Study on Epoxidation of Cyclopentene Catalyzed by Diniobium Pentoxide Loaded on Carbon@Silica Composite Material

doi:10.6023/cjoc202506014

Abstract

Using polybenzoxazine as carbon and nitrogen sources and tetraethyl silicate as silicon source, a hollow carbon nitride@silica composite material was synthesized by limited carbonization method. Using niobium pentachloride as niobium source, Nb₂O₅ was loaded on hollow carbon nitride@silica composite by impregnation-calcination method. The epoxidation of cyclopentene was catalyzed by the amphiphilic catalyst Nb₂O₅/CN_x@mSiO₂ with H₂O₂ (aqueous solution) as oxidant. The catalytic active center Nb₂O₅ is mainly anchored to the hollow and hydrophobic carbon nitride skeleton through nitrogen atoms, and the inner cavity structure can enrich more cyclopentene. The outer hydrophilic mesoporous silica can not only protect the catalytic active center to reduce its loss, but also facilitate the separation and recovery of the catalyst. Under the optimal reaction conditions, the conversion of cyclopentene was 94.0% and the selectivity of cyclopentane oxide was 92.1%. The catalyst can be recycled three times. This study provides a new green and efficient method for the preparation of cyclopentane oxide and a new idea for the aqueous oxidation of olefin catalyzed by amphiphilic catalyst.

Key words: amphiphilicity, carbon@silica, niobium oxide, epoxidation, cyclopentane oxide

Cite this article

Jiahao Li, Bing Yuan, Fengli Yu. Study on Epoxidation of Cyclopentene Catalyzed by Diniobium Pentoxide Loaded on Carbon@Silica Composite Material[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 624-632.

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Fig. & Tab. 16

Figure 1. Nitrogen adsorption-desorption isotherm (A) and pore size distribution curve (B) of BJH for CNx@mSiO2

Figure 2. XPS total spectrum (A), high-resolution XPS spectrum of C 1s (B), high-resolution XPS spectrum of N 1s (C) and Raman spectrum (D) of the material CNx@mSiO2

Figure 3. SEM image (A), low-resolution TEM images (B, C) and HRTEM image (D) of Nb2O5/CNx@mSiO2

Figure 4. HAADF-STEM image (A) and element mapping images (B~F) of Nb2O5/CNx@mSiO2

Figure 5. XRD patterns of CNx@mSiO2 (a) and Nb2O5/CNx@- mSiO2 (b)

Figure 6. XPS total spectra of Nb2O5/CNx@mSiO2 (A) with niobium oxalate (a), niobium ammonium oxalate (b) and niobium chloride (c) as niobium sources, and high resolution XPS spectrum of Nb 3d (B)

Figure 7. Thermogravimetric curve in an air atmosphere (A) and NH3-TPD curve (B) of Nb2O5/CNx@mSiO2

Solvent	Conv./%	Selectivity/%
Solvent	Conv./%
DMF	56.7	42.7	54.8	1.4	1.1
MeCN	90.5	74.4	7.5	7.9	10.2
EtOH	89.5	81.5	1.8	6.6	10.1
t-BuOH	72.3	83.2	2.5	5.7	8.6
Acetone	95.4	89.0	3.5	3.5	4.0

Table 1. Solvent-affected performances of Nb2O5/CNx@mSiO2 for the epoxidation of cyclopentene

Figure 8. 丙酮用量对反应的影响 Catalyst (50 mg), CPE (10 mmol), H2O2 (30 mmol), 35 ℃, 6 h. Influence of acetone dosage on the reaction

Figure 9. 催化剂用量对反应的影响 CPE (10 mmol), acetone (5 mL), H2O2 (30 mmol), 35 ℃, 6 h. Influence of catalyst dosage on the reaction

Figure 10. 过氧化氢用量对反应的影响 Catalyst (50 mg), CPE (10 mmol), acetone (5 mL), 35 ℃, 6 h. Influence of hydrogen peroxide dosage on the reaction

Figure 11. 温度对反应的影响 Catalyst (50 mg), CPE (10 mmol), acetone (5 mL), H2O2 (30 mmol), 6 h. Influence of temperature on the reaction

Figure 12. 时间对反应的影响 Catalyst (50 mg), CPE (10 mmol), acetone (5 mL), H2O2 (30 mmol), 35 ℃. Influence of time on the reaction

Figure 13. 催化剂的循环使用性能 Catalyst (50 mg), CPE (10 mmol), acetone (4 mL), H2O2 (40 mmol), 35 ℃, 6 h. Recycling performance of the catalyst

Entry	Catalyst	Conv./%	Sel./%
1	Nb₂O₅	17.1	58.6
2	Nb₂O₅/CN_x	56.6	84.4
3	Nb₂O₅/mSiO₂	84.1	89.2
4	Nb₂O₅/CN_x@mSiO₂^b	94.0	92.1
5	Nb₂O₅/CN_x@mSiO₂^c	76.2	94.9
6	Nb₂O₅/CN_x@mSiO₂^d	66.7	94.7

Table 2. Epoxidation of cyclopentene catalyzed by different catalysts

Entry	Catalyst	Experiment condition	Conv./%	Sel./%	Recycle number	Ref.
1	Co@MCM(F)	MeCN, 60 ℃, 3 h	45.2	80.7	1	[3]
2	R-Ti-MWW-PI	MeCN, 60 ℃, 2 h	97.8	99.9	6	[4]
3	TS-1_P-0.05K	MeOH, 40 ℃, 2 h	52.0	98.2	5	[5]
4	Mg_0.5Co_0.5Fe₂O₄	1,4-Dioxane, 60 ℃, 8 h	95.2	96.3	5	[34]
5	SBA-15-ImCl-PF₆-W	No solvent, 35 ℃, 3 h	53.0	99.0	7	[35]
6	Nb₂O₅/CN_x@mSiO₂	Acetone, 35 ℃, 4 h	94.0	92.1	3	This work

Table 3. Catalytic performance comparison of catalysts reported before in the literatures

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碳@硅复合材料负载的五氧化二铌催化环戊烯环氧化反应研究