碳球为模板水热合成Mg-Co复合氧化物及其催化分解N<sub>2</sub>O

ZHENG Li; LI He-jian; XU Xiu-feng

碳球为模板水热合成Mg-Co复合氧化物及其催化分解N₂O

烟台大学化学化工学院, 应用催化研究所, 山东烟台 264005

基金项目:

the Shandong Provincial Natural Science Foundation ZR2017MB020

Graduate Innovation Foundation of Yantai University GIFYTU

详细信息

中图分类号: O643.3
计量
- 文章访问数: 74
- HTML全文浏览量: 20
- PDF下载量: 7
- 被引次数: 0
出版历程
- 收稿日期: 2018-01-18
- 修回日期: 2018-03-13
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-05-10

Catalytic decomposition of N₂O over Mg-Co composite oxides hydrothermally prepared by using carbon sphere as template

School of Chemistry and Chemical Engineering, Institute of Applied Catalysis, Yantai University, Yantai 264005, China

Funds:

the Shandong Provincial Natural Science Foundation ZR2017MB020

Graduate Innovation Foundation of Yantai University GIFYTU

More Information

Corresponding author: XU Xiu-feng, Tel: 0535-6902746, E-mail: xxf@ytu.edu.cn

摘要

摘要: 用自制的碳球为模板剂，尿素为沉淀剂，120℃水热合成尖晶石型Mg-Co复合氧化物（MgCo₂O₄），在其表面浸渍K₂CO₃溶液制得K改性催化剂，用于催化分解N₂O。用X射线衍射（XRD）、N₂物理吸附-脱附、扫描电镜（SEM）、H₂程序升温还原（H₂-TPR）、O₂程序升温脱附（O₂-TPD）、X射线光电子能谱（XPS）等技术对催化剂进行结构表征，考察了钴镁离子/碳球的质量比、尿素/钴镁离子的物质的量比等制备参数对催化剂活性的影响。结果表明，钴镁离子/碳球的质量比为0.192、尿素/钴镁离子的物质的量比为2，制得的MgCo₂O₄催化剂活性较高。K改性MgCo₂O₄催化剂在400℃有氧无水、有氧有水条件下连续反应50 h，N₂O转化率分别保持在91%和62%，稳定性较好。
- N₂O催化分解 /
- Mg-Co复合氧化物 /
- K改性催化剂 /
- 催化活性
Abstract: MgCo₂O₄ composite oxides with spinel structure were hydrothermally prepared at 120℃ by using carbon sphere as template and urea as precipitant. K₂CO₃ solution was impregnated on MgCo₂O₄ and the K-modified catalyst was obtained. These catalysts were applied in catalytic decomposition of N₂O and characterized by X-ray diffraction(XRD), nitrogen physisorption, scanning electron microscopy (SEM), temperature-programmed reduction of hydrogen (H₂-TPR), temperature-programmed desorption of oxygen (O₂-TPD), and X-ray photoelectron spectroscopy (XPS). Effect of catalysts preparation parameters such as mass ratio of cobalt and magnesium to carbon sphere, molar ratio of urea to metallic cations, on their catalytic activity was investigated. It is shown that the catalyst prepared with mass ratio 0.192 of cobalt and magnesium to carbon sphere, molar ratio 2 of urea to cobalt and magnesium cations, exhibits higher catalytic activity than others. Furthermore, 91% and 62% conversions of N₂O could be reached over 0.02 K/MgCo₂O₄ catalyst at 400℃ after continuous running for 50 h under the atmosphere of oxygen-alone and oxygen-steam together, respectively, revealing that K-modified MgCo₂O₄ catalyst is stable under both reaction atmospheres.
- catalytic decomposition of N₂O /
- Mg-Co composite oxides /
- K-modified catalyst /
- catalytic activity

HTML全文

Figure 1 XRD patterns of MgCo₂O₄ prepared by changing the mass ratio of cobalt and magnesium to carbon sphere

a: MgCo₂O₄-0.149; b: MgCo₂O₄-0.192; c: MgCo₂O₄-0.234; d: MgCo₂O₄-0.320

下载: 全尺寸图片幻灯片

Figure 2 N₂O conversions over MgCo₂O₄ prepared by changing the mass ratio of cobalt and magnesium to carbon sphere

下载: 全尺寸图片幻灯片

Figure 3 H₂-TPR profiles of MgCo₂O₄ prepared by changing the mass ratio of cobalt and magnesium to carbon sphere

a: MgCo₂O₄-0.149; b: MgCo₂O₄-0.192; c: MgCo₂O₄-0.234; d: MgCo₂O₄-0.320

下载: 全尺寸图片幻灯片

Figure 4 O₂-TPD profiles of MgCo₂O₄ prepared by changing the mass ratio of cobalt and magnesium to carbon sphere

a: MgCo₂O₄-0.149; b: MgCo₂O₄-0.192; c: MgCo₂O₄-0.234; d: MgCo₂O₄-0.320

下载: 全尺寸图片幻灯片

Figure 5 XRD patterns of MgCo₂O₄ prepared by changing the molar ratio of urea to cobalt and magnesium cations

a: MgCo₂O₄(1.5); b: MgCo₂O₄(2); c: MgCo₂O₄(4)

下载: 全尺寸图片幻灯片

Figure 6 SEM images of MgCo₂O₄ prepared by changing the molar ratio of urea to cobalt and magnesium cations

(a): MgCo₂O₄(1.5); (b): MgCo₂O₄(2); (c): MgCo₂O₄(4)

下载: 全尺寸图片幻灯片

Figure 7 N₂O conversions over MgCo₂O₄ prepared by changing the molar ratio of urea to cobalt and magnesium cations

下载: 全尺寸图片幻灯片

Figure 8 XPS spectra of cobalt element in MgCo₂O₄ prepared by changing the molar ratio of urea to cobalt and magnesium cations

a: MgCo₂O₄(1.5); b: MgCo₂O₄(2); c: MgCo₂O₄(4)

下载: 全尺寸图片幻灯片

Figure 9 H₂-TPR profiles of MgCo₂O₄ prepared by changing the molar ratio of urea to cobalt and magnesium cations

a: MgCo₂O₄(1.5); b: MgCo₂O₄(2); c: MgCo₂O₄(4)

下载: 全尺寸图片幻灯片

Figure 10 XRD patterns of K-modified MgCo₂O₄ catalysts

a: MgCo₂O₄; b: 0.02K/MgCo₂O₄

下载: 全尺寸图片幻灯片

Figure 11 SEM images of K-modified MgCo₂O₄ catalysts

(a): MgCo₂O₄; (b): 0.02K/MgCo₂O₄

下载: 全尺寸图片幻灯片

Figure 12 N₂O conversions over K-modified MgCo₂O₄ catalysts

下载: 全尺寸图片幻灯片

Figure 13 XPS spectra of Co element on the surface of K-modified MgCo₂O₄ catalysts

a: MgCo₂O₄; b: 0.02 K/MgCo₂O₄

下载: 全尺寸图片幻灯片

Figure 14 H₂-TPR profiles of K-modified MgCo₂O₄ catalysts

a: MgCo₂O₄; b: 0.02 K/MgCo₂O₄

下载: 全尺寸图片幻灯片

Figure 15 Initial activity of K-modified MgCo₂O₄ in the presence of oxygen and steam

■: MgCo₂O₄; ●: MgCo₂O₄(O₂); ▲: MgCo₂O₄(O₂+H₂O); ▼: 0.02K/MgCo₂O₄; ◆: 0.02K/MgCo₂O₄ (O₂); : 0.02K/MgCo₂O₄(O₂+H₂O)

下载: 全尺寸图片幻灯片

Figure 16 Catalytic stability of 0.02 K/MgCo₂O₄ for N₂O decomposition at 400 ℃

下载: 全尺寸图片幻灯片

Table 1 Crystallite size and BET surface area of MgCo₂O₄ prepared by changing the mass ratio of cobalt and magnesium to carbon sphere

Catalyst	Crystallite size d/nm^a	BET surface area A/(m²·g^-1)
MgCo₂O₄-0.149	33.2	32.1
MgCo₂O₄-0.192	32.1	25.8
MgCo₂O₄-0.234	33.3	21.1
MgCo₂O₄-0.320	47.6	25.4
^a: calculated by scherrer equation on the basis of (311) crystallographic plane data in XRD patterns

下载: 导出CSV

Table 2 XPS data of K-modified MgCo₂O₄ catalyst

Catalyst	Binding energies of Co 2p_3/2 /eV		Co²⁺/ Co³⁺ ratio
Catalyst	Co²⁺	Co³⁺	Co²⁺/ Co³⁺ ratio
MgCo₂O₄	780.0	782.0	1.80
0.02K/MgCo₂O₄	779.8	781.9	2.10

下载: 导出CSV

参考文献(26)

[1]	PACHATOURIDOU E, PAPISTA E, DELIMITIS A, VASILIADES M A, EFSTATHIOU A M, AMIRIDIS M D, ALEXEEV O S, BLOOM D, MARNELLOS G E, KONSOLAKIS M, ILIOPOULOU E. N₂O decomposition over ceria-promoted Ir/Al₂O₃ catalysts:The role of ceria[J]. Appl Catal B:Environ, 2016, 187:259-268. doi: 10.1016/j.apcatb.2016.01.049
[2]	CARABINEIRO S A C, PAPISTA E, MARNELLOS G E, TAVARES P B, MALDONADO-HÓDAR F J, KONSOLAKIS M. Catalytic decomposition of N₂O on inorganic oxides:Effect of doping with Au nanoparticles[J]. Mol Catal, 2017, 436:78-89. doi: 10.1016/j.mcat.2017.04.009
[3]	LIN Y, MENG T, MA Z. Catalytic decomposition of N₂O over RhO_x supported on metal phosphates[J]. J Ind Eng Chem, 2015, 28:138-146. doi: 10.1016/j.jiec.2015.02.009
[4]	LIU Z M, HE C X, CHEN B H, LIU H Y. CuO-CeO₂ mixed oxide catalyst for the catalytic decomposition of N₂O in the presence of oxygen[J]. Catal Today, 2017, 297:78-83. doi: 10.1016/j.cattod.2017.05.074
[5]	GRZYBEK G, WÓJCIK S, CIURA K, GRYBO Ś J, INDYKA P, OSZAJCA M, STELMACHOWSKI P, WITKOWSKI S, INGER M, WILK M, KOTARBA A, SOJKA Z. Influence of preparation method on dispersion of cobalt spinel over alumina extrudates and the catalyst deN₂O activity[J]. Appl Catal B:Environ, 2017, 210:34-44. doi: 10.1016/j.apcatb.2017.03.053
[6]	XIE P F, MA Z, ZHOU H B, HUANG C Y, YUE Y H, SHEN W, XU H L, HUA W M, GAO Z. Catalytic decomposition of N₂O over Cu-ZSM-11 catalysts[J]. Microporous Mesoporous Mater, 2014, 191:112-117. doi: 10.1016/j.micromeso.2014.02.044
[7]	WU M F, WANG H, ZHONG L S, ZHANG X Y, HAO Z P, SHEN Q, WEI W, QIAN G G, SUN Y H. Effects of acid pretreatment on Fe-ZSM-5 and Fe-beta catalysts for N₂O decomposition[J]. Chin J Catal, 2016, 37(6):898-907. doi: 10.1016/S1872-2067(15)61052-X
[8]	ABU-ZIED B M, SOLIMAN S A, ABDELLAH S E. Pure and Ni-substituted Co₃O₄ spinel catalysts for direct N₂O decomposition[J]. Chin J Catal, 2014, 35(7):1105-1112. doi: 10.1016/S1872-2067(14)60058-9
[9]	KLYUSHINA A, PACULTOVÁ K, KARÁSKOVÁK, JIRÁTOVÁ K, RITZ M, FRIDRICHOVÁ D, VOLODARSKAJA A, OBALOVÁ L. Effect of preparation method on catalytic properties of Co-Mn-Al mixed oxides for N₂O decomposition[J]. J Mol Catal A:Chem, 2016, 425:237-247. doi: 10.1016/j.molcata.2016.10.014
[10]	OBALOVÁL, PACULTOVÁ K, BALABÁNOVÁ J, JIRÁTOVÁ K, BASTL Z, VALÁŠKOVÁ M, LACNY Z, KOVANDA F. Effect of Mn/Al ratio in Co-Mn-Al mixed oxide catalysts prepared from hydrotalcite-like precursors on catalytic decomposition of N₂O[J]. Catal Today, 2007, 119(1/4):233-238. https://www.researchgate.net/publication/229168042_Effect_of_MnAl_ratio_in_Co-Mn-Al_mixed_oxide_catalysts_prepared_from_hydrotalcite-like_precursors_on_catalytic_decomposition_of_N2O
[11]	PU Z Y, LIU Y, ZHOU H, HUANG W Z, ZHENG Y F, LI X N. Catalytic combustion of lean methane at low temperature over ZrO₂-modified Co₃O₄ catalysts[J]. Appl Surf Sci, 2017, 422:85-93. doi: 10.1016/j.apsusc.2017.05.231
[12]	CHELLAM U, XU Z P, ZENG H C. Low-temperature synthesis of Mg_xCo_1-xCo₂O₄ spinel catalysts for N₂O decomposition[J]. Chem Mater, 2000, 12(3):650-658. doi: 10.1021/cm990355l
[13]	ABU-ZIED B M. Nitrous oxide decomposition over alkali-promoted magnesium cobaltite catalysts[J]. Chin J Catal, 2011, 32(2):264-272. https://www.sciencedirect.com/science/article/pii/S187220671060174X
[14]	ZHENG L, WU C C, XU X F. Catalytic decomposition of N₂O over Mg-Co and Mg-Mn-Co composite oxides[J]. J Fuel Chem Technol, 2016, 44(12):1494-1501. doi: 10.1016/S1872-5813(17)30005-1
[15]	SEVILLA M, FUERTES A B. Chemical and structural properties of carbonaceous products obtained by hydrothermal carbonization of saccharides[J]. Chem Eur J, 2009, 15(16):4195-4203. doi: 10.1002/chem.v15:16
[16]	SUN X M, LI Y D. Colloidal carbon spheres and their core/shell structures with noble-metal nanoparticles[J]. Angew Chem Int Ed, 2004, 43(5):597-601. doi: 10.1002/(ISSN)1521-3773
[17]	TITIRICI M M, ANTONIETTI M, THOMAS A. A generalized synthesis of metal oxide hollow spheres using a hydrothermal approach[J]. Chem Mater, 2006, 18(16):3808-3812. doi: 10.1021/cm052768u
[18]	YU J G, YU X X, HUANG B B, ZHANG X Y, DAI Y. Hydrothermal synthesis and visible-light photocatalytic activity of novel cage-like ferric oxide hollow spheres[J]. Cryst Growth Des, 2009, 9(3):1474-1480. doi: 10.1021/cg800941d
[19]	JIA G, YANG M, SONG Y H, YOU H P, ZHANG H J. General and facile method to prepare uniform Y₂O₃:Eu hollow microspheres[J]. Cryst Growth Des, 2009, 9(1):301-307. doi: 10.1021/cg8004823
[20]	FRANKEN T, PALKOVITS R. Investigation of potassium doped mixed spinels Cu_x Co_3-xO₄ as catalysts for an efficient N₂O decomposition in real reaction conditions[J]. Appl Catal B:Environ, 2015, 176-177:298-305. doi: 10.1016/j.apcatb.2015.04.002
[21]	KIM M J, LEE S J, RYU I S, JEON M W, MOON S H, ROH H S, JEON S G. Catalytic decomposition of N₂O over cobalt based spinel oxides:The role of additives[J]. Mol Catal, 2017, 442:202-207. doi: 10.1016/j.mcat.2017.05.029
[22]	GRZYBEK G, WÓJCIK S, LEGUTKO P, GRYBOS J, INDYKA P, LESZCZYNSKI B, KOTARBA A, SOJKA Z. Thermal stability and repartition of potassium promoter between the support and active phase in the K-Co_2.6Zn_0.4O₄\|α -Al₂O₃ catalyst for N₂O decomposition:Crucial role of activation temperature on catalytic performance[J]. Appl Catal B:Environ, 2017, 205:597-604. doi: 10.1016/j.apcatb.2017.01.005
[23]	KLYUSHINA A, PACULTOVÁK, KREJCOVÁ S, SŁOWIK G, JIRÁTOVÁ K, KOVANDA F, RYCZKOWSKI J, OBALOVÁ L. Advantages of stainless steel sieves as support for catalytic N₂O decomposition over K-doped Co₃O₄[J]. Catal Today, 2015, 257:2-10. doi: 10.1016/j.cattod.2015.05.015
[24]	WANG S L, QIAN L Q, XU H, LÜ G L, DONG W J, TANG W H. Synthesis and structural characterization of cobalt hydroxide carbonate nanorods and nanosheets[J]. J Alloys Compd, 2009, 476(1/2):739-743. https://www.sciencedirect.com/science/article/pii/S0925838808015570
[25]	AMROUSSE R, TSUTSUMI A, BACHAR A, LAHCENE D. N₂O catalytic decomposition over nano-sized particles of Co-substituted Fe₃O₄substrates[J]. Appl Catal A:Gen, 2013, 450(2):253-260. http://www.doc88.com/p-9905362717867.html
[26]	ZABILSKIY M, DJINOVI ĆP, TCHERNYCHOVA E, PINTAR A. N₂O decomposition over CuO/CeO₂ catalyst:New insights intoreaction mechanism and inhibiting action of H₂O and NO by operando techniques[J]. Appl Catal B:Environ, 2016, 197:146-158. doi: 10.1016/j.apcatb.2016.02.024