Ce掺杂固体酸活化的碱木质素的抗氧化性能

doi:10.7503/cjcu20170746

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (6): 1255.doi: 10.7503/cjcu20170746

Ce掺杂固体酸活化的碱木质素的抗氧化性能

张岩²(), 张盛明¹, 方桂珍¹

1. 东北林业大学材料科学与工程学院, 2. 理学院, 哈尔滨 150040
2. 理学院, 哈尔滨 150040

收稿日期:2017-11-03 出版日期:2018-06-10 发布日期:2018-04-25
基金资助:
中央高校基本科研业务费专项资金项目B(批准号: 2572015BB16)和国家自然科学基金(批准号: 31170542)资助.

Antioxidant Property of Catalyzed Lignosulfonate Using S₂ $O 8 2 -$ /ZrO₂ Doped Cerium as Catalysts^†

ZHANG Yan^2,^*(), ZHANG Shengming¹, FANG Guizhen¹

1. School of Material Science and Engineering
2. School of Science, Northeast Forestry University, Harbin 150040, China

Received:2017-11-03 Online:2018-06-10 Published:2018-04-25
Contact: ZHANG Yan E-mail:zhangyan0727@nefu.edu.cn
Supported by:
† Supported by the Basic Science Special Foundation of Central University, China(No. 2572015BB16) and the National Natural Science Foundation of China(No.31170542).

摘要/Abstract

摘要：

采用共沉淀法, 将硝酸铈与硝酸锆溶液混合, 制备了掺杂CeO₂的ZrO₂载体, 再通过浸渍焙烧法负载S₂ $O 8 2 -$ 制备了稀土固体酸催化剂, 将其应用于碱木质素多羟基活化反应. 通过Hamment指示剂法、 X射线小角衍射(XRD)分析、 BET比表面积和硫含量测定, 研究了不同Ce掺杂比例对固体酸的酸强度、载体晶型和比表面积的影响. 用该固体酸催化木质素氢化反应后, 木质素的酚羟基和总羟基含量及还原能力提高, 对1,1-二苯基-2-三硝基苦肼(DPPH)自由基及2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)二铵盐(ABTS)自由基的清除能力增强. 实验结果表明, 与S₂ $O 8 2 -$ /ZrO₂相比, 掺杂Ce后, 催化剂S₂ $O 8 2 -$ /ZrO₂-CeO₂的比表面积增大, 硫含量增加, 反应后木质素酚羟基和总羟基含量分别从1.52%和2.31%提高至3.35%和10.35%, 总羟基含量显著提高. 这表明掺杂Ce后的催化剂对碱木质素氢化活化反应具有良好的催化作用, 同时保留了木质素芳香环不饱和键, 且活化后的木质素具有较好的抗氧化能力.

关键词: Ce掺杂, 稀土固体酸, 碱木质素, 抗氧化性

Abstract:

To improve catalysis activity of S₂ $O 8 2 -$ /ZrO₂ for the hydrogenation of lignosulfonate, rare earth cerium was doped onto the catalysts. Through Hammett indicator method and the determination of X-ray small diffraction(XRD), specific surface area(S_BET) and sulfur content, the influence of different Cerium doping ratio on the acid strength of solid acid, carrier crystal type and S_BET were discussed. Doping cerium promoted to form amorphous ZrO₂ crystal, contributed to increasing S_BET and sulfur content for solid acid enhancement. The contents of phenol hydroxyl and total hydroxyl were considered as a fractions of active groups in lignin, increased from 1.52% and 2.31% to 3.35% and 10.35%, combined with the data of ¹H nuclear magnetic spectra(¹H NMR). The results proved that the cerium doping improved S₂ $O 8 2 -$ /ZrO₂ catalytic properties through increasing the hydroxyl groups content of lignosulfonate. It confirmed that the catalyst coping Cerium was an excellent catalyst for hydrogenation of lignosulfonate dispersing in water. And hydroxylated ligno-sulfonate has good antioxidant capacity.

Key words: Coping cerium, Rare Earth solid acid, Lignonsulfonate, Antioxidant

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张岩, 张盛明, 方桂珍. Ce掺杂固体酸活化的碱木质素的抗氧化性能. 高等学校化学学报, 2018, 39(6): 1255.

ZHANG Yan, ZHANG Shengming, FANG Guizhen. Antioxidant Property of Catalyzed Lignosulfonate Using S₂ $O 8 2 -$ /ZrO₂ Doped Cerium as Catalysts^†. Chem. J. Chinese Universities, 2018, 39(6): 1255.

图/表 7

参考文献 24

[1]	Adler E., Wood Science and Technology, 1977, 11, 169—218
[2]	Benner R., Fogel M. L., Sprague E. K., Hodson R. E., Nature, 1987, 329(6141), 708—710
[3]	Li C. Z., Zhao X. C., Wang A. Q., Chem. Rev., 2015, 115(21), 11559—11624
[4]	Li Z. Z., Qiao W. C., China Pulp and Paper, 2003, 22(5), 47—51
	(李忠正, 乔维川. 中国造纸, 2003, 22(5), 47—51)
[5]	Jiang T.D., Lignin, Chemical Industry Press, Beijing, 2009, 29—34
	(蒋挺大. 木质素, 北京:化学化工出版社, 2009, 29—34)
[6]	Zhang S. M., Liu L., Ma Y. L., Fang G. Z., Chemistry and Industry of Forest Products, 2014, 34(5), 15—21
	(张盛明, 刘亮, 马艳丽, 方桂珍. 林产化学与工业, 2014, 34(5), 15—21)
[7]	Fang G. Z., Li L. Y., Ren S. X., Transactions of China Pulp and Paper, 2005, 20(2), 71—74
	(方桂珍, 李丽英, 任世学. 中国造纸学报, 2005, 20(2), 71—74)
[8]	Liu L., Zhang S. M., Fang G. Z., Chemistry and Industry of Forest Products, 2014, 34(6), 13—20
	(刘亮, 张盛明, 方桂珍. 林产化学与工业, 2014, 34(6), 13—20)
[9]	Sun Y. C., Efficient Separation and Structural Characterization of Ligni, and Lignin Degradation in Ionic Liquid—Based System, Beijing Forest Universit., Beijing, 2014
	(孙永昌. 木质素高效分离、结构表征及基于离子液体的降解机理研究, 北京: 北京林业大学, 2014)
[10]	Masuda K., Sano T., Mizukami F., Miyazaki M., Cataly. Lett., 1995, 32, 139—145
[11]	Liu R., Zha F., Yang A. M., Chang Y., Chem. J. Chinese Universities, 2016, 37(5), 964—971
	(刘蓉, 查飞, 杨爱梅, 常月. 高等学校化学学报, 2016, 37(5), 964—971)
[12]	Watanabe K., Oshio N., Kawakami T., Kimura T., Appl. Catal. A, 2004, 272, 281—287
[13]	Lin S. Y., Yang X., Yang L. Y., Zhou R. X., Appl. Surf. Sci., 2015, 327, 335—343
[14]	Guo J. X., Shi Z. H., Wu D. D., Yin H. Q., Gong M., Chen Y. Q., J. Alloys Compd., 2015, 621, 104—115
[15]	Montini T., Melchionna M., Monai M., Fornasiero P., Chem. Rev., 2016, 116, 5987—6041
[16]	Fan G. D., Shen M., Zhang Z., Jia F., J. Rare Earth, 2009, 27(3), 437—442
[17]	Wang J. D., Li W. Z., Du Z. J., Ma Q. Z., Acta Energiae Solaris Sinica, 2017, 38(4), 7—13
[18]	Xu X. H., Chen X., Wu J. F., He D. Z., Liu Y., Ren X., Bulletin of the Chinese Ceramic Society, 2016, 35(10), 45—52
	(徐晓虹, 陈霞, 吴建峰, 何德志, 刘溢, 任潇. 硅酸盐通报, 2016, 35(10), 45—52)
[19]	Braca A ., Tommasi N. D., Bari L. D., Pizza C., Politi M., Ivano M., J. Nat. Prod., 2001, 64(7), 892—895
[20]	Zhou S., Liu L., Wang B., Xu F., Sun R., Process. Biochem., 2012, 47(12), 1799—1806
[21]	Alriols M.G., Tejado A., Blanco M., Mondragon I., Labidi J., Chem. Eng. J., 2009, 148(1), 106—114
[22]	Faix O., Holzforschung, 1991, 45, 21—27
[23]	Li H., McDonald A. G., Industrial Crops Products, 2014, 62, 67—76
[24]	Ge Y., Wei Q., Li Z., BioResources, 2014, 9(4), 6699—6706

Sample	Proportion of coping cedium(%)	Calcination temperature/℃	Hammett acidity function	S_BET/(m²·g^-1)	Sulfer content(%)
ZC0	0	600	-12.70	36.2742	3.87
ZC1-1	1	550	-12.70	50.7799	5.11
ZC1-2	1	600	-12.70	52.1891	5.12
ZC1-3	1	650	-12.70	51.2678	5.12
ZC2	2	600	-12.70	51.5304	5.09
ZC3	3	600	-12.70	51.4652	5.11

Sample	Proportion of coping cedium(%)	Calcination temperature/℃	Hammett acidity function	S_BET/(m²·g^-1)	Sulfer content(%)
ZC0	0	600	-12.70	36.2742	3.87
ZC1-1	1	550	-12.70	50.7799	5.11
ZC1-2	1	600	-12.70	52.1891	5.12
ZC1-3	1	650	-12.70	51.2678	5.12
ZC2	2	600	-12.70	51.5304	5.09
ZC3	3	600	-12.70	51.4652	5.11

Sample	Proportion of catalyst(%)	Content of hydroxyl groups(%)
Sample	Proportion of catalyst(%)	Total hydroxyl group	Phenolic hydroxyl group	Alcohol hydroxyl group
LS_ZC0	10	3.28	1.70	1.58
LS_ZC1-1	5	5.03	3.00	2.03
LS_ZC1-2	7	6.12	2.13	3.99
LS_ZC1-3	10	10.79	7.34	3.45
LS_ZC2	10	8.66	5.62	3.04
LS_ZC3	10	6.28	2.03	4.25

Sample	Proportion of catalyst(%)	Content of hydroxyl groups(%)
Sample	Proportion of catalyst(%)	Total hydroxyl group	Phenolic hydroxyl group	Alcohol hydroxyl group
LS_ZC0	10	3.28	1.70	1.58
LS_ZC1-1	5	5.03	3.00	2.03
LS_ZC1-2	7	6.12	2.13	3.99
LS_ZC1-3	10	10.79	7.34	3.45
LS_ZC2	10	8.66	5.62	3.04
LS_ZC3	10	6.28	2.03	4.25

Sample	IC₅₀/(mg·mL^-1)		Sample	IC₅₀/(mg·mL^-1)
Sample	DPPH·	ABTS·	Sample	DPPH·	ABTS·
BHT	0.0316	0.0497	LS_ZC1	0.0412	0.1002
LS	0.1498	0.1499	LS_ZC2	0.0457	0.0998
LS_ZC0	0.1266	0.1094

Ce掺杂固体酸活化的碱木质素的抗氧化性能

Antioxidant Property of Catalyzed Lignosulfonate Using S₂ $O 8 2 -$ /ZrO₂ Doped Cerium as Catalysts^†

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Ce掺杂固体酸活化的碱木质素的抗氧化性能

Antioxidant Property of Catalyzed Lignosulfonate Using S2O82-/ZrO2 Doped Cerium as Catalysts†

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Antioxidant Property of Catalyzed Lignosulfonate Using S₂ $O 8 2 -$ /ZrO₂ Doped Cerium as Catalysts^†