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[HKUST-1] Methyl-Shield Cu-BTC with High Water Stability through One-Step Synthesis and In Situ Functionalization
Summary:
The authors from Tiangong University developed a Cu-BTC-IPA material with enhanced water stability through one-step synthesis and in situ functionalization, achieving significant results in gas adsorption applications.
Background:
1. Metal−organic frameworks (MOFs) have great potential in gas storage and separation due to their high surface areas and adjustable pore functionalities. However, most MOFs are unstable in moisture, limiting their practical applications. Previous researchers have explored various strategies to enhance MOF stability, such as coating with hydrophobic materials or introducing hydrophobic functional groups, but these methods often require complex processes or secondary treatments.
2. The authors in this work proposed a one-step synthesis strategy to functionalize Cu-BTC with isopropanol (IPA), resulting in a material (Cu-BTC-IPA) that exhibits excellent water stability while retaining high surface area and gas adsorption capacity.
Research Content:
1. Synthesis:
The authors synthesized Cu-BTC-IPA by mixing Cu(NO₃)₂·3H₂O, 1,3,5-benzenetricarboxylic acid (H₃BTC), and IPA in a hydrothermal process. The addition of IPA was crucial for in situ functionalization.
2. Characterizations:
1) BET surface area of Cu-BTC-IPA3 was 1365 m²/g, with a pore size distribution centered around 8.0 Å.
2) SEM tests showed that the particle size of Cu-BTC-IPA was slightly smaller than that of Cu-BTC, indicating IPA affected crystal growth.
3) FT-IR and ¹H NMR confirmed the presence of IPA in the framework, with new peaks corresponding to IPA's functional groups.
3. Application:
Cu-BTC-IPA3 demonstrated excellent gas adsorption performance, preserving 95% of its initial BET surface area and 90% of its CO₂ adsorption capacity after 4 days in water. It also maintained 83% of its initial BET surface area after 12 h in diluted HCl solution.
4. Mechanism:
The enhanced water stability was attributed to the methyl-shielding microenvironment created by IPA, which reduced the affinity of Cu sites to water molecules and increased steric hindrance. DFT calculations supported this mechanism, showing stronger Cu−OIPA bonds compared to Cu−Owater bonds.
Outlook:
This research provides a simple and efficient method to enhance the water stability of MOFs, making Cu-BTC-IPA a promising candidate for practical applications in gas adsorption and separation. The one-step synthesis process is scalable and applicable to other MOFs with open metal sites.
Methyl-Shield Cu-BTC with High Water Stability through One-Step Synthesis and In Situ Functionalization
Authors: Shanshan Xu, Xiangyu Guo, Zhihua Qiao, Hongliang Huang, Chongli Zhong
DOI: 10.1021/acs.iecr.0c02156
Link: https://pubs.acs.org/doi/10.1021/acs.iecr.0c02156
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