Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C=O over C=C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C=O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes.

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.

Ag alloyed Pd single-atom catalysts for efficient selective hydrogenation of acetylene to ethylene in excess ethylene

Semihydrogenation of acetylene in an ethylene-rich stream is an industrially important process. Conventional supported monometallic Pd catalysts offer high acetylene conversion, but they suffer from very low selectivity to ethylene due to overhydrogenation and the formation of carbonaceous deposits. Herein, a series of Ag alloyed Pd single-atom catalysts, possessing only ppm levels of Pd, supported on silica gel were prepared by a simple incipient wetness coimpregnation method and applied to the selective hydrogenation of acetylene in an ethylene-rich stream under conditions close to the front-end employed by industry. High acetylene conversion and simultaneous selectivity to ethylene was attained over a wide temperature window, surpassing an analogous Au alloyed Pd single-atom system we previously reported. Restructuring of AgPd nanoparticles and electron transfer from Ag to Pd were evidenced by in situ FTIR and in situ XPS as a function of increasing reduction temperature. Microcalorimetry and XANES measurements support both geometric and electronic synergetic effects between the alloyed Pd and Ag. Kinetic studies provide valuable insight into the nature of the active sites within these AgPd/SiO2 catalysts, and hence, they provide evidence for the key factors underpinning the excellent performance of these bimetallic catalysts toward the selective hydrogenation of acetylene under ethylene-rich conditions while minimizing precious metal usage.

Thermochemical conversion of Brewers Spent Grain combined with catalytic reforming of pyrolysis vapours

The brewing process is an energy intensive process that uses large quantities of heat and electricity. To produce this energy requires a high, mainly fossil fuel consumption and the cost of this is increasing each year due to rising fuel costs. One of the main by-products from the brewing process is Brewers Spent Grain (BSG), an organic residue with very high moisture content. It is widely available each year and is often given away as cattle feed or disposed of to landfill as waste. Currently these methods of disposal are also costly to the brewing process. The focus of this work was to investigate the energy potential of BSG via pyrolysis, gasification and catalytic steam reforming, in order to produce a tar-free useable fuel gas that can be combusted in a CHP plant to develop heat and electricity. The heat and electricity can either be used on site or exported. The first stage of this work was the drying and pre-treatment of BSG followed by characterisation to determine its basic composition and structure so it can be evaluated for its usefulness as a fuel. A thorough analysis of the characterisation results helps to better understand the thermal behaviour of BSG feedstock so it can be evaluated as a fuel when subjected to thermal conversion processes either by pyrolysis or gasification. The second stage was thermochemical conversion of the feedstock. Gasification of BSG was explored in a fixed bed downdraft gasifier unit. The study investigated whether BSG can be successfully converted by fixed bed downdraft gasification operation and whether it can produce a product gas that can potentially run an engine for heat and power. In addition the pyrolysis of BSG was explored using a novel “Pyroformer” intermediate pyrolysis reactor to investigate the behaviour of BSG under these processing conditions. The physicochemical properties and compositions of the pyrolysis fractions obtained (bio-oil, char and permanent gases) were investigated for their applicability in a combined heat power (CHP) application.

Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions

The selective liquid phase hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on SiO2, ZnO, γ-Al2O3, CeO2 is reported under extremely mild conditions. Ambient hydrogen pressure, and temperatures as low as 50 °C are shown sufficient to drive furfural hydrogenation with high conversion and >99% selectivity to furfuryl alcohol. Strong support and solvent dependencies are observed, with methanol and n-butanol proving excellent solvents for promoting high furfuryl alcohol yields over uniformly dispersed 4 nm Pt nanoparticles over MgO, CeO2 and γ-Al2O3. In contrast, non-polar solvents conferred poor furfural conversion, while ethanol favored acetal by-product formation. Furfural selective hydrogenation can be tuned through controlling the oxide support, reaction solvent and temperature.

Platinum-catalysed cinnamaldehyde hydrogenation in continuous flow

Platinum is one of the most widely used hydrogenation catalysts. Here we describe the translation of batch reactions to continuous flow, affording tunable C=O versus C=C hydrogenation over a Pt/SiO2 catalyst, resulting in high steady state activity and single-pass yields in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol under mild conditions. Negligible catalyst deactivation occurs under extended flow operation due to removal of reactively-formed poisons from the reaction zone. Process intensification imparts a four-fold enhancement in cinnamyl alcohol productivity.

Catalytic supercritical water gasification of plastics with supported RuO2:a potential solution to hydrocarbons-water pollution problem

Here we report on a potential catalytic process for efficient clean-up of plastic pollution in waters, such as the Great Pacific Garbage Patch (CPGP). Detailed catalytic mechanisms of RuO2 during supercritical water gasification of common polyolefin plastics including low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP) and polystyrene (PP), have been investigated in a batch reactor at 450 °C, 60 min. All four plastics gave very high carbon gasification efficiencies (CGE) and hydrogen gasification efficiencies (HGE). Methane was the highest gas component, with a yield of up to 37 mol kg−1LDPE using the 20 wt% RuO2 catalyst. Evaluation of the gas yields, CGE and HGE revealed that the conversion of PS involved thermal degradation, steam reforming and methanation; whereas hydrogenolysis was a possible additional mechanism during the conversion of aliphatic plastics. The process has the benefits of producing a clean-pressurized methane-rich fuel gas as well as cleaning up hydrocarbons-polluted waters.

An investigation of support effects on the Pt-catalysed selective transformation of α,β-unsaturated substrates

Pt catalyst series were prepared on mesoporous SBA-15, SBA-16, KIT-6, true liquidcrystal-templated meso-macroporous SBA-15 and a commercial, low surface area silicasupport. Support structure can be easily fabricated using surfactant templating as a mode ofstringent control on porosity, surface area and internal structure. The impact of varying Pt-support physicochemical properties was systematically studied for the selective transformation of allylic substrates under chemoselective oxidation and hydrogenation regimes, a class of reactions highly applicable to industry. Pt-based heterogeneous catalysts are well-known for their utilisation in the hydrogenation of α,β-unsaturated aldehydes,although the mode of action and lack of systematic studies in the literature fuels continuing debate into the role of Pt nanoparticles and support choice for this area. This project attempts to shed some light on several frequently asked questions in this field. Successful support synthesis and stability after Pt impregnation is confirmed through HRTEM, XRD and N2 porosimetry. Decreasing metal loading promoted dispersion values,regardless of support choice, with surface PtO2 content also showing visible enhancement.Increasing support surface area and mesoporosity exhibited the following trend on Pt dispersion augmentation; low surface area commercial silica < true liquid crystal-templated SBA-15 < SBA-15 < SBA-16 ~ KIT-6. For the selective oxidation of cinnamyl alcohol,increasing PtO2 surface population confers substantial rate enhancements, with turnover frequencies evidencing PtO2 to be the active species .In the Pt-catalysed hydrogenation of cinnamaldehyde, strong support insensitivity was observed towards catalytic activity; as turnover frequencies normalised to Pt metal reveal constant values. However, structure sensitivity to the desired unsaturated alcohol arose,evidencing the requirement of flat, extended Pt (111) facets for C=O hydrogenation. Pt/SBA-15 proved the most selective, reflecting suppressed cinnamyl alcohol hydrogenation, with DRIFTS and in-situ ATR-IR evidencing the key role of support polarity in re-orientation of cinnamaldehyde to favour di-σCO adsorption and C=O versus C=C hydrogenation. High pressures increased activity, whilst a dramatic shift in selectivity from dominant C=C (1 bar)to C=O hydrogenation (10 bar) was also observed, attributed to surface crowding and suppression of di-σCC and η4 di-σCO+πC=C cinnamaldehyde binding modes.

Effect of Cu and Sn promotion on the catalytic deoxygenation of model and algal lipids to fuel-like hydrocarbons over supported Ni catalysts

The ability of Cu and Sn to promote the performance of a 20% Ni/Al2O3 catalyst in the deoxygenation of lipids to fuel-like hydrocarbons was investigated using model triglyceride and fatty acid feeds, as well as algal lipids. In the semi-batch deoxygenation of tristearin at 260 °C a pronounced promotional effect was observed, a 20% Ni-5% Cu/Al2O3 catalyst affording both higher conversion (97%) and selectivity to C10-C17 alkanes (99%) in comparison with unpromoted 20% Ni/Al2O3 (27% conversion and 87% selectivity to C10-C17). In the same reaction at 350 °C, a 20% Ni-1% Sn/Al2O3 catalyst afforded the best results, giving yields of C10-C17 and C17 of 97% and 55%, respectively, which contrasts with the corresponding values of 87 and 21% obtained over 20% Ni/Al2O3. Equally encouraging results were obtained in the semi-batch deoxygenation of stearic acid at 300 °C, in which the 20% Ni-5% Cu/Al2O3 catalyst afforded the highest yields of C10-C17 and C17. Experiments were also conducted at 260 °C in a fixed bed reactor using triolein − a model unsaturated triglyceride − as the feed. While both 20% Ni/Al2O3 and 20% Ni-5% Cu/Al2O3 achieved quantitative yields of diesel-like hydrocarbons at all reaction times sampled, the Cu-promoted catalyst exhibited higher selectivity to longer chain hydrocarbons, a phenomenon which was also observed in experiments involving algal lipids as the feed. Characterization of fresh and spent catalysts indicates that Cu enhances the reducibility of Ni and suppresses both cracking reactions and coke-induced deactivation.

Catalytic applications of waste derived materials

Sustainability has become a watchword and guiding principle for modern society, and with it a growing appreciation that anthropogenic 'waste', in all its manifold forms, can offer a valuable source of energy, construction materials, chemicals and high value functional products. In the context of chemical transformations, waste materials not only provide alternative renewable feedstocks, but also a resource from which to create catalysts. Such waste-derived heterogeneous catalysts serve to improve the overall energy and atom-efficiency of existing and novel chemical processes. This review outlines key chemical transformations for which waste-derived heterogeneous catalysts have been developed, spanning biomass conversion to environmental remediation, and their benefits and disadvantages relative to conventional catalytic technologies.

Supercritical water gasification of RDF and its components over RuO2/γ-Al2O3 catalyst:new insights into RuO2 catalytic reaction mechanisms

Five samples including a composite refuse derived fuel (RDF) and four combustible components of municipal solid wastes (MSW) have been reacted under supercritical water conditions in a batch reactor. The reactions have been carried out at 450 °C for 60 min reaction time, with or without 20 wt% RuO2/gamma-alumina catalyst. The reactivities of the samples depended on their compositions; with the plastic-rich samples, RDF and mixed waste plastics (MWP), giving similar product yields and compositions, while the biogenic samples including mixed waste wood (MWW) and textile waste (TXT) also gave similar reaction products. The use of the heterogeneous ruthenium-based catalyst gave carbon gasification efficiencies (CGE) of up to 99 wt%, which was up by at least 83% compared to the non-catalytic tests. In the presence of RuO2 catalyst, methane, hydrogen and carbon dioxide became the dominant gas products for all five samples. The higher heating values (HHV) of the gas products increased at least two-fold in the presence of the catalyst compared to non-catalytic tests. Results show that the ruthenium-based catalyst was active in feedstock steam reforming, methanation and possible direct hydrogenolysis of C-C bonds. This work provides new insights into the catalytic mechanisms of RuO2 during SCWG of carbonaceous materials, along with the possibility of producing high yields of methane from MSW fractions.

Hierarchical mesoporous Pd/ZSM-5 for the selective catalytic hydrodeoxygenation of m-cresol to methylcyclohexane

Mesopore incorporation into ZSM-5 enhances the dispersion of Pd nanoparticles throughout the hierarchical framework, significantly accelerating m-cresol conversion relative to a conventional microporous ZSM-5, and dramatically increasing selectivity towards the desired methylcyclohexane deoxygenated product. Increasing the acid site density further promotes m-cresol conversion and methylcyclohexane selectivity through efficient dehydration of the intermediate methylcyclohexanol.

Acetylene hydrogenation over structured Au-Pd catalysts

Acknowledgements We thank the University of Aberdeen for financial support and Dr K. McManus (University of Aberdeen) for performing preliminary experiments with these samples. Electron microscopy and EDS were performed by RTB at the Electron Microscopy Facility, University of St Andrews.

Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

We acknowledge the contribution of Dr. N. Perret to this work. EPSRC support for free access to the TEM/SEM facility at the University of St. Andrews and financial support to Dr. X. Wang and Y. Hao through the Overseas Research Students Award Scheme (ORSAS) are also acknowledged.