A Pd/Monolayer Titanate Nanosheet with Surface Synergetic Effects for Precise Synthesis of Cyclohexanones

作者：Son, Yujie; Wang, Hao; Gao, Xiaomei; Feng, Yingxin; Liang, Shijing^*; Bi, Jinhong; Lin, Sen^*; Fu, Xianzhi; Wu, Ling^*

来源：ACS Catalysis, 2017, 7(12): 8664-8674.

DOI：10.1021/acscatal.7b03463

• monolayer titanate nanosheet
• hydrogenation of phenol
• precision synthesis
• green photocatalysis

A catalyst composed of monolayer nonstoichiometric titanate nanosheets (denoted as TN) and Pd clusters is constructed for precise synthesis of cyclohexanone from phenol hydrogenation with high conversion (>99%) and selectivity (>99%) in aqueous media under light irradiation. Experimental and DFT calculation results reveal that the surface exposed acid and basic sites on TN could interact with phenol molecules in a nonplanar fashion via a hexahydroxy hydrogen-bonding ring to form a surface coordination species. This greatly facilitates the adsorption and activation of phenol molecules and suppresses the further hydrogenation of cyclohexanone. Moreover, the surface Pd clusters serve as the active sites for the adsorption and dissociation of hydrogen molecules to provide active H atoms. The synergistic effect of the surface coordination species, TN and Pd clusters remarkably facilitate the high yield of cyclohexanone in photocatalysis. Finally, the possible thermo/photocatalytic mechanisms on Pd/TN are proposed. This work not only highlights the great potential for monolayer nonstoichiometric composition nanosheets in the construction of catalysts for precise organic synthesis but also provides insight into the inherent catalytic behavior at a molecular level.

• 出版日期2017-12
• 单位福州大学