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Functionalizing porous zirconium terephthalate UiO-66(Zr) for natural gas upgrading: a computational exploration
Summary:
The authors from Beijing University of Chemical Technology, Institut Charles Gerhardt Montpellier, Laboratoire Chimie Provence and Institut Lavoisier computationally designed –SO₃H and –CO₂H-functionalized UiO-66(Zr) MOFs that exhibit record CO₂/CH₄ selectivity (up to 23), high working capacity and mild-regeneration enthalpy, offering a robust adsorbent for natural-gas upgrading via PSA.
Background:
1. To remove CO₂ from CH₄, prior studies tested zeolites, carbons and amine scrubbers, yet suffered from low selectivity, harsh regeneration or poor hydrothermal stability.
2. The team now proposes a computational ligand-functionalization strategy and identifies –SO₃H/–CO₂H grafted UiO-66(Zr) as top performers.
Research Content:
1. Synthesis: DFT-guided geometry optimization starting from experimental unit-cell parameters; functional groups grafted onto terephthalate linkers.
2. Characterizations:
1) BET: Sₐcc 361–848 m² g⁻¹, Vₚₒᵣₑ 0.22–0.40 cm³ g⁻¹ (Table S1).
2) TEM/SEM-like structural models show 11 Å octahedral & 8 Å tetrahedral cages unchanged after functionalization.
3) GCMC + microcalorimetry: CO₂ ΔH −33 kJ mol⁻¹, CH₄ ΔH −20 kJ mol⁻¹; validated against 303 K isotherms (Fig. S10–S11).
3. Application: Equimolar CO₂/CH₄ PSA simulation (1–10 bar) gives selectivity 16.8–23.2 and working capacity 45–57 cm³(STP) cm⁻³, outperforming zeolite 13X.
4. Mechanism: Electrostatic + confinement; –SO₃H forms 1.92 Å CO₂···H hydrogen bond; –CO₂H balances low CH₄ affinity, maximizing S = (xCO₂/xCH₄)/(yCO₂/yCH₄).
Outlook:
The work delivers experimentally verifiable, water-stable UiO-66(Zr) adsorbents that merge high selectivity, capacity and mild regeneration, paving the way for pilot-scale PSA tests on biogas upgrading.
Functionalizing porous zirconium terephthalate UiO-66(Zr) for natural gas upgrading: a computational exploration
Authors: Qingyuan Yang, Andrew D. Wiersum, Philip L. Llewellyn, Vincent Guillerm, Christian Serre, Guillaume Maurin
DOI: 10.1039/c1cc13543k
Link: https://pubs.rsc.org/en/content/articlelanding/2011/cc/c1cc13543k
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