碳化的MOF用于电催化还原二氧化碳制备乙烯和乙醇

doi:10.11949/0438-1157.20220250

化工学报 ›› 2022, Vol. 73 ›› Issue (8): 3576-3585.DOI: 10.11949/0438-1157.20220250

• 催化、动力学与反应器 • 上一篇下一篇

碳化的MOF用于电催化还原二氧化碳制备乙烯和乙醇

王磊¹^,²(), 蒋勇¹^,², 钟达忠¹^,², 李佳元³, 郝根彦¹^,², 赵强¹^,²(), 李晋平¹^,²()

^1.太原理工大学化学工程与技术学院，山西太原 030024
^2.气体能源高效利用山西省重点实验室，山西太原 030024
^3.太原理工大学材料科学与工程学院，山西太原 030024

收稿日期:2022-02-24 修回日期:2022-05-22 出版日期:2022-08-05 发布日期:2022-09-06
通讯作者: 赵强,李晋平
作者简介:王磊（1996—），男，硕士研究生，wanglei0533@link.tyut.cn
基金资助:
国家自然科学基金项目(21878202);山西省自然科学基金项目(201801D121052)

Carbonized metal-organic framework for carbon dioxide reduction to ethylene and ethanol

Lei WANG¹^,²(), Yong JIANG¹^,², Dazhong ZHONG¹^,², Jiayuan LI³, Genyan HAO¹^,², Qiang ZHAO¹^,²(), Jinping LI¹^,²()

^1.College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan 030024, Shanxi, China
^3.College of Materials Science and Engineering，Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2022-02-24 Revised:2022-05-22 Online:2022-08-05 Published:2022-09-06
Contact: Qiang ZHAO, Jinping LI

摘要/Abstract

摘要：

电化学催化还原二氧化碳是一种有效的能源储存手段。探索具有高乙烯选择性和高产率的高效电催化剂是非常必要的，但仍然具有挑战性。通过对金属有机骨架（Cu-BTC）的简单碳化制备了多孔Cu-Cu₂O/C催化剂，用于高效且选择性地电催化CO₂还原为C₂₊产物。碳化的MOF表现出优异的还原CO₂为C₂₊的性能，在电位为-1.3 V（vs RHE）时，C₂₊的最大法拉第效率（FE）为47.8%，其部分电流密度为4.33 mA·cm^-2。研究表明，较低的碳化温度有助于保留Cu-MOF的形貌，抑制活性金属位点团聚，而多孔特性也能提升其电化学活性面积，进而提高其对CO₂电化学还原为C₂₊产物的性能。

关键词: Cu-BTC, 碳化, 二氧化碳还原, 电催化, 乙烯

Abstract:

Electrochemical catalytic reduction of carbon dioxide provides an efficient route for energy storage. Exploring efficient electrocatalysts with high ethylene selectivity and high yields is highly desirable but still challenging. Here, porous Cu-Cu₂O/C catalysts were prepared by simple carbonization of metal-organic framework (Cu-BTC) for efficient and selective electrocatalytic reduction of CO₂ to C₂₊ products. The carbonized MOF showed efficient performance for CO₂ reduction to C₂₊, with a maximum FE of 47.8% and a partial current density of 4.33 mA·cm^-2 at a potential of -1.3 V (vs RHE). The results show that the lower carbonization temperature is helpful to preserve the morphology of Cu-MOF, and the porous properties can also improve the electrochemical active area of Cu-MOF, and thus improve its performance for the electrochemical reduction of CO₂ to C₂₊ products.

Key words: Cu-BTC, carbonization, carbon dioxide reduction, electrocatalysis, ethylene

中图分类号:

TQ 151.1

王磊, 蒋勇, 钟达忠, 李佳元, 郝根彦, 赵强, 李晋平. 碳化的MOF用于电催化还原二氧化碳制备乙烯和乙醇[J]. 化工学报, 2022, 73(8): 3576-3585.

Lei WANG, Yong JIANG, Dazhong ZHONG, Jiayuan LI, Genyan HAO, Qiang ZHAO, Jinping LI. Carbonized metal-organic framework for carbon dioxide reduction to ethylene and ethanol[J]. CIESC Journal, 2022, 73(8): 3576-3585.

图/表 9

图1 样品制备过程及表征结果

Fig.1 Sample preparation flow chart and characterization of Cu-BTC

图2 Cu-BTC在氮气中的热重分析曲线

Fig.2 Thermogravimetric analysis (TGA) curves of pristine Cu-BTC in N2 atmosphere

图3 Cu-BTC-X的结构表征和SEM图

Fig.3 Structural characterization and SEM images of Cu-BTC-X

图4 Cu-BTC-300℃的透射电镜图、高倍透射电镜图和元素分析图

Fig.4 TEM, HRTEM, and TEM EDX of Cu-BTC-300℃

图5 Cu-BTC-X的产物法拉第效率及C2+产物法拉第效率对比

Fig.5 Comparison of Faradic efficiency of Cu-BTC-X products and C2+ products

图6 Cu-BTC-X的总电流密度、C2+部分电流密度、H2部分电流密度、EIS谱图及Cu-BTC-300℃的稳定性测试结果

Fig.6 Total current density, partial current density of C2+ products and H2， and EIS spectra of Cu-BTC-X and stability test result of Cu-BTC-300℃

图7 恒电位-1.1 V还原的时间和电流密度；Cu-BTC-300℃还原前后的XRD谱图；Cu-BTC-300℃还原后的TEM图

Fig.7 Time and current density of potentiostatic -1.1 V reduction; XRD patterns of Cu-BTC-300℃ before and after reduction; TEM of Cu-BTC-300℃ after reduction

图8 Cu-BTC-X在N2饱和的0.1 mol·L-1 KHCO3中不同扫速测定的CV曲线及对应的电流密度差与扫描速率的关系[双层电容(Cdl)为线性斜率的一半]

Fig.8 CV curves collected in N2-saturated 0.1 mol·L-1 KHCO3 with different scan rates and the corresponding charging current density difference vs scan rate plots of Cu-BTC-X[Double-layer capacitance (Cdl) is equal to half of the linear slope]

图9 H2SO4搅拌洗后的Cu-BTC-300℃的XRD谱图、SEM图、产物法拉第效率及H2SO4搅拌洗前后的电流密度对比

Fig.9 XRD patterns, SEM, FE of Cu-BTC-300℃ after agitator treating of H2SO4, and comparison of current density before and after agitator treating of H2SO4

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碳化的MOF用于电催化还原二氧化碳制备乙烯和乙醇

Carbonized metal-organic framework for carbon dioxide reduction to ethylene and ethanol

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