Efficient Decarbonylation of Furfural to Furan Catalyzed by Zirconia-Supported Palladium Clusters with Low Atomicity.
Decarbonylation of furfural to furan was efficiently catalyzed by ZrO2-supported Pd clusters in the liquid phase under a N2atmosphere without additives. Although Pd/C and Pd/Al2O3have frequently been used for decarbonylation, Pd/ZrO2exhibited superior catalytic performance compared with these conventional catalysts. Transmission electron microscopy and X-ray absorption fine structure measurements revealed that the size of the Pd particles decreased with an increase in the specific surface area of ZrO2. ZrO2with a high surface area immobilized Pd as clusters consisting of several (three to five) Pd atoms, whereas Pd aggregated to form nanoparticles on other supports such as carbon and Al2O3despite their high surface areas. The catalytic activity of Pd/ZrO2was enhanced with a decrease in particle size, and the smallest Pd/ZrO2was the most active catalyst for decarbonylation. When CeO2was used as the support, a decrease in Pd particle size with an increase in surface area was also observed. Single Pd atoms were deposited on CeO2with a high surface area, with a strong interaction through the formation of a Pd-O-Ce bond, which led to a lower catalytic activity than that of Pd/ZrO2. This result suggests that zero-valent small Pd clusters consisting of more than one Pd atom are the active species for the decarbonylation reaction. Recycling tests proved that Pd/ZrO2maintained its catalytic activity until its sixth use.
Department of Chemistry, Graduate School of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.|Research Center for Gold Chemistry, Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo, 192-0397, Japan.
Tamao
T
Ishida
Department of Chemistry, Graduate School of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Kurumi
K
Kume
Department of Chemistry, Graduate School of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Kota
K
Kinjo
Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, 1-1-1 Kouto, Sayo, Hyogo, 679-5198, Japan.
Tetsuo
T
Honma
Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, 1-1-1 Kouto, Sayo, Hyogo, 679-5198, Japan.
Kengo
K
Nakada
Division of Environment System Management, Faculty of Symbiotic Systems Science, Fukushima University, 1 Kanayagawa, Fukushima, 960-1296, Japan.
Hironori
H
Ohashi
Department of Chemistry, Graduate School of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Takushi
T
Yokoyama
Department of Chemistry, Graduate School of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Akiyuki
A
Hamasaki
Department of Chemistry, Graduate School of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Haruno
H
Murayama
Mitsubishi Chemical Corporation Yokkaichi Plant, 1 Toho-cho, Yokkaichi, Mie, 510-8530, Japan.
Yusuke
Y
Izawa
Mitsubishi Chemical Corporation, 1-1 Marunouchi 1-chome, Chiyoda-ku, Tokyo, 100-8251, Japan.
Masaru
M
Utsunomiya
Department of Chemistry, Graduate School of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.|International Research Center for Molecular Systems (IRCMS), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Makoto
http://orcid.org/0000-0003-1032-3199
M
Tokunaga
D000537:Aluminum Oxide / Q000737:chemistry; D002384:Catalysis; D002563:Cerium / Q000737:chemistry; D005662:Furaldehyde / Q000737:chemistry*; D005663:Furans / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D015040:Zirconium / Q000737:chemistry*
D005663:Furans; D002563:Cerium; D010165:Palladium; C030583:ceric oxide; D015040:Zirconium; D005662:Furaldehyde; D000537:Aluminum Oxide; C028541:zirconium oxide; C039281:furan
XAFS; aldehyde; decarbonylation; furfural; palladium