双金属催化剂Ni-Co/SiO2空心球的可控制备及催化性能

doi:10.15541/jim20150580

无机材料学报 ›› 2016, Vol. 31 ›› Issue (9): 923-928.DOI: 10.15541/jim20150580

双金属催化剂Ni-Co/SiO₂空心球的可控制备及催化性能

孙新枝^1,2, 杜芳林¹

(1. 青岛科技大学材料科学与工程学院, 青岛266042; 2. 青岛农业大学化学与药学院, 青岛 266109)

收稿日期:2015-11-13 修回日期:2016-04-08 出版日期:2016-09-20 网络出版日期:2016-08-29
作者简介:孙新枝(1976–), 女, 博士研究生, 讲师. E-mail: sunxinzhi616@sina.com
基金资助:
国家自然科学基金(51272115);山东省自然科学基金(ZR2012EMM001)

Controlled Synthesis and Catalytic Property of Mesoporous Bimetal Ni-Co/SiO₂ Hollow Spheres

SUN Xin-Zhi^1,2, DU Fang-Lin¹

(1. College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China; 2. College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, China)

Received:2015-11-13 Revised:2016-04-08 Published:2016-09-20 Online:2016-08-29
About author:SUN Xin-Zhi. E-mail: sunxinzhi616@sina.com
Supported by:
National Natural Science Foundation of China (51272115);Natural Science Foundation of Shandong Province, China (ZR2012EMM001)

摘要/Abstract

摘要：

以二氧化硅为模板, 采用牺牲模板/界面反应法制备具有介孔结构的碱式硅酸镍钴空心球。采用透射电子显微镜(TEM)、X 射线衍射(XRD)、氮气吸脱附曲线(BET)和程序升温还原(TPR)等方法, 对样品的结构和形貌进行了表征, 探索了碱式硅酸镍钴空心球还原规律, 并研究了双金属催化剂Ni-Co/SiO₂的催化性能。研究发现, 140℃下反应6 h, 产物为核壳结构, 反应12 h时变为空心球结构; 在氢气气氛中800℃下反应5 h, 碱式硅酸镍钴被完全还原为Ni-Co/SiO₂, 还原前后形貌基本不变, 但比表面积有所减小, 孔径增大。Ni-Co/SiO₂空心球用于催化硝基苯加氢反应1 h后, 硝基苯的转化率为67%, 比商用Raney Ni 提高约28%。

关键词: 双金属催化剂, Ni-Co/SiO2, 空心球, 催化性能

Abstract:

Using silica as template, mesoporous bimetal Ni-Co silicate hydroxide hollow spheres were synthesized by sacrificial template/interface reaction. There morphologies and structures were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), and temperature procedure reduction (TPR). Their reduction rule was explored and catalytic properties of the reduction products on nitrobenzene hydrogenation were investigated. The results show that the structures of bimetal nickel cobalt silicate are core-shell and hollow spheres under 140℃ for 6 h and 12 h, respectively. Bimetal Ni-Co/SiO₂ hollow spheres are obtained after reduction of N silicate hydroxide hollow spheres within 5 h at 800℃ with less specific surface area and bigger pore size than before reduction. But the hollow spheres before and after reduction still share the same morphology. Using bimetal Ni-Co/SiO₂ hollow spheres as catalyst for conversion of nitrobenzene, the conversion rate attains 67% within 1 h, about 28% higher than that of using commercial Raney Ni.

Key words: bimetal Ni-Co/SiO2 catalyst, hollow spheres, catalytic property

中图分类号:

O643

孙新枝, 杜芳林. 双金属催化剂Ni-Co/SiO₂空心球的可控制备及催化性能[J]. 无机材料学报, 2016, 31(9): 923-928.

SUN Xin-Zhi, DU Fang-Lin. Controlled Synthesis and Catalytic Property of Mesoporous Bimetal Ni-Co/SiO₂ Hollow Spheres[J]. Journal of Inorganic Materials, 2016, 31(9): 923-928.

图/表 10

图1 碱式硅酸镍钴的XRD图谱

Fig. 1 XRD patterns of nickel cobalt silicate hydroxide

图2 反应6 h (a)和12 h(b)后所制备的碱式硅酸镍钴的TEM照片

Fig. 2 TEM images of nickel cobalt silicate hydroxide after reaction for 6 h (a) and 12 h (b)

图3 碱式硅酸镍钴(a)、碱式硅酸钴(b)和碱式硅酸镍(c)的TEM照片

Fig. 3 TEM images of nickel cobalt silicate hydroxide (a), cobalt silicate hydroxide (b) and nickel silicate hydroxide (c)

图4 碱式硅酸镍钴空心球的形成过程示意图

Fig. 4 Preparation processing of the Ni-Co silicate hollow spheres

图5 不同碱式硅酸盐的H2-TPR图谱

Fig. 5 H2-TPR profiles of nickel (a), cobalt (b) and nickel/cobalt (c) silicate hydroxide

图6 不同反应时间下所制备产物的H2-TPR图谱

Fig. 6 H2-TPR profiles of the products prepared at 6 h (a) and 12 h (b)

图7 还原后样品的XRD图谱

Fig. 7 XRD patterns of the reduced samples

图8 碱式硅酸镍钴还原前(a)和还原后(Ni-Co/SiO2)(b)的TEM照片

Fig. 8 TEM images of Ni-Co silicate hydroxide before (a) and after (b) reduction

图9 样品的N2吸附-脱附等温线及孔径分布图

Fig. 9 N2 adsorption-desorption isotherms and pore diameter distribution of the samples

图10 不同催化剂对硝基苯催化加氢的转化率

Fig. 10 Conversion of nitrobenzene using different catalysts

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双金属催化剂Ni-Co/SiO₂空心球的可控制备及催化性能

Controlled Synthesis and Catalytic Property of Mesoporous Bimetal Ni-Co/SiO₂ Hollow Spheres

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