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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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The effect of water on the catalytic oxidation of 1,4-butanediol in methanol over Au/TiO2 has been investigated by catalytic reaction studies and NMR diffusion and relaxation studies. The addition of water to the dry catalytic system led to a decrease of both conversion and selectivity towards dimethyl succinate. Pulsed-field gradient (PFG)-NMR spectroscopy was used to assess the effect of water addition on the effective self-diffusivity of the reactant within the catalyst. NMR relaxation studies were also carried out to probe the strength of surface interaction of the reactant in the absence and presence of water. PFG-NMR studies revealed that the addition of water to the initial system, although increasing the dilution of the system, leads to a significant decrease of effective diffusion rate of the reactant within the catalyst. From T1 and T2 relaxation measurements it was possible to infer the strength of surface interaction of the reactant with the catalyst surface. The addition of water was found to inhibit the adsorption of the reactant over the catalyst surface, with the T1/ T2 ratio of 1,4-butanediol decreasing significantly when water was added. The results overall suggest that both the decrease of diffusion rate and adsorption strength of the reactant within the catalyst, due to water addition, limits the access of reactant molecules to the catalytic sites, which results in a decrease of reaction rate and conversion. [ABSTRACT FROM AUTHOR]

Tuning biochar surface properties: Biochars have a high surface area to volume ratio, making them ideal for adsorption-dependant environmental applications like wastewater treatment. Controlling both the chemistry and morphology of this surface area is key to optimising biochars for specific applications. Mild alkaline pretreatment of walnut shells is shown to modulate responses of these properties in derived biochars to production temperature. [Display omitted] • Surface chemistry of biochars was non-destructively analysed via NMR measurements. • Carbon bonding state of biochars by particle surface proximity was determined via XPS with ion beam etching. • Alkaline pretreatment modulates effects of pyrolysis conditions on adsorption properties of biochars. • Surface interactions of biochars with –OH groups increase, and those with –CH 3 groups decrease, due to alkaline pretreatment. • The hydrophilicity advantage of pretreatment is greatest at low pyrolysis temperatures (<250 °C). The surface chemistry and morphology of biochars produced by pyrolysis of walnut shells affects their utility for adsorption applications. Yet, little is known about surface interactions in the pores of these materials, mostly due to the challenging nature of accessing information at this length scale in a non-destructive manner. Here, for the first time, the relative adsorption strengths of solvents comprising different functional groups to internal (pore) surfaces of walnut shells and derived biochars were investigated using low-field nuclear magnetic resonance (NMR) relaxation time measurements to non-destructively probe interactions of fluids with pore surfaces. Carbon bonding state compositions of these materials with respect to distance from the particle surface were determined using X-ray photoelectron spectroscopy coupled with ion beam etching. Alkaline pretreatment was found to increase the hydrophilicity of both walnut shells and derived biochars. It was found to increase surface interactions with hydroxyl groups, and to decrease those with methyl groups. Results were contextualised by thermogravimetric analysis, scanning electron microscopy, and previous in-situ X-ray imaging results. Taken together, results showed that alkaline pretreatment may be used to modulate responses to pyrolysis temperature of several factors that affect adsorption properties including surface hydrophilicity, particle size, porosity, pore accessibility, and surface texture. [ABSTRACT FROM AUTHOR]