A STUDY OF SURFACE OXYGEN SPECIES FROM LA-ME-O (ME=MG, CA, SR, BA) CATALYSTS FOR METHANE OXIDATIVE COUPLING

CO2-TPD was used to study the surface basicity of La-Me-O mixed oxides and O-2-TPD, CH4-TPD were employed to study the surface active oxygen species. Comparing the CO2-TPD with O-2-TPD, we can see that the basicity of catalyst is in parallel with the catalystic activity. The stronger basicity is more profitable for the catalyst to adsorb oxygen to form active oxygen species and to activate CH4 by breaking a C-H bond, By comparing the catalytic activity, the results showed that La-Ba-O(La/Ba=7/3) catalyst had the strongest basicity, and it gave the highest CH4 conversion and C-2 selectivity, The results from the pulse reaction showed that the lattice oxygen participated in the OCM reaction without gas oxygen, and it was the selective oxygen species.

Investigations into enhanced wax production with combustion synthesized Fischer-Tropsch catalysts

Combustion synthesized (CS) cobalt catalysts deposited over two supports, alumina and silica doped alumina (SDA), were characterized and tested for its Fischer-Tropsch (FT) activity. The properties of CS catalysts were compared to catalysts synthesized by conventional impregnation method (IWI). The CS catalysts resulted in 40-70% increase in the yield of C6+ hydrocarbons compared to MI catalysts. The FT activity for CS catalysts showed formation of long chain hydrocarbon waxes (C24+) compared to the formation of middle distillates (C-10-C-20) for IWI synthesized catalysts, indicating higher hydrocarbon chain growth probability for CS catalysts. This is ascribed to the smaller crystallite sizes, increased degree of cobalt reduction and consequentially, a higher number of active metal sites, exposed over the catalyst surface. Additionally, 12-13% increase in the overall C6+ hydrocarbon yield is realized for SDA-CS catalysts, compared to Al2O3-CS catalysts. The improved performance of CS-SDA catalysts is attributed to 48% increase in cobalt dispersion compared to Al2O3 supported CS catalysts, which is again caused by the decrease in the cobalt -support interaction for SDA supports. The metal support interactions were analyzed using XPS and H-2 TPR-TPD experiments. Combustion method produced catalysts with smaller crystallite size (17-18 nm), higher degree of reduction (similar to 92%) and higher metal dispersion (16.1%) compared to the IWI method. Despite its enhanced properties, the CS catalysts require prominently higher reduction temperatures (similar to 1100-1200 K). The hydrocarbon product analysis for Al2O3 supported catalyst showed higher paraffin wax concentrations compared to SDA supported catalysts, due to the lower surface basicity of Al2O3. This work reveals the impact of the CS catalysts and the nature of support on FT activity and hydrocarbon product spectrum. (C) 2016 Elsevier Ltd. All rights reserved.

Characterisation of the acid-base properties of pillared montmorillonites

Iron and mixed iron aluminium pillared montrnorillonites prepared by partial hydrolysis method were subjected to room temperature exchange with transition metals of the first series. The resulting materials were characterised by different spectroscopic techniques and surface area measurements. About 1-3% transition metals were incorporated into the porous network. The structural stability of the porous network was not affected by exchange. XRD and AI NMR spectroscopy evidenced the presence of iron substituted Al13 like polymers in FeAl pillared systems. Acidity and basicity benefited much as a result of metal exchange. Acidity and basicity were quantified by model reactions, viz., cumene cracking and cyclohexanol decomposition respectively. The presence of basic sites in otherwise acidic pillared clays, though diminutive in amount can be of much importance in acid base catalysed reactions.

New solid base catalysts for biodiesel synthesis

The application of heterogeneous catalysts for the manufacture of renewable biodiesel fuels offers an exciting, alternative clean chemical technology to current energy intensive processes employing soluble base catalysts. We recently synthesised tuneable MgO nanocrystals as efficent solid base catalysts for biodiesel synthesis, and have developed a simple X-ray spectroscopic method to quantitatively determine surface basicity, thereby providing a rapid screening tool for predicting the reactivity of new solid base catalysts. Promotion of these MgO nanocrystals through Cs doping dramatically enhances biodiesel production rates due to the formaion of a mixed Cs Mg(CO ) phase. These MgO derived nanocatalysts permit energy efficent, continuous processing of diverse, sustainable oil feedstocks in flow reactors.

Designer catalysts for biodiesel synthesis

The combination of dwindling oil reserves and growing concerns over carbon dioxide emissions and associated climate change is driving the urgent development of clean, sustainable energy supplies. Biodiesel is a non-toxic and biodegradable fuel, with the potential for closed CO2 cycles and thus vastly reduced carbon footprints compared with petroleum. However, current manufacturing routes employing soluble catalysts are very energy inefficient, with their removal necessitating an energy intensive separation to purify biodiesel, which in turn produces copious amounts of contaminated aqueous waste. The introduction of non-food based feedstocks and technical advances in heterogeneous catalyst and reactor design are required to ensure that biodiesel remains a key player in the renewable energy sector for the 21st century. Here we report on the development of tuneable solid acid and bases for biodiesel synthesis, which offer several process advantages by eliminating the quenching step and allowing operation in a continuous reactor. Significant progress has been made towards developing tuneable solid base catalysts for biodiesel synthesis, including Li/CaO [1], Mg-Al hydrotalcites [2] and calcined dolomite [3] which exhibit excellent activity for triglyceride transesterification. However, the effects of solid base strength on catalytic activity in biodiesel synthesis remains poorly understood, hampering material optimisation and commercial exploitation. To improve our understanding of factors influencing solid base catalysts for biodiesel synthesis, we have applied a simple spectroscopic method for the quantitative determination of surface basicity which is independent of adsorption probes. Such measurements reveal how the morphology and basicity of MgO nanocrystals correlate with their biodiesel synthesis activity [4]. While diverse solid acids and bases have been investigated for TAG transesterification, the micro and mesoporous nature of catalyst systems investigated to date are not optimal for the diffusion of bulky and viscous C16-C18 TAGs typical of plant oils. The final part of this presentation will address the benefits of designing porous networks comprising interconnected hierarchical macroporous and mesoporous channels (Figure 1) to enhance mass-transport properties of viscous plant oils during biodiesel synthesis [5]. References: [1] R.S. Watkins, A.F. Lee, K. Wilson, Green Chem., 2004, 6, 335. [2]D.G. Cantrell, L.J. Gillie, A.F. Lee and K. Wilson, Appl. Catal. A, 2005, 287,183. [3] C. Hardacre, A.F. Lee, J.M. Montero, L. Shellard, K.Wilson, Green Chem., 2008, 10, 654. [4] J.M. Montero, P.L. Gai, K. Wilson, A.F. Lee, Green Chem., 2009, 11, 265. [5] J. Dhainaut, J.-P. Dacquin, A.F. Lee, K. Wilson, Green Chem., 2010, 12, 296.

Surface acidity/basicity and catalytic activity of Zr-Sm mixed oxide systems

The surface acidity and basicity of oxides of Sm and Zr and their mixed oxides have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cyclo-hexanone in 2-propanol.

Surface acidity/basicity of yttria and its mixed oxides with alumina catalysts

Acid/base strength distribution of Y2O3 and its mixed oxides with alumina catalysts are measured on Hammett acidity function scale and expressed in terms of H0max value. Basicity of Y2O3 increases with increase in activation temperature and for mixed oxides the basicity increases with increase in concentration of Y2O3, in the catalyst.

The surface acidity/basicity and catalytic activity of ternary oxides of La, Ce and AI

The surface acidity and basicity of ternary oxides of La, Ce and AI have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cycIohexanone in 2-propanol.

Surface acidity/basicity and catalytic activity of ternary oxides of Al, Ce and Dy

The surface acidity and basicity of ternary oxides of AI, Ce and Dy have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cyclohexanone in 2-propanol. The reaction is favoured by the higher basicity of the ternary oxide.

Surface acidity/basicity and catalytic activity of mixed oxides of Zr, La and Al

The surface acidity/basicity of binary oxides of Zr and La and the ternary oxides of Zr, La and Al are reported. The data have been correlated with their catalytic activity towards liquid phase reduction of cyclohexanone.

Surface acidity and catalytic activity of sulphated samaria

We have investigated the changes in surface acidity/basicity and catalytic pro~erties of samarium oxide due to surface modification by SO42- ion. The acidity/basicity of the catalysts is determined by titration method using Hammett indicators. Esterification of acetic acid by n-butanol is chosen as a test reaction. Sm203, owing to its high basicity and low acidity, does not catalyze the reaction. But sulphated Sm20J catalyzes the esterification reaction effectively. Activation temperature does not have much effect on the acidity of sulphated samaria.

Surface electron properties and catalytic activity of cerium-zirconium mixed oxides

The electron donating properties, surface acidity/ basicity and catalytic activity of cerium - zirconium mixed oxides at various compositions have been reported at an activation temperature of 500 degree C. The catalytic activity for the esterification of acetic acid with n-butanol has heen correlated with electron donating properties and surface acidity/basicity of the oxides.

Acidity/basicity, electron donor properties and catalytic activity of sulphate modified stannic oxide

The surface electron donor properties of sulphate modified stannic oxide have been determined from the adsorption of electron acceptors of various electron affinities on the oxide surface. The acid base properties of stannic oxide have been determined by titration method using Hammett indicators. Catalytic activities of the oxide for esterification of acetic acid using n-butanol.reduction of cyclohexanone in 2-propanol and oxidation of cyclohexanol with benzophenone have been studied. The data have been correlated with the surface electron donor properties of these oxides. The activity for reduction and oxidation decreases and that for esterification reaction increases on modification with sulphate ion. It has heen found that electron donating capacity decreased when stannic oxide was modified with sulphate ion.

Acidity / basicity and electron donor properties and catalytic activity of sulphated titania

The surface acidity/ basicity of TiO2 (rutile) and its sulphate modified form have been determined by titration method using Hammett indicators after activation at different temperatures. The electron donating properties of these oxides are also studied from the adsorption of electron acceptors of different electron affinity values. The data have been correlated with the catalytic activity of these oxides towards esterification of acetic acid using n-butanol, reduction of cyclohexanone in isopropanol and oxidation of cyclohexanol in benzophenone. Catalytic activity for esterification and oxidation reaction parallels the acidity while that for reduction reaction parallels the basicity of these oxides.

Acidity/basicity, electron donor properties and catalytic activity of sulphate modified ceria

The changes in surface acidity/basicity and catalytic activity of cerium oxide due to surface modification by sulphate ion have been investigated. Electron donor properties of both the modified and unmodified oxides have been studied using electron acceptors of various electron affinity values, viz. 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrachloro--l, 4-benzoquinone. p-dinitrobenzene and m-dinitrobenzene in order to find out whether the increase in acidity on suphation is due to the generation of new acidic sites or they are formed at the expense of some of the basic sites. The surface acidity/basicity has been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of the oxides for esterification of acetic acid using l-butanol, reduction of cyclohexanone with 2- propanol and oxidation of cyclohexanol using benzophenone.