Amin Osatiashtiani

Bifunctional SO4/ZrO2 catalysts for 5-hydroxymethylfufural (5-HMF) production from glucose

The telescopic conversion of glucose to fructose and then 5-hydroxymethylfurfural (5-HMF), the latter a potential, bio-derived platform chemical feedstock, has been explored over a family of bifunctional sulfated zirconia catalysts possessing tuneable acid–base properties. Characterisation by acid–base titration, XPS, XRD and Raman reveal that submonolayer SO4 coverages offer the ideal balance of basic and Lewis–Bronsted acid sites required to respectively isomerise glucose to fructose, and subsequently dehydrate fructose to 5-HMF. A constant acid site normalised turnover frequency is observed for fructose dehydration to 5-HMF, confirming a common Bronsted acid site is responsible for this transformation.

Influence of alkyl chain length on sulfated zirconia catalysed batch and continuous esterification of carboxylic acids by light alcohols

The impact of alkyl chain length on the esterification of C2–C16 organic acids with C1–C4 alcohols has been systematically investigated over bulk and SBA-15 supported sulfated zirconias (SZs). Rates of catalytic esterification for methanol with acetic acid are directly proportional to the sulfur content for both SZ and SZ/SBA-15, with the high dispersion of SZ achievable in conformal coatings over mesoporous SBA-15 confering significant rate-enhancements. Esterification over the most active 0.24 mmol gcat−1 bulk SZ and 0.29 mmol gcat−1 SZ/SBA-15 materials was inversely proportional to the alkyl chain length of alcohol and acid reactants; being most sensitive to changes from methanol to ethanol and acetic to hexanoic acids respectively. Kinetic analyses reveal that these alkyl chain dependencies are in excellent accord with the Taft relationship for polar and steric effects in aliphatic systems and the enthalpy of alcohol adsorption, implicating a Langmuir–Hinshelwood mechanism. The first continuous production of methyl propionate over a SZ fixed-bed is also demonstrated.

Impact of macroporosity on catalytic upgrading of fast pyrolysis bio-oil by esterification over silica sulfonic acids

Abstract Fast pyrolysis bio‐oils possess unfavorable physicochemical properties and poor stability, in large part, owing to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom‐ and energy‐efficient route to upgrade pyrolysis bio‐oils. Propyl sulfonic acid (PrSO3H) silicas are active for carboxylic acid esterification but suffer mass‐transport limitations for bulky substrates. The incorporation of macropores (200 nm) enhances the activity of mesoporous SBA‐15 architectures (post‐functionalized by hydrothermal saline‐promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of the turnover frequency (TOF) enhancement increasing with carboxylic acid chain length from 5 % (C3) to 110 % (C12). Macroporous–mesoporous PrSO3H/SBA‐15 also provides a two‐fold TOF enhancement over its mesoporous analogue for the esterification of a real, thermal fast‐pyrolysis bio‐oil derived from woodchips. The total acid number was reduced by 57 %, as determined by GC×GC–time‐of‐flight mass spectrometry (GC×GC–ToFMS), which indicated ester and ether formation accompanying the loss of acid, phenolic, aldehyde, and ketone components.

Niobic acid nanoparticle catalysts for the aqueous phase transformation of glucose and fructose to 5-hydroxymethylfurfural

A family of bulk and SBA-15 supported peroxo niobic acid sols were prepared by peptisation of niobic acid precipitates with H2O2 as heterogeneous catalysts for aqueous phase glucose and fructose conversion to 5-hydroxymethylfurfural (5-HMF). Niobic acid nanoparticles possess a high density of Bronsted and Lewis acid sites, conferring good activity towards glucose and fructose conversion, albeit with modest 5-HMF yields under mild reaction conditions (100 °C). Thermally-induced niobia crystallisation suppresses solid acidity and activity. Nanoparticulate niobic acid dispersed over SBA-15 exhibits pure Bronsted acidity and an enhanced Turnover Frequency for fructose dehydration.

Efficient one-pot production of γ-valerolactone from xylose over Zr-Al-Beta zeolite: rational optimization of catalyst synthesis and reaction conditions

The one-pot conversion of xylose into γ-gammavalerolactone in 2-propanol over bifunctional Zr-Al-Beta zeolites, prepared via a post-synthetic route, was optimized in terms of both catalyst synthesis and reaction conditions. In the catalyst preparation, the use of Zr(NO3)4 as zirconium source as well as the tuning of the amount of water used during the impregnation had a strong impact on the activity of the Zr species due to an improved dispersion of Zr species. As for the aluminium to zirconium exchange, an optimal Al/Zr ratio of 0.20 was identified to provide a catalyst with better activity. The modelization of the catalytic system through experimental design methodology allowed to identify the optimal values of the most influential reaction conditions: temperature 190 °C, catalyst loading 15 g L−1, and starting xylose concentration 30.5 g L−1. Under these optimized reaction conditions, Zr-Al-Beta catalyst provides a GVL yield from xylose (ca. 34%) after only 10 h. The catalysts are stable and reusable after thermal regeneration at 550 °C.

Zirconia catalysed acetic acid ketonisation for pre-treatment of biomass fast pyrolysis vapours

Crude pyrolysis bio-oil contains significant quantities of carboxylic acids which limit its utility as a biofuel. Vapour phase ketonisation of organic acids contained within biomass fast-pyrolysis vapours offers a potential pre-treatment to improve the stability and energy content of resulting bio-oils formed upon condensation. Zirconia is a promising catalyst for such reactions, however little is known regarding the impact of thermal processing on the physicochemical properties of zirconia in the context of their corresponding reactivity for the vapour phase ketonisation of acetic acid. Here we show that calcination progressively transforms amorphous Zr(OH)4 into small tetragonal ZrO2 crystallites at 400 °C, and subsequently larger monoclinic crystallites >600 °C. These phase transitions are accompanied by an increase in the density of Lewis acid sites, and concomitant decrease in their acid strength, attributed to surface dehydroxylation and anion vacancy formation. Weak Lewis acid sites (and/or resulting acid-base pairs) are identified as the active species responsible for acetic acid ketonisation to acetone at 350 °C and 400 °C, with stronger Lewis acid sites favouring competing unselective reactions and carbon laydown. Acetone selectivity is independent of acid strength.

ZrO2-SBA-15 catalysts for the one-pot cascade synthesis of GVL from furfural

Controlling the thickness of zirconia monolayers coated over SBA-15 offers an effective way to tune catalytic performance for the acid-mediated and hydrogen transfer (Meerwein Ponndorf Verley, MPV) cascade transformation of furfural to γ-valerolactone. Complementary mechanistic and kinetic modelling establishes the existence of the two distinct zirconium active species (weak and strong acid sites), whose balancing enables optimisation of the cascade and hence maximal γ-valerolactone (GVL) production.