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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2015, Vol. 9 Issue (5) : 888-896     https://doi.org/10.1007/s11783-015-0774-1
RESEARCH ARTICLE
Catalytic activity of noble metal nanoparticles toward hydrodechlorination: influence of catalyst electronic structure and nature of adsorption
Man ZHANG1,Feng HE2,*(),Dongye ZHAO1,*()
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
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Abstract

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 including 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 dependence 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-Cl bond, suggesting that C-Cl bond cleavage, which is the first step for dissociative adsorption of the alkyl polychlorides, controlled the catalytic hydrodechlorination 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-Cl bond strength, suggesting that molecular adsorption governs the reaction rate for hydrodechlorination of the vinyl polychlorides.

Keywords catalytic hydrodechlorination      electronic structure      metal nanoparticles      reaction mechanisms     
Corresponding Author(s): Feng HE,Dongye ZHAO   
Online First Date: 10 February 2015    Issue Date: 08 October 2015
 Cite this article:   
Man ZHANG,Feng HE,Dongye ZHAO. Catalytic activity of noble metal nanoparticles toward hydrodechlorination: influence of catalyst electronic structure and nature of adsorption[J]. Front. Environ. Sci. Eng., 2015, 9(5): 888-896.
 URL:  
http://journal.hep.com.cn/fese/EN/10.1007/s11783-015-0774-1
http://journal.hep.com.cn/fese/EN/Y2015/V9/I5/888
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Man ZHANG
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Fig.1  Scheme 1 Molecular structures of TCE, PCE, 1,1,1-TCA and 1,1,1,2-TeCA
metal NP D/nm ρ/(kg?m−3) αs/(m2?g−1) Δ H H /(kcal/ atomic H) χ/cgs kSA/(L?min−1?m−2)
TCE PCE 1,1,1-TCA 1,1,1,2-TeCA
Pd 2.4±0.5 12,023 207.9 −2.39 5.23 × 10−6 3.5 1.5 0.06 0.95
Pt 3.9±0.5 21,450 71.7 + 18.7 9.71 × 10−7 2.4 0.22 0.005 0.11
Au 3.1±0.9 19,320 100.2 + 8.61 1.43 × 10−7 0.07 0.01 0.003 0.03
Tab.1  Physical parameters of the metal nanoparticles (NPs) and their pseudo-first-order reaction rate constants
Fig.2  TEM images of (a) Pt nanoparticles, and (b) Au nanoparticles stabilized using 0.15 wt.% CMC in the aqueous phase
Fig.3  Catalytic hydrodechlorination kinetics of TCE (a), PCE (b), 1,1,1-TCA (c) and 1,1,1,2-TeCA (d). Lines represent pseudo-first-order model simulations except controls. Reaction conditions: Initial contaminant concentration= 50 mg?L−1, catalyst dosage= 0.01 mmol?L−1. Data plotted as mean of duplicates, error bars indicate standard deviation from the mean
Fig.4  (a) log kSA for TCE, PCE, 1,1,1-TCA and 1,1,1,2-TeCA versus the Δ H H of Pd, Au and Pt (from left to right in the plots). Lines are interpolated (not fitted) to visual convenience; (b) Correlation between log kSA and log χ of Au, Pt and Pd (from left to right in the plots). Lines represent least-squares linear regression fits to the experimental data.
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