物理化学学报 >> 2024, Vol. 40 >> Issue (11): 2403032.doi: 10.3866/PKU.WHXB202403032

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具有高传质和亲和表面的NH2-UIO-66基疏水多孔液体用于增强CO2光还原

徐阳锐1, 任叶炜1, 刘馨琳2,*(), 李宏平3, 逯子扬1,4,*()   

  1. 1 环境健康与生态安全研究所, 应急管理学院, 环境与安全工程学院, 江苏大学, 江苏 镇江 212013
    2 能源与动力工程学院, 江苏大学, 江苏 镇江 212013
    3 能源研究院, 江苏大学, 江苏 镇江 212013
    4 江苏省水处理技术与材料协同创新中心, 苏州科技大学, 江苏 苏州 215009
  • 收稿日期:2024-03-28 修回日期:2024-05-02 录用日期:2024-05-06 发布日期:2024-10-14
  • 通讯作者: Email: liuxl@ujs.edu.cn (刘馨琳)luziyang126@126.com (逯子扬)

NH2-UIO-66 Based Hydrophobic Porous Liquid with High Mass Transfer and Affinity Surface for Enhancing CO2 Photoreduction

Yangrui Xu1, Yewei Ren1, Xinlin Liu2,*(), Hongping Li3, Ziyang Lu1,4,*()   

  1. 1 Institute of Environmental Health and Ecological Security, School of Emergency Management, School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu Province, China
    2 School of Energy and Power Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu Province, China
    3 Institute for Energy Research, Jiangsu University, Jiangsu, Zhenjiang 212013, Jiangsu Province, China
    4 Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment, Suzhou University of Science and Technology, Suzhou 215009, Jiangsu Province, China
  • Received:2024-03-28 Revised:2024-05-02 Accepted:2024-05-06 Published:2024-10-14
  • Contact: Email: liuxl@ujs.edu.cn (Xinlin Liu)luziyang126@126.com (Ziyang Lu)
  • Supported by:
    the National Natural Science Foundation of China(22278190); Zhenjiang Carbon Emissions Peak/Carbon Neutrality Science and Technology Innovation Special Fund Project(CQ2022009); Open Project of State Key Laboratory of Structural Chemistry(20230022); Qing Lan Project of Jiangsu Province(2023); Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment, Project of Research on Educational Reform and Talent Development of School of Emergency Management of Jiangsu University(JG-03-11); the Special Scientific Research Project of School of Emergency Management of Jiangsu University(KY-C-12)

摘要:

增加光催化剂表面的CO2浓度有助于提高光催化还原CO2的反应动力学速率。然而,CO2在水相中的低溶解度和较差的传质严重阻碍了CO2在活性位点的吸附和转化。在本工作中,将疏水性液体端长链(PDMS)嫁接到金属有机骨架(NH2-UIO-66)的氨基位点上,合成了具有强疏水性的多孔液体光催化剂(NH2-UIO-66 PL)。研究发现,具有永久孔隙率的NH2-UIO-66 PL能够使大量CO2富集在多孔液体的空腔中,便于CO2的快速运输并扩散到光催化剂表面。通过嫁接疏水性PDMS形成具有高正电位的CO2亲和表面和活化还原反应的关键中间体,从而形成更强的电子富集Zr活性位点,增强整体的光还原CO2能力。NH2-UIO-66 PL的CO产率为24.70 μmol·g−1 h−1,CH4产率为7.93 μmol·g−1 h−1,分别是亲水性NH2-UIO-66的2.3倍和2.7倍。这项研究提供了一种新颖的疏水性多孔液体的设计,为高CO2吸附和还原提供了工业应用的可能性。

关键词: 多孔液体, UIO-66, 疏水表面, CO2传输通道, CO2光还原

Abstract:

Increasing the CO2 concentration on the surface of the photocatalysts helps to increase the reaction dynamic rate of the photocatalytic CO2 reduction. However, the low solubility and poor mass transfer of CO2 in aqueous phase seriously hinder the adsorption and conversion of CO2 at the active site. In this work, the porous liquid photocatalyst (NH2-UIO-66 PL) with strong hydrophobicity has been synthesized by grafting the hydrophobic liquid end long-chain (PDMS) onto the amino site of metal-organic framework (NH2-UIO-66). It is found that the NH2-UIO-66 PL with permanent porosity causes a large amount of CO2 to be concentrated in the porous liquid cavity for transporting and diffusing CO2 onto the photocatalyst surface rapidly, and then the CO2 affinity surface with high positive potential and key intermediates for activation reduction reactions are formed with the grafting of hydrophobic PDMS, leading to stronger electron enrichment Zr active sites for enhancement of the overall CO2 reduction ability. As a result, NH2-UIO-66 PL achieved CO2 photoreduction with a CO yield of 24.70 μmol∙g−1∙h−1 and CH4 yield of 7.93 μmol∙g−1∙h−1, which is 2.3-fold and 2.7-fold compared to hydrophilic NH2-UIO-66, respectively. This research provides a novel design of hydrophobic porous liquids to provide industrial possibilities for high CO2 adsorption and reduction.

Key words: Porous liquids, UIO-66, Hydrophobic surface, CO2 transport channel, CO2 photoreduction