A Pd/Monolayer Titanate Nanosheet with Surface Synergetic Effects for Precise Synthesis of Cyclohexanones
A Pd/Monolayer Titanate Nanosheet with Surface Synergetic Effects for Precise Synthesis of Cyclohexanones
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具有表面协同效应的 Pd/单层钛酸盐纳米片用于环己酮的精确合成
DOI：
10.1021/acscatal.7b03463
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发表时间：
2017
期刊：
影响因子：
12.9
通讯作者：
Wu Ling
中科院分区：
文献类型：
--
作者：
Son Yujie;Wang Hao;Gao Xiaomei;Feng Yingxin;Liang Shijing;Bi Jinhong;Lin Sen;Fu Xianzhi;Wu Ling
构建了一种由单层非化学计量比的钛酸盐纳米片（TN）和钯簇组成的催化剂，用于在水相光催化下苯酚加氢精确合成环己酮，具有较高的转化率（>99%）和选择性（>99%）。实验和密度泛函理论计算结果表明，TN表面暴露的酸和碱位点可以通过六羟基氢键环与苯酚分子以非平面方式相互作用，形成表面配位物种.这极大地促进了苯酚分子的吸附和活化，并抑制了环己酮的进一步氢化。此外，表面Pd团簇作为吸附和解离氢分子以提供活性H原子的活性位点。表面配位物种、TN和Pd簇合物的协同作用显著促进了环己酮的高产率。最后，对Pd/TN的热/光催化机理进行了初步探讨。
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 propo...