Chemically accurate predictions for water adsorption on Brønsted sites of zeolite H-MFI.

We investigate the adsorption of water molecules in the zeolite H-MFI at isolated Brønsted acid sites (BAS) for loadings of 1, 2, and 3 H2O/BAS. We consider two approaches to the O3Al-O(H)-Si sites: the Brønsted-type approach of H2O to the acidic proton and the Lewis-type approach to the aluminium atom of the AlO4 tetrahedron. From the twelve crystallographically inequivalent framework sites for Al, a representative set of six active site positions is chosen. For them, we calculate CCSD(T)-quality adsorption energies at MP2-quality adsorption structures for different approaches, 48 in total. The Brønsted-type approach is favoured for most cases but the Lewis-type approach has similar stability for some framework positions. We predict heats of adsorption per molecule ranging from 60 to 76, 56 to 65, and 56 to 64 kJ mol-1 for loadings of 1, 2, and 3 H2O/BAS, respectively. For 1 H2O/BAS, the experimental result (70 kJ mol-1) falls into the range of our predictions, whereas for 2 and 3 H2O/BAS, the measured adsorption heats per molecule (74 and 70 kJ mol-1, respectively) are larger than our predictions. For 2 H2O/BAS, the ion-pair structure generated by proton transfer to the water dimer competes with the neutral adsorption complex. The DFT adsorption energies (PBE+D2) deviate significantly from the CCSD(T)-quality reference energies, by up to 25 kJ mol-1 for 1 H2O/BAS, 25 kJ mol-1 per H2O for 2 H2O/BAS, and 18 kJ mol-1 per H2O for 3 H2O/BAS. Specifically, PBE+D2 overstabilises the ion-pair structure, i.e. in many cases the PBE+D2 error is much larger for ionic than for neutral adsorption structures.

Spectroscopic Signatures of Internal Hydrogen Bonds of Brønsted-Acid Sites in the Zeolite H-MFI.

The location of Brønsted-acid sites (bridging OH groups, b-OH) at different crystallographic positions of zeolite catalysts influences their reactivity due to varying confinement. Selecting the most stable b-OH conformers at each of the 12 T-sites (T=Si/Al) of H-MFI, a representative set of 26 conformers is obtained which includes free b-OH groups pointing into the empty pore space and b-OH groups forming H-bonds across five- or six-membered rings of TO4 tetrahedra. Chemically accurate coupled-cluster-quality calculations for periodic models show that the strength of internal H-bonds and, hence, the OH bond length vary substantially with the framework position. For 11 of the 19 H-bonded b-OH groups examined, our predictions fall into the full width at half maximum range of the experimental signals at 3250±175 cm-1 and 7.0±1.4 ppm which supports previously debated assignments of these signals to H-bonded b-OH sites.