Oxidative carbonylation of glycerol to glycerol carbonate catalyzed by PdCl2(phen)/KI

被引：120

作者：

Hu, Jianglin ^{[1
]}

Li, Jinjin ^{[1
]}

Gu, Yanlong ^{[1
,2
]}

Guan, Zhenhong ^{[1
]}

Mo, Wanling ^{[1
]}

Ni, Youming ^{[1
]}

Li, Tao ^{[1
,2
]}

Li, Guangxing ^{[1
,2
]}

机构：

[1] Huazhong Univ Sci & Technol, Sch Chem & Chem Engn, Wuhan 430074, Hubei, Peoples R China

[2] Huazhong Univ Sci & Technol, Hubei Key Lab Mat Chem & Serv Failure, Wuhan 430074, Hubei, Peoples R China

来源：

APPLIED CATALYSIS A-GENERAL | 2010年 / 386卷 / 1-2期

关键词：

Oxidative carbonylation; Glycerol carbonate; PdCl2(phen)/KI; Valorize glycerol; Cyclic voltammetry; DIMETHYL CARBONATE; PALLADIUM COMPLEXES; EFFICIENT; CHEMICALS; DIOXIDE; TRANSESTERIFICATION; METHANOL; PERFORMANCE;

D O I：

10.1016/j.apcata.2010.07.059

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：

We present a direct and highly efficient approach for synthesizing glycerol carbonate, via the catalytic oxidative carbonylation of glycerol, using PdCl2(phen) (phen = 1,10-phenanthroline) as catalyst with the aid of RI. The palladium catalyst loading as low as 0.25 mol% is sufficient for high conversion (92%) and selectivity (99%) at the reaction condition: 2.0 MPa CO, 1.0 MPa O-2, 140 degrees C, 2h. The turnover frequency (TOF) reaches 184 h(-1). Furthermore, using crude glycerol, we achieved 85% conversion of glycerol. We discuss in detail a plausible mechanism based on PdI2(phen) as an intermediate. We propose that there is synergistic effect of l- and 1,10-phenanthroline on the performance of the Pd complex catalyst. Based on the cyclic voltammograms, the reduction of PdI2(phen) occurred at a more positive potential than that of PdCl2(phen). This may explain why the catalytic activity of PdI2(phen) was more effective than that of PdCl2(phen). (C) 2010 Elsevier B.V. All rights reserved.

引用

页码：188 / 193

页数：6

共 33 条

[1] ROLE AND EFFECTS OF HALIDE-IONS ON THE RATES AND MECHANISMS OF OXIDATIVE ADDITION OF IODOBENZENE TO LOW-LIGATED ZEROVALENT PALLADIUM COMPLEXES PD0(PPH3)2 [J].

AMATORE, C ;

AZZABI, M ;

JUTAND, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (22) :8375-8384

[2] Synthesis and solid state and solution characterization of mono- and Di-(η1-C) carbamoyl-palladium complexes.: New efficient palladium-catalyzed routes to carbamoyl chlorides:: Key intermediates to isocyanates, carbamic esters, and ureas [J].

Aresta, M ;

Gianneccaro, P ;

Tommasi, I ;

Dibenedetto, A ;

Lanfredi, AMM ;

Ugozzoli, F .

ORGANOMETALLICS, 2000, 19 (19) :3879-3889

[3] A study on the carboxylation of glycerol to glycerol carbonate with carbon dioxide: The role of the catalyst, solvent and reaction conditions [J].

Aresta, Michele ;

Dibenedetto, Angela ;

Nocito, Francesco ;

Pastore, Carlo .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2006, 257 (1-2) :149-153

[4] Influence of solid acids as co-catalysts on glycerol hydrogenolysis to propylene glycol over Ru/C catalysts [J].

Balaraju, M. ;

Rekha, V. ;

Prasad, P. S. Sai ;

Devi, B. L. A. Prabhavathi ;

Prasad, R. B. N. ;

Lingaiah, N. .

APPLIED CATALYSIS A-GENERAL, 2009, 354 (1-2) :82-87

[5] REDUCTIVE CARBONYLATION OF NITROAROMATIC COMPOUNDS TO URETHANES CATALYZED BY [PD(1,10-PHENANTHROLINE)2][PF6]2 AND RELATED COMPLEXES [J].

BONTEMPI, A ;

ALESSIO, E ;

CHANOS, G ;

MESTRONI, G .

JOURNAL OF MOLECULAR CATALYSIS, 1987, 42 (01) :67-80

[6] Chemicals from biomass: Synthesis of glycerol carbonate by transesterification and carbonylation with urea with hydrotalcite catalysts. The role of acid-base pairs [J].

Climent, Maria J. ;

Corma, Avelino ;

De Frutos, Pilar ;

Iborra, Sara ;

Noy, Maria ;

Velty, Alexandra ;

Concepcion, Patricia .

JOURNAL OF CATALYSIS, 2010, 269 (01) :140-149

[7] Palladium complexes anchored on silica functionalized by 1,2-diaminocyclohexane: Preparation and catalytic application [J].

Fan, Guozhi ;

Huang, Jiao ;

Li, Zhiqiang ;

Li, Tao ;

Li, Guangxing .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2007, 267 (1-2) :34-40

[8]

Franklin S., 1948, United States, Patent No. [US2446145A, 2446145]

[9] Oxidative Carbonylations [J].

Gabriele, Bartolo ;

Salerno, Giuseppe ;

Costa, Mirco .

CATALYTIC CARBONYLATION REACTIONS, 2006, 18 :239-272

[10] A novel and efficient method for the catalytic direct oxidative carbonylation of 1,2-and 1,3-diols to 5-membered and 6-membered cyclic carbonates [J].

Gabriele, Bartolo ;

Mancuso, Raffaella ;

Salerno, Giuseppe ;

Ruffolo, Giuseppe ;

Costa, Mirco ;

Dibenedetto, Angela .

TETRAHEDRON LETTERS, 2009, 50 (52) :7330-7332

← 1 2 3 4 →