二氧化硅担载铬基催化剂的XAFS研究

考察了二氧化硅担载铬基催化剂Na-7.5%Cr/SiO2在甲烷-二氧化碳共活化制芳烃(SAMCA)新反应中的催化活性, 最佳结果为甲烷转化率4.0%,芳烃选择性48.7%.用扩展X射线吸收精细结构(EXAFS)和X射线吸收近边结构(XANES), 以及X光电子能谱(XPS)等方法研究了SAMCA反应催化剂Na-7.5%Cr/SiO2的结构.结果表明, 催化剂表面主要存在Cr(VI)和 Cr(III)两种物种, 六价铬相对在表面富集,催化剂呈明显的无定形特征.结合其SAMCA反应活性结果, 认为催化剂中单金属(铬)双中心(两种氧化态)混合位置对称性结构, 即配位不饱和的 Td-Cr(VI)/Oh-Cr(III)是该催化剂在SAMCA反应中显示活性的重要原因,提出了可能的SAMCA反应催化剂双位活化机制模型.

XAFS Study of Silica-supported Chromium-based Catalyst

Silica-supported sodium-modified chromium catalyst Na-7.5%Cr/SiO2is found to be active for simultaneous activation of methane and carbon dioxide to aromatics(SAMCA). The best result shows the methane conversion of 4.0% and the selectivity of 48.7% to aromatics (benzene+toluene). X-ray absorption Cr K-edge fine structure analyses (XANES and EXAFS) and XPS are employed to study the surface structure of the catalyst. Both Cr6+and Cr3+are present on the surface, while the prosperous of Cr6+on the surface is observed. The results demonstrate that the dual-center(mixed oxidation state)/mixed site-symmetric structure—Td-Cr(VI)/Oh-Cr(III) is the catalytic active sites of Na-7.5%Cr/SiO2in SAMCA. A possible catalyst model of double-sites activation mechanism in SAMCA has been tentatively proposed.