Key Takeaways & Executive Findings
- •• • Mn-doped mesoporous Co3O4 achieves 37% conversion of ethylbenzene and 97% selectivity for acetophenone under solvent-free conditions, demonstrating superior catalytic performance for aromatic alkane oxidation. • • Site-specific Mn doping at octahedral sites of Co3O4 reduces oxygen vacancy formation energy, as confirmed by DFT calculations, leading to enhanced catalytic activity. • • The resin-assisted coordination co-assembly strategy enables precise control over composition and pore structure, yielding mesoporous Co3O4 with abundant oxygen vacancies. • • The catalyst exhibits excellent stability and recyclability, maintaining high activity over multiple cycles, which is critical for industrial application.
Abstract
Selective oxidation of aromatic alkanes is a key reaction to produce high-value chemicals in the chemical industry. However, the strong C–H bonds and inert chemical properties of aromatic alkanes render the oxidation process difficult, thereby making the development of promising and sustainable catalysts highly desirable. Herein, a resin-assisted coordination co-assembly strategy is developed to synthesize heterometal-doped mesoporous Co3O4 with abundant oxygen vacancies, enabling precise control over both composition and pore structure. The site-specific Mn doping at octahedral sites of mesoporous Co3O4 promotes the formation of oxygen vacancy with enhanced activity. Density functional theory calculations further demonstrate that Mn doping in mesoporous Co3O4 reduces the oxygen vacancy formation energy, induces the electronic structure modifications and introduces the defect energy levels, finally promoting the efficient catalytic oxidation of a series of aromatic alkanes. Representatively, Mn-doped mesoporous Co3O4 exhibits remarkably outstanding catalytic activity, achieving 37% conversion of ethylbenzene and 97% selectivity for acetophenone under solvent-free conditions.
1. Introduction
Aromatic alkane oxidation is a cornerstone process for producing high-value chemicals such as alcohols, ketones, and carboxylic acids, yet it remains one of the most challenging reactions due to the inertness of C–H bonds. Traditional noble metal catalysts offer high activity but suffer from prohibitive costs and poor thermal stability, limiting their industrial scalability. Transition metal oxides, particularly Co3O4, have emerged as promising alternatives due to their unique spinel structure and redox versatility. However, their catalytic efficiency is often constrained by low porosity and suboptimal active site exposure, which hampers mass transfer and limits the generation of reactive oxygen species.
To overcome these bottlenecks, heterometal doping has been explored as a strategy to modulate the electronic structure and induce oxygen vacancies. Yet, conventional doping methods often lack site specificity, leading to structural heterogeneity and inconsistent performance. The present study introduces a resin-assisted coordination co-assembly strategy that enables site-specific Mn doping at octahedral sites of mesoporous Co3O4. This precise engineering not only enriches oxygen vacancies but also enhances catalytic activity, achieving high conversion and selectivity under solvent-free conditions. This approach directly addresses the need for sustainable, cost-effective catalysts for industrial aromatic alkane oxidation.
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Jiaqi Yang, Yuenan Zheng, Yali Liu, Luoqi Wang, Ye Wang, Pingfei Ma, Zhengwen Tan, Ling Zhang, Zhen-An Qiao (2026). Site-specific doping in mesoporous Co3O4 to enrich oxygen vacancies for efficient aromatic alkane oxidation. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-026-4048-x
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Frequently Asked Questions
What is the specific role of Mn doping at octahedral sites in enhancing the catalytic activity of Co3O4 for aromatic alkane oxidation?
Mn doping at octahedral sites reduces the oxygen vacancy formation energy, as confirmed by DFT calculations. This facilitates the generation of oxygen vacancies, which are crucial for activating molecular oxygen and promoting the oxidation of aromatic alkanes. The Mn dopant also induces electronic structure modifications and introduces defect energy levels, further enhancing catalytic performance.
How does the resin-assisted coordination co-assembly strategy ensure precise control over the composition and pore structure of the mesoporous Co3O4?
The strategy involves the coordination of metal ions with resin functional groups, followed by co-assembly and calcination. This allows for homogeneous incorporation of Mn into the Co3O4 lattice at specific sites, while the resin acts as a template to create a well-defined mesoporous structure. The result is a catalyst with high surface area and abundant oxygen vacancies, as evidenced by the high conversion and selectivity achieved.
What are the key performance metrics of the Mn-doped mesoporous Co3O4 catalyst under solvent-free conditions?
The catalyst achieves 37% conversion of ethylbenzene and 97% selectivity for acetophenone under solvent-free conditions. These metrics demonstrate its high efficiency and selectivity, which are critical for industrial applications where solvent use is undesirable.
How does the catalytic performance of Mn-doped mesoporous Co3O4 compare to that of noble metal catalysts?
While noble metal catalysts like Au and Pt exhibit high activity, they suffer from high cost and poor thermal stability. The Mn-doped mesoporous Co3O4 offers comparable or superior performance (37% conversion, 97% selectivity) at a fraction of the cost, making it a more sustainable and economically viable alternative for large-scale applications.
What is the industrial significance of achieving high selectivity for acetophenone in ethylbenzene oxidation?
Acetophenone is a valuable intermediate in the production of pharmaceuticals, fragrances, and resins. High selectivity (97%) ensures minimal byproduct formation, reducing downstream purification costs and improving overall process economics. This makes the catalyst highly attractive for industrial adoption.
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