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

Abstract: Besides the dominant NaCl, natural seawater/river water contains trace multivalent ions, which can provide effective screening to surface charges. Here, in both negatively and positively charged nanopores, influences from divalent ions as counterions and coions have been investigated on 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 enhanced diffusion of Cl ions which simultaneously decreases the net ion penetration and ionic selectivity of the nanopore. While as coions, Ca2+ ions have weak effects on the OEC performance. The promotion from charged exterior surfaces on OEC processes for ultra-short nanopores is also studied, which effective region is ~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.