Sol-gel entrapped Au0- and Ag0 -nanoparticles catalyze reductive de-halogenation of halo-organic compounds by BH4-

被引：30

作者：

Adhikary, Jaydeep ^{[1
]}

Meyerstein, Dan ^{[1
,2
]}

Marks, Vered ^{[1
]}

Meistelman, Michael ^{[3
]}

Gershinsky, Gregory ^{[4
]}

Burg, Ariela ^{[5
]}

Shamir, Dror ^{[6
]}

Kornweitz, Haya ^{[1
]}

Albo, Yael ^{[3
]}

机构：

[1] Ariel Univ, Dept Chem Sci, Ariel, Israel

[2] Ben Gurion Univ Negev, Dept Chem, Beer Sheva, Israel

[3] Ariel Univ, Chem Engn Biotechnol & Mat Dept, Ariel, Israel

[4] Bar Ilan Univ, Inst Nanotechnol & Adv Mat, Ramat Gan, Israel

[5] Sami Sharmoon Coll Engn, Dept Chem Engn, Beer Sheva, Israel

[6] Nucl Res Ctr Negev, Dept Chem, Beer Sheva, Israel

来源：

APPLIED CATALYSIS B-ENVIRONMENTAL | 2018年 / 239卷

关键词：

Sol-gel; Silica matrix; Gold and silver nanoparticles; Dehalogenation; Mechanistic study; PRESSURE PULSE-RADIOLYSIS; DISINFECTION BY-PRODUCTS; CARBON SIGMA-BONDS; SILVER NANOPARTICLES; TRICHLOROACETIC-ACID; METHYL RADICALS; GOLD NANOPARTICLES; CHLOROACETIC ACIDS; HALOACETIC ACIDS; ELECTROCATALYTIC DECHLORINATION;

D O I：

10.1016/j.apcatb.2018.08.040

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：

This study investigated the reductive de-halogenations of toxic Br3CCO2-, Br2CHCO2-, BrCH2CO2-, CH3CHBrCO2-, CH2BiCH2CO2-, CH2BrCHBrCO2-, CI3CCO2-, Cl2CHCO2- and C1CH2CO2- by sodium borohydride catalyzed by sol-gel silica entrapped Au-0 and Ag-0 nanoparticles. The results indicate that the mechanism of reduction of Br3CCO2- differs from that of Cl3CCO2-. Calculated by DFT, the source of this difference lies in the larger bond strength of C-Cl compared to that of C-Br and the weaker M-0-C bond strength in Au-0-CBr2CO2- compared to those of Au-0-CCl2CO2- and Au-0-CH2CO2-. Furthermore, the de-halogenation mechanisms catalyzed by Ag-0-NPs differ from those catalyzed by Au-0-NPs. The latter observation is attributed to the different Ag-C and Au-C bond strengths and to the different over-potentials for H-2 release of these M-0-NPs. In addition, product composition depends on the rate of BH4- addition. Proton labeling experiments prove that nearly all the hydrogen atoms in the products originated from the water solvent and not from the BH4-. The detailed mechanistic conclusions that can be drawn from these results differ considerably from those commonly accepted for de-halogenation processes.

引用

页码：450 / 462

页数：13

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