Xie Xiaowei, Li Yong, Liu Zhi-Quan, Haruta Masatake, Shen Wenjie
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Nature. 2009 Apr 9;458(7239):746-9. doi: 10.1038/nature07877.
Low-temperature oxidation of CO, perhaps the most extensively studied reaction in the history of heterogeneous catalysis, is becoming increasingly important in the context of cleaning air and lowering automotive emissions. Hopcalite catalysts (mixtures of manganese and copper oxides) were originally developed for purifying air in submarines, but they are not especially active at ambient temperatures and are also deactivated by the presence of moisture. Noble metal catalysts, on the other hand, are water tolerant but usually require temperatures above 100 degrees C for efficient operation. Gold exhibits high activity at low temperatures and superior stability under moisture, but only when deposited in nanoparticulate form on base transition-metal oxides. The development of active and stable catalysts without noble metals for low-temperature CO oxidation under an ambient atmosphere remains a significant challenge. Here we report that tricobalt tetraoxide nanorods not only catalyse CO oxidation at temperatures as low as -77 degrees C but also remain stable in a moist stream of normal feed gas. High-resolution transmission electron microscopy demonstrates that the Co(3)O(4) nanorods predominantly expose their {110} planes, favouring the presence of active Co(3+) species at the surface. Kinetic analyses reveal that the turnover frequency associated with individual Co(3+) sites on the nanorods is similar to that of the conventional nanoparticles of this material, indicating that the significantly higher reaction rate that we have obtained with a nanorod morphology is probably due to the surface richness of active Co(3+) sites. These results show the importance of morphology control in the preparation of base transition-metal oxides as highly efficient oxidation catalysts.
一氧化碳的低温氧化或许是多相催化历史上研究最为广泛的反应,在净化空气和降低汽车排放的背景下正变得愈发重要。霍普卡利特催化剂(锰和铜氧化物的混合物)最初是为净化潜艇内空气而研发的,但它们在环境温度下活性并不特别高,而且会因水分的存在而失活。另一方面,贵金属催化剂耐水,但通常需要100摄氏度以上的温度才能高效运行。金在低温下表现出高活性,在有水分的情况下稳定性也较好,但只有以纳米颗粒形式沉积在碱性过渡金属氧化物上时才如此。开发在环境气氛下用于低温一氧化碳氧化的无贵金属活性和稳定催化剂仍然是一项重大挑战。在此我们报告,四氧化三钴纳米棒不仅能在低至 -77摄氏度的温度下催化一氧化碳氧化,而且在正常进料气的潮湿气流中仍保持稳定。高分辨率透射电子显微镜表明,Co(3)O(4)纳米棒主要暴露其{110}面,有利于表面存在活性Co(3+)物种。动力学分析表明,与纳米棒上单个Co(3+)位点相关的周转频率与这种材料的传统纳米颗粒相似,这表明我们通过纳米棒形态获得的显著更高的反应速率可能归因于活性Co(3+)位点的表面丰富性。这些结果表明了在制备作为高效氧化催化剂的碱性过渡金属氧化物时形态控制的重要性。