非水介质如何引导Ca(OH)2与CO2的反应生成不同形式的CaCO3: operando中红外和x射线吸收光谱研究

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-04-22 DOI:10.1039/d4cp04774e

Thokozile A. Kathyola, Sin-Yuen Chang, Elizabeth A. Willneff, Colin J. Willis, Giannantonio Cibin, Paul Wilson, Anna B. Kroner, Elizabeth J. Shotton, Peter J. Dowding, Sven L. M. Schroeder

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引用次数: 0

摘要

利用中红外（midir）和x射线吸收近边结构（XANES）光谱技术记录了Ca(OH)2和CO2在水环境和非水环境下形成不同CaCO3多晶体时的时间分辨结构变化。结果表明，Ca(OH)2在纯水分散中直接转化为方解石。在低含水量的甲醇介质中，形成二甲基碳酸钙（Ca(OCOOCH3)2），在足够的水存在下水解成无定形碳酸钙（ACC）和水晶石。甲苯的加入可能通过影响甲氧基中间体的活性，使平衡组成进一步从Ca(OH)2转变为ACC和CaCO3的结晶形式。它能促进文石的形成。在纯乙醇、异丙醇和甲苯分散体中均未检测到Ca(OH)2的转化，但在乙醇分散体中存在纳米级Ca(OH)2，形成二乙基碳酸钙（Ca(OCOOCH2CH3)2）。我们的研究结果强调，水晶石的形成是由溶液和固态化学驱动的，这些化学与醇的烷氧化物和碳酸酯的反应有关，而不是溶液中的成核过程。在这些体系中，酒精不仅充当溶剂，而且充当反应物。

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How non-aqueous media direct the reaction of Ca(OH)2 with CO2 to different forms of CaCO3: operando mid-infrared and X-ray absorption spectroscopy studies

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How non-aqueous media direct the reaction of Ca(OH)2 with CO2 to different forms of CaCO3: operando mid-infrared and X-ray absorption spectroscopy studies

Time-resolved structural changes taking place during the reaction of Ca(OH)₂ and CO₂ forming different CaCO₃ polymorphs, in aqueous and non-aqueous environments, were recorded operando using mid-infrared (mid-IR) and X-ray absorption near-edge structure (XANES) spectroscopy. Results show that Ca(OH)₂ directly transforms into calcite in a pure water dispersion. In methanolic media with low water content, calcium di-methylcarbonate (Ca(OCOOCH₃)₂) is formed, which is hydrolysed to amorphous calcium carbonate (ACC) and vaterite in the presence of sufficient water. The addition of toluene shifts the equilibrium composition further from Ca(OH)₂ to ACC and the crystalline forms of CaCO₃, probably by affecting the activity of the methoxide intermediate. It can facilitate the formation of aragonite. No Ca(OH)₂ conversion was detected in pure ethanol, isopropanol and toluene dispersions, except for nanoscale Ca(OH)₂ in ethanolic dispersion, which formed calcium di-ethylcarbonate (Ca(OCOOCH₂CH₃)₂). Our findings underline that vaterite formation is driven by the solution and solid state chemistry related to the reaction via alkoxides and carbonic acid esters of the alcohols, rather than the nucleation process in solution. The alcohol in these systems does not just act as a solvent but as a reactant.

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.