Abstract
CO2 capture, especially under low-pressure range, is of significance to maintain long-duration human operation in confined spaces and decrease the CO2 corrosion and freezing effect for the liquefaction of natural gas. Herein, we for the first time report a novel anion-functionalized ZU-16-Co (TIFSIX-3-Co, TIFSIX=hexafluorotitanate (TiF62−), 3=pyrazine), which exhibits one-dimensional pore channels decorated by abundant F atoms, for efficient CO2 capture at a concentration around 400–10,000 ppm. Among its isostructural MFSIX-3 (M=Si, Ti, Ge) family materials, ZU-16-Co with fine-tuned pore size of 3.62 Å exhibits the highest CO2 uptake at 0.01 bar (10,000 ppm) and 1 bar (2.63 and 2.87 mmol g−, respectively). The high CO2 capture ability of ZU-16-Co originates from the fine-tuned pore dimensions with strong F⋯C=O host-guest interactions and relatively large pore volumes coming from its longer coordinated Ti-F-Co distance (3.9 Å) in c direction. The excellent carbon trapping performance was further verified by dynamic breakthrough tests for CO2/N2 (1/99 and 15/85) and CO2/CH4 (50/50) mixtures. The adsorption and separation performances, resulting from the fine-tuned pore system with periodic arrays of exposed functionalities, demonstrate that ultramicroporous ZU-16-Co can be a promising adsorbent for low-concentration carbon capture.
摘要
CO2 捕获, 尤其低浓度CO2 捕获, 对人类在限域空间中长时间 工作、降低天然气液化过程中CO2 腐蚀及冻结效应极为重要. 本文 首次报道了一种具有一维孔道的ZU-16-Co (TIFSIX-3-Co)材料, 该 材料孔道中含大量电负性F原子, 可实现400–10,000 ppm浓度下 CO2 的高效捕获. 相比同构材料, 孔径为3.62 Å的ZU-16-Co在0.01 和1.0 bar表现出最高的吸附量, 分别为2.63和2.87 mmol g−1. 模拟 研究表明, ZU-16-Co具有优异的CO2 捕获性能是由于其精准调控 的孔道与CO2 较强的主客体相互作用(F···C=O)及相对较大的孔容. 此外, 动态混合气(1/99和15/85 CO2/N2, 50/50 CO2/CH4)固定床穿 透实验也表明ZU-16-Co具有优良的CO2 捕获性能. 精准调控的孔 化学尺度及周期性排布的电负性功能位点带来的良好的CO2 捕 获、分离性能使得超微孔ZU-16-Co成为极具前景的低浓度CO2 吸 附剂.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (21938011, U1862110, 21890764 and 21725603), and the National Program for Support of Top-notch Young Professionals (H. X.).
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Zhang Z, Xing H, and Cui X designed the experiments; Ding Q and Cui J performed the experiments; Zhang Z wrote the paper with support from Cui X and Xing H. All authors contributed to the general discussion.
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The authors declare that they have no conflict of interest.
Zhaoqiang Zhang received his PhD degree from the College of Chemical and Biological Engineering, Zhejiang University in 2019. He is currently working with Prof. Dan Zhao at the National University of Singapore as a post-doctoral fellow. His research interests focus on the design and application of functional ultramicroporous materials in the fields of hydrocarbon adsorption and separation.
Xili Cui obtained her PhD degree from Zhejiang University in 2016. During her postdoctoral research at the University of South Florida from 2018 to 2019, she focused on the syntheses of porous materials for separation and purification of structure-similar mixtures. She joined the College of Chemical and Biological Engineering at Zhejiang University by “Hundred-Talent Program” in 2019. Her current research interest focuses on the design and syntheses of functional porous materials for the separation of hydrocarbons. She has received several awards such as the CPCIF-Clariant Youth Innovation Award for Sustainable Development-Excellent Award.
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High and selective capture of low-concentration CO2 with an anion-functionalized ultramicroporous metal-organic framework
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Zhang, Z., Ding, Q., Cui, J. et al. High and selective capture of low-concentration CO2 with an anion-functionalized ultramicroporous metal-organic framework. Sci. China Mater. 64, 691–697 (2021). https://doi.org/10.1007/s40843-020-1471-0
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DOI: https://doi.org/10.1007/s40843-020-1471-0