Are Non-Six-Membered Ring Defects Formed in Single-Walled Carbon Nanotubes Treated by a Fluorination-Defluorination Process?

Single-walled carbon nanotubes (SWCNTs) modified by introducing non-six-membered ring defects, such as five- and seven-membered rings, have attracted considerable attention because their conductivity is enhanced by increasing the electronic density of states at the Fermi energy level. However, no preparation method exists to efficiently introduce non-six-membered ring defects into SWCNTs. Herein, we attempt to introduce non-six-membered ring defects into SWCNTs by defect rearrangement of the nanotube framework using a fluorination-defluorination process. Defect-introduced SWCNTs were fabricated from SWCNTs fluorinated at 25 °C for different reaction times. Their structures were evaluated, and their conductivities were measured by operating a temperature program. Structural analysis of the defect-induced SWCNTs using X-ray photoelectron spectroscopy, Raman spectroscopy, high-resolution transmission electron microscopy, and visible-near-infrared spectroscopy did not reveal the presence of non-six-membered ring defects in the SWCNTs but indicated the introduction of vacancy defects. Meanwhile, conductivity measurements performed by operating a temperature program showed that the defluorinated SWCNTs prepared from SWCNTs fluorinated for 3 min (deF-RT-3m) exhibited decreased conductivity owing to the adsorption of water molecules to non-six-membered ring defects, thereby implying the possibility of non-six-membered ring defects being introduced into deF-RT-3m.

Controlled introduction of defects into single-walled carbon nanotubes via a fluorination-defluorination strategy using xenon difluoride and their alkaline oxygen reduction reaction catalytic activity.

The defect edges in carbon nanomaterials have attracted attention as catalytic active sites for the oxygen reduction reaction (ORR) of the cathode in electrolyte fuel cells, and the defect control in carbon nanomaterials is becoming increasingly important. This study evaluates a fluorination-defluorination strategy for the controlled introduction of defects into single-walled carbon nanotubes (SWCNTs) involving the fluorination of SWCNTs using xenon difluoride (XeF2) and their subsequent defluorination through thermal annealing. We synthesized fluorinated SWCNTs with different fluorine contents using gaseous XeF2 and annealed the fluorinated SWCNTs at 1000 °C for 3 h under nitrogen gas flow. Structural analyses revealed that SWCNTs derived from fluorinated SWCNTs with low fluorine contents primarily had single point defects. In contrast, SWCNTs derived from fluorinated SWCNTs with high fluorine contents had vacancy defects with edges. According to the ORR catalyst evaluation in alkaline aqueous solution, SWCNTs with edge defects, rather than point defects, can improve the efficiency of ORR catalytic activity. The proposed fluorination-defluorination strategy using gaseous XeF2 is expected to enable the controlled introduction of defects in different types of carbon materials.

Isolation and characterization of cbbL and cbbS genes encoding form I ribulose-1,5-bisphosphate carboxylase/oxygenase large and small subunits in Nitrosomonas sp. strain ENI-11.

The cbbL and cbbS genes encoding form I ribulose-1,5-bisphosphate carboxylase/oxygenase (RubisCO) large and small subunits in the ammonia-oxidizing bacterium Nitrosomonas sp. strain ENI-11 were cloned and sequenced. The deduced gene products, CbbL and CbbS, had 93 and 87% identity with Thiobacillus intermedius CbbL and Nitrobacter winogradskyi CbbS, respectively. Expression of cbbL and cbbS in Escherichia coli led to the detection of RubisCO activity in the presence of 0.1 mM isopropyl-beta-D-thiogalactopyranoside (IPTG). To our knowledge, this is the first paper to report the genes involved in the carbon fixation reaction in chemolithotrophic ammonia-oxidizing bacteria.