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A concise synthesis of Se/Fe materials for catalytic oxidation reactions of anthracene and polyene
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Xiaoxue Lia, Hongwei Zhoub, Rongrong Qianc, Xu Zhanga, *, Lei Yua, *
Chinese Chemical Letters | 2025, 36(3) : 110036
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Chinese Chemical Letters | 2025, 36(3): 110036
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A concise synthesis of Se/Fe materials for catalytic oxidation reactions of anthracene and polyene
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Xiaoxue Lia, Hongwei Zhoub, Rongrong Qianc, Xu Zhanga, *, Lei Yua, *
Affiliations
  • a School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China
  • b College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, China
  • c Jiangsu College of Tourism, Yangzhou 225009, China
Published: 2025-03-15 doi: 10.1016/j.cclet.2024.110036
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The synergistic effect of Se with Fe can enhance the catalytic activities of the system for oxidation reactions. Based on this principle, a series of Se/Fe materials have been invented to develop the heterogeneous catalysts with industrial application potential. However, the present methods suffer from the tedious procedures, the high reaction temperature, and the low synthetic efficiency. In this paper, we report the synthesis of Se/Fe materials just by precipitating Fe(NO3)3 with the in situ prepared aqueous NaSe/NaSeO3 under mild conditions. The concise method may resolve the issues hindering the large-scale applications of Se/Fe materials.

Selenium  /  Anthracene  /  Polyene  /  Oxidation  /  Deoximation
Xiaoxue Li, Hongwei Zhou, Rongrong Qian, Xu Zhang, Lei Yu. A concise synthesis of Se/Fe materials for catalytic oxidation reactions of anthracene and polyene[J]. Chinese Chemical Letters, 2025 , 36 (3) : 110036 - . DOI: 10.1016/j.cclet.2024.110036
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Selenium (Se) is a unique chalcogen element with broad application scopes [1-7]. The atomic radius of Se is larger than sulphur (S), resulting in the weaker binding force to its outer electrons. Thus, Se is more easily oxidized than S. Comparatively, the hybrid orbital and bond length of Se═O are longer than that of S═O, resulting in the weaker π bonds that can be easily reduced [8]. The above features make Se to be a good oxygen carrier that can be employed as the catalyst for oxidation reactions [9]. In 2019, we found that, introducing iron salts into the organoselenium catalyst system could significantly enhance its activity for oxidative deoximation reactions, as being reflected by the fact that molecular oxygen could be employed as the oxidant in the presence of the PhCH2Se(O)OH/FeSO4 bi-component catalytic system [10]. In the reaction, Se catalysed the oxidative deoximation reaction, while Fe facilitates the activation of molecular oxygen, i.e., catalysed by Fe, the aerobic oxidation of low valent Se to the active Se═O could be achieved, resulting in the less consumption of chemical oxidants such as H2O2. Later, a series of bi-component Se/metal catalysts have been developed such as the Se/Cu [11], Se/Ag [12], Se/Mn [13], and Se/Al [14].
On the other hand, heterogeneous catalysts are practical for large-scale applications [15-19], while using iron as catalyst component is also preferable for the low cost of the metal [20-25]. Thus, developing heterogeneous Se/Fe catalysts may be a good research topic with industrial application potential. However, the present technologies for preparing Se/Fe materials are not practical. For example, Se/Fe materials could be fabricated via the nucleophilic addition at Fe2O3 with NaHSe, which was generated in situ by the reduction of Se powder with NaBH4 (Scheme 1, Method 1) [26]. The process may release H2Se, which is a toxic gas hazardous to the environments. Moreover, H2 gas is also generated during the reaction, and it must be carefully treated to avoid explosion accident in large-scale production [27]. Another method for preparing Se/Fe catalyst is by calcining the Se and Fe powders with melamine, but it requires high calcination temperature at 500 ℃ and most of the weight of melamine lost during the process (Scheme 1, Method 2) [28]. Se/Fe material can be prepared by calcining methylselenized glucose [29] with FeCl3 [30]. However, despite the high calcining temperature (500 ℃), the expensive price of methylselenized glucose may bottleneck the application of the method in industry (Scheme 1, Method 3). Recently, we developed a new concise method to fabricate Se/Fe materials more efficiently (Scheme 1, Method 4). Herein, we wish to report our findings.
The material was fabricated via the co-precipitation of iron salt with selenium species under alkaline conditions. Heating selenium powder with aqueous NaOH initially led to the mixture of Na2Se and Na2SeO3 via the disproportionated reaction of Se0 to Se2− and Se4+ (Scheme 1, Method 4). After cooling to room temperature, aqueous Fe(NO3)3 was added to precipitate selenium. The precipitations were dried at 100 ℃ in a simple bake out furnace just in open air to afford the iron oxide-supported selenium marked as Se/FeOx·yH2O.
Transmission electron microscopy (TEM) image shows that selenium dispersed uniformly on the surface of the material, and it may be in amorphous state (Fig. 1a). Energy dispersive X-ray spectroscopy (EDX) confirmed the successful loading of selenium onto the iron oxide support (Fig. 1b). High angle annular dark field scanning electron microscopy (HAADF-STEM) and element mapping images can effectively reflect the composition and dispersion of the elements in the material. HAADF-STEM images are highly sensitive to changes in atomic number of atoms in the sample (Z-contrast images). Specifically, the contrast intensity of Z is directly proportional to the square of the atomic number [31]. Therefore, the bright area may be attributed to the Se element in the HAADF-STEM image of Se/FeOx·yH2O (Figs. 1c and d). The element mapping images in Figs. 1e–h reflect the uniform dispersion of Se, Fe, O, and Na elements. Dispersive distribution of Se indicates that the element may also be involved by physical adsorption (Fig. 1e).
Fourier-transform infrared (FT-IR) and ultraviolet-visible (UV–vis) analyses of the materials were then conducted to get the information of the functional groups in the materials. Unselenized Fe2O3·xH2O was prepared in similar method and analysed for comparison. The IR spectra of Se/FeOx·yH2O and Fe2O3·xH2O were generally the same, and no additional peak emerged. This indicates that the selenium content in the material was particularly low, and the formed selenium-containing bonds were difficult to be observed in its IR spectrum (Fig. 2a). This conclusion was then verified by the inductively coupled plasma mass spectroscopy (ICP-MS) analysis of the material, which verified that selenium content in Se/FeOx·yH2O was only 3.5%. IR spectra indicated that the water-content of Fe2O3·xH2O was higher than that of Se/FeOx·yH2O, as being reflected by the even stronger signals at ca. 3500 cm−1. The influence of water content was more significant in UV–vis spectra, and it caused the red-shift in the spectrum and led to the peaks at 250–350 nm (Fig. 2b).
As a material containing both selenium and iron, Se/FeOx·yH2O was supposed to be a nice catalyst for oxidation reactions. Its catalytic activity was initially evaluated via the oxidation reaction of anthracene to anthraquinone (Eq. 1). Anthracene is a pollutant that was abundantly produced from coal chemical industry, while anthraquinone is now a basic raw material for the synthesis of organic light-emitting materials (OLEMs), which are electronic chemicals of profound market prospect [32-34]. Thus, the reaction is a significant industrial process and deserves investigations.
As shown in Fig. 3a, catalysed by Se/FeOx·yH2O, the oxidation of anthracene occurred smoothly and produced the desired anthraquinone in good yields. As a heterogeneous catalyst with magnetic features, Se/FeOx·yH2O could be removed from the mixture by magnetic separation after reaction. It is reusable, and the recycled catalyst could be directly reused without deactivation. In the reactions, both the conversion ratio of anthracene and the selectivity of anthraquinone were over 90%, showing sufficient utilization of the atoms in starting materials from the industrial viewpoint (Fig. 3a). The catalytic activity of unselenized Fe2O3·xH2O was also tested for comparison, but led to poor anthracene conversion, and the selectivity of anthraquinone also decreased (Fig. 3b). Thus, it may be concluded that the oxygen-carrier properties of selenium endow the material good catalytic activity for oxidation reactions, which has been well summarized by literatures [35-40].
It has been reported that selenization may change the surface properties of the materials and affect the mass-transfer processes during the catalytic reactions [41,42]. Thus, the elevated catalytic activity of Se/FeOx·yH2O versus unselenized Fe2O3·xH2O may also attribute to the improved mass-transfer properties of the materials. To verify or exclude this possibility, anthracene adsorption experiments were performed with Se/FeOx·yH2O and Fe2O3·xH2O. As shown in Fig. 3c, ca. 31% of anthracene was adsorbed on Se/FeOx·yH2O after 24 h immersing, but for Fe2O3·xH2O, this value was only 22% after the same time immersing (Fig. 3d). The result clearly demonstrated that the mass-transfer process on Se/FeOx·yH2O was better than the unselenized Fe2O3·xH2O.
On the other hand, polyenes are common pollutants in pharmaceutical industry [43,44], and they may be treated by the oxidative degradation splitting the C═C bond. Our recent investigations have demonstrated that the oxidative C═C cleavage reaction could be catalysed by selenium, while iron significantly promoted the catalytic activity [45,46]. Thus, as a heterogeneous catalyst containing both selenium and iron, Se/FeOx·yH2O may be applied in polyene degradation reaction. In this work, we chose the degradation of β-carotene as the model reaction to evaluate the catalytic activity of Se/FeOx·yH2O. As shown in Fig. 4a, the colour of β-carotene faded smoothly during the process. Moreover, UV–vis spectra in Fig. 4b clearly indicated the blue shift of the samples along with the reaction time, reflecting the C═C bond cleavage leading to the colourless small molecules. Mass-spectra of the reaction mixtures (Figs. S2–S5 in Supporting information) could verify that the Se/FeOx·yH2O-catalyzed oxidation reaction of β-carotene could result in the C═C bond splitting leading to produce a variety of fragments such as the β-ionone.
X-ray photoelectron spectroscopy (XPS) analysis was then conducted to evaluate the stability of the catalysts during the reaction processes. In the XPS spectra, the signals of Se 3d5/2 and Se 3d3/2 of fresh Se/FeOx·yH2O emerged at 55.8 and 56.8 eV respectively. They did not change much after the five times reaction (Fig. 3a), showing that the valence of selenium was stable during the catalytic oxidation reaction process (Fig. 5a). In the Fe 2p spectra, signals at 711.5 and 725.1 eV reflected Fe 2p3/2 and Fe 2p1/2 respectively, and their compositions were generally stable during the reaction process (Fig. 5b). There were only Se4+ and Se2+ species in the material, while the Se2− species disappeared. For iron, both Fe2+ and Fe3+ species were observed in XPS spectra. This phenomenon demonstrated that the redox reaction occurred between the disproportionated reaction-generated reductive Se2− and the oxidative Fe3+. The O 1s spectra of the materials (Fig. S1 in Supporting information) indicated there were three kinds of oxygen, such as OL, OV and the hydroxyl oxygen, and the strength of the signals were determined by the concentration of the oxygen vacancy. The content of hydroxyl oxygen decreased obviously after reaction, reflecting the aging process releasing water from the material.
In conclusion, we have reported a new method for preparing Se/Fe materials concisely. It was found that, just by heating Se with NaOH could lead to the water soluble selenium salts such as Na2Se and Na2SeO3, which were precipitated by Fe(NO3)3 and led to Se/FeOx·yH2O after simple drying at 100 ℃. The material could catalyse the selective oxidation of anthracene to produce anthraquinone, a basic material of OLEM industry. It is also applicable for polyene degradation. Indeed, the purpose of this work is not only limited on the synthesis of anthraquinone or the degradation of polyene. It proposes a new approach for the rapid synthesis of selenium containing materials, which will have a profound impact in the field of selenium science and materials and industry.
Declaration of competing interest
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The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
CRediT authorship contribution statement
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Xiaoxue Li: Writing – original draft, Investigation. Hongwei Zhou: Writing – review & editing, Supervision. Rongrong Qian: Writing – original draft. Xu Zhang: Supervision, Investigation. Lei Yu: Writing – review & editing, Supervision, Project administration, Conceptualization.
Acknowledgments
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We thank the Jiangsu Provincial Six Talent Peaks Project (No. XCL-090), the Cooperation Project of Yangzhou City with Yangzhou University (No. YZ2023209), Jiaxing Key Laboratory for Creation of Animal Models & Synthesis of Lead Compounds of New Drug (No. jxsz21006), and the Priority Academic Program Development of Jiangsu Higher Education Institutions for support.
Supplementary materials
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Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.cclet.2024.110036.
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Year 2025 volume 36 Issue 3
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Article Info
doi: 10.1016/j.cclet.2024.110036
  • Receive Date：2024-03-19
  • Online Date：2025-11-07
  • Published：2025-03-15
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  • Received：2024-03-19
  • Revised：2024-05-10
  • Accepted：2024-05-21
Affiliations
    a School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China
    b College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, China
    c Jiangsu College of Tourism, Yangzhou 225009, China
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表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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