Water in PHI Nanopores: Modeling Adsorption, Solvent Structure, and Thermodynamics

[Image: see text] We modeled the uptake of water molecules into the nanopores of potassium-polyheptazineimide (K-PHI), a 2D covalent material that is one of the best water-splitting photocatalysts to date possessing experimentally reported strong water binding. In the current models, we find that first water molecules are bound with −94.5 kJ/mol, i.e., twice the cohesion energy of water and one of the highest adsorption enthalpies reported so far. This strong binding proceeds unexpectedly on a similar enthalpy level until the pore is filled, while the binding strength is passed through a conjugated water network. The tight binding is also expressed in calculated, strongly shortened O–O distances, which are on average about 5% shorter than in bulk water, which corresponds to a much higher water density, for a 2D structure above 1.1 g/ cm(3). The H-bridges are strongly aligned in the direction perpendicular to the covalent planes, which could give reasons for the experimentally observed ultrahigh ion fluxes and conductivity of K-PHI membranes. Decomposition of the adsorption energy into components reveals an unexpectedly high charge transfer contribution, where the partly naked K(+) ions play a key role. The latter fact not only offers a new structural lead motif for the design of more strongly, but reversibly binding adsorption materials involving metal ions on their surface but also puts cations as known cofactors in enzymes into a new light.