Experimental and molecular insights on the regulatory effects of solvent on CaC2 reaction activity

IF 3.5 3区工程技术 Q2 ENGINEERING, CHEMICAL AIChE Journal Pub Date : 2024-06-20 DOI:10.1002/aic.18511

Zhengrun Chen, Hui Xu, Xiaoteng Zang, Hong Meng, Hongwei Fan, Yingzhou Lu, Chunxi Li

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引用次数: 0

Abstract

Calcium carbide (CaC₂) is a valuable carbanion resource, but the reactivity is highly restricted by its insolubility and super-basicity. For this, the effect of solvent and mechanical forces on its reactivity is investigated extensively here via quantum chemistry calculation, molecular dynamic simulation, and experiments. The dissolution free energy of CaC₂ in over 100 solvents has been evaluated. DMSO, CH₃CN, and DMF can enhance the negative potential and reactivity of CaC₂, especially DMSO. The electrostatic interaction of CaC₂-solvent mainly originates from the interaction between Ca²⁺ and O or N atom. The increased electron density around

C_{2}^{2 -} $$ {\mathrm{C}}_2^{2\hbox{-} } $$

is mainly ascribed to the electron transfer from solvent. DMSO can change the ionic orientation of CaC₂ interface. The solvent may be deprotonated by

C_{2}^{2 -} $$ {\mathrm{C}}_2^{2\hbox{-} } $$

, compromising the solvent stability. The interface interaction of CaC₂ with DMF and DMSO is verified through FT-IR, and the lattice structure of CaC₂ is lost virtually after 0.5 h mechanical milling.

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溶剂对 CaC2 反应活性调控作用的实验和分子见解

碳化钙（CaC2）是一种宝贵的碳阴离子资源，但由于其不溶性和超碱性，其反应活性受到很大限制。为此，本文通过量子化学计算、分子动力学模拟和实验，广泛研究了溶剂和机械力对其反应性的影响。我们评估了 CaC2 在 100 多种溶剂中的溶解自由能。DMSO、CH3CN 和 DMF 可以增强 CaC2 的负电位和反应活性，尤其是 DMSO。CaC2 与溶剂的静电作用主要来自 Ca2+ 与 O 原子或 N 原子的相互作用。C22-$$ {\mathrm{C}}_2^{2\hbox{-} 周围的电子密度增加了。}$$ 主要归因于来自溶剂的电子转移。二甲基亚砜可以改变 CaC2 界面的离子取向。溶剂可能被 C22-$ {\{mathrm{C}}_2^{2\hbox{-} }$ 去质子化。}$$ ，从而影响溶剂的稳定性。通过傅立叶变换红外光谱验证了 CaC2 与 DMF 和 DMSO 的界面相互作用，并且在机械研磨 0.5 小时后，CaC2 的晶格结构几乎消失。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

AIChE Journal 工程技术-工程：化工

CiteScore

7.10

自引率

10.80%

发文量

411

审稿时长

3.6 months

期刊介绍： The AIChE Journal is the premier research monthly in chemical engineering and related fields. This peer-reviewed and broad-based journal reports on the most important and latest technological advances in core areas of chemical engineering as well as in other relevant engineering disciplines. To keep abreast with the progressive outlook of the profession, the Journal has been expanding the scope of its editorial contents to include such fast developing areas as biotechnology, electrochemical engineering, and environmental engineering. The AIChE Journal is indeed the global communications vehicle for the world-renowned researchers to exchange top-notch research findings with one another. Subscribing to the AIChE Journal is like having immediate access to nine topical journals in the field. Articles are categorized according to the following topical areas: Biomolecular Engineering, Bioengineering, Biochemicals, Biofuels, and Food Inorganic Materials: Synthesis and Processing Particle Technology and Fluidization Process Systems Engineering Reaction Engineering, Kinetics and Catalysis Separations: Materials, Devices and Processes Soft Materials: Synthesis, Processing and Products Thermodynamics and Molecular-Scale Phenomena Transport Phenomena and Fluid Mechanics.