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

doi:10.6023/cjoc202506014

摘要/Abstract

以聚苯并恶嗪为碳源和氮源, 硅酸四乙酯为硅源, 通过限域碳化法合成一种中空的氮化碳@二氧化硅复合材料. 以五氯化铌为铌源, 通过浸渍-煅烧的方法将Nb₂O₅负载在中空的氮化碳@二氧化硅复合材料上. 以H₂O₂(水溶液)为氧化剂, 将合成的两亲性催化剂Nb₂O₅/CN_x@mSiO₂用于催化环戊烯的环氧化反应. 催化活性中心Nb₂O₅主要通过氮原子锚定在内部中空的具有疏水性的氮化碳骨架上, 而内部的空腔结构可以富集更多的环戊烯; 外部亲水性的介孔二氧化硅壳不仅可以保护催化活性中心减少其流失, 而且有利于催化剂的分离回收. 在最优反应条件下, 环戊烯转化率为94.0%, 环氧环戊烷选择性为92.1%. 催化剂可以循环使用三次. 本研究为环氧环戊烷的制备提供了一种绿色、高效的新方法, 为两亲性催化剂催化烯烃的水相氧化反应提供了一种新思路.

关键词: 两亲性, 碳@硅, 铌氧化物, 环氧化, 环氧环戊烷

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

引用此文

李佳豪, 袁冰, 于凤丽. 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[J]. 有机化学, 2026, 46(2): 624-632.

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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图/表 16

图1. CNx@mSiO2的氮气吸附-脱附等温线(A)和BJH的孔径分布曲线(B)

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

图2. 材料CNx@mSiO2的XPS总谱图(A), C 1s的高分辨XPS谱图(B), N 1s的高分辨XPS谱图(C)和拉曼谱图(D)

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

图3. Nb2O5/CNx@mSiO2的SEM图像(A), 低分辨的TEM图像(B, C)和HRTEM图像(D)

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

图4. Nb2O5/CNx@mSiO2的HAADF-STEM图像(A)和元素映射图像(B~F)

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

图5. CNx@mSiO2 (a)和Nb2O5/CNx@mSiO2 (b)的XRD谱图

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

图6. 草酸铌(a), 草酸铌铵(b)和氯化铌(c)为铌源的Nb2O5/ CNx@mSiO2的XPS总谱图(A)和Nb 3d的高分辨XPS谱图(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)

图7. Nb2O5/CNx@mSiO2在空气气氛下的热重曲线(A)和NH3-TPD曲线(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

表1. 溶剂种类对Nb2O5/CNx@mSiO2催化环戊烯环氧化性能的影响a

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

图8.

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

图9.

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

图10.

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

图11.

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

图12.

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

图13.

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

表2. 不同催化剂催化环戊烯环氧化反应a

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

表3. 与文献报道的催化剂的催化性能比较

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

参考文献 35

[13]	Chen Y.; Lv G. J.; Zou X. Y.; Su S. H.; Wang J. Z.; Zhou C. Y.; Shen J. L.; Shen Y. B.; Liu Z. M. J. Colloid Interface Sci. 2024, 664, 626.
[14]	De La Garza L. C.; Vigier K. D.; Chatel G.; Moores A. Green Chem. 2017, 19, 2855.
[15]	Shi Y. M.; Guo Z. J.; Wang Q.; Zhang L. Y.; Li J.; Zhou Y.; Wang J. ChemCatChem 2017, 9, 4426.
[16]	Wang W. Y.; Li C. P.; Pi Y. B.; Wang J. J.; Tan R.; Yin D. H. Catal. Sci. Technol. 2019, 9, 5626.
[17]	Zhang Z. Y.; Tang J.; Chen J. B.; Cui P. X.; Jiao S. Y.; Yi W.; Ke Q. P.; Yang H. Q. Catal. Today 2023, 410, 222.
[18]	Zha Q. Y.; An J. G.; Jiang B. W.; Liu Y.; Zhang Z. G.; Liu J.; Zhang Z. B. J. Colloid Interface Sci. 2024, 657, 903.
[19]	Ding Y.; Xu H.; Wu H. H.; He M. Y.; Wu P. Chem. Commun. 2018, 54, 7932
[20]	Xiang G. H.; Zhang L. S.; Chen J. N.; Zhang B. S.; Liu Z. G. Nanoscale 2021, 13, 18140.
[21]	Xiang G. H.; Zhang L. S.; Yi C. F.; Liu Z. G. Appl. Surf. Sci. 2022, 577, 151829.
[22]	Yu F. L.; Shi Y. L.; Wu F. Z.; Yuan B.; Xie C. X.; Yu S. T. Ind. Crops Prod. 2022, 185, 115140.
[23]	Chen S. N.; Ren T. F.; Lu K. C.; Ouyang C. P.; Huang X.; Zhang X. Y. Chem. Eng. J. 2023, 466, 143110.
[1]	Mel'nik L. V.; Meshechkina A. E.; Rybina G. V.; Srednev S. S.; Moskvichev Y. A.; Kozlova O. S. Pet. Chem. 2012, 52, 313.
[2]	Yang X. L.; Dai W. L.; Chen H.; Xu J. H.; Cao Y.; Li H. X.; Fan K. N. Appl. Catal. A-Gen. 2005, 283, 1.
[3]	Solórzano C.; Méndez F. J.; Brito J. L.; Silva P.; Anacona J. R.; Bastardo-González E. J. Organomet. Chem. 2020, 908, 121073.
[4]	Tong W.; Yin J. P.; Ding L. Y.; Xu H.; Wu P. Front. Chem. 2020, 8, 585347.
[5]	Chang X. Y.; Sun Y. T.; Song X. J.; Yang X. T.; Wu Y. Q.; Jia M. J. Catalysts 2022, 12, 1241.
[6]	Sun G. H.; Li M. M. J.; Nakagawa K.; Li G. C.; Wu T. S.; Peng Y. K. Appl. Catal. B-Environ. 2022, 313, 121461.
[24]	Zhu H. Y.; Du R. R.; Zhao H. Y.; Liu M. T.; Wang Y. Y.; Yu C.; Guo Z. J.; Tang S.; Ang E. H.; Yang F. J. Mater. Chem. A 2024, 12, 8487.
[25]	Prieto G.; Tüysüz H.; Duyckaerts N.; Knossalla J.; Wang G. H.; Schüth F. Chem. Rev. 2016, 116, 14056.
[26]	Cao Y. L.; Mao S. J.; Li M. M.; Chen Y. Q.; Wang Y. ACS Catal. 2017, 7, 8090.
[27]	Liu S. K.; Yu F. L.; Yuan B.; Xie C. X.; Yu S. T. ChemPlusChem 2023, 88, e202200443.
[28]	Bao M. H.; Yu F. L.; Yuan B.; Xie C. X.; Yu S. T. BioResources 2023, 18, 4032.
[29]	Zhang Z. M.; Xu H.; Li H. Fuel 2022, 324, 124400.
[7]	Kholdeeva O. A.; Ivanchikova I. D.; Maksimchuk N. V.; Skobelev I. Y. Catal. Today 2019, 333, 63.
[8]	Zhou Q. Q.; Ye M.; Ma W. B.; Li D. F.; Ding B. J.; Chen M. Y.; Yao Y. F.; Gong X. Q.; Hou Z. S. Chem.-Eur. J. 2019, 25, 4206.
[9]	Zhou Q. Q.; Xu B. B.; Tang X.; Dai S.; Ding B. J.; Li D. F.; Zheng A. N.; Zhang T.; Yao Y. F.; Gong X. Q.; Hou Z. S. Langmuir 2021, 37, 8190.
[10]	Ding B. J.; Zhang R.; Zhou Q. Q.; Ma W. B.; Zheng A. N.; Li D. F.; Yao Y. F.; Hou Z. S. Mol. Catal. 2021, 500, 111342.
[11]	Talukdar H.; Gogoi S. R.; Saikia G.; Sultana S. Y.; Ahmed K.; Islam N. S. Mol. Catal. 2021, 516, 111988.
[12]	Chung S. H.; Lachman V.; Slot T. K.; Shiju N. R. Catal. Commun. 2023, 182, 106754.
[30]	Qi Y. M.; Han Q.; Wu L.; Li J. New J. Chem. 2021, 45, 19264.
[31]	Chen P. Y.; Fang Y. X.; Xie K. H.; Chen Y.; Liu Y.; Zuo H. L.; Lu W. J.; Liu B. Y. Chin. J. Chem. Eng. 2023, 56, 152.
[32]	Jin M. M.; Meng S. X.; Liu G. D.; Si C. D.; Lv Z. G.; Han H.; Niu Q. T. Mol. Catal. 2024, 564, 114273.
[33]	Jin M. M.; Meng S. X.; Liu G. D.; Si C. D.; Lv Z. G.; Han H.; Niu Q. T. Mater. Res. Bull. 2024, 179, 112927.
[34]	Tong J. H.; Liu F. F.; Wang W. H.; Bo L. L.; Mahboob A.; Fan H. Y. ChemistrySelect 2016, 1, 6356.
[35]	Niu Q. T.; Liu G. D.; Lv Z. G.; Si C. D.; Jin M. M. ChemistrySelect 2021, 6, 2111.