Superparamagnetic particles in ZSM-5-type ferrisilicates

As-synthesized, low iron content, ferrisilicates of ZSM-5-type contain well-separated Fe(III) ions in a tetrahedral environment and display paramagnetic behavior. After hydrothermal treatment, the iron ions are partially extracted from the framework, generating nanosize iron oxide or oxyhydroxide ferrimagnetic particles. This process has been studied by transmission electron microscopy (TEM), Mossbauer spectroscopy, magnetic ac susceptibility (chi(ac)), and field dependent magnetization, on samples containing up to 6.7 wt. % Fe. The experiments evidence the growth of nonaggregated particles, with a typical size around 3 nm, presumably located at the surface of the ferrisilicate crystallites, From a thorough granulometric analysis involving TEM and chi(ac) data, it is concluded that, in the range from 1.5 to 4.6 wt. % Fe, the particle size distributions are significantly independent of the iron content

Synthesis and structure of polymorph B of zeolite Beta

[EN] It was found that either polymorph B or polymorph C of zeolite beta can be obtained from the same structure directing agent: 4,4-dimethyl-4-azonia-tricyclo[5.2.2.0(2,6)] undec-8-ene hydroxide. The synthesis occurs through a consecutive process where polymorph B is first formed and then transformed into polymorph C. It is possible to produce a zeolite highly enriched in polymorph B, provided that the transformation of this phase into polymorph C is slowed down up to the point where polymorph C is only detected at trace levels. The structure of polymorph B was determined for the first time by electron crystallography with SAED and HRTEM from areas of unfaulted polymorph B crystals.Financial support from the Spanish Government (Project MAT2006-14274-C02–01) and the EU Commission (TOPCOMBI Project) is gratefully acknowledged. M.M. thanks CSIC for an I3P grant. J.S. is supported by a postdoctoral grant from the Carl Trygger Foundation. The Berzelii Centre EXSELENT is supported by the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA).Corma Canós, A.; Moliner Marin, M.; Cantin Sanz, A.; Díaz Cabañas, MJ.; Jorda Moret, JL.; Zhang, D.; Sun, J.... (2008). Synthesis and structure of polymorph B of zeolite Beta. Chemistry of Materials. 20(9):3218-3223. doi:10.1021/cm8002244S3218322320

hITeQ: A new workflow-based computing environment for streamlining discovery. Application in materials science

[EN] This paper presents the implementation of the recent methodology called Adaptable Time Warping (ATW) for the automatic identification of mixture of crystallographic phases from powder X-ray diffraction data, inside the framework of a new integrative platform named hITeQ. The methodology is encapsulated into a so-called workflow, and we explore the benefits of such an environment for streamlining discovery in R&D. Beside the fact that ATW successfully identifies and classifies crystalline phases from powder XRD for the very complicated case of zeolite ITQ-33 for which has been employed a high throughput synthesis process, we stress on the numerous difficulties encountered by academic laboratories and companies when facing the integration of new software or techniques. It is shown how an integrative approach provides a real asset in terms of cost, efficiency, and speed due to a unique environment that supports well-defined and reusable processes, improves knowledge management, and handles properly multi-disciplinary teamwork, and disparate data structures and protocols.EU Commission FP6 (TOPCOMBI Project) is gratefully acknowledged.Baumes, LA.; Jiménez Serrano, S.; Corma Canós, A. (2011). hITeQ: A new workflow-based computing environment for streamlining discovery. Application in materials science. Catalysis Today. 159(1):126-137. doi:10.1016/j.cattod.2010.03.067S126137159

Experimental energetics of large and extra-large pore zeolites: Pure silica beta polymorph C (BEC) and Ge-containing ITQ-33

[EN] The enthalpies of formation of the large pore pure silica beta polymorph C (BEC) and the extra-large pore germanosilicate ITQ-33 zeolite are investigated by high temperature oxide melt solution calorimetry. The enthalpies of formation from quartz for two BECs synthesized with different organic structure directing agents, SDA1 and SDA9 differ by 4 kJ/mol. The two SDAs produce phases with different properties as well as different energetics for the same framework and composition, due to the different amount of structural defects, while the more defective BEC is energetically less stable by 4 kJ/mol. The enthalpy of formation of defect-free pure silica BEC agrees with the predicted value proposed several years ago. Moreover, the enthalpy of formation of ITQ-33 (Ge/(Ge + Si) = 0.3) supports the energetic trends seen previously, namely that the enthalpy of formation becomes more endothermic as the content of double four rings (D4R) increases. The previous trend of energetics of porous materials versus molar volume is supported by the present data, with a diminishing destabilization for very open structures.This calorimetric work at UC Davis was supported by the U.S. Department of Energy, Grant DE-FG02-05ER15667.Wu, L.; Hughes, J.; Moliner Marin, M.; Navrotsky, A.; Corma Canós, A. (2014). Experimental energetics of large and extra-large pore zeolites: Pure silica beta polymorph C (BEC) and Ge-containing ITQ-33. Microporous and Mesoporous Materials. 187:77-81. https://doi.org/10.1016/j.micromeso.2013.12.013S778118

FCC testing at bench scale: New units, new processes, new feeds

As the FCC process has evolved over decades, several laboratory scale equipment have appeared to maintain a proper assessment of catalysts activity. Several laboratory equipments are available for simulating the FCC process, from the well known fixed bed, MicroActivity Test to newer, fluid bed or transported bed units. As well, a number of units have been created to simulate other parts of the process such as regenerator or stripper, The increased pressure for treating non-conventional feeds, from reprocessing gasoline to extra-heavy feeds or oils produced from biomass containing large amounts of heteroatoms, increase the needs to have a laboratory test which is as close as possible to the process so that data extraction from the laboratory test are simplified, thus less prone to errors or misunderstanding.Financial support by MICINN (Consolider-Ingenio 2010 MULTICAT) and MINECO (Project MAT2011-29020-0O2-02 and Subprogram for excellence Severo Ochoa, SEV 2012 0267) is gratefully acknowledged.Corma Canós, A.; Sauvanaud, LL. (2013). FCC testing at bench scale: New units, new processes, new feeds. Catalysis Today. 218-219:107-114. doi:10.1016/j.cattod.2013.03.038S107114218-21

MOFs as multifunctional catalysts: One-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst

A bifunctional MOF catalyst containing coordinatively unsaturated Cr3+ sites and palladium nanoparticles (Pd@MIL-101) has been used for the cyclization of citronellal to isopulegol and for the one-pot tandem isomerization/hydrogenation of citronellal to menthol. The MOF was found to be stable under the reaction conditions used, and the results obtained indicate that the performance of this bifunctional solid catalyst is comparable with other state-of-the-art materials for the tandem reaction: Full citronellal conversion was attained over Pd@MIL-101 in 18 h, with 86% selectivity to menthols and a diastereoselectivity of 81% to the desired (-)-menthol, while up to 30 h were necessary for attaining similar values over Ir/H-beta under analogous reaction conditions.Financial support by Ministerio de Educacion y Ciencia e Innovacion (Project MIYCIN, CSD2009-00050; PROGRAMA CONSOLIDER. INGENIO 2009), Generalidad Valenciana (GV PROMETEO/2008/130) and the CSIC (Proyectos Intramurales Especiales 201080I020) is gratefully acknowledged.García Cirujano, F.; Llabrés I Xamena, FX.; Corma Canós, A. (2012). MOFs as multifunctional catalysts: One-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst. Dalton Transactions. 41:4249-4254. https://doi.org/10.1039/c2dt12480gS4249425441Corma, A., García, H., & Llabrés i Xamena, F. X. (2010). Engineering Metal Organic Frameworks for Heterogeneous Catalysis. Chemical Reviews, 110(8), 4606-4655. doi:10.1021/cr9003924Farrusseng, D., Aguado, S., & Pinel, C. (2009). Metal-Organic Frameworks: Opportunities for Catalysis. Angewandte Chemie International Edition, 48(41), 7502-7513. doi:10.1002/anie.200806063Lee, J., Farha, O. K., Roberts, J., Scheidt, K. A., Nguyen, S. T., & Hupp, J. T. (2009). Metal–organic framework materials as catalysts. Chemical Society Reviews, 38(5), 1450. doi:10.1039/b807080fWang, Z., & Cohen, S. M. (2009). Postsynthetic modification of metal–organic frameworks. Chemical Society Reviews, 38(5), 1315. doi:10.1039/b802258pBanerjee, M., Das, S., Yoon, M., Choi, H. J., Hyun, M. H., Park, S. M., … Kim, K. (2009). Postsynthetic Modification Switches an Achiral Framework to Catalytically Active Homochiral Metal−Organic Porous Materials. Journal of the American Chemical Society, 131(22), 7524-7525. doi:10.1021/ja901440gGASCON, J., AKTAY, U., HERNANDEZALONSO, M., VANKLINK, G., & KAPTEIJN, F. (2009). Amino-based metal-organic frameworks as stable, highly active basic catalysts. Journal of Catalysis, 261(1), 75-87. doi:10.1016/j.jcat.2008.11.010Hasegawa, S., Horike, S., Matsuda, R., Furukawa, S., Mochizuki, K., Kinoshita, Y., & Kitagawa, S. (2007). Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand:  Selective Sorption and Catalysis. Journal of the American Chemical Society, 129(9), 2607-2614. doi:10.1021/ja067374yCho, S.-H., Ma, B., Nguyen, S. T., Hupp, J. T., & Albrecht-Schmitt, T. E. (2006). A metal–organic framework material that functions as an enantioselective catalyst for olefin epoxidation. Chem. Commun., (24), 2563-2565. doi:10.1039/b600408cZhang, X., Llabrés i Xamena, F. X., & Corma, A. (2009). Gold(III) – metal organic framework bridges the gap between homogeneous and heterogeneous gold catalysts. Journal of Catalysis, 265(2), 155-160. doi:10.1016/j.jcat.2009.04.021Meilikhov, M., Yusenko, K., Esken, D., Turner, S., Van Tendeloo, G., & Fischer, R. A. (2010). Metals@MOFs - Loading MOFs with Metal Nanoparticles for Hybrid Functions. European Journal of Inorganic Chemistry, 2010(24), 3701-3714. doi:10.1002/ejic.201000473Henschel, A., Gedrich, K., Kraehnert, R., & Kaskel, S. (2008). Catalytic properties of MIL-101. Chemical Communications, (35), 4192. doi:10.1039/b718371bVermoortele, F., Ameloot, R., Vimont, A., Serre, C., & De Vos, D. (2011). An amino-modified Zr-terephthalate metal–organic framework as an acid–base catalyst for cross-aldol condensation. Chem. Commun., 47(5), 1521-1523. doi:10.1039/c0cc03038dWu, P., Wang, J., Li, Y., He, C., Xie, Z., & Duan, C. (2011). Luminescent Sensing and Catalytic Performances of a Multifunctional Lanthanide-Organic Framework Comprising a Triphenylamine Moiety. Advanced Functional Materials, 21(14), 2788-2794. doi:10.1002/adfm.201100115Pan, Y., Yuan, B., Li, Y., & He, D. (2010). Multifunctional catalysis by Pd@MIL-101: one-step synthesis of methyl isobutyl ketone over palladium nanoparticles deposited on a metal–organic framework. Chemical Communications, 46(13), 2280. doi:10.1039/b922061eCliment, M. J., Corma, A., Guil-López, R., Iborra, S., & Primo, J. (1998). Use of Mesoporous MCM-41 Aluminosilicates as Catalysts in the Preparation of Fine Chemicals. Journal of Catalysis, 175(1), 70-79. doi:10.1006/jcat.1998.1970Climent, M. J., Corma, A., Iborra, S., & Velty, A. (2002). Designing the adequate base solid catalyst with Lewis or Bronsted basic sites or with acid–base pairs. Journal of Molecular Catalysis A: Chemical, 182-183, 327-342. doi:10.1016/s1381-1169(01)00501-5Boronat, M., Climent, M. J., Corma, A., Iborra, S., Montón, R., & Sabater, M. J. (2010). Bifunctional Acid-Base Ionic Liquid Organocatalysts with a Controlled Distance Between Acid and Base Sites. Chemistry - A European Journal, 16(4), 1221-1231. doi:10.1002/chem.200901519Corma, A., Díaz, U., García, T., Sastre, G., & Velty, A. (2010). Multifunctional Hybrid Organic−Inorganic Catalytic Materials with a Hierarchical System of Well-Defined Micro- and Mesopores. Journal of the American Chemical Society, 132(42), 15011-15021. doi:10.1021/ja106272zFerey, G. (2005). A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area. Science, 309(5743), 2040-2042. doi:10.1126/science.1116275Corma, A., & Renz, M. (2004). Sn-Beta zeolite as diastereoselective water-resistant heterogeneous Lewis-acid catalyst for carbon–carbon bond formation in the intramolecular carbonyl–ene reaction. Chem. Commun., (5), 550-551. doi:10.1039/b313738dIosif, F., Coman, S., Pârvulescu, V., Grange, P., Delsarte, S., Vos, D. D., & Jacobs, P. (2004). Ir-Beta zeolite as a heterogeneous catalyst for the one-pot transformation of citronellal to menthol. Chem. Commun., (11), 1292-1293. doi:10.1039/b403692aNeaţu, F., Coman, S., Pârvulescu, V. I., Poncelet, G., De Vos, D., & Jacobs, P. (2009). Heterogeneous Catalytic Transformation of Citronellal to Menthol in a Single Step on Ir-Beta Zeolite Catalysts. Topics in Catalysis, 52(9), 1292-1300. doi:10.1007/s11244-009-9270-9MERTENS, P., VERPOORT, F., PARVULESCU, A., & DEVOS, D. (2006). Pt/H-beta zeolites as productive bifunctional catalysts for the one-step citronellal-to-menthol conversion. Journal of Catalysis, 243(1), 7-13. doi:10.1016/j.jcat.2006.06.017Da Silva Rocha, K. A., Robles-Dutenhefner, P. A., Sousa, E. M. B., Kozhevnikova, E. F., Kozhevnikov, I. V., & Gusevskaya, E. V. (2007). Pd–heteropoly acid as a bifunctional heterogeneous catalyst for one-pot conversion of citronellal to menthol. Applied Catalysis A: General, 317(2), 171-174. doi:10.1016/j.apcata.2006.10.019Trasarti, A. F., Marchi, A. J., & Apesteguı́a, C. R. (2004). Highly selective synthesis of menthols from citral in a one-step process. Journal of Catalysis, 224(2), 484-488. doi:10.1016/j.jcat.2004.03.016TRASARTI, A., MARCHI, A., & APESTEGUIA, C. (2007). Design of catalyst systems for the one-pot synthesis of menthols from citral. Journal of Catalysis, 247(2), 155-165. doi:10.1016/j.jcat.2007.01.016Alaerts, L., Séguin, E., Poelman, H., Thibault-Starzyk, F., Jacobs, P. A., & De Vos, D. E. (2006). Probing the Lewis Acidity and Catalytic Activity of the Metal–Organic Framework [Cu3(btc)2] (BTC=Benzene-1,3,5-tricarboxylate). Chemistry - A European Journal, 12(28), 7353-7363. doi:10.1002/chem.200600220Horcajada, P., Surblé, S., Serre, C., Hong, D.-Y., Seo, Y.-K., Chang, J.-S., … Férey, G. (2007). Synthesis and catalytic properties of MIL-100(Fe), an iron(iii) carboxylate with large pores. Chem. Commun., (27), 2820-2822. doi:10.1039/b704325bRavon, U., Chaplais, G., Chizallet, C., Seyyedi, B., Bonino, F., Bordiga, S., … Farrusseng, D. (2010). Investigation of Acid Centers in MIL-53(Al, Ga) for Brønsted-Type Catalysis: In Situ FTIR and Ab Initio Molecular Modeling. ChemCatChem, 2(10), 1235-1238. doi:10.1002/cctc.201000055Vimont, A., Leclerc, H., Maugé, F., Daturi, M., Lavalley, J.-C., Surblé, S., … Férey, G. (2007). Creation of Controlled Brønsted Acidity on a Zeotypic Mesoporous Chromium(III) Carboxylate by Grafting Water and Alcohol Molecules. The Journal of Physical Chemistry C, 111(1), 383-388. doi:10.1021/jp064686

Improved THETA-1 for light olefins oligomerization to diesel: Influence of textural and acidic properties

The increase in diesel demand, especially in Europe, and the need for high fuel quality requirements are forcing refiners to move into additional processes for production of high cetane diesel in order to meet the present market trends. Oligomerization of light olefins into middle distillate range products is a viable option. The fuel produced through this technology is environmentally friendly, free of sulfur and aromatics, and the adequate choice of the heterogeneous catalyst will direct the selectivity towards low branched oligomers, which will result in a high quality product. In this work we show the benefits of combining basic desilication treatments for generation of additional mesoporosity in mono-directional Theta-1 zeolite, with selective acid dealumination steps that restore not only the microporosity to values close to those of the parent samples, but also the total and strong Bronsted acidity. These modified Theta-1 zeolites present an outstanding catalytic behavior for oligomerization of propene, with a largely increased initial activity, a much higher resistance to deactivation with time on stream, and an improved selectivity to products in the diesel fraction, as compared to the original microporous Theta-1.The authors thank BP Products of North America for their financial support and permission to publish this work, and Consolider Ingenio 2010-Multicat, the "Severo Ochoa Program", and MAT2012-31657 for financial support. R. Sanchis is acknowledged for technical support.Martínez, C.; Doskocil, EJ.; Corma Canós, A. (2014). Improved THETA-1 for light olefins oligomerization to diesel: Influence of textural and acidic properties. Topics in Catalysis. 57(6-9):668-682. https://doi.org/10.1007/s11244-013-0224-xS668682576-9Bellussi G, Mizia F, Calemma V, Pollesel P, Millini R (2012) Microporous Mesoporous Mater 164:127–134Bellussi G, Carati A, Millini R (2010) In: Cejka J, Corma A, Zones S (eds) Zeolites and Catalysis. Wiley-VCH Verlag GmbH & Co., Weinheim, pp 449–491Martinez C, Corma A (2011) Coord Chem Rev 255:1558–1580de Klerk A (2005) Ind Eng Chem Res 44:3887–3893de Klerk A (2006) Energy Fuels 20:439–445de Klerk A (2006) Energy Fuels 20:1799–1805Egloff G (1936) Ind Eng Chem Res 28:1461–1467Degnan TF Jr, Smith CM, Venkat CR (2001) Appl Catal A Gen 221:283–294Apelian MR, Boulton JR, Fung AS (1994) US5284989, to Mobil OilQuann RJ, Green LA, Tabak SA, Krambeck FJ (1988) Ind Eng Chem Res 27:565–570Tabak SA, Krambeck FJ, Garwood WE (1986) AIChE J 32:1526–1531Corma A, Martínez C, Doskocil EJ (2013) J Catal 300:183–196Martens JA, Ravishankar R, Mishin IE, Jacobs PE (2000) Angew Chem Int Ed Engl 39:4376–4379Martens JA, Verrelst WH, Mathys GM, Brown SH, Jacobs PA (2005) Angew Chem Int Ed Engl 117(5833–583):6Pater JPG, Jacobs PA, Martens JA (1998) J Catal 179:477–482Tabak SA (1981) US4254295, to Mobil OilOccelli ML, Hsu JT, Galya LG (1985) J Mol Catal A: Chem 32:377–390Tabak SA (1984) US4504693, to Mobil Oil CorpKholer E, Schmidt F, Wernicke HJ, Pontes MD, Roberts HL (1995, Summer) Hydrocarbon Technology InternationalMartens JA, Verduijn JP (1995) WO95/19945, to Exxon Chemical Patents Inc.Verrelst WH (1995) Martens LRM, WO95/22516, to Exxon Chemical Patents Inc.Verrelst WH, Martens LRM (2000) US6143942, to Exxon Chemical Patents Inc.Verrelst WH, Martens LRM, Verduijn JP (2006) US6013851, to Exxon Chemical Patents Inc.Dakka JM, Mathys GMK, Puttemans MPH (2003) WO03/035583 to Exxon-Mobil Chemical LimitedMatias P, Sa CC, Graca I, Lopes JM, Carvalho AP, Ramoa RF, Guisnet M (2011) Appl Catal A 399:100–109Chal R, Gérardin C, Bulut M, van Donk S (2011) ChemCatChem 3:67–81Perez-Ramirez J, Christensen CH, Egeblad K, Groen JC (2008) Chem Soc Rev 37:2530–2542Verboekend D, Perez-Ramirez J (2011) Catal Sci Technol 1:879–890Serrano DP, Escola JM, Pizarro P (2013) Chem Soc Rev 42:4004–4035Verboekend D, Chabaneix AM, Thomas K, Gilson JP, Perez-Ramirez J (2011) Cryst Eng Comm 13:3408–3416Emeis CA (1993) J Catal 141:347–354Perego C, Peratello S (1999) Catal Today 52:133–145Abello S, Bonilla A, Perez-Ramirez J (2009) Appl Catal A Gen 364:191–198Corma A, Martinez C, Doskocil EJ, Yaluris G (2011) WO2011002631A2, to BP Oil International Limited. BP Corporation North America Inc., UKCorma A, Martinez C, Doskocil EJ, Yaluris G (2011) WO2011002630A2, to BP Oil International Limited. BP Corporation North America Inc, UKHan S, Heck RH, DiGuiseppi FT (1993) US5234875, to Mobil Oil CorporationPeratello S, Molinari M, Bellussi G, Perego C (1999) Catal Today 52:271–27

Evolution and stabilization of subnanometric metal species in confined space by in situ TEM

Understanding the behavior and dynamic structural transformation of subnanometric metal species under reaction conditions will be helpful for understanding catalytic phenomena and for developing more efficient and stable catalysts based on single atoms and clusters. In this work, the evolution and stabilization of subnanometric Pt species confined in MCM-22 zeolite has been studied by in situ transmission electron microscopy (TEM). By correlating the results from in situ TEM studies and the results obtained in a continuous fix-bed reactor, it has been possible to delimitate the factors that control the dynamic agglomeration and redispersion behavior of metal species under reaction conditions. The dynamic reversible transformation between atomically dispersed Pt species and clusters/nanoparticles during CO oxidation at different temperatures has been elucidated. It has also been confirmed that subnanometric Pt clusters can be stabilized in MCM-22 crystallites during NO reduction with CO and H2

Pure silica nanoparticles for liposome/lipase system encapsulation: Application in biodiesel production

In this work we report the synthesis of organic inorganic solid with spherical morphology where enzyme, as active compounds, is encapsulated. The organic phase of nanospheres is composed of l-phosphatidylcholine, as liposome, and lipase from Rhizomucor miehei, as enzyme. The organic phase is covered with porous inorganic silica shell that could stabilize the internal liposomal phase and, consequently, isolate and protect the bioactive molecules. The liposome and silica amount used during the immobilization procedure have been optimized in order to obtain active and stable heterogeneous biocatalyst. Hybrid-nanospheres containing the enzyme were used to catalyze the transesterification reaction of triolein with methanol to methyl esters, typical biodiesel mixture compounds. The encapsulated enzyme retains its activity after 5 reaction cycles. The total productivity of the best catalyst obtained is higher than that of the free enzyme.The authors, A.C. and U.D., thank the Spanish MICINN (Consolider Ingenio 2010-MULTICAT (CSD2009-00050) and MAT2011-29020-C02-01) for their financial support.Macario, A.; Verri, F.; Díaz Morales, UM.; Corma Canós, A.; Giordano, G. (2013). Pure silica nanoparticles for liposome/lipase system encapsulation: Application in biodiesel production. Catalysis Today. 204:148-155. doi:10.1016/j.cattod.2012.07.014S14815520

Gold catalysts for the synthesis of aromatic azocompounds from nitroaromatics in one step

[EN] One-step selective hydrogenation of nitroaromatics to obtain symmetric azocompounds with high yields has been performed with a gold supported on cerium oxide catalysts. Au/TiO2 and Au/CeO2 catalysts direct the reaction by two different pathways and with different selectivities. In situ FTIR studies reveal that the surface concentration of the intermediate nitrosobenzene is decisive in directing the reaction trough the different reaction pathways. In this way, while on Au/TiO2 a fast hydrogenation of the nitrosobenzene intermediate leads to a low surface concentration of the nitrosocompound, on Au/CeO2 nitrosobenzene is more stabilized on the catalyst surface leading to a lower hydrogenation and a higher coupling rate, resulting in high selectivities to azobenzene. On Au/CeO2, the relative weak adsorption of the azo with respect to the azoxycompound on the catalyst surface avoids the consecutive hydrogenation of azocompounds to the corresponding anilines until all the azoxy has been consumed. Asymmetric azobenzenes have also been obtained with very high yields on TiO2, through the Mills reaction.The authors wish to acknowledge the financial support from the Spanish Ministries of Education and Science and Economy and Competitiveness under the project Consolider-Ingenio 2010 (CSD2009-00050 "Development of more efficient catalysts for the design of sustainable chemical processes and clean energy production") and the Severo Ochoa program (SEV-2012-0267), respectively. D.C. thanks the Spanish MEC for postgraduate scholarship, project MAT2006-14274-C02-01.Cómbita Merchán, DF.; Concepción Heydorn, P.; Corma Canós, A. (2014). Gold catalysts for the synthesis of aromatic azocompounds from nitroaromatics in one step. Journal of Catalysis. 311:339-349. https://doi.org/10.1016/j.jcat.2013.12.014S33934931