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A challenge in the synthesis of single‐wall carbon nanotubes (SWCNTs) is the lack of control over the formation and evolution of catalyst nanoparticles and the lack of control over their size or chirality. Here, zeolite MFI nanosheets (MFI‐Ns) are used to keep cobalt (Co) nanoparticles stable during prolonged annealing conditions. Environmental transmission electron microscopy (ETEM) shows that the MFI‐Ns can influence the size and shape of nanoparticles via particle/support registry, which leads to the preferential docking of nanoparticles to four or fewer pores and to the regulation of the SWCNT synthesis products. The resulting SWCNT population exhibits a narrow diameter distribution and SWCNTs of nearly all chiral angles, including sub‐nm zigzag (ZZ) and near‐ZZ tubes. Theoretical simulations reveal that the growth of these unfavorable tubes from unsupported catalysts leads to the rapid encapsulation of catalyst nanoparticles bearing them; their presence in the growth products suggests that the MFI‐Ns prevent nanoparticle encapsulation and prologue ZZ and near‐ZZ SWCNT growth. These results thus present a path forward for controlling nanoparticle formation and evolution, for achieving size‐ and shape‐selectivity at high temperature, and for controlling SWCNT synthesis.

 

Vapor phase ligand treatment (VPLT) of 2‐aminobenzimidazole (2abIm) for 2‐methylimidazole (2mIm) in ZIF‐8 membranes prepared by two different methods (LIPS: ligand induced permselectivation and RTD: rapid thermal deposition) results in a notable shift of the molecular level cut‐off to smaller molecules establishing selectivity improvements from ca. 1.8 to 5 for O₂/N₂; 2.2 to 32 for CO₂/CH₄; 2.4 to 24 for CO₂/N₂; 4.8 to 140 for H₂/CH₄and 5.2 to 126 for H₂/N₂. Stable (based on a one‐week test) oxygen‐selective air separation performance at ambient temperature, 7 bar(a) feed, and 1 bar(a) sweep‐free permeate with a mixture separation factor of 4.5 and oxygen flux of 2.6×10⁻³ mol m⁻² s⁻¹is established. LIPS and RTD membranes exhibit fast and gradual evolution upon a 2abIm‐VPLT, respectively, reflecting differences in their thickness and microstructure. Functional reversibility is demonstrated by showing that the original permeation properties of the VPLT‐LIPS membranes can be recovered upon 2mIm‐VPLT.

 

Nanosheet-based MFI membranes, known to be highly selective for hydrocarbon isomer separations, exhibit an NH 3 /N 2 mixture separation factor of 2236 with NH 3 permeance of 1.1 × 10 −6 mol m −2 s −1 Pa −1 , and NH 3 /H 2 separation factor of 307 with NH 3 permeance of 2.3 × 10 −6 mol m −2 s −1 Pa −1 at room temperature. Consistent with a competitive sorption-based separation, lower operating temperatures and higher pressures result in increased separation factor. At 323 K, with an equimolar mixed feed of NH 3 /N 2 , the fluxes and separation factors at 3 and 7 bar are 0.13 mol m −2 s −1 and 191, and 0.26 mol m −2 s −1 and 220, respectively. This performance compares favorably with that of other membranes and suggests that MFI membranes can be used in separation and purification processes involving mixtures of NH 3 /N 2 /H 2 encountered in ammonia synthesis and utilization. The membranes also exhibit high performance for the separation of ethane, n -propane and n -butane from H 2 .