ABSTRACT
A nickel-phosphorus-alumina xerogel catalyst was prepared by a carbon-templating epoxide-driven sol-gel method (denoted as CNPA catalyst), and it was applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel-phosphorus-alumina xerogel catalyst was also prepared by a similar method in the absence of carbon template (denoted as NPA catalyst). The effect of carbon template addition on the physicochemical properties and catalytic activities of the catalysts in the steam reforming of LNG was investigated. Both CNPA and NPA catalysts showed excellent textural properties with well-developed mesoporous structure. However, CNPA catalyst retained a more reducible nickel aluminate phase than NPA catalyst. XRD analysis of the reduced CNPA and NPA catalysts revealed that nickel sintering on the CNPA catalyst was suppressed compared to that on the NPA catalyst. From H2-TPD and CH4-TPD measurements of the reduced CNPA and NPA catalysts, it was also revealed that CNPA catalyst with large amount of hydrogen uptake and strong hydrogen-binding sites showed larger amount of methane adsorption than NPA catalyst. In the hydrogen production by steam reforming of LNG, CNPA catalyst with large methane adsorption capacity showed a better catalytic activity than NPA catalyst.
ABSTRACT
Nano-structured alkaline-earth metal oxide adsorbents (denoted as MgO-Al2O3 and CaO-Al2O3) were prepared by an epoxide-driven one-pot sol-gel method, and they were applied to the dynamic and static CO2 adsorption. For comparison, a nano-structured aluminum oxide adsorbent (denoted as Al2O3) was also prepared by a similar method. MgO-Al2O3 adsorbent exhibited a well-developed mesopore structure through the formation of MgAl2O4 spinel phase, whereas CaO-Al2O3 adsorbent was composed of nano-sized CaO and CaAl2O4, resulting in a pore plugging. It was revealed that total basicity increased in the order of Al2O3 (0.11 mmol-CO2/g) < MgO-Al2O3 (0.37 mmol-CO2/g) < CaO-Al2O3, (1.21 mmol-CO2/g), which is in concurrent with adsorption energy obtained from DFT calculations. However, it was found that both basicity and base strength of the adsorbents played an important role in determining the CO2 adsorptive performance at different operating temperature. Among the adsorbents tested, MgO-Al2O3, which mostly retained medium basic sites, exhibited a best CO2 adsorptive performance at 200 degrees C. Furthermore, the experimental results are well supported by theoretical estimation, suggesting a useful design method of adsorbents for facile and regenerative adsorption in the applications of CO2 capture.
ABSTRACT
Nano-structured α-K5PW11(M x OH2)O39 (M = Mn(II), Co(II), Ni(II), and Zn(II)) Keggin heteropolyacids (HPAs) were investigated by scanning tunneling microscopy (STM) and tunneling spectroscopy (TS) measurements in order to elucidate their redox property and oxidation catalysis. HPA molecules formed two-dimensional self-assembled monolayer arrays on highly oriented pyrolytic graphite (HOPG) surface. Furthermore, HPAs exhibited a distinctive current-voltage behavior referred to as negative differential resistance (NDR) phenomenon. The measured NDR peak voltage of HPAs was correlated with the reduction potential and the absorption edge energy determined by electrochemical method and UV-visible spectroscopy, respectively. NDR peak voltage of HPAs appeared at less negative voltage with increasing reduction potential and with decreasing UV-visible absorption edge energy. The correlations strongly suggested that NDR phenomenon was closely related to the redox property of HPAs. Vapor-phase oxidation of benzyl alcohol to benzaldehyde was carried out as a model reaction to track the oxidation catalysis of HPAs. NDR peak voltage appeared at less negative voltage with increasing yield for benzaldehyde.
