Mesostructured zeolites: bridging the gap between zeolites and MCM-41

Surfactant-templating is one of the most versatile and useful techniques to implement mesoporous systems into solid materials. Various strategies based on various interactions between surfactants and solid precursors have been explored to produce new structures. Zeolites are invaluable as size- and shape-selective solid acid catalysts. Nevertheless, their micropores impose limitations on the mass transport of bulky feed and/or product molecules. Many studies have attempted to address this by utilizing surfactant-assisting technology to alleviate the diffusion constraints. However, most efforts have failed due to micro/mesopore phase separation. Recently, a new technique combining the uses of cationic surfactants and mild basic solutions was introduced to synthesise mesostructured zeolites. These materials sustain the unique characteristics of zeolites (i.e., strong acidity, crystallinity, microporosity, and hydrothermal stability), including tunable mesopore sizes and degrees of mesoporosity. The mesostructured zeolites are now commercially available through Rive Technology, and show superior performance in VGO cracking. This feature article provides an overview of recent explorations in the introduction of mesoporosity into zeolites using surfactant-templating techniques. Various porous materials, preparation methods, physical and catalytic properties of mesostructured zeolites will be discussed.

Proton conductivity of mesoporous sol-gel zirconium phosphates for fuel cell applications

Zirconium phosphate has been extensively studied as a proton conductor for proton exchange membrane (PEM) fuel cell applications. Here we report the synthesis of mesoporous, templated sol-gel zirconium phosphate for use in PEM applications in an effort to determine its suitability for use as a surface functionalised, solid acid proton conductor in the future. Mesoporous zirconium phosphates were synthesised using an acid-base pair mechanism with surface areas between 78 and 177 m(2) g(-1) and controlled pore sizes in the range of 2-4 nm. TEM characterisation confirmed the presence of a wormhole like pore structure. The conductivity of such materials was up to 4.1 x 10(-6) S cm(-1) at 22degreesC and 84% relative humidity (RH), while humidity reduction resulted in a conductivity decrease by more than an order of magnitude. High temperature testing on the samples confirmed their dependence on hydration for proton conduction and low hydroscopic nature. It was concluded that while the conductivity of these materials is low compared to Nafion, they may be a good candidate as a surface functionalised solid acid proton conductor due to their high surface area, porous structure and inherent ability to conduct protons.

Recent developments in heterogeneous catalysis for the sustainable production of biodiesel

The quest for energy security and widespread acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from combusting fossil derived carbon sources, is driving academic and commercial research into new routes to sustainable fuels to meet the demands of a rapidly rising global population. Biodiesel is one of the most readily implemented and low cost, alternative source of transportation fuels to meet future societal demands. However, current practises to produce biodiesel via transesterification employing homogeneous acids and bases result in costly fuel purification processes and undesired pollution. Life-cycle calculations on biodiesel synthesis from soybean feedstock show that the single most energy intensive step is the catalytic conversion of TAGs into biodiesel, accounting for 87% of the total primary energy input, which largely arises from the quench and separation steps. The development of solid acid and base catalysts that respectively remove undesired free fatty acid (FFA) impurities, and transform naturally occurring triglycerides found within plant oils into clean biodiesel would be desirable to improve process efficiency. However, the microporous nature of many conventional catalysts limits their ability to convert bulky and viscous feeds typical of plant or algal oils. Here we describe how improved catalyst performance, and overall process efficiency can result from a combination of new synthetic materials based upon templated solid acids and bases with hierarchical structures, tailored surface properties and use of intensified process allowing continuous operation.

Heterogeneous catalysis in an oscillatory baffled flow reactor

The first demonstration of heterogeneous catalysis within an oscillatory baffled flow reactor (OBR) is reported, exemplified by the solid acid catalysed esterification of organic acids, an important prototypical reaction for fine chemicals and biofuel synthesis. Suspension of a PrSOH-SBA-15 catalyst powder is readily achieved within the OBR under an oscillatory flow, facilitating the continuous esterification of hexanoic acid. Excellent semi-quantitative agreement is obtained between OBR and conventional stirred batch reaction kinetics, demonstrating efficient mixing, and highlighting the potential of OBRs for continuous, heterogeneously catalysed liquid phase transformations. Kinetic analysis highlights acid chain length (i.e. steric factors) as a key predictor of activity. Continuous esterification offers improved ester yields compared with batch operation, due to the removal of water by-product from the catalyst, evidencing the versatility of the OBR for heterogeneous flow chemistry and potential role as a new clean catalytic technology. © The Royal Society of Chemistry 2013.

Heterogeneous catalysts for clean technology:spectroscopy, design, and monitoring

Reactive, but not a reactant. Heterogeneous catalysts play an unseen role in many of today's processes and products. With the increasing emphasis on sustainability in both products and processes, this handbook is the first to combine the hot topics of heterogeneous catalysis and clean technology. It focuses on the development of heterogeneous catalysts for use in clean chemical synthesis, dealing with how modern spectroscopic techniques can aid the design of catalysts for use in liquid phase reactions, their application in industrially important chemistries - including selective oxidation, hydrogenation, solid acid- and base-catalyzed processes - as well as the role of process intensification and use of renewable resources in improving the sustainability of chemical processes. With its emphasis on applications, this book is of high interest to those working in the industry.

Designing heterogeneous catalysts for biodiesel synthesis

Concerns over dwindling oil reserves, carbon dioxide emissions from fossil fuel sources and associated climate change is driving the urgent need for clean, renewable energy supplies. The conversion of triglycerides to biodiesel via catalytic transesterification remains an energetically efficient and attractive means to generate transportation fuel1. However, current biodiesel manufacturing routes employing soluble alkali based catalysts are very energy inefficient producing copious amounts of contaminated water waste during fuel purification. Technical advances in catalyst and reactor design and introduction of non-food based feedstocks are thus required to ensure that biodiesel remains a key player in the renewable energy sector for the 21st century. This presentation will give an overview of some recent developments in the design of solid acid and base catalysts for biodiesel synthesis. A particular focus will be on the benefits of designing materials with interconnected hierarchical macro-mesoporous networks to enhance mass-transport of viscous plant oils during reaction.

Hierarchical macroporous mesoporous materials 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 routes to utilize renewable feedstocks as sustainable sources of fuels. Catalysis has a rich history of facilitating energy efficient selective molecular transformations and contributes to 90% of chemical manufacturing processes and to more than 20% of all industrial products. In a post-petroleum era catalysis will be central to overcoming the engineering and scientific barriers to economically feasible routes to bio-fuels. This article will highlight some of the recent developments in the development of solid acid and base catalysts for the transesterification of oils to biodiesel. Particular attention will be paid to the challenges faced when developing new catalysts and importance of considering the design of pore architectures to improve in-pore diffusion of bulky substrates. © 2011 Materials Research Society.

Hierarchical porous catalysts tailored for biodiesel production

There is a pressing need for sustainable transportation fuels to combat both climate change and dwindling fossil fuel reserves. Biodiesel, synthesised from non-food plant (e.g., Jatropha curcas) or algal crops is one possible solution, but its energy efficient production requires design of new solid catalysts optimized for the bulky triglyceride and fatty acid feedstocks. Here we report on the synthesis of hierarchical macroporous-mesoporous silica and alumina architectures, and their subsequent functionalization by propylsulfonic acid groups or alkaline earth oxides to generate novel solid acid and base catalysts. These materials possess high surface areas and well-defined, interconnected macro-mesopore networks with respective narrow pore size distributions tuneable around 300 nm and 5 nm. Their high conductivity and improved mass transport characteristics enhance activity towards transesterification of bulky tricaprylin and palmitic acid esterification, over mesoporous analogues. This opens the way to the wider application of hierarchical catalysts in biofuel synthesis and biomass conversion.

Heterogeneous catalysts for biodiesel production

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 non-toxic and biodegradable, with the potential for closed CO2 cycles and thus vastly reduced carbon footprints compared with petroleum fuels. However, current manufacturing routes employing soluble catalysts are very energy inefficient and produce copious amounts of contaminated water waste. This review highlights the significant progress made in recent years towards developing solid acid and base catalysts for biodiesel synthesis. Issues to be addressed in the future are also discussed including the introduction of non-edible oil feedstocks, as well as technical advances in catalyst and reactor design to ensure that biodiesel remains a key player in the renewable energy sector for the 21st century.

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.

Promoter effects in the polymerisation of a mixed hydrocarbon feed with silica-supported BF3

The activity of a silica-supported BF3–methanol solid acid catalyst in the cationic polymerisation of an industrial aromatic C9 feedstock has been investigated. Reuse has been achieved under continuous conditions. Titration of the catalyst acid sites with triethylphosphine oxide (TEPO) in conjunction with 31P MAS NMR shows the catalyst to have two types of acid sites. Further analysis with 2,6 di-tert-butyl-4-methylpyridine (DBMP) has revealed the majority of these acid sites to be Brønsted in nature. The role of α-methylstyrene in promoting resin polymerisation via chain transfer is proposed.

Polymerisations in mesoporous environments

The solid acid supported aluminium chloride is an effective cationic initiator for the polymerisation of hydrocarbons. Reactions are highly dependent on the nature of the active sites and the Lewis/Bronsted acid balance in particular.

Catalytic upgrading of bio-oils by esterification

Biomass is the term given to naturally-produced organic matter resulting from photosynthesis, and represents the most abundant organic polymers on Earth. Consequently, there has been great interest in the potential exploitation of lignocellulosic biomass as a renewable feedstock for energy, materials and chemicals production. The energy sector has largely focused on the direct thermochemical processing of lignocellulose via pyrolysis/gasification for heat generation, and the co-production of bio-oils and bio-gas which may be upgraded to produce drop-in transportation fuels. This mini-review describes recent advances in the design and application of solid acid catalysts for the energy efficient upgrading of pyrolysis biofuels.

Valorisation of vietnamese rice straw waste:catalytic aqueous phase reforming of hydrolysate from steam explosion to platform chemicals

A family of tungstated zirconia solid acid catalysts were synthesised via wet impregnation and subsequent thermochemical processing for the transformation of glucose to 5-hydroxymethylfurfural (HMF). Acid strength increased with tungsten loading and calcination temperature, associated with stabilisation of tetragonal zirconia. High tungsten dispersions of between 2 and 7 W atoms·nm−2 were obtained in all cases, equating to sub-monolayer coverages. Glucose isomerisation and subsequent dehydration via fructose to HMF increased with W loading and calcination temperature up to 600 °C, indicating that glucose conversion to fructose was favoured over weak Lewis acid and/or base sites associated with the zirconia support, while fructose dehydration and HMF formation was favoured over Brönsted acidic WOx clusters. Aqueous phase reforming of steam exploded rice straw hydrolysate and condensate was explored heterogeneously for the first time over a 10 wt% WZ catalyst, resulting in excellent HMF yields as high as 15% under mild reaction conditions.

Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF

The grafting and sulfation of zirconia conformal monolayers on SBA-15 to create mesoporous catalysts of tunable solid acid/base character is reported. Conformal zirconia and sulfated zirconia (SZ) materials exhibit both Brönsted and Lewis acidity, with the Brönsted/Lewis acid ratio increasing with film thickness and sulfate content. Grafted zirconia films also exhibit amphoteric character, whose Brönsted/Lewis acid site ratio increases with sulfate loading at the expense of base sites. Bilayer ZrO2/SBA-15 affords an ordered mesoporous material with a high acid site loading upon sulfation and excellent hydrothermal stability. Catalytic performance of SZ/SBA-15 was explored in the aqueous phase conversion of glucose to 5-HMF, delivering a 3-fold enhancement in 5-HMF productivity over nonporous SZ counterparts. The coexistence of accessible solid basic/Lewis acid and Brönsted acid sites in grafted SZ/SBA-15 promotes the respective isomerization of glucose to fructose and dehydration of reactively formed fructose to the desired 5-HMF platform chemical.