{"title":"无溶剂条件下具有 S 型异质结的 CeO2/g-C3N4 复合材料对环己烷的光热氧化作用","authors":"Fangruo Ding, Ya Wang, Zhijun Shi, Changsheng Gao, Mei Kan, Qianli Liang, Zheng Gao, Shiqing Li, Rusi Peng, Ying Ma, Wenchao Shangguan, Sugang Meng, Shifu Chen","doi":"10.1007/s10562-024-04880-y","DOIUrl":null,"url":null,"abstract":"<div><p>The selective oxidation of saturated C-H bonds has long been a significant challenge in chemical research, with the partial oxidation of cyclohexane (Cy) to KA oil (a mixture of cyclohexanol and cyclohexanone) using molecular oxygen (O<sub>2</sub>) recognized as one of the most important reactions. In this study, we demonstrate the selective oxidation of cyclohexane via photothermal synergism under solvent-free conditions and in the presence of a co-catalyst system. We have elucidated the synergistic effect of the CeO<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> composite catalyst in the photothermal oxidation of cyclohexane. The CeO<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> composite achieved a cyclohexane conversion of 13% and a KA oil selectivity of 97.5%, surpassing the simple additive effects of photocatalysis and thermal catalysis. Through extensive characterization techniques, we present a detailed mechanistic study. Photo-generated electron–hole pairs facilitate the valence cycling of metals during thermal processes, while heat promotes the efficient utilization of these carriers. Furthermore, lattice oxygen can trap holes, reducing the recombination probability of photo-generated charge carriers. This interaction results in a synergistic effect between light and heat, elucidating the phenomenon of photothermal cooperative catalysis in the composite catalyst. These findings suggest that photothermal co-catalysis holds considerable potential for widespread application in green industrial catalytic processes, offering high selectivity and efficiency in organic transformations.</p><h3>Graphical Abstract</h3><p>Herein, we synthesized a CeO2/g−C3N4 composite with S−scheme heterojunction as a photothermal catalyst, and employed it for the oxidation of Cy to K−A oil in a solvent−free system. CeO2 demonstrates prominent photothermal synergy, and the addition of g−C3N4 can enhance the utilization of electron–hole pairs. This method significantly improves cyclohexane conversion and KA oil selectivity and exceeds the sum of generations of pure photocatalysis and thermal catalysis. The results provide a mechanistic description for photothermal co−catalysis and demonstrate its potential for widespread use in green industrial catalysis</p>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 1","pages":""},"PeriodicalIF":2.3000,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photothermal Oxidation of Cyclohexane Over CeO2/g-C3N4 Composite with S-Scheme Heterojunction in Solvent-Free Conditions\",\"authors\":\"Fangruo Ding, Ya Wang, Zhijun Shi, Changsheng Gao, Mei Kan, Qianli Liang, Zheng Gao, Shiqing Li, Rusi Peng, Ying Ma, Wenchao Shangguan, Sugang Meng, Shifu Chen\",\"doi\":\"10.1007/s10562-024-04880-y\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The selective oxidation of saturated C-H bonds has long been a significant challenge in chemical research, with the partial oxidation of cyclohexane (Cy) to KA oil (a mixture of cyclohexanol and cyclohexanone) using molecular oxygen (O<sub>2</sub>) recognized as one of the most important reactions. In this study, we demonstrate the selective oxidation of cyclohexane via photothermal synergism under solvent-free conditions and in the presence of a co-catalyst system. We have elucidated the synergistic effect of the CeO<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> composite catalyst in the photothermal oxidation of cyclohexane. The CeO<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> composite achieved a cyclohexane conversion of 13% and a KA oil selectivity of 97.5%, surpassing the simple additive effects of photocatalysis and thermal catalysis. Through extensive characterization techniques, we present a detailed mechanistic study. Photo-generated electron–hole pairs facilitate the valence cycling of metals during thermal processes, while heat promotes the efficient utilization of these carriers. Furthermore, lattice oxygen can trap holes, reducing the recombination probability of photo-generated charge carriers. This interaction results in a synergistic effect between light and heat, elucidating the phenomenon of photothermal cooperative catalysis in the composite catalyst. These findings suggest that photothermal co-catalysis holds considerable potential for widespread application in green industrial catalytic processes, offering high selectivity and efficiency in organic transformations.</p><h3>Graphical Abstract</h3><p>Herein, we synthesized a CeO2/g−C3N4 composite with S−scheme heterojunction as a photothermal catalyst, and employed it for the oxidation of Cy to K−A oil in a solvent−free system. CeO2 demonstrates prominent photothermal synergy, and the addition of g−C3N4 can enhance the utilization of electron–hole pairs. This method significantly improves cyclohexane conversion and KA oil selectivity and exceeds the sum of generations of pure photocatalysis and thermal catalysis. 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引用次数: 0
摘要
长期以来，饱和 C-H 键的选择性氧化一直是化学研究中的一项重大挑战，利用分子氧（O2）将环己烷（Cy）部分氧化为 KA 油（环己醇和环己酮的混合物）被认为是最重要的反应之一。在本研究中，我们展示了在无溶剂条件下和辅助催化剂系统存在的情况下，通过光热协同作用选择性氧化环己烷的过程。我们阐明了 CeO2/g-C3N4 复合催化剂在环己烷光热氧化过程中的协同效应。CeO2/g-C3N4 复合催化剂实现了 13% 的环己烷转化率和 97.5% 的 KA 油选择性，超越了光催化和热催化的简单相加效应。通过广泛的表征技术，我们进行了详细的机理研究。在热过程中，光产生的电子-空穴对促进了金属的价态循环，而热则促进了这些载流子的有效利用。此外，晶格氧还能捕获空穴，降低光生电荷载流子的重组概率。这种相互作用产生了光与热之间的协同效应，阐明了复合催化剂中的光热协同催化现象。这些研究结果表明，光热协同催化在绿色工业催化过程中具有相当大的广泛应用潜力，可在有机转化过程中提供高选择性和高效率。图解 摘要本文合成了具有 S 型异质结的 CeO2/g-C3N4 复合材料作为光热催化剂，并将其用于无溶剂体系中 Cy 到 K-A 油的氧化反应。CeO2 表现出显著的光热协同作用，而 g-C3N4 的加入可以提高电子-空穴对的利用率。这种方法大大提高了环己烷的转化率和 KA 油的选择性，超过了纯光催化和热催化两代方法的总和。研究结果提供了光热协同催化的机理描述，并证明了其在绿色工业催化中广泛应用的潜力
Photothermal Oxidation of Cyclohexane Over CeO2/g-C3N4 Composite with S-Scheme Heterojunction in Solvent-Free Conditions
The selective oxidation of saturated C-H bonds has long been a significant challenge in chemical research, with the partial oxidation of cyclohexane (Cy) to KA oil (a mixture of cyclohexanol and cyclohexanone) using molecular oxygen (O2) recognized as one of the most important reactions. In this study, we demonstrate the selective oxidation of cyclohexane via photothermal synergism under solvent-free conditions and in the presence of a co-catalyst system. We have elucidated the synergistic effect of the CeO2/g-C3N4 composite catalyst in the photothermal oxidation of cyclohexane. The CeO2/g-C3N4 composite achieved a cyclohexane conversion of 13% and a KA oil selectivity of 97.5%, surpassing the simple additive effects of photocatalysis and thermal catalysis. Through extensive characterization techniques, we present a detailed mechanistic study. Photo-generated electron–hole pairs facilitate the valence cycling of metals during thermal processes, while heat promotes the efficient utilization of these carriers. Furthermore, lattice oxygen can trap holes, reducing the recombination probability of photo-generated charge carriers. This interaction results in a synergistic effect between light and heat, elucidating the phenomenon of photothermal cooperative catalysis in the composite catalyst. These findings suggest that photothermal co-catalysis holds considerable potential for widespread application in green industrial catalytic processes, offering high selectivity and efficiency in organic transformations.
Graphical Abstract
Herein, we synthesized a CeO2/g−C3N4 composite with S−scheme heterojunction as a photothermal catalyst, and employed it for the oxidation of Cy to K−A oil in a solvent−free system. CeO2 demonstrates prominent photothermal synergy, and the addition of g−C3N4 can enhance the utilization of electron–hole pairs. This method significantly improves cyclohexane conversion and KA oil selectivity and exceeds the sum of generations of pure photocatalysis and thermal catalysis. The results provide a mechanistic description for photothermal co−catalysis and demonstrate its potential for widespread use in green industrial catalysis
期刊介绍：
Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis.
The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.
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