Interfacial Super-Assembly of Ordered Mesoporous Silica-Alumina Heterostructure Membranes with pH-Sensitive Properties for Osmotic Energy Harvesting.

Osmotic energy existing between seawater and freshwater is a potential blue energy source that can mitigate the energy crisis and environmental pollution problems. Nanofluidic devices are widely utilized to capture this blue energy owing to their unique ionic transport properties in the nanometer scale. However, with respect to nanofluidic membrane devices, high membrane inner resistance and a low power density induced by disordered pores and thick coating as well as difficulty in manufacturing still impede their real-world applications. Here, we demonstrate an interfacial super-assembly strategy that is capable of fabricating ordered mesoporous silica/macroporous alumina (MS/AAO) framework-based nanofluidic heterostructure membranes with a thin and ordered mesoporous silica layer. The presence of a mesoporous silica layer with abundant silanol and a high specific surface area endows the heterostructure membrane with a low membrane inner resistance of about 7 KΩ, excellent ion selectivity, and osmotic energy conversion ability. The power density can reach up to 4.50 W/m by mixing artificial seawater and river water through the membrane, which is 20 times higher than that of the conventional 2D nanofluidic membrane, and outperforms about 30% compared to other 3D porous membranes. More intriguingly, the interesting pH-sensitive osmotic energy conversion property of the MS/AAO membrane is subsequently recognized, which can realize a higher power density even in acidic or alkaline wastewater, expanding the application range, especially in practical applications. This work presents a valuable paradigm for the use of mesoporous materials in nanofluidic devices and provides a way for large-scale production of nanofluidic devices.