金属有机骨架高温自还原制备高性能等级孔碳负载Co基催化剂

doi:10.7503/cjcu20190687

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (4): 639.doi: 10.7503/cjcu20190687

• 庆祝《高等学校化学学报》复刊40周年专栏 • 上一篇下一篇

金属有机骨架高温自还原制备高性能等级孔碳负载Co基催化剂

何小可¹,李小云³,王朝^1,^*(),胡念¹,邓兆¹,陈丽华¹,苏宝连^1,^2,^*()

^1. 武汉理工大学材料复合新技术国家重点实验室, 武汉 430070
^2. 那慕尔大学无机材料化学实验室, 那幕尔 B-5000
^3. 武汉理工大学硅酸盐建筑材料国家重点实验室, 武汉 430070

收稿日期:2019-12-18 出版日期:2020-04-10 发布日期:2020-01-17
通讯作者: 王朝,苏宝连 E-mail:zhao.wang@whut.edu.cn;bao-lian.su@unamur.be
基金资助:
国家自然科学基金(21671155, 21805216, 21902122);国家博士后科研基金(2019M652723);湖北省重大技术创新专项(2018AAA012)

Self-reduction for the Synthesis of Co Supported on Hierarchically Porous Carbon for Selective Hydrogenation Reaction ^†

HE Xiaoke¹,LI Xiaoyun³,WANG Zhao^1,^*(),HU Nian¹,DENG Zhao¹,CHEN Lihua¹,SU Baolian^1,^2,^*()

^1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
^2. Laboratory of Inorganic Materials Chemistry(CMI), University of Namur, Namur B-5000, Belgium
^3. State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China

Received:2019-12-18 Online:2020-04-10 Published:2020-01-17
Contact: Zhao WANG,Baolian SU E-mail:zhao.wang@whut.edu.cn;bao-lian.su@unamur.be
Supported by:
† Supported by the National Natural Science Foundation of China(21671155, 21805216, 21902122);the Postdoctoral Science Foundation of China(2019M652723);the Major Programs of Technical Innovation in Hubei Province, China(2018AAA012)

摘要/Abstract

摘要：

以钴基金属有机框架为前驱体, 利用一步高温碳化自还原法, 通过精确调控碳化过程, 实现等级孔道结构及钴纳米颗粒分散性的可控调节, 制备出高催化活性及产物选择性的等级孔碳负载Co基催化剂. 研究发现, 600 ℃碳化后的催化剂为具有高比表面积的等级孔道结构和高分散的钴纳米颗粒, 在选择性催化1,3-丁二烯加氢反应中, 丁二烯完全转化温度低至60 ℃, 对应丁烯的选择性高达61%, 实现了低温高选择性催化加氢.

关键词: 等级孔结构, 催化剂, 非贵金属, 金属有机框架, 选择性加氢

Abstract:

A series of supported cobalt-based nanocatalysts were synthesized by a one-step self-reduction method using cobalt-based organic framework as precursor. The effect of self-reduction of carbonization on the catalytic performance of supported cobalt-based catalysts was studied. This method successfully controlled the hierarchically porous structure of supports and the size of cobalt nanoparticles. The prepared Co-based catalysts had high catalytic activity and product selectivity for selective hydrogenation of 1,3-butadiene. Specially, it was found that the catalyst carbonized at 600 ℃ contained a hierarchically porous structure with large surface area, and a uniform distribution of cobalt nanoparticles without obvious aggregation. Most importantly, the corresponding sample exhibited a rather low 100% conversion temperature at 60 ℃ for selective hydrogenation of 1,3-butadiene, but with butenes selectivity as high as 61%. This work provides a new strategy for the preparation of supported non-noble metal catalysts with high-performance for hydrogenation reactions.

Key words: Hierarchically porous structure, Catalyst, Non-noble metal, Metal organic framework, Selective hydrogenation

中图分类号:

O643.38
O611

TrendMD:

何小可, 李小云, 王朝, 胡念, 邓兆, 陈丽华, 苏宝连. 金属有机骨架高温自还原制备高性能等级孔碳负载Co基催化剂. 高等学校化学学报, 2020, 41(4): 639.

HE Xiaoke, LI Xiaoyun, WANG Zhao, HU Nian, DENG Zhao, CHEN Lihua, SU Baolian. Self-reduction for the Synthesis of Co Supported on Hierarchically Porous Carbon for Selective Hydrogenation Reaction ^†. Chem. J. Chinese Universities, 2020, 41(4): 639.

图/表 6

Fig.1 PXRD and simulated XRD patterns(A), SEM image(B), the N2 adsorption-desorption isotherms(C) and TGA-DSC curves(D) of ZIF-67Inset of (C): the corresponding pore size distribution curve of ZIF-67.

Fig.2 PXRD patterns of Co-N/C-T samples

Fig.3 SEM images(A—H) and size distributions(I—L) of Co-N/C-550(A, E, I), Co-N/C-600(B, F, J), Co-N/C-700(C, G, K) and Co-N/C-800(D, H, L)

Fig.4 N2 adsorption-desorption isotherms(A) and pore diameter distribution(B) of Co-N/C-T nanoparticles

Table 1 Summary of the textural properties of samples

Sample	$S a BET$ /(m²·g^-1)	$S b micro$ /(m²·g^-1)	$V c tol$ /(cm³·g^-1)	$V d micro$ /(cm³·g^-1)	Pore size/nm
ZIF-67	1755	1728	0.72	0.70	1.00, 1.48
Co-N/C-550	185	175	0.14	0.07	0.34, 0.47
Co-N/C-600	322	284	0.14	0.08	0.34, 0.47, 1.76, 3.90
Co-N/C-700	321	214	0.19	0.11	0.47, 1.57, 3.90
Co-N/C-800	313	147	0.21	0.06	0.59, 1.86, 4.00

Table 1 Summary of the textural properties of samples

Sample	$S a BET$ /(m²·g^-1)	$S b micro$ /(m²·g^-1)	$V c tol$ /(cm³·g^-1)	$V d micro$ /(cm³·g^-1)	Pore size/nm
ZIF-67	1755	1728	0.72	0.70	1.00, 1.48
Co-N/C-550	185	175	0.14	0.07	0.34, 0.47
Co-N/C-600	322	284	0.14	0.08	0.34, 0.47, 1.76, 3.90
Co-N/C-700	321	214	0.19	0.11	0.47, 1.57, 3.90
Co-N/C-800	313	147	0.21	0.06	0.59, 1.86, 4.00

Fig.5 Evolution of 1,3-butadiene conversion with the increase of reaction temperature(A) and selectivity to butenes with the butadiene conversion(B) of Co-N/C-T catalysts

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金属有机骨架高温自还原制备高性能等级孔碳负载Co基催化剂

Self-reduction for the Synthesis of Co Supported on Hierarchically Porous Carbon for Selective Hydrogenation Reaction ^†

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金属有机骨架高温自还原制备高性能等级孔碳负载Co基催化剂

Self-reduction for the Synthesis of Co Supported on Hierarchically Porous Carbon for Selective Hydrogenation Reaction †

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Self-reduction for the Synthesis of Co Supported on Hierarchically Porous Carbon for Selective Hydrogenation Reaction ^†