Carmine D'Agostino

Molecular motion and ion diffusion in choline chloride based deep eutectic solvents studied by 1H pulsed field gradient NMR spectroscopy.

Deep Eutectic Solvents (DESs) are a novel class of solvents with potential industrial applications in separation processes, chemical reactions, metal recovery and metal finishing processes such as electrodeposition and electropolishing. Macroscopic physical properties such as viscosity, conductivity, eutectic composition and surface tension are already available for several DESs, but the microscopic transport properties for this class of compounds are not well understood and the literature lacks experimental data that could give a better insight into the understanding of such properties. This paper presents the first pulsed field gradient nuclear magnetic resonance (PFG-NMR) study of DESs. Several choline chloride based DESs were chosen as experimental samples, each of them with a different associated hydrogen bond donor. The molecular equilibrium self-diffusion coefficient of both the choline cation and hydrogen bond donor was probed using a standard stimulated echo PFG-NMR pulse sequence. It is shown that the increasing temperature leads to a weaker interaction between the choline cation and the correspondent hydrogen bond donor. The self-diffusion coefficients of the samples obey an Arrhenius law temperature-dependence, with values of self-diffusivity in the range of [10(-10)-10(-13) m(2) s(-1)]. In addition, the results also highlight that the molecular structure of the hydrogen bond donor can greatly affect the mobility of the whole system. While for ethaline, glyceline and reline the choline cation diffuses slower than the associated hydrogen bond donor, reflecting the trend of molecular size and molecular weight, the opposite behaviour is observed for maline, in which the hydrogen bond donor, i.e. malonic acid, diffuses slower than the choline cation, with self-diffusion coefficients values of the order of 10(-13) m(2) s(-1) at room temperature, which are remarkably low values for a liquid. This is believed to be due to the formation of extensive dimer chains between malonic acid molecules, which restricts the mobility of the whole system at low temperature (<30 °C), with malonic acid and choline chloride having almost identical diffusivity values. Diffusion and viscosity data were combined together to gain insights into the diffusion mechanism, which was found to be the same as for ionic liquids with discrete anions.

Solvent Effect and Reactivity Trend in the Aerobic Oxidation of 1,3‐Propanediols over Gold Supported on Titania: NMR Diffusion and Relaxation Studies

In recent work, it was reported that changes in solvent composition, precisely the addition of water, significantly inhibits the catalytic activity of Au/TiO2 catalyst in the aerobic oxidation of 1,4-butanediol in methanol due to changes in diffusion and adsorption properties of the reactant. In order to understand whether the inhibition mechanism of water on diol oxidation in methanol is generally valid, the solvent effect on the aerobic catalytic oxidation of 1,3-propanediol and its two methyl-substituted homologues, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol, over a Au/TiO2 catalyst has been studied here using conventional catalytic reaction monitoring in combination with pulsed-field gradient nuclear magnetic resonance (PFG-NMR) diffusion and NMR relaxation time measurements. Diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Combined NMR diffusion and relaxation time measurements suggest that molecular diffusion and, in particular, the relative strength of diol adsorption, are important factors in determining the conversion. These results highlight NMR diffusion and relaxation techniques as novel, non-invasive characterisation tools for catalytic materials, which complement conventional reaction data.

Assessing the surface modifications following the mechanochemical preparation of a Ag/Al2O3 selective catalytic reduction catalyst

The surface modification of a mechanochemically prepared Ag/Al2O3 catalyst compared with catalysts prepared by standard wet impregnated methods has been probed using two-dimensional T1–T2 NMR correlations, H2O temperature programmed desorption (TPD) and DRIFTS. The catalysts were examined for the selective catalytic reduction of NOx using n-octane in the presence and absence of H2. Higher activities were observed for the ball milled catalysts irrespective of whether H2 was added. This higher activity is thought to be related to the increased affinity of the catalyst surface towards the hydrocarbon relative to water, following mechanochemical preparation, resulting in higher concentrations of the hydrocarbon and lower concentrations of water at the surface. DRIFTS experiments demonstrated that surface isocyanate was formed significantly quicker and had a higher surface concentration in the case of the ball milled catalyst which has been correlated with the stronger interaction of the n-octane with the surface. This increased interaction may also be the cause of the reduced activation barrier measured for this catalyst compared with the wet impregnated system. The decreased interaction of water with the surface on ball milling is thought to reduce the effect of site blocking whilst still providing a sufficiently high surface concentration of water to enable effective hydrolysis of the isocyanate to form ammonia and, thereafter, N2.

Interpretation of NMR Relaxation as a Tool for Characterising the Adsorption Strength of Liquids inside Porous Materials

Nuclear magnetic resonance (NMR) relaxation times are shown to provide a unique probe of adsorbate–adsorbent interactions in liquid-saturated porous materials. A short theoretical analysis is presented, which shows that the ratio of the longitudinal to transverse relaxation times (T1/T2) is related to an adsorbate–adsorbent interaction energy, and we introduce a quantitative metric esurf (based on the relaxation time ratio) characterising the strength of this surface interaction. We then consider the interaction of water with a range of oxide surfaces (TiO2 anatase, TiO2 rutile, γ-Al2O3, SiO2, θ-Al2O3 and ZrO2) and show that esurf correlates with the strongest adsorption sites present, as determined by temperature programmed desorption (TPD). Thus we demonstrate that NMR relaxation measurements have a direct physical interpretation in terms of the characterisation of activation energy of desorption from the surface. Further, for a series of chemically similar solid materials, in this case a range of oxide materials, for which at least two calibration values are obtainable by TPD, the esurf parameter yields a direct estimate of the maximum activation energy of desorption from the surface. The results suggest that T1/T2 measurements may become a useful addition to the methods available to characterise liquid-phase adsorption in porous materials. The particular motivation for this work is to characterise adsorbate–surface interactions in liquid-phase catalysis.

The effect of grafting zirconia and ceria onto alumina as a support for silicotungstic acid for the catalytic dehydration of glycerol to acrolein

The effect of ceria and zirconia grafting onto alumina (α and θ-δ phases) as supports for silicotungstic acid for the dehydration of glycerol to acrolein was studied. 30 % Silicotungstic acid (STA) supported on 5 % zirconia/δ,θ-alumina was the best catalyst, producing 85 % selectivity to acrolein at 100 % glycerol conversion, and it showed stable activity without using oxygen as a co-feed. The catalyst produced a STA of 90 g(acrolein)  kg(cat)(-1)  h(-1), which was greater than the STA simply supported on δ,θ-alumina, which only demonstrated 75 % selectivity towards acrolein. The effect of grafting on the support material was investigated by means of nitrogen adsorption, ammonia temperature-programmed desorption, thermogravimetric analysis, Raman spectroscopy, and powder X-ray diffraction. A pulsed-field gradient (PFG) NMR technique was also used to study diffusion processes associated with the catalysts. Diffusion studies of the grafted catalysts showed that zirconia contributes to the formation of more tortuous pathways within the pore structure, leading to the diminution of acid strength and making the catalyst less susceptible to coke formation.

Structure and dynamics of aqueous 2-propanol: a THz-TDS, NMR and neutron diffraction study

Aqueous liquid mixtures, in particular, those involving amphiphilic species, play an important role in many physical, chemical and biological processes. Of particular interest are alcohol/water mixtures; however, the structural dynamics of such systems are still not fully understood. Herein, a combination of terahertz time-domain spectroscopy (THz-TDS) and NMR relaxation time analysis has been applied to investigate 2-propanol/water mixtures across the entire composition range; while neutron diffraction studies have been carried out at two specific concentrations. Excellent agreement is seen between the techniques with a maximum in both the relative absorption coefficient and the activation energy to molecular motion occurring at ∼90 mol% H2O. Furthermore, this is the same value at which well-established excess thermodynamic functions exhibit a maximum/minimum. Additionally, both neutron diffraction and THz-TDS have been used to provide estimates of the size of the hydration shell around 2-propanol in solution. Both methods determine that between 4 and 5 H2O molecules per 2-propanol are found in the 2-propanol/water clusters at 90 mol% H2O. Based on the acquired data, a description of the structure of 2-propanol/water across the composition range is presented.

The effect of coke deposition on the activity and selectivity of the HZSM-5 zeolite during ethylbenzene alkylation reaction in the presence of ethanol

The alkylation of ethylbenzene (EB) with ethanol over HZSM-5 zeolite catalysts was carried out using a riser simulator reactor at different reaction temperatures and contact times. It was observed that the amount of coke deposited over the zeolite has a great influence on the reaction pathway. At higher temperature (400 °C), the spent catalyst was found to exhibit a much higher activity towards the alkylation products (DEB) as compared to the fresh catalyst. This difference between spent and fresh samples became less significant at lower temperature (250 °C). The highest yield of DEB products over the spent catalyst was obtained for intermediate temperatures (300–350 °C). The coke deposition was further analyzed using terahertz time-domain spectroscopy (THz-TDS), 27Al MAS NMR spectroscopy, TPO measurements and pyridine-FTIR. THz-TDS and TPO results revealed that the structure of coke formed on all catalysts is essentially the same, while pyridine-FTIR studies revealed that coke leads to a reduction in the acidity of the catalyst. 27Al MAS NMR results of spent samples suggested a relationship between alkylation activity and extra-framework aluminium species, which is possibly associated with the formation of very active Lewis sites. This work shows that an understanding and control of different types of catalytic sites over zeolite surfaces may improve and optimize reaction performances during alkylation of aromatics.

Deactivation studies of a carbon supported AuPt nanoparticulate catalyst in the liquid-phase aerobic oxidation of 1,2-propanediol

The aerobic oxidation of 1,2-propanediol in alkaline aqueous solvent over bimetallic AuPt/C catalysts has been studied and catalyst reusability has been assessed. A systematic decrease of catalytic conversion was observed after each reuse of the catalyst. In order to understand the causes of deactivation, the catalyst samples were characterised by N2 adsorption, temperature-programmed oxidation (TPO) and pulsed-field gradient nuclear magnetic resonance (PFG-NMR) diffusion measurements. The results revealed that the catalyst surface area and pore volume decrease significantly after each reuse of the catalyst. The intra-particle diffusion is characterised by two distinct diffusion regimes, a fast regime with self-diffusivities of 10−9–10−11 m2 s−1 and a slow diffusion regime, with values of self-diffusivities on the order of 10−11–10−13 m2 s−1. Self-diffusivity in the fast regime is assigned to diffusion within the mesoporous space of the catalyst. Self-diffusivity in the slow diffusion region is assigned to diffusion within the microporous space and decreases after each reuse of the catalyst in a trend similar to that of pore volume, suggesting that changes in catalyst porosity and pore structure affect molecular mobility within the micropores. TPO studies of these systems showed a different distribution of oxidation products in the reused catalyst samples compared to the fresh catalyst, which suggests changes of the combustion mechanism. Altogether, the results reveal that catalyst deactivation is caused by deposition and build-up of heavy molecular species on the catalyst surface, which reduce the catalyst porosity by pore blockage and narrowing of channels, which in turn affects the diffusion rate within the micropores.

Assessing the effect of reducing agents on the selective catalytic reduction of NOx over Ag/Al2O3 catalysts

We gratefully acknowledge funding for this work from the EPSRC CASTech grant (EP/G012156/1). Carmine D’Agostino would like to acknowledge Wolfson College, Cambridge, for supporting his research activities. The authors would also like to thank Dr Jonathan Mitchell for useful discussions.

Solvent inhibition in the liquid-phase catalytic oxidation of 1,4-butanediol: understanding the catalyst behaviour from NMR relaxation time measurements

Catalytic reaction studies and nuclear magnetic resonance (NMR) relaxation time measurements have been compared to study the influence of competitive adsorption of reactant and solvent on catalytic conversion. The reaction chosen is the aerobic catalytic oxidation of 1,4-butanediol in methanol over different supported-metal catalysts. From the NMR T1/T2 ratio, where T1 is the longitudinal and T2 the transverse spin relaxation time, the relative affinity of reactant and solvent for different catalytic surfaces is determined. The catalysts with the lowest activity show a preferential surface affinity for the solvent compared to the reactant. Conversely, the catalyst with the highest activity shows a preferential surface affinity for the reactant compared to the solvent. Significantly, Ru/SiO2, which is totally inactive for the oxidation of 1,4-butanediol, exhibited a lower T1/T2 ratio (surface affinity) for 1,4-butanediol (reactant) than for a “weakly-interacting” alkane, indicating a very poor surface affinity for the diol functionality. The results provide direct evidence of the importance of the adsorbate–adsorbent interactions on catalyst activity in liquid-phase oxidations and indicate that the competitive adsorption of the solvent plays an important role in these reactions. This work demonstrates that NMR relaxation time analysis is a powerful method for comparing adsorption of liquids in porous catalysts, providing valuable information on the affinity of different chemical species for a catalyst surface. Moreover, the results demonstrate that NMR relaxation time measurements can be used not only to guide selection of solvent for use with a specific catalyst, but also selection of the catalyst itself. The results suggest that this method may be used to predict catalyst behaviour, enabling improved design and optimisation of heterogeneous catalytic processes.