Covalent organic frameworks (COFs) have been proposed as alternative candidates for molecular sieving membranes due to their chemical stability. However, developing COF membranes with narrowed apertures close to the size of common gas molecules is a crucial task for selective gas separation. Herein, we demonstrate a new type of a two-dimensional layered-stacking COF-COF composite membrane in bilayer geometry synthesized on a porous support by successively regulating the growth of imine-based COF-LZU1 and azine-based ACOF-1 layers via a temperature-swing solvothermal approach. The resultant COF-LZU1-ACOF-1 bilayer membrane has much higher separation selectivity for H/CO, H/N, and H/CH gas mixtures than the individual COF-LZU1 and ACOF-1 membranes due to the formation of interlaced pore networks, and the overall performance surpasses the Robeson upper bounds. The COF-LZU1-ACOF-1 bilayer membrane also shows high thermal and long-time stabilities.
Two types of metal-organic frameworks (MOFs) have been synthesized and evaluated in the separation of C2 and C3 olefins and paraffins. Whereas Co2(dhtp) (=Co-CPO-27 = Co-MOF-74) and Mg2(dhtp) show an adsorption selectivity for the olefins ethene and propene over the paraffins ethane and propane, the zeolitic imidazolate framework ZIF-8 behaves in the opposite way and preferentially adsorbs the alkane. Consequently, in breakthrough experiments, the olefins or paraffins, respectively, can be separated.
Covalent organic frameworks (COFs) are promising materials for advanced molecular-separation membranes, but their wide nanometer-sized pores prevent selective gas separation through molecular sieving. Herein, we propose a MOF-in-COF concept for the confined growth of metal-organic framework (MOFs) inside a supported COF layer to prepare MOF-in-COF membranes. These membranes feature a unique MOF-in-COF micro/nanopore network, presumably due to the formation of MOFs as a pearl string-like chain of unit cells in the 1D channel of 2D COFs. The MOF-in-COF membranes exhibit an excellent hydrogen permeance (>3000 GPU) together with a significant enhancement of separation selectivity of hydrogen over other gases. The superior separation performance for H2/CO2 and H2/CH4 surpasses the Robeson upper bounds, benefiting from the synergy combining precise size sieving and fast molecular transport through the MOF-in-COF channels. The synthesis of different combinations of MOFs and COFs in robust MOF-in-COF membranes demonstrates the versatility of our design strategy.
In
this study, we propose a new concept of vertically aligned 2D
covalent organic framework (COF) layers forming a membrane for efficient
gas separation on the basis of precise size exclusion. Gas transport
takes place through the COF interlayer space (typically 0.3–0.4
nm) rather than through the nanometer-sized pore apertures. Construction
of such a unique membrane architecture was implemented via in situ oriented growth of 2D COFs inside a skeleton of
vertically aligned CoAl-layered double hydroxide (LDH) nanosheets.
The resultant vertical COF-LZU1 membrane exhibits a high H2 permeance of ∼3600 GPU together with a desirable separation
selectivity for gas mixtures such as H2/CO2 (31.6)
and H2/CH4 (29.5), thus surpassing the 2008
Robeson upper bounds. The universality of this approach was demonstrated
by successfully producing two types of high-quality vertical COF membranes
with superior performance as well as outstanding running stability.
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