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

doi:10.1007/s11783-015-0774-1

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, k_SA, 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:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-015-0774-1
https://academic.hep.com.cn/fese/EN/Y2015/V9/I5/888

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)	α_s/(m²?g⁻¹)	$Δ H H ∞$ /(kcal/ atomic H)	χ/cgs	k_SA/(L?min⁻¹?m⁻²)
metal NP	D/nm	ρ/(kg?m⁻³)	α_s/(m²?g⁻¹)	$Δ H H ∞$ /(kcal/ atomic H)	χ/cgs	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 k_SA 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 k_SA 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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