原位蒸汽辅助法用于一步制备多级孔Cu-BTC

doi:10.11949/0438-1157.20240280

摘要/Abstract

摘要：

金属有机骨架材料（MOF）因其比表面积大、孔隙率高、结构高度可调等优势在气体吸附分离、催化、传感及生物医学等领域展现出巨大的应用潜力。但大多数MOF的孔结构在微孔范围，狭窄的孔隙环境限制了其应用过程中的传质扩散以及活性位点释放，在微孔MOF结构的基础上进行多级孔的构建则可以解决这一问题。为实现经典Cu-BTC结构上的多级孔构筑，基于原位蒸汽辅助合成加刻蚀过程开发了一步制备多级孔Cu-BTC的新方法。通过绿色刻蚀剂乙酸用量、蒸汽辅助时间的调节，获得了孔径范围可调的多级孔Cu-BTC。由于多级孔结构对的传质过程和活性位点的提升作用，该材料在CO₂电还原实验中展现出优秀的转化效率，最高乙烯的选择性可提升157%。通过蒸汽辅助耦合材料制备和刻蚀过程使得多级孔MOF的一步制备成为了可能，其具有的减少反应物用量和反应步骤的特点将进一步推动多级孔MOF在实际应用中的发展。

关键词: 金属有机骨架, 多级孔, 原位蒸汽辅助, 一步制备, 绿色刻蚀

Abstract:

Metal-organic framework(MOF)exhibit significant potential across various domains including gas adsorption and separation, catalysis, sensing, and biomedicine due to their expansive specific surface area, pronounced porosity, and highly adaptable structure. However, the pore structure of most MOF falls within the micropore range, and the narrow pore environment limits mass transfer diffusion and active site release during their application. Constructing hierarchical pores based on the microporous MOF structure can address this issue. To achieve hierarchically porous construction within the classic Cu-BTC structure, a novel single-step method combining in-situ vapor-assisted synthesis and etching was devised. Fine-tuning parameters such as the quantity of eco-friendly etchant acetic acid and steam assist duration yielded hierarchically porous Cu-BTC with customizable pore size ranges. Capitalizing on the enhanced mass transfer and active site accessibility conferred by the hierarchical pore architecture, the material demonstrated outstanding conversion efficiency in CO₂ electroreduction experiments, culminating in a remarkable 157% increase in ethylene selectivity. Integrating material preparation and etching procedures through steam-assisted techniques enables streamlined fabrication of hierarchical porous MOF in a single step. This approach not only reduces reactant consumption and simplifies reaction steps but also propels the advancement of hierarchical porous MOF in practical applications.

Key words: metal-organic frameworks, hierarchically porous MOF, in situ steam-assisted, one-step preparation, green etching

中图分类号:

TQ 028.8

代艳辉, 熊启钊, 房强, 杨东晓, 王毅, 陈杨, 李晋平, 李立博. 原位蒸汽辅助法用于一步制备多级孔Cu-BTC[J]. 化工学报, DOI: 10.11949/0438-1157.20240280.

Yanhui DAI, Qizhao XIONG, Qiang FANG, Dongxiao YANG, Yi WANG, Yang CHEN, Jinping LI, Libo LI. In situ steam-assisted method for one-step synthesis of hierarchically porous Cu-BTC[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240280.

图/表 6

图1 原位蒸汽辅助法一步合成制备HP-Cu-BTC的方法及机理图

Fig. 1 One-step synthesis of HP-Cu-BTC by in-situ steam-assisted method and schematic diagram of the mechanism

图2 蒸汽相合成Cu-BTC及不同反应时间和乙酸用量下合成HP-Cu-BTC的PXRD谱图

Fig. 2 PXRD spectra of Cu-BTC synthesized in steam phase and HP-Cu-BTC synthesized with different reaction time and acetic acid dosages.

图3 蒸汽相合成HP-Cu-BTC及不同反应时间和乙酸用量下HP-Cu-BTC的77 K N2吸脱附等温线和孔径分布曲线

Fig. 3 77 K N2 adsorption and desorption isotherms and pore size distribution curves of Cu-BTC synthesized in steam phase and HP-Cu-BTC with different reaction times and acetic acid dosages

表1 不同反应条件下得到的HP-Cu-BTC的孔结构参数

Table 1 The pore structure parameters of HP-Cu-BTC obtained by different reaction conditions

Reaction conditions	S_BET（m²/g）	S_micro （m²/g）	S_meso/S_micro	V_t （cm³/g）	V_meso （cm³/g）	D_meso （nm）
0.1 mL-12 h	1005	887	0.13	0.41	0.09	11
0.3 mL-12 h	1355	1177	0.15	0.58	0.15	11
0.5 mL-12 h	1663	1465	0.13	0.68	0.13	10
0.1 mL-24 h	1689	1459	0.16	0.77	0.23	11
0.3 mL-24 h	2209	1893	0.17	0.94	0.24	15
0.5 mL-24 h	1401	1193	0.17	0.68	0.24	18

图4 （a, b）不同反应时间和乙酸用量下HP-Cu-BTC的SEM图; （c）反应时间24 h和乙酸用量0.3 mL时HP-Cu-BTC的TEM图; （d）原始Cu-BTC及反应时间24 h和乙酸用量0.3 mL时HP-Cu-BTC的TG曲线

Fig. 4 （a, b） SEM images of HP-Cu-BTC at different reaction times and acetic acid dosages; （c） TEM image of HP-Cu-BTC at reaction time of 24 h and acetic acid dosage of 0.3 mL; （d） TG curves of origional Cu-BTC and HP-Cu-BTC at reaction time of 24 h and acetic acid dosage of 0.3 mL

图5 H型电解池中进行的电化学二氧化碳还原测试

Fig. 5 Electrochemical carbon dioxide reduction measurements in H-cell.

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