Mesoporous tantalum oxide photocatalysts for Schrauzer-type conversion of dinitrogen to ammonia

摘要

Mesoporous tantalum oxide,Fe~(3+)-doped mesoporous tantalum oxide,and bis(toluene)titanium reduced mesoporous tantalum oxide were used for the first time as Schrauzer-type photocatalysts for the conversion of dinitrogen to ammonia.The materials were characterized by XRD,TEM,XPS,and nitrogen absorption before and after catalytic runs.The results showed low to moderate activities depending on the composition.In contrast to previously studied Ti catalysts,Fe doping and heat pretreatment were not prerequisites for photocatalytic activity,but did improve the turnover rates by up to a factor of two.The optimal Fe loading for the tantalum oxides was found to be 1 wt% and the optimal heating condition at 300 CC for 3 h.Increased surface area and heat treatment were also found to improve activities.Contrary to our expectations,reduction of the mesostructure with bis(toluene)titanium had little effect on the catalytic activity.In spite of the dramatically higher surface areas of the mesoporous tantalum oxides as compared with bulk titanias used previously in this process,the overall catalytic activities were still less than those obtained in the Schrauzer system.This suggests that the increase in diffusion and surface area offered by the mesoporous structure is offset by the smaller crystalline domain sizes in the walls of the structure,leading to poor electron-hole separation and a reduction in catalytic efficiency.