Co3O4表面物种对甲醛氧化催化性能的影响

doi:10.7503/cjcu20140757

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (12): 2598.doi: 10.7503/cjcu20140757

Co₃O₄表面物种对甲醛氧化催化性能的影响

张叶¹, 周佳佳¹, 吴贵升¹(), 毛东森¹, 卢冠忠^1,²

1. 上海应用技术学院化学与环境工程学院催化研究所, 上海 201418
2. 华东理工大学化学系工业催化研究所, 上海 200237

收稿日期:2014-08-18 出版日期:2014-12-10 发布日期:2014-11-29
作者简介:联系人简介: 吴贵升, 男, 博士, 教授, 主要从事催化新材料的设计、合成及应用研究. E-mail:gswu@sit.edu.cn
基金资助:
上海市教育委员会重点学科建设项目(批准号: J51503)资助

Influence of the Surface Species over Co₃O₄ on the Formaldehyde Catalytic Oxidation Performance^†

ZHANG Ye¹, ZHOU Jiajia¹, WU Guisheng^1,^*(), MAO Dongsen¹, LU Guanzhong^1,²

1. Research Institute of Applied Catalysis, Academy of Chemical and Environmental Engineering,Shanghai Institute of Technology, Shanghai 201418, China
2. Institute of Industrial Catalysis, Department of Chemistry, East China University of Science and Technology, Shanghai 200237, China

Received:2014-08-18 Online:2014-12-10 Published:2014-11-29
Contact: WU Guisheng E-mail:gswu@sit.edu.cn
Supported by:
† Supported by the Shanghai Leading Academic Discipline Project, China(No. J51503).

摘要/Abstract

摘要：

采用沉淀法制备了Co₃O₄催化剂, 并将催化剂在流动的N₂或O₂气氛中于不同温度下进行预处理. 通过X射线衍射(XRD)、热重-差示扫描量热分析(TG-DSC)、程序升温脱附(O₂/CO₂-TPD, HCHO-TPSR)和原位漫反射傅里叶变换红外光谱(in situ DRIFTS) 等手段对催化剂表面物种进行了表征. 结果表明, Co₃O₄-N₂-200催化剂表面存在Co³⁺不饱和配位中心和丰富的弱配位氧负离子, 容易形成双配位的甲酸盐, 并转化成单配位的甲酸盐, 进一步分解为产物.

关键词: 甲醛催化氧化, 四氧化三钴, 甲酸盐, 程序升温脱附, 原位漫反射红外光谱, 表面氧

Abstract:

The Co₃O₄ catalysts were prepared via precipitation methods, and then were pretreated in N₂ or O₂ at different temperatures. Based on the study of formaldehyde catalytic oxidation, the catalytic performances were investigated with the detailed surface characterization via temperature programmed desorption(O₂/CO₂-TPD, HCHO-TPSR), thermogravimetric-differential scanning calorimetry(TG-DSC) and in situ diffuse reflectance infrared fourier transform spectroscopy(in situ DRIFTS). The results presented that Co₃O₄-N₂-200 showed the optimal catalytic performance, because there were rich unsaturated coordination centers of Co³⁺ and negative oxygen ions with weak bond strength on the surface of Co₃O₄-N₂-200, which was ready to adsorb formaldehyde to form bidentate formate, and then decompose to products via monodentate formate. With increasing pretreatment temperature, the amount of negative oxygen ions decreased, accordingly the catalytic activity for formaldehyde catalytic oxidation decreased due to slow decomposition rate of desorbed bidentate formate.

Key words: Formaldehyde catalytic oxidation, Co₃O₄, Formate, Temperature programmed desorption, In situ diffuse reflectance infrared Fourier transform spectroscopy, Surface oxygen species

中图分类号:

O646

TrendMD:

张叶, 周佳佳, 吴贵升, 毛东森, 卢冠忠. Co₃O₄表面物种对甲醛氧化催化性能的影响. 高等学校化学学报, 2014, 35(12): 2598.

ZHANG Ye, ZHOU Jiajia, WU Guisheng, MAO Dongsen, LU Guanzhong. Influence of the Surface Species over Co₃O₄ on the Formaldehyde Catalytic Oxidation Performance^†. Chem. J. Chinese Universities, 2014, 35(12): 2598.

图/表 8

Fig.1 Catalytic activity(A) and CO2 selectivity(B) of Co3O4 pretreated in N2 or O2 at different temperatures a. Room temperature; b. N2, 200 ℃; c. N2, 300 ℃; d. N2, 400 ℃; e. O2, 200 ℃; f. O2, 400 ℃.

Fig.2 Dependency of formaldehyde conversion(A) and CO2 selectivity(B) on the reaction time over Co3O4-N2-200(a) and Co3O4-N2-400(b) at 100 ℃

Fig.3 XRD pattern(A) of Co3O4 as prepared and IR spectra(B) of Co3O4 pretreated in N2 at 200 ℃(a), 300 ℃(b) and 400 ℃(c)

Fig.4 TG-DSC curve of Co3O4 catalyst in N2(50 mL/min) at a rate of 5 ℃/min

Fig.5 O2-TPD(A) and CO2-TPD(B) profiles over Co3O4 catalysts pretreated in N2 at 200 ℃(a), 300 ℃(b) and 400 ℃(c)

Fig.6 FTIR spectra of adsorbed formaldehyde over Co3O4-N2-25(a), Co3O4-N2-200(b) and Co3O4-N2-400(c) for 20 min

Fig.7 HCHO-TPSR profiles over Co3O4-N2-200(A) and Co3O4-N2-400(B)

Scheme 1 Reaction mechanism diagram of formaldehyde oxidation over Co3O4

参考文献 36

[1]	Tang X. F., Li Y. G., Huang X. M., Xu Y. D., Zhu H. Q., Wang J. G., Shen W. J., Appl. Catal. B, 2006, 62(3/4), 265—273
[2]	Spivey J. J., Ind. Eng. Chem. Res., 1987, 26(11), 2165—2180
[3]	Guo S., Wang W. N., Jin L. X., Wang S., Wang W. L., Chem. J. Chinese Universities, 2014, 35(6), 1300—1306
	(郭莎, 王渭娜, 靳玲侠, 王帅, 王文亮. 高等学校化学学报, 2014, 35(6), 1300—1306)
[4]	He Y. B., Ji H. B., Wang L. F., Chem. Ind. Eng. Prog., 2007, 26(8), 1104—1109
	(何运兵, 纪红兵, 王乐夫. 化工进展, 2007, 26(8),1104—1109)
[5]	Collins J. J., Ness R., Tyl R. W., Krivanek N., Esmen N. A., Hall T. A., Regul. Toxicol. Pharm., 2001, 34, 17—34
[6]	Sherman M. H., Hodgson A. T., Indoor Air, 2004, 14(1), 2—8
[7]	Boonamnuayvitaya V., Sae-ung S., Tanthapanichakoon W., Sep. Purif. Technol., 2005, 42(2), 159—168
[8]	Khan F. I., Ghoshal A. K., J. Loss. Prevent. Proc., 2000, 13(6), 527—545
[9]	Zhang C. B., He H., Tanaka K., Appl. Catal. B: Environ., 2006, 65(1), 37—43
[10]	He Y. B., Ji H. B., Chin. J. Catal., 2009, 31(2), 171—175
	(何运兵, 纪红兵. 催化学报, 2009, 31(2), 171—175)
[11]	Shi Y. Z., Zhang N., Luo M. F., Lu J. Q., J. Chin. Soc. Rare. Earths,2011, 29(3), 271—276
	(石艳芝, 张娜, 罗孟飞, 鲁继青. 中国稀土学报,2011, 29(3), 271—276)
[12]	Zhang J., Jin Y., Li C. Y., Shen Y. N., Han L., Hu Z. X., Di X. W., Liu Z. L., Appl. Catal. B: Environ., 2009, 91(1/2), 11—20
[13]	Christoskova S. G., Danova N., Georgieva M., Argirov O. K., Mehandzhiev D., Appl. Catal. A: Gen., 1995, 128(2), 219—229
[14]	Sekine Y., Nishimurab A., Atmos. Environ., 2001, 35(11), 2001—2007
[15]	Ma L., Wang D. S., Li J. H., Bai B. Y., Fu L. X., Li Y. D., Appl. Catal. B: Environ., 2014, 148/149, 36—43
[16]	Li C. Y., Shen Y. N., Jia M. L., Sheng S. S., Adebajo M. O., Zhu H. Y., Catal. Commun., 2008, 9(3), 355—361
[17]	Ma C. Y., Wang D. H., Xue W. J., Dou B. J., Wang H. L., Hao Z. P., Environ. Sci. Technol., 2011, 45(8), 3628—3634
[18]	Álvarez-Galván M. C., Pawelec B., De la Peña O’Shea V. A., Fierro J. L. G., Arias P. L., Appl. Catal. B: Environ., 2004, 51(2), 83—91
[19]	Álvarez-Galván M. C., De la Peña O’Shea V. A., Fierro J. L. G., Arias P. L., Catal. Commun., 2003, 4(5), 223—228
[20]	Mochida I., Iwai Y., Kamo T., Fujitsu H., J. Phys. Chem., 1985, 89(25), 5439—5442
[21]	Xie X. W., Li Y., Liu Z. Q., Haruta M., Shen W. J., Nature,2009, 458(7239), 746—749
[22]	Tang C. W., Kuo C. C., Kuo M. C., Wang C. B., Chien S. H., Appl. Catal. A: Gen., 2006, 309(1), 37—43
[23]	Jansson J., Palmqvist A. E. C., Fridell E., Skoglundh M., Osterlund L., Thormahlen P., Langer V., J. Catal., 2002, 211(2), 387—397
[24]	Wang Y. Z., Zhao Y. X., Gao C. G., Liu D. S., Catal. Lett., 2008, 125(1/2), 134—138
[25]	Lou Y., Wang L., Zhao Z. Y., Zhang Y. H., Zhang Z. G., Lu G. Z., Guo Y., Guo Y. L., Appl. Catal. B: Environ., 2014, 146, 43—49
[26]	Liu B., Liu Y., Li C., Hu W., Jing P., Wang Q., Zhang J., Appl. Catal. B: Environ., 2012, 127, 47—58
[27]	Bai B., Arandiyan H., Li J., Appl. Catal. B: Environ., 2013, 142/143, 677—683
[28]	Yu Y. B., Takei T., Ohashi H., He H., Zhang X. L., Haruta M., J. Catal., 2009, 267(2), 121—128
[29]	Li J., Lu G. Z., Wu G. S., Mao D. S., Wang Y. Q., Guo Y., Catal. Sci. Technol., 2012, 2(9), 1865—1871
[30]	Wang Y. Z., Zhao Y. X., Gao C. G., Liu D. S., Catal. Lett., 2007, 116(3/4), 136—142
[31]	Nethravathi C., Sen S., Ravishankar N., Rajamathi M., Pietzonka C., Harbrecht B. J., Phys. Chem. B: Environ., 2005, 109(23), 11468—11472
[32]	Fujita J., Martell A. E., Nakamoto K., J. Chem. Phys., 1962, 36(2), 339—345
[33]	Davydov A. A., Ed.: Rochester C. H., Infrared Spectroscopy of Adsorbed Species on the Surface of Transition Metal Oxides, Wiley, New York, 1990, 6
[34]	Haneda M., Kintaichi Y., Bion N., Hamada H., Appl. Catal. B: Environ., 2003, 46(3), 473—482
[35]	Wang C. B., Lin H. K., Tang C. W., Catal. Lett., 2004, 1/2(1/2), 69—74
[36]	Köck E. M., Kogler M., Bielz T., Klötzer B., Penner S., J. Phys. Chem. C, 2013, 117(34), 17666—17673

Co₃O₄表面物种对甲醛氧化催化性能的影响

Influence of the Surface Species over Co₃O₄ on the Formaldehyde Catalytic Oxidation Performance^†

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