Structural Characterization of Phosphate Species Adsorbed on γ-Alumina by Combining DNP Surface Enhanced NMR Spectroscopy and DFT Calculations

Abstract

Obtaining an atomic-scale description of the chemical interactions of phosphates with an oxide support, such as γ-Al 2 O 3 , is essential to get a rational understanding of the role of phosphate additives for a great number of heterogeneous catalysts, as well as to improve the use of this element. Combining cutting-edge Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) techniques with Density Functional Theory (DFT) calculations, we provide an accurate molecular description of phosphate speciation on γ-Al 2 O 3 surfaces for various P surface coverages after drying at 120 °C. Thanks to 31 P doubleand triple-quantum filtered NMR experiments as well as to 27 Al− 31 P dipolar-and scalar-based correlation spectra, we demonstrate the presence of polyphosphates and of Al−O−P connectivities at the exposed facets of γ-Al 2 O 3 . DFT-based thermodynamics shows that phosphates (mono-or di-) are preferentially covalently bonded on the (1 1 0) γ-Al 2 O 3 facet with high-dentation modes. These high-dentation modes are favored by entropy gain due to water desorption. We used the gauge-including projector-augmented wave (GIPAW) DFT method for 31 P NMR chemical shifts calculations and propose a systematic identification of the various types of phosphates covalently or noncovalently bonded to the alumina surface. The calculations confirm the existence of polyphosphates as observed experimentally. Since the surface condensation into polyphosphates is endergonic, the presence of polyphosphates on the surface is likely to result from their direct adsorption in impregnation solution. The observed increasing concentration of polyphosphates with the coverage could be related to a less likely hydrolysis due to the reduced availability of sites to stabilize the fragmented oligomers. This understanding opens the way to a better control over the speciation of phosphate species that are known to be key in the preparation of supported catalysts over alumina.

Effect of Crystalline Phase and Facet Nature on the Adsorption of Phosphate Species onto TiO2 Nanoparticles

“…As discussed in the Materials and Methods part, our experimental work focused on a pH of 2, promoting the dihydrogen phosphate adsorption onto the particles, although H 3 PO 4 , which is present at a similar concentration, can also be adsorbed. ,,, …”

“…At this pH value, H 3 PO 4 and H 2 PO 4 – exist at comparable concentrations. Even if dihydrogen phosphate anion may adsorb preferentially to the surface of the nanoparticles, since the TiO 2 surface is positively charged at this pH, H 3 PO 4 can also adsorb . We therefore refer to phosphate species in the following text.…”

“…Even if dihydrogen phosphate anion may adsorb preferentially to the surface of the nanoparticles, since the TiO 2 surface is positively charged at this pH, H 3 PO 4 can also adsorb. 31 We therefore refer to phosphate species in the following text. Note also that in the rest of the experimental protocol, the given values correspond to the total amount of phosphate species in solution.…”

“…As discussed in the Materials and Methods part, our experimental work focused on a pH of 2, promoting the dihydrogen phosphate adsorption onto the particles, although H 3 PO 4 , which is present at a similar concentration, can also be adsorbed. 25,31,50,51 Phosphate Species Adsorption Isotherms. The adsorption isotherm curves shown in Figure 6 depict the adsorption behaviors of anatase and rutile.…”

Enhanced phosphate removal with fine activated alumina synthesized from a sodium aluminate solution: performance and mechanism

“…12 The peak at 133.4 eV corresponds to H 3 PO 4 or AlPO 4 and resulted from the chemisorption of H 2 PO 4 − on AlO 4 sites. 45,46…”