High-Capacity, Cooperative CO2 Capture in a Diamine-Appended Metal-Organic Framework through a Combined Chemisorptive and Physisorptive Mechanism

Ziting Zhu; Hsinhan Tsai; Surya T Parker; Jung-Hoon Lee; Yuto Yabuuchi; Henry Z H Jiang; Yang Wang; Shuoyan Xiong; Alexander C Forse; Bhavish Dinakar; Adrian Huang; Chaochao Dun; Phillip J Milner; Alex Smith; Pedro Guimarães Martins; Katie R Meihaus; Jeffrey J Urban; Jeffrey A Reimer; Jeffrey B Neaton; Jeffrey R Long

doi:10.1021/jacs.3c13381

High-Capacity, Cooperative CO₂ Capture in a Diamine-Appended Metal-Organic Framework through a Combined Chemisorptive and Physisorptive Mechanism

J Am Chem Soc. 2024 Mar 6;146(9):6072-6083. doi: 10.1021/jacs.3c13381. Epub 2024 Feb 24.

Authors

Ziting Zhu^{1

2

3}, Hsinhan Tsai^{1

4

3}, Surya T Parker^{5

3}, Jung-Hoon Lee⁶, Yuto Yabuuchi^{1

4

3}, Henry Z H Jiang^{1

4}, Yang Wang^{1

5}, Shuoyan Xiong^{1

4

3}, Alexander C Forse⁵, Bhavish Dinakar⁵, Adrian Huang^{1

4

3}, Chaochao Dun⁷, Phillip J Milner⁴, Alex Smith^{6

3}, Pedro Guimarães Martins^{6

3}, Katie R Meihaus^{1

4}, Jeffrey J Urban⁷, Jeffrey A Reimer^{1

5

3}, Jeffrey B Neaton^{1

6

3}, Jeffrey R Long^{1

4

5

3}

Affiliations

¹ Institute for Decarbonization Materials, University of California, Berkeley, California 94720, United States.
² Department of Materials Science and Engineering, University of California, Berkeley, California 94720, United States.
³ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
⁴ Department of Chemistry, University of California, Berkeley, California 94720, United States.
⁵ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States.
⁶ Department of Physics, University of California, Berkeley, California 94720, United States.
⁷ Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.

Abstract

Diamine-appended Mg₂(dobpdc) (dobpdc^4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are promising candidates for carbon capture that exhibit exceptional selectivities and high capacities for CO₂. To date, CO₂ uptake in these materials has been shown to occur predominantly via a chemisorption mechanism involving CO₂ insertion at the amine-appended metal sites, a mechanism that limits the capacity of the material to ∼1 equiv of CO₂ per diamine. Herein, we report a new framework, pip2-Mg₂(dobpdc) (pip2 = 1-(2-aminoethyl)piperidine), that exhibits two-step CO₂ uptake and achieves an unusually high CO₂ capacity approaching 1.5 CO₂ per diamine at saturation. Analysis of variable-pressure CO₂ uptake in the material using solid-state nuclear magnetic resonance (NMR) spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that pip2-Mg₂(dobpdc) captures CO₂ via an unprecedented mechanism involving the initial insertion of CO₂ to form ammonium carbamate chains at half of the sites in the material, followed by tandem cooperative chemisorption and physisorption. Powder X-ray diffraction analysis, supported by van der Waals-corrected density functional theory, reveals that physisorbed CO₂ occupies a pocket formed by adjacent ammonium carbamate chains and the linker. Based on breakthrough and extended cycling experiments, pip2-Mg₂(dobpdc) exhibits exceptional performance for CO₂ capture under conditions relevant to the separation of CO₂ from landfill gas. More broadly, these results highlight new opportunities for the fundamental design of diamine-Mg₂(dobpdc) materials with even higher capacities than those predicted based on CO₂ chemisorption alone.