TY - JOUR
T1 - The Key Indicator for the Control of Metal Particle Sizes on Supports from First-Principles and Experimental Observation
AU - Nakao, Takuya
AU - Tada, Tomofumi
AU - Kitano, Masaaki
AU - Sasase, Masato
AU - Hosono, Hideo
N1 - Funding Information:
This study was supported by the Element strategy Initiative to Form Core Research Center of the Ministry of Education, Culture, Sports, Science and Technology of Japan and by the Japan Science and Technology Agency ACCEL program.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/9/29
Y1 - 2016/9/29
N2 - The size of metal particles is a key factor governing the catalytic performance of metal-supported catalysis, and revealing the essential factor controlling the size of metal particles on support materials is crucial for a new guideline in metal-supported catalysts. In this study, we found adsorption and migration energies of a single metal atom on supports are useful for the qualitative prediction of metal particle sizes on supports by means of the first-principles electronic structure calculations of Ru loaded Ca3N2, CaO, CaF2, and Ca2Si and transmission electron microscopy (TEM) measurements. The first-principles calculations revealed that the adsorption and migration energies of a Ru atom on Ca3N2 and Ca2Si are larger than those on CaO and CaF2 and that the energetic trend shows an excellent correspondence with the bond strengths of Ru anions. In accordance with the first-principles calculations, TEM measurements showed that Ru particles sizes on Ca3N2 and Ca2Si are much smaller than those on CaO and CaF2; the hemisphere-shaped particles on Ca3N2 and Ca2Si are smaller than 15 nm, whereas the needle-like particles on CaO and CaF2 are in the range from 10 to 100 nm. The theoretical and experimental results clearly indicate the presence of a correlation between the strength of Ru-anion chemical bonds and Ru particle sizes on supports, which will be a good indicator for metal particle size on supports.
AB - The size of metal particles is a key factor governing the catalytic performance of metal-supported catalysis, and revealing the essential factor controlling the size of metal particles on support materials is crucial for a new guideline in metal-supported catalysts. In this study, we found adsorption and migration energies of a single metal atom on supports are useful for the qualitative prediction of metal particle sizes on supports by means of the first-principles electronic structure calculations of Ru loaded Ca3N2, CaO, CaF2, and Ca2Si and transmission electron microscopy (TEM) measurements. The first-principles calculations revealed that the adsorption and migration energies of a Ru atom on Ca3N2 and Ca2Si are larger than those on CaO and CaF2 and that the energetic trend shows an excellent correspondence with the bond strengths of Ru anions. In accordance with the first-principles calculations, TEM measurements showed that Ru particles sizes on Ca3N2 and Ca2Si are much smaller than those on CaO and CaF2; the hemisphere-shaped particles on Ca3N2 and Ca2Si are smaller than 15 nm, whereas the needle-like particles on CaO and CaF2 are in the range from 10 to 100 nm. The theoretical and experimental results clearly indicate the presence of a correlation between the strength of Ru-anion chemical bonds and Ru particle sizes on supports, which will be a good indicator for metal particle size on supports.
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U2 - 10.1021/acs.jpcc.6b03400
DO - 10.1021/acs.jpcc.6b03400
M3 - Article
AN - SCOPUS:84989338123
SN - 1932-7447
VL - 120
SP - 21879
EP - 21887
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 38
ER -