Fluids and Electrolytes under Confinement in Single-Digit Nanopores


Confined fluids and electrolytes in nanopores exhibit rich and surprising physics and chemistry that impact the mass transport and energy efficiency in many important natural systems and industrial applications. Existing theories often fail to predict the exotic effects observed in the narrowest of such pores, called Single Digit Nanopores (SDNs), which have diameters or conduit widths of less than 10 nm and have only recently become accessible for experimental measurements. What SDNs unveil have been surprising, including a rapidly increasing number of examples such as extraordinarily fast water transport, distorted fluid phase boundaries, strong ion correlation and quantum effects, breakdown of the Nernst-Einstein relation, and dielectric anomalies not observed in larger pores. Exploiting these effects presents myriad opportunities in both basic and applied research that stand to impact a host of new technologies at the water-energy nexus, from new membranes for precise separations and water purification to new gas permeable materials for water electrolyzers and energy storage devices. SDNs also present unique opportunities to achieve ultrasensitive and selective chemical sensing at the single ion single molecule limit. In this review article, we summarize the progress on nanofluidics of SDNs, with a focus on the confinement effects that arise in these extremely narrow nanopores. The recent development of precision model systems, transformative experimental tools, and multi-scale theories that have played enabling roles in advancing this frontier are reviewed. We also identify new knowledge gaps in our understanding of nanofluidic transport and provide an outlook for the future challenges and opportunities at this rapidly advancing frontier.

Chem. Rev., 123 2737-2831 (2023)
Heather J. Kulik
Heather J. Kulik
Professor of Chemical Engineering and Chemistry