The lubrication properties of nanoconfined liquids underpin countless natural and industrial processes. However, our current understanding of lubricated friction is still limited, especially for nonideal interfaces exhibiting nanoscale chemical and topographical defects. Here, we use atomic force microscopy to explore the equilibrium and dynamical behavior of a model lubricant, squalane, confined between a diamond tip and graphite in the vicinity of an atomic step. We combine high-resolution imaging of the interface with highly localized shear measurements at different velocities and temperatures to derive a quantitative picture of the lubricated friction around surface defects. We show that defects tend to promote local molecular order and increase friction forces by reducing the number of stable molecular configurations in their immediate vicinity. The effect is general, can propagate over hundreds of nanometers, and can be quantitatively described by a semiempirical model that bridges the molecular details and mesoscale observations.

Group effect allows non-tethered small molecules to form a wide variety of self-assembled structures at solid–liquid interfaces.

Methanol occupies a central role in chemical synthesis and is considered an ideal candidate for cleaner fuel storage and transportation. It can be catalyzed from water and volatile organic compounds, such as carbon dioxide, thereby offering an attractive solution for reducing carbon emissions. However, molecular-level experimental observations of the catalytic process are scarce, and most existing catalysts tend to rely on empirically optimized, expensive, and complex nanocomposite materials. This lack of molecular-level insights has precluded the development of simpler, more cost-effective alternatives. Here, we show that graphite immersed in ultrapure water is able to spontaneously catalyze methanol from volatile organic compounds in ambient conditions. Using single-molecule resolution atomic force microscopy (AFM) in liquid, we directly observe the formation and evolution of methanol-water nanostructures at the surface of graphite. These molecularly ordered structures nucleate near catalytically active surface features, such as atomic step edges, and grow progressively as further methanol is being catalyzed. Complementary nuclear magnetic resonance analysis of the liquid confirms the formation of methanol and quantifies its concentration. We also show that electric fields significantly enhance the catalysis rate, even when as small as that induced by the natural surface potential of the silicon AFM tip. These findings could have a significant impact on the development of organic catalysts and on the function of nanoscale carbon devices.

* This criticism can be levelled at all hypotheses based on the results of feeding experiments in which production alone is studied. The errors that may thus arise have been pointed out bv Thomas (1940), and will be discussed in a later paper.