Wet flue gas CO2 capture and utilization using one-dimensional metal–organic chains

Abstract

Herein, we describe the use of an ultramicroporous metal–organic framework (MOF) with a composition of [Ni₃(pzdc)₂(ade)₂(H₂O)_1.5]·(H₂O)_1.3 (pzdc: 3,5-pyrazole dicarboxylic acid; ade: adenine), for the selective capture of carbon dioxide (CO₂) from wet flue gas followed by its conversion to value-added products. This MOF is comprised of one-dimensional Ni(II)-pyrazole dicarboxylate-adenine chains; through pi–pi stacking and H-bonding interactions, these one-dimensional chains stack into a three-dimensional supramolecular structure with a one-dimensional pore network. Upon heating, our MOF undergoes a color change from light blue to lavender, indicating a change in the coordination geometry of Ni(II). Variable temperature ultraviolet-visible (UV/vis) spectroscopy data revealed a blue shift of the d–d transitions, suggesting a change in the Ni-coordination geometry from octahedral to a mixture of square planar and square pyramidal. The removal of the water molecules coordinated to Ni(II) leads to the generation of a MOF with open Ni(II) sites. Nitrogen isotherms collected at 77 K and 1 bar revealed that this MOF is microporous with a pore volume of 0.130 cm³ g⁻¹. Carbon dioxide isotherms show a step in the uptake at low pressure, after which the CO₂ uptake is saturated. The step in the CO₂ uptake is likely attributable to the rearrangement of the three-dimensional supramolecular structure to accommodate CO₂ within its pores. The affinity of this MOF for CO₂ is 35.5 kJ mol⁻¹ at low loadings, and it increases to 41.9 kJ mol⁻¹ at high loadings. While our MOF is porous to CO₂ and water (H₂O) at 298 K, it is not porous to N₂, and the CO₂/N₂ selectivity increases from 28.5 to 31.5 as a function of pressure. Breakthrough experiments reveal that this MOF can capture CO₂ from dry and wet flue gas with uptake capacities of 1.48 ± 0.01 and 1.14 ± 0.06 mmol g⁻¹, respectively. The MOF can be regenerated and reused at least three times, demonstrating consistent CO₂ uptake capacities. Upon understanding the sorption behavior of this MOF, catalysis experiments show that the MOF is catalytically active in the fixation of CO₂ into an epoxide ring for the formation of a cyclic carbonate. The turnover frequency for this reaction is 21.95 ± 0.03 h⁻¹. The MOF showed no catalytic deterioration after two cycles and maintained comparable catalytic activity when dry and wet CO₂/N₂ mixtures were used. This highlights that both N₂ and H₂O do not dramatically affect the catalytic activity of our MOF toward CO₂ fixation.