研究氧空位对锐钛矿二氧化钛 (101) 吸附醋酸的影响

IF 2.8 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Research on Chemical Intermediates Pub Date : 2024-08-23 DOI:10.1007/s11164-024-05379-2
Song Guo, Juan Wang
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引用次数: 0

摘要

酮化是消除生物油中的羧酸并增加碳链的有效方法。金属氧化物中的氧空位缺陷会影响催化性能。然而,很少有研究调查了氧空位缺陷对羧酸吸附的具体影响。本研究采用密度泛函理论(DFT)分析了乙酸与缺陷锐钛矿二氧化钛(101)之间的相互作用。表面氧空位比亚表面更难形成,但乙酸更容易在表面缺陷处被吸收。表面路易斯酸位点和碱性位点之间的静点电位差促进了乙酸在完整表面和缺陷表面的解离,尤其是在表面氧空位上,这降低了酮化过程中水形成的反应能垒。此外,表面氧空位还能将完美表面上形成的双齿羧酸盐转化为活性更强的单齿羧酸盐,从而降低酮化过程中碳碳偶联反应的能量障碍。这些结果表明,表面氧空位能增强乙酸的酮化反应,并证明催化剂对大分子有机物的吸附受路易斯酸强度、静电位点分布、界面结构和反应物活性位点等因素的综合影响。我们的研究结果从分子水平详细揭示了乙酸吸附对表面氧空位的影响,为进一步研究催化反应机理以及催化剂的调控奠定了基础。
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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Investigation of oxygen vacancy effects on acetic acid adsorption on anatase TiO2 (101)

Ketonization is an effective means of eliminating carboxylic acids from bio-oil and increasing the carbon chain. Oxygen vacancy defects in metal oxides affect the catalytic performance. However, few studies have investigated the specific effect of oxygen vacancy defects on carboxylic acid adsorption. In this work, the interaction between acetic acid and defect anatase TiO2 (101) was analyzed using density functional theory (DFT). Surface oxygen vacancies are more difficult to form than subsurface, but acetic acid is more readily absorbed at the surface defects. The static point potential difference between surface Lewis acid and basic sites promotes the dissociation of acetic acid on both intact and defective surfaces, especially on the surface oxygen vacancies, which decreases the reaction energy barrier for water formation during ketonization. Additionally, surface oxygen vacancies convert the bidentate carboxylates formed on the perfect surface into more active monodentate carboxylates, which reduces the energy barrier for carbon–carbon coupling reactions in the ketonization. These results indicate that the surface oxygen vacancies can enhance the ketonization of acetic acid and demonstrate that the adsorption of macromolecular organics on catalysts is influenced by a combination of Lewis acidic strength, electrostatic site distribution, interfacial structure, and reactant active sites. Our results reveal in detail the effect of acetic acid adsorption on surface oxygen vacancies at the molecular level, which lays the foundation for further studies on the catalytic reaction mechanism as well as the regulation of catalysts.

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来源期刊
CiteScore
5.70
自引率
18.20%
发文量
229
审稿时长
2.6 months
期刊介绍: Research on Chemical Intermediates publishes current research articles and concise dynamic reviews on the properties, structures and reactivities of intermediate species in all the various domains of chemistry. The journal also contains articles in related disciplines such as spectroscopy, molecular biology and biochemistry, atmospheric and environmental sciences, catalysis, photochemistry and photophysics. In addition, special issues dedicated to specific topics in the field are regularly published.
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