Influences of Divalent Ions in Natural Seawater/River Water on Nanofluidic Osmotic Energy Generation

Besides the dominant NaCl, natural seawater/river water contains trace multivalent ions, which can provide effective screening of surface charges. Here, in both negatively and positively charged nanopores, influences from divalent ions as counterions and co-ions have been investigated with respect to the performance of osmotic energy conversion (OEC) under natural salt gradients. As counterions, trace Ca²⁺ ions can suppress the electric power and conversion efficiency significantly. The reduced OEC performance is due to the bivalence and low diffusion coefficient of Ca²⁺ ions instead of the uphill transport of divalent ions discovered in the previous work. Effectively screened charged surfaces by Ca²⁺ ions induce an enhanced diffusion of Cl^- ions which simultaneously decreases the net ion penetration and ionic selectivity of the nanopore. As co-ions, Ca²⁺ ions have weak effects on the OEC performance. The promotion from charged exterior surfaces in OEC processes for ultrashort nanopores is also studied, with an effective region of ∼200 nm in width beyond pore boundaries independent of the presence of Ca²⁺ ions. Our results shed light on the physical details of the nanofluidic OEC process under natural seawater/river water conditions, which can provide a useful guide for high-performance osmotic energy harvesting.