Selectivity Control in Palladium-Catalyzed Alcohol Oxidation through Selective Blocking of Active Sites

被引：57
作者：
Campisi, Sebastiano [1 ]
Ferri, Davide [2 ]
Villa, Alberto [1 ]
Wang, Wu [3 ]
Wang, Di [3 ,4 ]
Krocher, Oliver [2 ,5 ]
Prati, Laura [1 ]
机构：
[1] Univ Milan, Dipartimento Chim, Via Golgi 19, I-20133 Milan, Italy
[2] Paul Scherrer Inst, CH-5232 Villigen, Switzerland
[3] Karlsruhe Inst Technol, Inst Nanotechnol, Hermann von Helmholtz Pl 1, D-76344 Eggenstein Leopoldshafen, Germany
[4] Karlsruhe Inst Technol, Karlsruhe Nano Micro Facil, Hermann von Helmholtz Pl 1, D-76344 Eggenstein Leopoldshafen, Germany
[5] Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn, CH-1015 Lausanne, Switzerland
来源：
JOURNAL OF PHYSICAL CHEMISTRY C | 2016年 / 120卷 / 26期
关键词：
LIQUID-PHASE OXIDATION; SUPPORTED METAL NANOPARTICLES; SELF-ASSEMBLED MONOLAYERS; BENZYL ALCOHOL; GOLD NANOPARTICLES; CAPPING AGENTS; ATR-IR; PD/AL2O3; SPECTROSCOPY; ALDEHYDES;
D O I：
10.1021/acs.jpcc.6b01549
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
Stabilized metal nanoparticles (NPs) have received wide interest in a number of liquid-phase catalytic transformations, but the role of the capping/protective agent is still debated. Operando attenuated total reflection infrared (ATR-IR) spectroscopy enabled us to obtain unprecedented molecular level insights into the selectivity issue induced by the presence of the protective agent by following the liquid-phase benzyl alcohol oxidation on Pd/Al2O3. Supported Pd NPs protected by poly(vinyl alcohol) (PVA) showed a lower rate of benzaldehyde decarbonylation compared to unprotected Pd nanoparticles and, as a result, an improved selectivity toward the aldehyde. In addition, also the further oxidation of benzaldehyde to benzoic acid was reduced by the presence of PVA. In combination with considerations on adsorption site occupancy from CO adsorption, we ascribed this behavior to a selective blocking operated by PVA especially of Pd(111) facets, which are active in the decarbonylation process of benzaldehyde during benzyl alcohol dehydrogenation.
引用
收藏
页码：14027 / 14033
页数：7
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