Probing the electronic effect of carbon nanotubes in catalysis: NH(3) synthesis with Ru nanoparticles.
Carbon nanotubes (CNTs) have been shown to modify some properties of nanomaterials and to modify chemical reactions confined inside their channels, which are formed by curved graphene layers. Here we studied ammonia synthesis over Ru as a probe reaction to understand the effect of the electron structure of CNTs on the confined metal particles and their catalytic activity. The catalyst with Ru nanoparticles dispersed almost exclusively on the exterior nanotube surface exhibits a higher activity than the CNT-confined Ru, although both have a similar metal particle size. Characterization with TEM, N(2) physisorption, H(2) chemisorption, temperature-programmed reduction, CO adsorption microcalorimetry, and first-principles calculations suggests that the outside Ru exhibits a higher electron density than the inside Ru. As a result, the dissociative adsorption of N(2), which is an electrophilic process and the rate-determining step of ammonia synthesis, is more facile over the outside Ru than that over the inside one.
Guo
Shujing
S
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Pan
Xiulian
X
Gao
Haili
H
Yang
Zhiqiang
Z
Zhao
Jijun
J
Bao
Xinhe
X