Effect of Cations on the Oxidation and Atmospheric Corrosion of Iron Interfaces to Minerals
Effect of Cations on the Oxidation and Atmospheric Corrosion of Iron Interfaces to Minerals
复制标题
DOI：
10.1021/acs.jpca.1c06451
复制
发表时间：
2021-09-07
影响因子：
2.9
通讯作者：
Perrine, Kathryn A.
中科院分区：
文献类型：
--
作者：
de Alwis, Chathura;Trought, Mikhail;Perrine, Kathryn A.
表面腐蚀涉及一系列由离子催化的氧化还原反应。在基础设施表面和复杂的自然环境中，铁表面容易发生氧化还原反应，影响化学过程。在这项研究中，阳离子如何影响铁表面上的矿物垢的形成及其与表面腐蚀的联系的影响进行了研究，在氯化钙（aq）和氯化钠（aq）电解质。偏振调制红外反射吸收光谱（PM-IRRAS）测量被用来测量氧化和碳酸盐的形成在空气/电解质/铁界面，这证实了铁表面的氧化速度在氯化钙（水溶液）比在NaCl（水溶液）。PM-IRRAS、衰减全反射-傅里叶变换红外光谱和X射线光电子能谱表明，在CaCl 2（aq）存在下，吸附大气中的O-2和CO2后，在铁表面生成了方解石和文石形式的碳酸钙（CaCO 3），而在NaCl（aq）存在下，在铁表面生成了菱铁矿（FeCO 3）。然而，在没有逐渐的O-2和CO2暴露的任一溶液中，在铁表面上生长纤铁矿（γ-FeOOH）和羟基碳酸铁（Fe-x（OH）（y）CO 3）的非均相混合物。原位液体原子力显微镜被用来测量在氯化钙（aq）和氯化钠（aq）的表面粗糙度，作为估计的腐蚀速率。在CaCl 2（aq）中，由于等摩尔浓度下的离子较多，发现Fe比NaCl（aq）中的Fe腐蚀更快。表面物理变化，通过非原位AFM测量，证实了存在的非均相混合物的γ-FeOOH和Fe-x（OH）（y）CO 3在淹没的区域。这表明阳离子不影响完全浸没在电解质中的区域中的Fe表面上生长的矿物的类型。这些结果表明，阳离子在界面区域腐蚀的初始阶段起着独特的作用，影响大气CO2的吸收和矿物成核。从这些界面反应中获得的知识对于理解表面腐蚀，矿物生长和CO2捕获封存之间的联系非常重要。
Surface corrosion involves a series of redox reactions that are catalyzed by the presence of ions. On infrastructure surfaces and in complex and natural environments, iron surfaces readily undergo redox reactions, impacting chemical processes. In this study, the effect of how cations influence the formation of the mineral scale on iron surfaces and its connection to surface corrosion was investigated in CaCl2(aq) and NaCl(aq) electrolytes. Polarized modulated-infrared reflection absorption spectroscopy (PM-IRRAS) measurements were used to measure the oxidation and formation of carbonates at the air/electrolyte/iron interface, which confirmed that the iron surface oxidized faster in CaCl2(aq) than in NaCl(aq). PM-IRRAS, attenuated total reflectance-Fourier transformed infrared spectroscopy, and X-ray photoelectron spectroscopy show that after the adsorption of atmospheric O-2 and CO2, calcium carbonate (CaCO3) in the form of calcite and aragonite was produced on iron in the presence of CaCl2(aq), whereas siderite (FeCO3) was produced on the surface of iron in the presence of NaCl(aq). However, in either solution without gradual O-2 and CO2 exposure, a heterogeneous mixture of lepidocrocite (gamma-FeOOH) and an iron hydroxy carbonate (Fe-x(OH)(y)CO3) was grown on the iron surface. In situ liquid AFM was used to measure the surface roughness in CaCl2(aq) and NaCl(aq), as an estimation of the corrosion rate. In CaCl2(aq), Fe was found to corrode faster than Fe in NaCl(aq) due to more ions at equimolar concentrations. Surface physical changes, as measured by ex situ AFM, confirmed the presence of a heterogeneous mixture of gamma-FeOOH and an Fe-x(OH)(y)CO3 in the submerged region. This indicates that the cation does not affect the type of mineral grown on the Fe surface in the region completely submerged in the electrolyte. These results suggest that the cations play a unique role in the initial stages of corrosion at the interface region, influencing the uptake of atmospheric CO2 and mineral nucleation. The knowledge gained from these interfacial reactions are important for understanding the connection between surface corrosion, mineral grown, and CO2 capture for sequestration.