Atomic-scale structures and dynamics at the growing calcite step edge investigated by high-speed frequency modulation atomic force microscopy

Faraday Discuss. 2022 Jul 14;235(0):551-561. doi: 10.1039/d1fd00084e.

Abstract

We have investigated the calcite growth mechanism by directly imaging atomic-scale structural changes at the growing step edges with high-speed frequency modulation atomic force microscopy (HS-FM-AFM). We compared the results with those previously obtained during dissolution, where a transition region (TR) consisting of a Ca(OH)2 monolayer was found to be formed along the step edges as an intermediate state. We found that the TR is created not only during dissolution but also during the growth process. Steps with and without a TR coexist with a ratio of 7 : 3 in both dissolution and growth, implying that their primary reaction pathways should involve TR formation. While all the dissolving steps show a linear shape, the growing steps additionally present a complex non-linear shape with many kinks. The TRs formed along the linear steps present a fixed and uniform width, while those along the complex steps present a non-uniform and dynamically varying width. The acute and obtuse steps show similar TR formation probability, TR width, and step velocity during growth, while a TR is preferentially formed along an acute step during dissolution. For both step types, TRs during growth are wider than those during dissolution. Based on these findings, we present possible reaction pathways triggered by the adsorption of either CO2 or HCO3- for the elementary steps in calcite growth.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adsorption
  • Calcium Carbonate* / chemistry
  • Microscopy, Atomic Force / methods

Substances

  • Calcium Carbonate