BE.; Rodriguez-Castellon, E.; López Nieto, JM. (2009). Selective propane oxidation over MoVSbO catalysts. On the preparation, characterization and catalytic behavior of M1 phase. Journal of Catalysis. 262(1):35-43. https://doi.org/10.1016/j.jcat.2008.11.021S3543262

Oxidative dehydrogenation of ethane: A study over the structure and robustness of Ni-W-O catalysts

[EN] The robustness of one selected Ni-W-O catalyst has been studied in the oxidative dehydrogenation of ethane. This catalyst initially deactivates for the first 10 h online decreasing 15% of its catalytic activity compared to its initial stable catalytic activity. However from 10 to 60 h online the catalytic activity keeps almost stable. On the other hand, it has been shown that the Ni-W-O catalyst cannot tolerate an oxygen-free atmosphere (C-2 and He) as nickel oxide is transformed into metallic nickel. Methane and hydrogen as well as abundant coke were formed on the surface of the catalyst in these O-free conditions. However a re-calcination in air leads to the removal of coke, the catalytic performance in the oxidative dehydrogenation of ethane being almost completely restored.Financial support from DGICYT in Spain (Projects CTQ2012-37925-C03-01 and CTQ2012-37925-C03-03) is gratefully acknowledged. The authors also want to thank the SCSIE, University of Valencia, for providing HRTEM facilities.Agouram, S.; Dejoz, A.; Ivars Barceló, F.; Vazquez, I.; López Nieto, JM.; Solsona, B. (2014). Oxidative dehydrogenation of ethane: A study over the structure and robustness of Ni-W-O catalysts. Fuel Processing Technology. 119:105-113. https://doi.org/10.1016/j.fuproc.2013.10.017S10511311