Catalytic behavior of size-controlled palladium nanoparticles in the hydrodechlorination of 4-chlorophenol in aqueous phase

被引:106
作者
Baeza, J. A. [1 ]
Calvo, L. [1 ]
Gilarranz, M. A. [1 ]
Mohedano, A. F. [1 ]
Casas, J. A. [1 ]
Rodriguez, J. J. [1 ]
机构
[1] Univ Autonoma Madrid, Secc Dept Ingn Quim, E-28049 Madrid, Spain
关键词
Colloidal nanoparticles; Palladium; Particle size; Hydrodechlorination; 4-Chlorophenol; SUPPORTED NICKEL-CATALYSTS; PD NANOPARTICLES; PARTICLE-SIZE; CHLOROPHENOLS; WATER; CHLOROBENZENE; SURFACE; 2,4-DICHLOROPHENOL; HECK; HYDRODEHALOGENATION;
D O I
10.1016/j.jcat.2012.06.009
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
Unsupported Pd nanoparticles of controlled size were tested as catalyst in liquid-phase hydrodechlorination (303-323 K, 1 atm) using 4-chlorophenol (4-CP) as target compound. The Pd nanoparticles were synthesized by chemical reduction, using ethanol and methanol as reducing agents and poly(N-vinyl-2-pyrrolidone) (PVP) as capping agent. The size of the nanoparticles and the Pdn+/Pd-0 ratio decreased with increasing alcohol concentration and PVP/Pd ratio, both being lower for ethanol medium. High 4-CP conversion values (80-100%) were achieved at low Pd concentration (2.45 x 10(-3) g/ L). Phenol was the only reaction by-product detected in contrast to the previous results with supported Pd catalysts, where the active phase-support interaction in 4-CP HDC led to obtain also cyclohexanone and cyclohexanol as by-products in equivalent experimental conditions. The smaller nanoparticles showed higher activity due to the higher available surface (m(2)/g(cat)). Thus, the smaller nanoparticles synthesized in ethanol medium ranged between 2.7 and 2.8 rim and yielded activity values between 16.7 and 39.1 mmol/g(cat) min, whereas the smaller particles obtained in methanol medium were in the 3.1-4.2 nm range and exhibited activity values of 20.1-25.7 mmol/g(cat) min. However, the large nanoparticles exhibited higher activity per unit of catalyst surface, for example, 0.34-0.43 mmol/min m(2) in the case of those synthesized in methanol medium. On the other hand, higher activity was observed for the nanoparticles synthesized in methanol medium when equivalent nanoparticle size was compared. Activation energy Values around 100 kJ/mol were obtained for Pd nanoparticles of different characteristics, significantly higher than the value reported for supported Pd catalysts. (C) 2012 Elsevier Inc. All rights reserved.
引用
收藏
页码:85 / 93
页数:9
相关论文
共 76 条
[1]  
Alonso F., 2003, CHEMINFORM, V34
[2]   Hydrodechlorination of chloromethanes with Pd on activated carbon catalysts for the treatment of residual gas streams [J].
Alvarez-Montero, M. A. ;
Gomez-Sainero, L. M. ;
Martin-Martinez, M. ;
Heras, F. ;
Rodriguez, J. J. .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2010, 96 (1-2) :148-156
[3]   Influence of the reaction conditions and catalytic properties on the liquid-phase hydrodebromination of bromobenzene over palladium supported catalysts:: activity and deactivation [J].
Aramendía, MA ;
Boráu, V ;
García, IM ;
Jiménez, C ;
Marinas, JM ;
Urbano, FJ .
APPLIED CATALYSIS B-ENVIRONMENTAL, 1999, 20 (02) :101-110
[4]   Influence of the reaction conditions and catalytic properties on the liquid-phase hydrodechlorination of chlorobenzene over palladium-supported catalysts:: Activity and deactivation [J].
Aramendía, MA ;
Boráu, V ;
García, IM ;
Jiménez, C ;
Lafont, F ;
Marinas, A ;
Marinas, JM ;
Urbano, FJ .
JOURNAL OF CATALYSIS, 1999, 187 (02) :392-399
[5]   Synthesis and characterization of Rh(PVP) nanoparticles studied by XPS and NEXAFS [J].
Ashida, T. ;
Miura, K. ;
Nomoto, T. ;
Yagi, S. ;
Sumida, H. ;
Kutluk, G. ;
Soda, K. ;
Namatame, H. ;
Taniguchi, M. .
SURFACE SCIENCE, 2007, 601 (18) :3898-3901
[6]   Liquid-phase hydrodechlorination of CCl4 in a medium of acetal and diethyl carbonate [J].
Bae, JW ;
Jang, EJ ;
Jo, DH ;
Lee, JS ;
Lee, KH .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2003, 206 (1-2) :225-238
[7]   Hydrodechlorination of CCl4 over Pt/Al2O3:: effects of platinum particle size on product distribution [J].
Bae, JW ;
Kim, IG ;
Lee, JS ;
Lee, KH ;
Jang, EJ .
APPLIED CATALYSIS A-GENERAL, 2003, 240 (1-2) :129-142
[8]   Kinetics and particle size effects in ethene hydrogenation over supported palladium catalysts at atmospheric pressure [J].
Binder, Axel ;
Seipenbusch, Martin ;
Muhler, Martin ;
Kasper, Gerhard .
JOURNAL OF CATALYSIS, 2009, 268 (01) :150-155
[9]   Hydrodechlorination of tetrachloromethane on alumina- and silica-supported platinum catalysts [J].
Bonarowska, Magdalena ;
Kaszkur, Zbigniew ;
Kepinski, Leszek ;
Karpinski, Zbigniew .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2010, 99 (1-2) :248-256
[10]   Conversion of chlorophenols into cyclohexane by a recyclable Pd-Rh catalyst [J].
Bovkun, TT ;
Sasson, Y ;
Blum, J .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2005, 242 (1-2) :68-73