CO2-philicity to CO2-phobicity Transition on Smooth and Stochastic Rough Cu-like Substrate Surfaces

CO2 on metal substrates is essential to CO2 liquefaction and transportation of CO2, yet the manipulation of the wettability of the CO2 and the elucidation of its underlying mechanism have not been fully achieved. Here, using molecular dynamics simulations, we report CO2 wetting characteristics on both smooth and stochastic rough Cu-like substrate surfaces. The results indicate that the apparent contact angle (CA) of the CO2 droplet on the smooth surface decreases from 180(degrees) to 0(degrees) as the CO2-solid characteristic interaction energy increases from 0.002 to 0.016 eV. In addition, the CAs become greater with increasing the density of surface asperities, regardless of the intrinsic surface wettability. This is attributed to the capillary drying-out of liquid CO2 molecules in gaps between surface asperities at the three-phase contact line of the droplet, which is usually overlooked in previous theoretical studies. Notably, the intrinsically CO2-philic surface transforms to the CO2-phobic due to an increase in the density of surface rugosity. Moreover, we verify the range of applicability of the CA prediction models concerning the nanoscale asperities. This work is beneficial for fully understanding the influence of nanoscale surface topography on CO2 wettability and shedding light on the design of functionalized and patterned surfaces to manipulate CO2 wettability.

Automated summary

Using molecular dynamics simulations, this study investigates the wetting characteristics of CO2 on smooth and rough surfaces. The results show that the contact angle of CO2 droplets decreases on smooth surfaces with increasing CO2-solid interaction energy, while it increases on rough surfaces with higher surface roughness. The study also uncovers the capillary drying-out phenomenon of CO2 molecules at the three-phase contact line of the droplets, which has been overlooked in previous theoretical studies.