Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aoba 6-6-07, Aramaki, Aoba-ku, Sendai, Miyagi, 980-8579, Japan.
Research Center for Rare Metal and Green Innovation, Tohoku University, Aoba 468-1, Aramaki, Aoba-ku, Sendai, Miyagi, 980-0845, Japan.
ChemSusChem. 2022 May 20;15(10):e202102663. doi: 10.1002/cssc.202102663. Epub 2022 Mar 25.
Olefin production from polyols via deoxydehydration (DODH) was carried out over Ag-modified CeO -supported heterogeneous Re catalysts with H as a reducing agent. Both high DODH activity and low hydrogenation ability for C=C bonds were observed in the reaction of erythritol, giving a 1,3-butadiene yield of up to 90 % under "solvent-free" conditions. This catalyst is applicable to other substrates such as methyl glycosides (methyl α-fucopyranoside: 91 % yield of DODH product; methyl β-ribofuranoside: 88 % yield), which were difficult to be converted to the DODH products over the DODH catalysts reported previously. ReO -Ag/CeO was reused 3 times without a decrease of activity or selectivity after calcination as regeneration. Although the transmission electron microscopy energy-dispersive X-ray spectroscopy and X-ray absorption fine structure analyses showed that Re species were highly dispersed and Ag was present as metal particles with various sizes from well-dispersed species (<1 nm) to around 5 nm particles, the catalysts prepared from size-controlled Ag nanoparticles showed similar performance, indicating that the catalytic performance is insensitive to the Ag particle size.
通过脱氧脱水(DODH)反应,以 H 为还原剂,在 Ag 改性 CeO 负载的多相 Re 催化剂上,实现了多元醇制备烯烃。在赤藓糖醇的反应中,观察到高 DODH 活性和低 C=C 键加氢能力,在“无溶剂”条件下,1,3-丁二烯的产率高达 90%。该催化剂适用于其他底物,如甲基糖苷(甲基α-岩藻吡喃糖苷:DODH 产物的 91%收率;甲基β-呋喃核糖苷:88%收率),这些底物在以前报道的 DODH 催化剂上很难转化为 DODH 产物。ReO-Ag/CeO 在煅烧再生后重复使用 3 次,活性和选择性没有下降。尽管透射电子显微镜能量色散 X 射线光谱和 X 射线吸收精细结构分析表明,Re 物种高度分散,Ag 以各种尺寸的金属颗粒存在,从高度分散的颗粒(<1nm)到约 5nm 的颗粒,但由尺寸控制的 Ag 纳米颗粒制备的催化剂表现出相似的性能,表明催化性能对 Ag 颗粒尺寸不敏感。