Catalytic activity of noble metal nanoparticles toward hydrodechlorination： influence of catalyst electronic structure and nature of adsorption  

作　　者：Man ZHANG Feng HE Dongye ZHAO 

机构地区：[1]Department of Civil Engineering, Auburn University, Auburn, AL 36849, USA [2]College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310014, China

出　　处：《Frontiers of Environmental Science & Engineering》2015年第5期888-896,共9页环境科学与工程前沿（英文）

基　　金：This work was partially supported by the National Natural Science Foundation of China （Grant Nos. 51308312 and 41230638）.

摘　　要：In this study, stabilized Pd, Pt and Au nanoparticles were successfully prepared in aqueous phase using sodium carboxymethyl cellulose （CMC） as a capping agent. These metal nanoparticles were then tested for catalytic hydrodechlorination toward two classes of organochlorinated compounds （vinyl polychlorides includ- ing trichloroethylene （TCE）, tetrachloroethylene （PCE）, and alkyl polychlorides including 1,1,1-trichloroethane （1,1,1-TCA）, and 1,1,1,2-tetrachloroethane （1,1,1,2- TeCA）） to determine the rate-limiting steps and to explore the reaction mechanisms. The surface area normalized reaction rate constant, ksA, showed a systematic depen- dence on the electronic structure （the density of states at the Fermi level） of the metals, suggesting that adsorption of organochlorinated reactants on the metal catalyst surfaces is the rate-limiting step for catalytic hydrodechlorination. Hydrodechlorination rates of 1,1,1-TCA and 1,1,1,2-TeCA agreed with the bond strength of the first （weakest） dissociated C-C1 bond, suggesting that C-C1 bond cleavage, which is the first step for dissociative adsorption of the alkyl polychlorides, controlled the catalytic hydro- dechlorination rate. However, hydrodechlorination rates of TCE and PCE correlated with the adsorption energies of their molecular （non-dissociative） adsorption on the noble metals rather than with the first C-C1 bond strength, suggesting that molecular adsorption governs the reaction rate for hydrodechlorination of the vinyl polychlorides.In this study, stabilized Pd, Pt and Au nanoparticles were successfully prepared in aqueous phase using sodium carboxymethyl cellulose （CMC） as a capping agent. These metal nanoparticles were then tested for catalytic hydrodechlorination toward two classes of organochlorinated compounds （vinyl polychlorides includ- ing trichloroethylene （TCE）, tetrachloroethylene （PCE）, and alkyl polychlorides including 1,1,1-trichloroethane （1,1,1-TCA）, and 1,1,1,2-tetrachloroethane （1,1,1,2- TeCA）） to determine the rate-limiting steps and to explore the reaction mechanisms. The surface area normalized reaction rate constant, ksA, showed a systematic depen- dence on the electronic structure （the density of states at the Fermi level） of the metals, suggesting that adsorption of organochlorinated reactants on the metal catalyst surfaces is the rate-limiting step for catalytic hydrodechlorination. Hydrodechlorination rates of 1,1,1-TCA and 1,1,1,2-TeCA agreed with the bond strength of the first （weakest） dissociated C-C1 bond, suggesting that C-C1 bond cleavage, which is the first step for dissociative adsorption of the alkyl polychlorides, controlled the catalytic hydro- dechlorination rate. However, hydrodechlorination rates of TCE and PCE correlated with the adsorption energies of their molecular （non-dissociative） adsorption on the noble metals rather than with the first C-C1 bond strength, suggesting that molecular adsorption governs the reaction rate for hydrodechlorination of the vinyl polychlorides.

关 键 词：catalytic hydrodechlorination ELECTRONICSTRUCTURE metal nanoparticles reaction mechanisms 

分 类 号：O623.611[理学—有机化学] TB383[理学—化学]