Fachbereich Physik, Universität Osnabrück, 49076 Osnabrück, Germany.
Department of Applied Physics, Aalto University, Helsinki FI-00076, Finland.
J Phys Chem Lett. 2023 Feb 23;14(7):1983-1989. doi: 10.1021/acs.jpclett.2c03243. Epub 2023 Feb 16.
Calcite, in the natural environment the most stable polymorph of calcium carbonate (CaCO), not only is an abundant mineral in the Earth's crust but also forms a central constituent in the biominerals of living organisms. Intensive studies of calcite(104), the surface supporting virtually all processes, have been performed, and the interaction with a plethora of adsorbed species has been studied. Surprisingly, there is still serious ambiguity regarding the properties of the calcite(104) surface: effects such as a row-pairing or a (2 × 1) reconstruction have been reported, yet so far without physicochemical explanation. Here, we unravel the microscopic geometry of calcite(104) using high-resolution atomic force microscopy (AFM) data acquired at 5 K combined with density functional theory (DFT) and AFM image calculations. A (2 × 1) reconstruction of a -symmetric surface is found to be the thermodynamically most stable form. Most importantly, a decisive impact of the (2 × 1) reconstruction on adsorbed species is revealed for carbon monoxide.
方解石是碳酸钙（CaCO3）在自然环境中最稳定的多晶型物，不仅在地壳中大量存在，而且还是生物体内生物矿物的主要组成部分。人们对方解石（104）表面进行了大量研究，这是几乎所有过程的支撑表面，也研究了与多种吸附物种的相互作用。令人惊讶的是，关于方解石（104）表面的性质仍然存在严重的不确定性：已经报道了例如行配对或（2×1）重构等效应，但迄今为止没有物理化学解释。在这里，我们使用在 5 K 下获得的高分辨率原子力显微镜 (AFM) 数据并结合密度泛函理论 (DFT) 和 AFM 图像计算来揭示方解石（104）的微观几何形状。结果发现，-对称表面的（2×1）重构是热力学上最稳定的形式。最重要的是，揭示了（2×1）重构对一氧化碳吸附物种的决定性影响。
