Okumura Kazu, Sugihara Sou, Yasui Yoshinao, Sugiyama Ryota, Ahmed Abubaker, Abdullahi Anas
Department of Applied Chemistry, School of Advanced Engineering, Kogakuin University, 2665-1 Nakano-machi Hachioji-city, Tokyo 192-0015, Japan.
ACS Omega. 2025 Jul 4;10(27):29510-29521. doi: 10.1021/acsomega.5c02830. eCollection 2025 Jul 15.
Solvent-free catalyst synthesis provides significant environmental benefits and simplifies the synthesis process. In this study, we utilized the interaction between metal oxide and support to prepare highly dispersed and active Ru catalysts using a simple, solvent-free method. Bulk ruthenium dioxide was physically mixed with six kinds of solid oxide supports (AlO, SiO, TiO, tetragonal ZrO, monoclinic ZrO, and CeO), followed by thermal treatment in air at 773-1273 K. Ru K-edge X-ray absorption fine structure analysis of the treated samples showed that atomically dispersed Ru species were obtained at 973-1073 K when monoclinic ZrO and CeO were used as supports. In contrast, RuO remained aggregated when AlO, SiO, and tetragonal ZrO were used, and a Ru-TiO solid solution was formed at 1173-1273 K when TiO was employed. The catalysts were tested in benzyl alcohol oxidation, levulinic acid hydrodeoxygenation, and ammonia decomposition. Among the different supports examined, Ru supported on monoclinic ZrO and CeO demonstrated remarkably high activity in the reactions, leading to high yields of benzaldehyde, γ-valerolactone, and hydrogen; in contrast, Ru on AlO, SiO, TiO, and tetragonal ZrO were either less active or completely inactive in the reactions.
无溶剂催化剂合成具有显著的环境效益，并简化了合成过程。在本研究中，我们利用金属氧化物与载体之间的相互作用，采用一种简单的无溶剂方法制备了高度分散且活性高的钌催化剂。将块状二氧化钌与六种固体氧化物载体（AlO、SiO、TiO、四方ZrO、单斜ZrO和CeO）进行物理混合，然后在773 - 1273 K的空气中进行热处理。对处理后的样品进行Ru K边X射线吸收精细结构分析表明，当使用单斜ZrO和CeO作为载体时，在973 - 1073 K可获得原子分散的Ru物种。相比之下，当使用AlO、SiO和四方ZrO时，RuO仍保持聚集状态，而当使用TiO时，在1173 - 1273 K形成了Ru - TiO固溶体。对这些催化剂进行了苯甲醇氧化、乙酰丙酸加氢脱氧和氨分解反应测试。在所研究的不同载体中，负载在单斜ZrO和CeO上的Ru在反应中表现出非常高的活性，生成了高产率的苯甲醛、γ - 戊内酯和氢气；相比之下，负载在AlO、SiO、TiO和四方ZrO上的Ru在反应中活性较低或完全无活性。
