溶胶凝胶法由细菌纤维素制备CuCe0.75Zr0.25Ox复合氧化物及其低温催化降解甲苯性能

杨青; 郝庆兰; 闫宁娜; 赵若竹; 赵晨晨; 张庆; 豆宝娟; 宾峰

溶胶凝胶法由细菌纤维素制备CuCe_0.75Zr_0.25O_x复合氧化物及其低温催化降解甲苯性能

1.
天津科技大学化工与材料学院, 天津 300457
2.
中国科学院力学研究所高温气体动力学国家重点实验室, 北京 100190

基金项目:

国家自然科学基金青年科学基金 21307088

详细信息

中图分类号: TQ426.83
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- 被引次数: 0
出版历程
- 收稿日期: 2017-06-23
- 修回日期: 2017-08-23
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-11-10

Preparation of CuCe_0.75Zr_0.25O_x composite by bacterial cellulose promoted sol-gel method and its catalytic performance in the toluene degradation at low temperature

1.
College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin 300457, China
2.
Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190, China

Funds:

the National Natural Science Foundation of China 21307088

More Information

Corresponding author: DOU Bao-juan, Tel:(022)60601278, E-mail:bjdou@tust.edu.cn

摘要

摘要: 以绿色廉价的天然椰果细菌纤维素（BC）为造孔剂，采用溶胶凝胶法制备了CuCe_0.75Zr_0.25O_x复合氧化物催化剂，通过TG/DTG、N₂低温物理吸脱附、XRD、H₂-TPR、O₂-TPD和Raman等手段对催化剂进行了表征，并对其在固定床上挥发性有机物（VOCs）降解的催化性能进行了研究。结果表明，利用BC精细的纤维网状结构和亲水性能与活性金属盐溶液形成凝胶，可有效制备介孔结构的复合氧化物催化剂。制备过程中，凝胶形式和成胶温度对催化剂降解甲苯的活性有较大影响；采用醇凝胶形式在70 ℃时制备的ACCZ-70催化剂完全降解甲苯的温度为205 ℃，明显低于已有文献报道的催化剂，这主要归因于该催化剂具有良好的低温还原性和高达0.81的氧空穴浓度。而采用水凝胶制备的催化剂降解甲苯时，在120-140 ℃存在吸附现象。
- 细菌纤维素 /
- 溶胶凝胶 /
- 复合氧化物催化剂 /
- VOCs
Abstract: Mesoporous CuCe_0.75Zr_0.25O_x composite was prepared by a simple sol-gel method with environmentally benign bacterial cellulose (BC) as a pore former and characterized by TG/DTG, N₂ adsorption-desorption, XRD, H₂-TPR, O₂-TPD and Raman; its catalytic activity in the degradation of toluene at low temperature was investigated in a fixed-reactor. The results indicated that BC with ultra fine three-dimensional networks and excellent compatibility is beneficial to the formation of gel with nitrate solution, to prepare the mesoporous catalyst. The catalyst performance of CuCe_0.75Zr_0.25O_x composite is significantly affected by the gel-form and gelling temperature during the preparation process. Over the ACCZ-70 catalyst prepared by alcohol gelling at 70 ℃, the temperature for a complete degradation of toluene (T₁₀₀) reaches 205 ℃, much lower than those reported in open literature; the excellent activity of ACCZ-70 is ascribed to its high reducibility at low temperature and high concentration of oxygen vacancies (0.81). In addition, adsorption phenomenon was observed in the range of 120-140 ℃ during the toluene degradation over WCCZ catalysts prepared by water gelling.
- bacterial cellulose /
- sol-gel /
- multiple oxide catalysts /
- VOCs

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图 1 催化剂的固定床评价装置示意图

Figure 1 Schematic diagram of apparatus for catalyst evaluation

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图 2 细菌纤维素的TG和DTG曲线及CuCe_0.75Zr_0.25O_x催化剂的TG曲线

Figure 2 TG/DTG curves of BC (a) and TG curves of CuCe_0.75Zr_0.25O_x catalysts (b)

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图 3 CuCe_0.75Zr_0.25O_x催化剂的N₂物理吸附-脱附等温曲线和孔径分布

Figure 3 N₂ adsorption/desorption isotherms (a) and pore size distributions (b) of CuCe_0.75Zr_0.25O_x catalysts

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图 4 不同CuCe_0.75Zr_0.25O_x催化剂的XRD谱图

Figure 4 XRD patterns of different CuCe_0.75Zr_0.25O_x catalysts

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图 5 不同CuCe_0.75Zr_0.25O_x催化剂的O₂-TPD谱图

Figure 5 O₂-TPD profiles of different CuCe_0.75Zr_0.25O_x catalysts

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图 6 CuCe_0.75Zr_0.25O_x催化剂的Raman谱图及氧空位浓度

Figure 6 Raman spectra (a) and oxygen vacancy concentration (b) of CuCe_0.75Zr_0.25O_x catalysts

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图 7 CuCe_0.75Zr_0.25O_x催化剂的H₂-TPR谱图

Figure 7 H₂-TPR profiles of different CuCe_0.75Zr_0.25O_x catalysts

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图 8 不同CuCe_0.75Zr_0.25O_x催化剂降解甲苯的转化率和CO₂选择性

Figure 8 Catalytic activity and CO₂ selectivity of different CuCe_0.75Zr_0.25O_x catalysts for toluene degradation

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图 9 WCCZ-80催化剂重复降解甲苯的活性

Figure 9 Repeated activities of WCCZ-80 catalysts for toluene degradation

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图 10 WCCZ-80和ACCZ-70催化降解甲苯的稳定性

Figure 10 Stability of WCCZ-80 and ACCZ-70 catalysts for toluene degradation

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表 1 不同CuCe_0.75Zr_0.25O_x催化剂的制备参数

Table 1 Preparation parameters of the different CuCe_0.75Zr_0.25O_x catalysts

Catalyst	Gel form	Gel temperature t/℃
WCCZ-70	water gel	70
ACCZ-70	alcohol gel	70
WCCZ-80	water gel	80
ACCZ-80	alcohol gel	80

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表 2 CuCe_0.75Zr_0.25O_x催化剂的比表面积、总孔容和平均孔径

Table 2 A_BET, v_pand d_pof different CuCe_0.75Zr_0.25O_x catalysts

Catalyst	A_BET /(m²·g^-1)	v_p /(cm³·g^-1)	d_p /nm
WCCZ-70	33.3	0.11	10.3
ACCZ-70	38.1	0.13	10.7
WCCZ-80	42.7	0.12	9.7
ACCZ-80	24.1	0.09	10.8

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表 3 CuCe_0.75Zr_0.25O_x催化剂氢气消耗量

Table 3 H₂ consumptions of different CuCe_0.75Zr_0.25O_x catalysts

Catalyst	H₂ consumption /(μmol·g^-1)
Catalyst	α	β	γ	total
WCCZ-70	13.0	95.0	37.6	145.6
ACCZ-70	16.0	50.0	78.0	144.0
WCCZ-80	14.0	98.6	35.1	147.7
ACCZ-80	15.0	50.0	70.0	135.0

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参考文献(29)

[1]	ZHONG Z M, SHA Q E, ZHENG J Y, YUAN Z B, GAO Z J, OU J M, ZHENG Z Y, LI C, HUANG Z J. Sector-based VOCs emission factors and source profiles for the surface coating industry in the Pearl River Delta region of China[J]. Sci Total Environ, 2017, 583(1):19-28. http://www.sciencedirect.com/science/article/pii/S0048969716328613
[2]	ZHANG Z X, ZHENG J, SHANGGUAN W F. Low-temperature catalysis for VOCs removal in technology and application:A state-of-the-art review[J]. Catal Today, 2016, 264(15):270-278. http://www.sciencedirect.com/science/article/pii/S0920586115007087
[3]	KAMIMURA Y, SHIMOMUR M, ENDO A. Simple template-free synthesis of high surface area mesoporous ceria and its new use as a potential adsorbent for carbon dioxide capture[J]. J Colloid Interf Sci, 2014, 436(15):52-62. http://europepmc.org/abstract/med/25265586
[4]	YE L Q, ZHANG Y L, SONG C C, LI Y Y, JIANG B. A simple sol-gel method to prepare superhydrophilic silica coatings[J]. Mater Lett, 2017, 188(1):316-318. https://www.researchgate.net/publication/308083416_A_simple_sol-gel_method_to_prepare_superhydrophilic_silica_coatings
[5]	MIN J E, LEE Y J, PARK H G, ZHANG C D, JUN K W. Carbon dioxide reforming of methane on Ni-MgO-Al₂O₃ catalysts prepared by sol-gel method:Effects of Mg/Al ratios[J]. J Ind Eng Chem, 2015, 26(25):375-383. http://www.sciencedirect.com/science/article/pii/S1226086X14006777
[6]	MARCELLO R D, EDUARDO H M N, WANDER L V. Use of a design-of-experiments approach for preparing ceria-zirconia-alumina samples by sol-gel process[J]. Ceram Int, 2016, 42(8):9488-9495. doi: 10.1016/j.ceramint.2016.03.021
[7]	TANG W X, WU X F, LIU G, LI S D, LI D Y, LI W H, CHEN Y F. Preparation of hierarchical layer-stacking Mn-Ce composite oxide for catalytic total oxidation of VOCs[J]. J Rare Earth, 2015, 33(1):62-69. doi: 10.1016/S1002-0721(14)60384-7
[8]	ZHANG X, WU D F. Ceramic monolith supported Mn-Ce-M ternary mixed-oxide (M=Cu, Ni or Co) catalyst for VOCs catalytic oxidation[J]. Ceram Int, 2016, 42(15):16563-16570. doi: 10.1016/j.ceramint.2016.07.076
[9]	LU H F, KONG X X, HUANG H F, ZHOU Y, CHEN Y F. Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene[J]. J Environ Sci, 2015, 32(1):102-107. http://d.wanfangdata.com.cn/Periodical/jes-e201506012
[10]	MANMEET S D, JEFFREY M C. Mechanical and structural property analysis of bacterial cellulose composites[J]. Carbohyd Polym, 2016, 144(25):447-453. http://www.ncbi.nlm.nih.gov/pubmed/27083837
[11]	WANG J Q, LU X K, NG P F, LEE K I, FEI B, XIN J H, WU J Y. Polyethylenimine coated bacterial cellulose nanofiber membrane and application as adsorbent and catalyst[J]. J Colloid Interf Sci, 2015, 440(15):32-38. http://www.sciencedirect.com/science/article/pii/S0021979714007991
[12]	ZHANG D Y, QI L M. Synthesis of mesoporous titania networks consisting of anatase nanowires by templating of bacterial cellulose membranes[J]. Chem Commun, 2005, 21:2735-2737. http://www.ncbi.nlm.nih.gov/pubmed/15917937
[13]	ZHANG T, ZHENG Y D, LIU S M, YUE L N, GAO Y, YAO Y. Bacterial cellulose membrane supported three-dimensionally dispersed silver nanoparticles used as membrane electrode for oxygen reduction reaction in phosphate buffered saline[J]. J Electroanal Chem, 2015, 750(1):43-48. http://www.sciencedirect.com/science/article/pii/S157266571500226X
[14]	ZHOU P P, WANG H H, YANG J Z, TANG J, SUN D P, TANG W H. Bacteria cellulose nanofibers supported palladium(0) nanocomposite and its catalysis evaluation in heck reaction[J]. Ind Eng Chem Res, 2012, 51(16):5743-5748. doi: 10.1021/ie300395q
[15]	YANG J Z, TANG W H, LIU X L, CHAO C, LIU J G, SUN D P. Bacterial cellulose-assisted hydrothermal synthesis and catalytic performance of La₂CuO₄ nanofiber for methanol steam reforming[J]. Int J Hydrogen Energy, 2013, 38(25):10813-10818. doi: 10.1016/j.ijhydene.2013.01.015
[16]	LIU S S, YAN W N, CAO X C, ZHOU Z F, YANG R Z. Bacterial-cellulose-derived carbon nanofiber-supported CoFe₂O₄ as efficient electrocatalyst for oxygen reduction and evolution reactions[J]. Int J Hydrogen Energy, 2016, 41(11):5351-5360. doi: 10.1016/j.ijhydene.2016.01.121
[17]	FORESTI M L, VÁZQUEZ A, BOURY B. Applications of bacterial cellulose as precursor of carbon and Composites with metal oxide, metal sulfide and metal nanoparticles:A review of recent advances[J]. Carbohyd Polym, 2017, 157(10):447-467. http://www.ncbi.nlm.nih.gov/pubmed/27987949
[18]	LI S M, HAO Q L, ZHAO R Z, LIU D L, DUAN H Z, DOU B J. Highly efficient catalytic removal of ethyl acetate over Ce/Zr promoted copper/ZSM-5 catalysts[J]. Chem Eng J, 2016, 285(1):536-543. http://www.sciencedirect.com/science/article/pii/S1385894715013686
[19]	DOU B J, LI S M, LIU D L, ZHAO R Z, LIU J G, HAO Q L, BIN F. Catalytic oxidation of ethyl acetate and toluene over Cu-Ce-Zr supported ZSM-5/TiO₂ catalysts[J]. RSC Adv, 2016, 6(59):53852-53859. doi: 10.1039/C6RA06421C
[20]	WANG Y L, ZHANG S N, MAI Y W, WAN Y Z, LIM S H, HE F, HUANG Y. Preparation and Thermo-Mechanical Characterization of Hydroxyapatite/Bacterial Cellulose Nanocomposites[J]. Nanotech Precis Eng, 2009, 7(2):95-101. https://www.researchgate.net/publication/288810559_Preparation_and_Thermo-Mechanical_Characterization_of_HydroxyapatiteBacterial_Cellulose_Nanocomposites
[21]	ZHANG Q L, XU L S, NING P, GU J J, GUAN Q Q. Surface characterization studies of CuO-CeO₂-ZrO₂ catalysts for selective catalytic reduction of NO with NH₃[J]. Appl Surf Sci, 2014, 317:955-961. doi: 10.1016/j.apsusc.2014.09.017
[22]	ZHOU G L, LAN H, GAO T T, XIE H M. Influence of Ce/Cu ratio on the performance of ordered mesoporous CeCu composite oxide catalysts[J]. Chem Eng J, 2014, 246(15):53-63. http://www.sciencedirect.com/science/article/pii/S1385894714002071
[23]	ZHANG Y W, WEN J, WANG J, PAN D C, SHEN M Q, LU Y F. Synthesis of monodisperse Ce_xZr_1-xO₂ nanocrystals and the size-dependent enhancement of their properties[J]. Nano Res, 2011, 4(5):494-504. doi: 10.1007/s12274-011-0105-1
[24]	CAI T, HUANG H, DENG W, DAI Q G, LIU W, WANG X Y. Catalytic combustion of 1, 2-dichlorobenzene at low temperature over Mn-modified Co₃O₄ catalysts[J]. Appl Catal B:Environ, 2015, 166-167:393-405. doi: 10.1016/j.apcatb.2014.10.047
[25]	HE C, YU Y K, YUE L, QIAO N L, LI J J, SHEN Q, YU W J, CHEN J S, HAO Z P. Low-temperature removal of toluene and propanal over highly active mesoporous CuCeO_x catalysts synthesized via a simple self-precipitation protocol[J]. Appl Catal B:Environ, 2014, 147:156-166. doi: 10.1016/j.apcatb.2013.08.039
[26]	RIVAS B, LÓPEZ-FONSECA R, GUTIÉRREZ-ORTIZ MÁ, GUTIÉRREZ-ORTIZ J I. Combustion of chlorinated VOCs using K-CeZrO₄ catalysts[J]. Catal Today, 2011, 176(1):470-473. doi: 10.1016/j.cattod.2010.10.044
[27]	YANG P, YANG S S, SHI Z N, MENG Z H, ZHOU R X. Deep oxidation of chlorinated VOCs over CeO₂-based transition metal mixed oxide catalysts[J]. Appl Catal B:Environ, 2015, 162:227-235. doi: 10.1016/j.apcatb.2014.06.048
[28]	LIAO Y N, FU M L, CHEN L M, WU J L, HUANG B C, YE D Q. Catalytic oxidation of toluene over nanorod-structured Mn-Ce mixed oxides[J]. Catal Today, 2013, 216(1):200-228. http://d.wanfangdata.com.cn/Conference/8734806
[29]	LU H F, ZHOU Y, HAN W F, HUANG H F, CHEN Y F. Promoting effect of ZrO₂ carrier on activity and thermal stability of CeO₂-based[J]. Appl Catal A:Gen, 2013, 464:101-108. http://www.sciencedirect.com/science/article/pii/S0926860X13003189