Controllable synthesis of core-shell Co@C@SiO2 catalysts for enhancing product selectivity in Fischer-Tropsch synthesis by tuning the mass transfer resistance

Fischer-Tropsch synthesis(FTS) is the key step in converting syngas into clean fuels. Traditional supported catalysts for FTS are problematic because the active metal crystalline size is positively related to metal loading. Therefore, increasing active metal loading may reduce the cobalt time yield(CTY) since a high CTY is usually obtained when the Co size is 8 nm. Here, a ZIF-67(Zeolitic imidazolate framework-67) with a MOF(Metal organic framework) structure is used as a precursor to prepare the Co@C catalyst with not only high cobalt loading(55.6 wt%) but also with a small cobalt crystal size(as small as 8.6 nm). Coreshell Co@C@SiO2-X catalysts with different SiO2 shell thicknesses were successfully prepared by coating different amounts of TEOS on the outer surface of Co@C to modify product selectivity. Compared with40 wt% Co/SiO2 catalyst, core-shell Co@C@SiO2-X catalysts exhibited improved FTS performance. Furthermore, different gaseous hourly space velocities(GHSVs) were used to obtain CO conversion at similar levels to compare CTY and the turnover frequency(TOF). Among the catalysts, the Co@C@SiO2-1 catalyst, with its better mass transfer ability and suitable hydrophilic property, presented the highest TOF(9.75 × 10-3 s-1) and lowest CH4 selectivity(9.75%). In addition, heavy hydrocarbons were effectively suppressed with the increase in shell thickness due to the increased mass transfer resistance.

IMPROVING HYDROPHILICITY AND PROTEIN ANTIFOULING OF ELECTROSPUN POLY(VINYLIDENEFLUORIDE-HEXAFLUOROPROPYLENE) NANOFIBER MEMBRANES

Poly（vinylidenefluoride-hexafluoropropylene） （PVDF-HFP） nanofiber membranes with improved hydrophilicity and protein fouling resistance via surface graft copolymerization of hydrophilic monomers were prepared. The surface modification involves atmospheric pressure glow discharge plasma （APGDP） pretreatment followed by graft copolymerization of poly（ethylene glycol） methyl ether methacrylate （PEGMA）. The success of the graft modification with PEGMA on the PVDF-HFP fibrous membrane is ascertained by X-ray photoelectron spectroscopy （XPS） and attenuated total reflectance Fourier transform infrared measurements （ATR-FTIR）. The hydrophilic property of the nanofiber membranes is assessed by water contact angle measurements. The results show that the PEGMA grafted PVDF-HFP nanofiber membrane has a water contact angle of 0° compared with the pristine value of 132°. The protein adsorption was effectively reduced after PEGMA grafting on the PVDF-HFP nanofiber membrane surface. The PEGMA polymer grafting density on the PVDF-HFP membrane surface is measured by the gravimetric method, and the filtration performance is characterized by the measurement of water flux. The results indicate that the water flux of the grafted PVDF-HFP fibrous membrane increases significantly with the increase of the PEGMA grafting density.