Cu-MOFs的生长调控及其催化水解羰基硫的性能

催化学报 ›› 2017, Vol. 38 ›› Issue (8): 1373-1381.

Cu-MOFs的生长调控及其催化水解羰基硫的性能

沈丽娟, 王高杰, 郑笑笑, 曹彦宁, 郭玉峰, 林科, 江莉龙

福州大学化肥催化剂国家工程研究中心, 福建福州 350002

收稿日期:2017-04-11 修回日期:2017-06-17 出版日期:2017-08-18 发布日期:2017-08-04
通讯作者: 江莉龙
基金资助:
国家自然科学基金（21603034，21576051）；国家高技术研究发展计划（863计划，2015AA03A402）.

Tuning the growth of Cu-MOFs for efficient catalytic hydrolysis of carbonyl sulfide

Lijuan Shen, Gaojie Wang, Xiaoxiao Zheng, Yanning Cao, Yufeng Guo, Ke Lin, Lilong Jiang

National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou 350002, Fujian, China

Received:2017-04-11 Revised:2017-06-17 Online:2017-08-18 Published:2017-08-04
Supported by:
This work was supported by the National Natural Science Foundation of China (21603034, 21576051) and the National High Technology Research and Development Program of China (863 Program, 2015AA03A402).

摘要/Abstract

摘要：

羰基硫（COS）广泛存在于以煤、焦炭、渣油和天然气等为原料生产的化工原料气中，不仅腐蚀管道设备，使下游催化剂发生硫中毒，而且还会造成环境污染.因此，COS脱除具有重要意义.在各种方法中，催化水解COS（COS+H₂O → CO₂+H₂S）由于具有反应条件温和、转化率高和副反应少等优点越来越受重视.其关键在于发展高效的催化剂.近年来，金属-有机骨架材料（metal-organic frameworks，MOFs）由于其独特的物理化学性质引起人们广泛关注.与传统材料相比，MOFs不仅拥有超高的比表面积和规则的孔道结构，而且其结构具有可设计性强和易调变等特点，是一类非常有潜力的多相催化剂.然而，目前MOFs在催化水解COS方面的研究应用未见报道.此外，MOFs的合成方法主要有水/溶剂热法、扩散法和微波辅助加热法等.近年来新发展的电化学法具有合成效率高、操作方便和环境友好等优点，在材料合成中显示出巨大的优越性，但利用电化学法合成MOFs相关研究还较少.
本文采用快速温和的电化学方法制备了典型的Cu-MOFs（HKUST-1）.该方法可以有效缩短反应时间，通过调节反应电压（15-30 V），在室温下电解3 h，可得到一系列HKUST-1样品.根据合成中设置的电压值，样品分别命名为HKUST-1-E15，HKUST-1-E20，HKUST-1-E25和HKUST-1-E30.XRD表征结果显示，不同电压下合成样品的XRD谱图与通过晶体数据拟合的HKUST-1图出峰位置基本一致.SEM结果表明，合成电压对样品形貌的影响很大.HKUST-1-E15主要呈长棒状结构，长约为15 μm.随着电压的增大，HKUST-1-E20的形貌逐渐转变为较短的四棱柱体.当电压为25 V时，所得HKUST-1-E25呈八面体状.进一步提高合成电压，HKUST-1-E30颗粒变小，没有特殊形貌，并出现明显的团聚.COS水解测试结果显示，不同电压下合成样品的活性差异大，这主要是由于样品的形貌及比表面积差异引起的.其中，HKUST-1-E25样品的活性较好.在150℃下，该样品对COS的转化率接近100%，比水热法合成的HKUST-1-Hy的活性更高.在此基础上，进一步对活性测试过程的条件进行优化，发现当原料气流速为30 mL/min，水温为40℃时，催化剂的COS水解性能最优.此外，样品的活性稳定性测试结果显示，相比传统的氧化铜材料，HKUST-1是一类较稳定的COS水解催化剂.

关键词: 金属-有机骨架材料, 羰基硫, 电化学合成, 催化水解, HKUST-1

Abstract:

Development of the high activity, promoter-free catalysts for carbonyl sulfide (COS) hydrolysis is important for the efficient utilization of various feedstocks. In this study, the Cu-based met-al-organic framework HKUST-1 is synthesized by a simple and mild anodic-dissolution electro-chemical method. The physical and chemical properties of the samples are characterized by several techniques, including scanning electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller analysis and X-ray photoelectron spectroscopy. The results reveal that the synthesis voltage plays a crucial role in controlling the morphology of the resulting HKUST-1. The obtained samples function as novel catalysts for the hydrolysis of COS. A high efficiency, approaching 100%, can be achieved for the conversion of COS at 150℃ over the optimal HKUST-1 synthesized at 25 V. This is significantly higher than that of the sample pre-pared by the traditional hydrothermal method. Additionally, the effects of the water temperature and the flow velocity on the hydrolysis of COS are also investigated in detail. Finally, a possible reaction pathway of COS hydrolysis over HKUST-1 is also proposed. This work represents the first example of MOFs applied to the catalytic hydrolysis of COS. The results presented in this study can be anticipated to give a feasible impetus to design novel catalysts for removing the sulfur-containing compounds.

Key words: Metal-organic framework, Carbonyl sulfide, Electrochemical synthesis, Catalytic hydrolysis, HKUST-1

沈丽娟, 王高杰, 郑笑笑, 曹彦宁, 郭玉峰, 林科, 江莉龙. Cu-MOFs的生长调控及其催化水解羰基硫的性能[J]. 催化学报, 2017, 38(8): 1373-1381.

Lijuan Shen, Gaojie Wang, Xiaoxiao Zheng, Yanning Cao, Yufeng Guo, Ke Lin, Lilong Jiang. Tuning the growth of Cu-MOFs for efficient catalytic hydrolysis of carbonyl sulfide[J]. Chinese Journal of Catalysis, 2017, 38(8): 1373-1381.

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