Hydrogen bonding of water confined in mesoporous silica MCM-41 and SBA-15 studied by 1H solid-state NMR

Chemistry. 2004 Nov 5;10(22):5689-96. doi: 10.1002/chem.200400351.

Abstract

The adsorption of water in two mesoporous silica materials with cylindrical pores of uniform diameter, MCM-41 and SBA-15, was studied by 1H MAS (MAS=magic angle spinning) and static solid-state NMR spectroscopy. All observed hydrogen atoms are either surface -SiOH groups or hydrogen-bonded water molecules. Unlike MCM-41, some strongly bound water molecules exist at the inner surfaces of SBA-15 that are assigned to surface defects. At higher filling levels, a further difference between MCM-41 and SBA-15 is observed. Water molecules in MCM-41 exhibit a bimodal line distribution of chemical shifts, with one peak at the position of inner-bulk water, and the second peak at the position of water molecules in fast exchange with surface -SiOH groups. In SBA-15, a single line is observed that shifts continuously as the pore filling is increased. This result is attributed to a different pore-filling mechanism for the two silica materials. In MCM-41, due to its small pore diameter (3.3 nm), pore filling by pore condensation (axial-pore-filling mode) occurs at a low relative pressure, corresponding roughly to a single adsorbed monolayer. For SBA-15, owing to its larger pore diameter (8 nm), a gradual increase in the thickness of the adsorbed layer (radial-pore-filling mode) prevails until pore condensation takes place at a higher level of pore filling.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Hydrogen Bonding
  • Magnetic Resonance Spectroscopy
  • Models, Chemical
  • Molecular Structure
  • Nitrogen / chemistry
  • Porosity
  • Protons
  • Silicon Dioxide / chemistry*
  • Water / chemistry*

Substances

  • MCM-41
  • Protons
  • SBA-15
  • Water
  • Silicon Dioxide
  • Nitrogen