氮修饰Ni2P-Nx/SiO2催化剂设计合成及间甲酚加氢脱氧性能研究

doi:10.6023/A24070217

摘要/Abstract

采用浸渍法制备了一系列N修饰的Ni₂P-N_x/SiO₂催化剂, 通过X射线衍射(XRD)、N₂物理吸脱附(BET)、H₂-程序升温还原(H₂-TPR)、NH₃-程序升温脱附(NH₃-TPD)、吡啶红外(Py-FTIR)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等表征手段对催化剂的结构进行分析, 系统地研究了Ni/N物质的量比对催化剂理化性质的影响. 以间甲酚为模型化合物, 研究了Ni/N物质的量比、反应温度、反应时间及反应压力对催化剂加氢脱氧(HDO)性能的影响. 结果表明, 适量N修饰可以促进更小活性颗粒的形成, 提高活性组分的分散性, 进而提高催化剂的催化活性. Ni/N比为1时制备的Ni₂P-N_1.0/SiO₂催化剂具有最优异的HDO活性, 在250 ℃、3 MPa、1 h条件下, 间甲酚转化率为93.2%, 目标产物甲基环己烷(MCH)的选择性达到94.2%. Ni₂P-N_x/SiO₂催化剂上间甲酚HDO主要以加氢-脱氧(HYD)路径为主.

关键词: N修饰, Ni₂P-N_x/SiO₂催化剂, 间甲酚, 加氢脱氧, 甲基环己烷

The gradual depletion of fossil fuels and increasing environmental pollution problems inspire researchers to seek renewable and clean energy. Lignocellulosic biomass is deemed to be a sustainable and promising resource to produce chemicals and fuels due to its abundant existence in nature. Hydrodeoxygenation (HDO) of phenolic compounds in bio-fuel is a promising technology to convert biomass materials to value-added chemicals and fuels. However, the development of highly efficient catalysts remains a great challenge. In this work, a series of N modified Ni₂P-N_x/SiO₂ catalysts were prepared by impregnation method. The structure of the catalysts was characterized by X-ray diffraction (XRD), N₂ physical adsorption desorption (BET), H₂ temperature programmed reduction (H₂-TPR), NH₃ temperature programmed desorption (NH₃-TPD), pyridine infrared (Py-FTIR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and the influence of Ni/N molar ratio on the physicochemical properties of the catalysts was systematically investigated. Using m-cresol as a model compound, the effects of Ni/N molar ratio, reaction temperature, reaction time, and reaction pressure on the HDO performance were studied. It was found that the appropriate introduction of N element can promote the formation of smaller active particles, improve the dispersion of active components, thus enhancing the catalytic activity. The Ni₂P-N_1.0/SiO₂ catalyst with a Ni/N ratio of 1.0 exhibited the best HDO activity. Under the conditions of 250 ℃, 3 MPa, and 1 h, m-cresol conversion reached 93.2%, and the selectivity of the target product methylcyclohexane (MCH) reached 94.2%. Based on the product distribution, it can be inferred HDO of m-cresol over Ni₂P-N_x/SiO₂ catalyst proceeded mainly via hydrogenation-deoxygenation (HYD) pathway. Furthermore, this series of catalysts also displayed excellent recyclability, m-cresol conversion, as well as the selectivity towards MCH did not decrease obviously even after 5 successive cycles. We believe that this strategy can provide a simple and repeatable route to synthesize high-performance HDO catalysts.

Key words: N modified, Ni₂P-N_x/SiO₂ catalyst, m-cresol, hydrodeoxygenation, methylcyclohexane

引用此文

王帅, 宋华. 氮修饰Ni₂P-N_x/SiO₂催化剂设计合成及间甲酚加氢脱氧性能研究[J]. 化学学报, 2024, 82(9): 979-986.

Shuai Wang, Hua Song. Preparation of N Modified Ni₂P-N_x/SiO₂ Catalysts and Hydrodeoxygenation Performance of m-Cresol[J]. Acta Chimica Sinica, 2024, 82(9): 979-986.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 17

图1. 不同Ni/N比的Ni2P-Nx/SiO2催化剂XRD谱图

Figure 1. XRD spectra of Ni2P-Nx/SiO2 catalysts with different Ni/N ratios

图2. Ni2P-Nx/SiO2催化剂的N2吸附-脱附等温线(a)及孔径分布(b)

Figure 2. N2 adsorption-desorption isotherms (a) and pore size distribution (b) for Ni2P-Nx/SiO2 catalysts

Sample	S_BET/(m²•g⁻¹)	Pore volume/(cm³•g⁻¹)	Pore size/nm	Ni loading^a/%	Surface N content^b	Surface P content^c
Ni₂P/SiO₂	381.2	0.776	7.9	8.79	—	2.68
Ni₂P-N_0.25/SiO₂	321.5	0.636	7.7	—	—	—
Ni₂P-N_0.5/SiO₂	331.2	0.653	7.5	—	—	—
Ni₂P-N_1.0/SiO₂	359.5	0.665	7.4	8.63	1.34	2.54
Ni₂P-N_1.5/SiO₂	354.4	0.650	7.7	—	—	—
Ni₂P-N_2.0/SiO₂	350.5	0.637	7.3	—	—	—

表1. Ni2P-Nx/SiO2催化剂的结构特征

Table 1. Structural properties of Ni2P-Nx/SiO2 catalysts

图3. 前驱体的H2-TPR谱图

Figure 3. H2-TPR spectra of the precursors

图4. Ni2P-Nx/SiO2催化剂的NH3-TPD谱图

Figure 4. NH3-TPD spectra of the Ni2P-Nx/SiO2 catalysts

图5. Ni2P-Nx/SiO2催化剂的Py-FTIR谱图

Figure 5. Py-FTIR spectra of the Ni2P-Nx/SiO2 catalysts

Sample	Total acid/ (μmol•g⁻¹)	Acid sites distribution^a/(μmol•g⁻¹)
Sample	Total acid/ (μmol•g⁻¹)	Brönsted acid	Lewis acid	B/L
Ni₂P/SiO₂	373.6	48.8	324.8	0.15
Ni₂P-N_0.5/SiO₂	271.4	31.3	240.0	0.14
Ni₂P-N_1.0/SiO₂	298.3	32.2	266.1	0.12
Ni₂P-N_1.5/SiO₂	230.2	22.9	207.3	0.11

表2. Ni2P-Nx/SiO2催化剂的酸性

Table 2. The acidity of the Ni2P-Nx/SiO2 catalysts

图6. Ni2P-N1.0/SiO2 (a, b)和Ni2P/SiO2 (c)催化剂的TEM图

Figure 6. TEM images of Ni2P-N1.0/SiO2 (a, b) and Ni2P/SiO2 (c) catalysts

图7. Ni2P-N1.0/SiO2催化剂的XPS谱图

Figure 7. XPS spectra of the Ni2P-N1.0/SiO2 catalyst

图8. Ni/N物质的量比对Ni2P-Nx/SiO2催化剂上间甲酚HDO性能的影响

Figure 8. Effect of Ni/N molar ratio on HDO performance of cresol over Ni2P-Nx/SiO2 catalysts

图9. 反应温度对Ni2P-N1.0/SiO2催化剂上间甲酚HDO性能的影响

Figure 9. Effect of reaction temperature on HDO performance of cresol over Ni2P-N1.0/SiO2 catalyst

图10. 反应时间对Ni2P-N1.0/SiO2催化剂上间甲酚HDO性能的影响

Figure 10. Effect of reaction time on HDO performance of cresol over Ni2P-N1.0/SiO2 catalyst

图11. 反应压力对Ni2P-N1.0/SiO2催化剂上间甲酚HDO性能的影响

Figure 11. Effect of reaction pressure on HDO performance of cresol over Ni2P-N1.0/SiO2 catalyst

Catalyst	t/h	T/℃	p/MPa	Con./%	O-free product sel/%	Ref.
Ni₂P-N_1.0/SiO₂	1	250	3	93.2	94.2	This work
MoS₂	5	250	4	48.9	96.2	[23]
FeS₂	5	250	4	1.1	90.6	[23]
FeS-MoS₂-0.3	5	250	4	98.3	98.4	[23]
Mo-S	5	275	4	33.3	85.9	[24]
Co-Mo-S	5	275	4	76.4	98.3	[24]
Co-MoS₂	4	300	4	33.1	95.6	[25]

表3. Ni2P-N1.0/SiO2与已报道金属催化剂上间甲酚HDO性能比较

Table 3. Comparison of m-cresol HDO performance over Ni2P-N1.0/SiO2 with reported metal catalysts

图12. Ni2P-N1.0/SiO2催化剂的稳定性实验

Figure 12. Stability of the Ni2P-N1.0/SiO2 catalyst

底物	目标产物	转化率/%	选择性/%
苯酚	环己烷	97.8	96.4
对甲酚	甲基环己烷	93.5	95.3
邻甲酚	甲基环己烷	91.9	93.4
愈创木酚	环己烷	87.6	92.9

表4. Ni2P-N1.0/SiO2催化剂的底物拓展a

Table 4. Substrates extension of Ni2P-N1.0/SiO2 catalyst

图13. Ni2P-N1.0/SiO2催化剂上间甲酚HDO反应路径

Figure 13. Reaction pathway for HDO of cresol over Ni2P-N1.0/SiO2 catalyst

参考文献 25

[1]	Chen S.; Miao C.; Xie H.; Jiao Z.; Zhang X.; Zhou G. Biomass Bioenergy 2024, 180, 107002.
[2]	Wang S.; Jiang N.; Zhu T.; Zhang Q.; Zhang C.; Wang H.; Chen Y.; Li F.; Song H. Catal. Sci. Technol. 2022, 12, 1586.
[3]	Zhang Q.; Wang S.; Jiang, N ; Jiang, B.; Liu Y.; Chen Y.; Li F.; Song H. J. Catal. 2024, 432, 115338.
[4]	Liu L.; Zhang J.; Wang L.; Xiao F. Acta Chim. Sinica 2023, 81, 533 (in Chinese).
	(刘露杰, 张建, 王亮, 肖丰收, 化学学报, 2023, 81, 533.) doi: 10.6023/A23020042
[5]	Li Z.; Ren X.; Wang Y.; Li Z.; Ma S.; Qiu Z. Journal of Molecular Catalysis 2022, 36, 42 (in Chinese).
	(李志勤, 任枭雄, 王元哲, 李宗轩, 马少博, 邱泽刚, 分子催化, 2022, 36, 42.)
[6]	Ochoa E.; Torres D.; Pinilla J. L.; Suelves I. J. Environ. Chem. Eng. 2021, 9, 105146.
[7]	LiBretto N.; Tacey S.; Zubair M.; Bui T.; Unocic K.; Baddour F.; Griffin M.; Schaidle J.; Farberow C.; Ruddy D.; Bedford N.; Habas S. J. Mater. Chem. A 2023, 11, 16788.
[8]	Pitakjakpipop P.; Song C. Energy Fuels 2023, 37, 8311.
[9]	Jiang B.; Zhang Y. ; Wang H.; Liu K.; Jiang N.; Li J.; Song H. Chem. Eng. J. 2024, 495, 153118.
[10]	Gou X.; Jiang B.; Zhu T.; Zhang Q.; Wang S.; Li F.; Wang H.; Song H. Fuel 2024, 375, 32580.
[11]	Zhu T.; Liu K.; Wang H.; Wang J.; Li F.; Wang C.; Song H. Fuel 2023, 331, 125663.
[12]	Xu B.; Wei X.; Sun J.; Liu J.; Ma L. Acta Chim. Sinica 2023, 81, 239 (in Chinese).
	(徐斌, 韦秀芝, 孙江敏, 刘建国, 马隆龙, 化学学报, 2023, 81, 239.) doi: 10.6023/A22120481
[13]	Wang S.; Li F.; Liu Y.; Zhang Q.; Song H. New J. Chem. 2022, 46, 16941.
[14]	Ning X.; Sun Y.; Fu H.; Qu X.; Xu Z.; Zheng S. Chemosphere 2020, 241, 124978.
[15]	Zhang Z.; Tang M.; Chen J. Appl. Surf. Sci. 2016, 360, 353.
[16]	Zhao H.; Liu C.; Zheng Y.; Li S.; Gao Y.; Ma Q.; Wang F.; Dong Z. ACS Catal. 2024, 14, 8619.
[17]	Feitosa L. F.; Berhault G.; Laurenti D.; Teixeira da Silva V. Ind. Eng. Chem. Res. 2019, 58, 16164. doi: 10.1021/acs.iecr.9b00491
[18]	Zhou M.; Ye J.; Liu P.; Xu J.; Jiang J. ACS Sustainable Chem. Eng. 2017, 5, 8824.
[19]	Zhang Q.; Wang H.; Wang S.; Wang Y.; Zhang M.; Song H. Acta Chim. Sinica 2024, 82, 287 (in Chinese).
	(张强, 王欢, 王帅, 王园园, 张梅, 宋华, 化学学报, 2024, 82, 287.) doi: 10.6023/A23120546
[20]	Wang W.; Wang X.; Wang Y.; Jiang B.; Song H. React. Chem. Eng. 2022, 7, 978.
[21]	Wu C.; Kopold P.; Aken P. A.; Maier J.; Yu Y. Adv. Mater. 2017, 29, 1604015.
[22]	Wang M.; Lin M.; Li J.; Huang L.; Zhuang Z.; Lin C.; Zhou L.; Mai L. Chem. Commun. 2017, 53, 8372.
[23]	Jampa S.; Puente-Urbina A.; Ma Z. Q.; Wongkasemjit S.; Luterbacher J. S.; van Bokhoven J. A. ACS Sustainable Chem. Eng. 2019, 7, 4058.
[24]	Antar M.; Lyu D. M.; Nazari M.; Shah A.; Zhou X. M.; Smith D. L. Renew. Sust. Energy Rev. 2021, 139, 110691.
[25]	Kabir G.; Hameed B. H. Renew. Sust. Energy Rev. 2017, 70, 945.

氮修饰Ni₂P-N_x/SiO₂催化剂设计合成及间甲酚加氢脱氧性能研究

Preparation of N Modified Ni₂P-N_x/SiO₂ Catalysts and Hydrodeoxygenation Performance of m-Cresol

RichHTML

PDF

可视化

摘要/Abstract

引用此文

分享此文

图/表 17

参考文献 25

相关文章 3

编辑推荐

相关统计

本文评价

[1]	张强, 王欢, 王帅, 王园园, 张梅, 宋华. NiCe(x)/FLRC-TiO₂催化剂的制备及其加氢脱氧性能研究[J]. 化学学报, 2024, 82(3): 287-294.
[2]	刘露杰, 张建, 王亮, 肖丰收. 生物质基多元醇的多相催化选择性氢解^★[J]. 化学学报, 2023, 81(5): 533-547.
[3]	田钊炜, 达伟民, 王雷, 杨宇森, 卫敏. 第二代生物柴油制备的多相催化剂的结构设计及研究进展[J]. 化学学报, 2022, 80(9): 1322-1337.