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. 2021 Apr 19;60(17):9604-9609.
doi: 10.1002/anie.202100584. Epub 2021 Mar 10.

Electrostatically Driven Selective Adsorption of Carbon Dioxide over Acetylene in an Ultramicroporous Material

Yi Xie  1 , Hui Cui  1 , Hui Wu  2 , Rui-Biao Lin  3   1 , Wei Zhou  2 , Banglin Chen  1
Affiliations

Electrostatically Driven Selective Adsorption of Carbon Dioxide over Acetylene in an Ultramicroporous Material

Yi Xie et al. Angew Chem Int Ed Engl. .

Abstract

Separating acetylene from carbon dioxide is important but highly challenging owing to their similar physical properties and molecular dimensions. Herein, we report highly efficient electrostatically driven CO2 /C2 H2 separation in an ultramicroporous cadmium nitroprusside (Cd-NP) with compact pore space and complementary electrostatic potential well fitting for CO2 , thus enabling molecular quadrupole moment recognition of CO2 over C2 H2 . This material shows a high CO2 /C2 H2 uptake ratio of 6.0 as well as remarkable CO2 /C2 H2 selectivity of 85 under ambient conditions with modest CO2 heat of adsorption. Neutron powder diffraction experiments and molecular simulations revealed that the electrostatic potential compatibility between pore structure and CO2 allows it to be trapped in a head-on orientation towards the Cd center, whereas the diffusion of C2 H2 is electrostatically forbidden. Dynamic breakthrough experiments have validated the separation performance of this compound for CO2 /C2 H2 separation.

Keywords: cadmium nitroprusside; carbon dioxide; electrostatic potential; gas separation; ultramicroporous materials.

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Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Figure 1.
Figure 1.
a) Local coordination environments of the nitroprusside linker and cadmium atom. Top: Crystal structure of Cd-NP viewed along the b-axis. Bottom: Side view of the ellipsoidal cavity unit. Cd light green, Fe orange, C gray, N blue. b) Electrostatic potential (ESP) of Cd-NP mapped onto the Connolly surface with a probe radius of 1.2 Å. c) Molecular electrostatic potential (MEP) of the CO2 and C2H2 molecule mapped onto the 0.015 e−Å−3 electron density isosurfaces. The gradation on the scale bar is in kcalmol−1.
Figure 2.
Figure 2.
a) CO2 and C2H2 sorption isotherms for Cd-NP at 298 K. b) Coverage-dependent adsorption enthalpy of CO2 calculated by the virial fitting method. c) Comparison of the zero-coverage heat of adsorption of Cd-NP with those of other materials for CO2/C2H2 separation. d) Comparison of CO2/C2H2 selectivity and uptake ratio between Cd-NP and other CO2-selective materials at 298 K and 1 bar.
Figure 3.
Figure 3.
a, b) Neutron diffraction crystal structure of Cd-NP⊃CO2 with close contacts indicated. Guest molecules are highlighted as CPK models. c) Electrostatic potential (ESP) of Cd-NP⊃CO2 mapped onto the 0.15 e−Å−3 electron density isosurface. The gradation on the scale bar is in kcalmol−1. d) Electrostatically driven adsorption mechanism towards CO2 and C2H2 molecules (see the Supporting Information for the CCDC deposition number).
Figure 4.
Figure 4.
Experimental column breakthrough curves for a) an equimolar CO2/C2H2 mixture and b) cycling tests of the equimolar CO2/C2H2 mixture (open symbols: C2H2, solid symbols: CO2) in a column packed with Cd-NP at 298 K and 1 bar.
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