Please wait a minute...

Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2015, Vol. 9 Issue (5) : 888-896
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
Download: PDF(638 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

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.
E-mail this article
E-mail Alert
Articles by authors
Feng HE
Dongye ZHAO
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.
1 Lowry  G V, Reinhard  M. Hydrodehalogenation of 1-to 3-carbon halogenated organic compounds in water using a palladium catalyst and hydrogen gas. Environmental Science & Technology, 1999, 33(11): 1905–1910
2 Chen  N, Rioux  R M, Ribeiro  F H. Investigation of reaction steps for the hydrodechlorination of chlorine-containing organic compounds on Pd catalysts. Journal of Catalysis, 2002, 211(1): 192–197
3 Mackenzie  K, Frenzel  H, Kopinke  F D. Hydrodehalogenation of halogenated hydrocarbons in water with Pd catalysts: Reaction rates and surface competition. Applied Catalysis B: Environmental, 2006, 63(3–4): 161–167
4 Ordonez  S, Sastre  H, Diez  F V. Hydrodechlorination of aliphatic organochlorinated compounds over commercial hydrogenation catalysts.  Applied  Catalysis  B:  Environmental,  2000,  25(1): 49–58
5 Bae  J W, Kim  I G, Lee  J S, Lee  K H, Jang  E J. Hydrodechlorination of CCl4 over Pt/Al2O3: effects of platinum particle size on product distribution. Applied Catalysis A, General, 2003, 240(1–2): 129–142
6 Hashimoto  Y, Uemichi  Y, Ayame  A. Low-temperature hydrodechlorination mechanism of chlorobenzenes over platinum-supported and palladium-supported alumina catalysts. Applied Catalysis A, General, 2005, 287(1): 89–97
7 Andersin  J, Honkala  K. First principles investigations of Pd-on-Au nanostructures for trichloroethene catalytic removal from groundwater. Physical Chemistry Chemical Physics, 2011, 13(4): 1386–1394 pmid: 21152633
8 Cwiertny  D M, Bransfield  S J, Roberts  A L. Influence of the oxidizing species on the reactivity of iron-based Bimetallic reductants. Environmental Science & Technology, 2007, 41(10): 3734–3740 pmid: 17547205
9 Gomez-Sainero  L M, Cortes  A, Seoane  X L, Arcoya  A. Hydrodechlorination of carbon tetrachloride to chloroform in the liquid phase with metal-supported catalysts. Effect of the catalyst components. Industrial & Engineering Chemistry Research, 2000, 39(8): 2849–2854
10 He  F, Liu  J, Roberts  C B, Zhao  D. One-step “green” synthesis of Pd nanoparticles of controlled size and their catalytic activity for trichloroethene hydrodechlorination. Industrial & Engineering Chemistry Research, 2009, 48(14): 6550–6557
11 Liu  J, He  F, Durham  E, Zhao  D, Roberts  C B. Polysugar-stabilized Pd nanoparticles exhibiting high catalytic activities for hydrodechlorination of environmentally deleterious trichloroethylene. Langmuir, 2008, 24(1): 328–336 pmid: 18044944
12 Bacik  D B, Zhang  M, Zhao  D, Roberts  C B, Seehra  M S, Singh  V, Shah  N. Synthesis and characterization of supported polysugar-stabilized palladium nanoparticle catalysts for enhanced hydrodechlorination of trichloroethylene. Nanotechnology, 2012, 23(29): 294004–294016 pmid: 22743584
13 Zhang  M, Bacik  D B, Roberts  C B, Zhao  D. Catalytic hydrodechlorination of trichloroethylene in water with supported CMC-stabilized palladium nanoparticles. Water Research, 2013, 47(11): 3706–3715 pmid: 23726707
14 He  F, Zhao  D. Preparation and characterization of a new class of starch-stabilized bimetallic nanoparticles for degradation of chlorinated hydrocarbons in water. Environmental Science & Technology, 2005, 39(9): 3314–3320 pmid: 15926584
15 Agency for Toxic Substances & Disease Registry (ATSDR). Trichloroethylene toxicity., accessed date 2014/<month>12</month>/<day>23</day>
16 Heck  K N, Janesko  B G, Scuseria  G E, Halas  N J, Wong  M S. Observing metal-catalyzed chemical reactions in situ using surface-enhanced Raman spectroscopy on Pd-Au nanoshells. Journal of the American Chemical Society, 2008, 130(49): 16592–16600 pmid: 19554693
17 Cwiertny  D M, Bransfield  S J, Livi  K J T, Fairbrother  D H, Robertst  A L. Exploring the influence of granular iron additives on 1,1,1-trichloroethane reduction. Environmental Science & Technology, 2006, 40(21): 6837–6843 pmid: 17144319
18 Gallaghe  P T, Oates  W A. Partial excess entropies of hydrogen in metals. Transactions of the Metallurgical Society of AIME, 1969, 245(1): 179–182
19 McLellan  R, Oates  W. The solubility of hydrogen in rhodium, ruthenium, iridium and nickel. Acta Metallurgica, 1973, 21(3): 181–185
20 Arcoya  A, Cortes  A, Fierro  J L G, Seoane  X L. Comparative study of the deactivation of group-VIII metal catalysts by thiophene poisoning in ethylbenzene hydrogenation. Studies in Surface Science and Catalysis, 1991, 68, 557–564
21 Phuong  T T, Massardier  J, Gallezot  P. Competitive hydrogenation of benzene and toluene on group-VIII metals- correlation with the electronic-structure. Journal of Catalysis, 1986, 102(2): 456–459
22 Cox  P A. The electronic structure and chemistry of solids. New York: Oxford University Press, 1987
23 Albert  H J, Rubin  L R. Magnetic properties of the platinum metals and their alloys. Platinum Group Metals and Compounds. Washington, DC: American Chemical Society, 1971
24 Garber  M, Henry  W G, Hoeve  H G. A magnetic susceptibility balance and the temperature dependence of the magnetic susceptibility of copper, silver, and gold. Canadian Journal of Physics, 1960, 38(12): 1595–1613
25 Weiss  A H, Gambhir  B S, Leon  R B. Hydrodechlorination of carbon tetrachloride. Journal of Catalysis, 1971, 22(2): 245–254
26 Gonzalez  C A, Montes de Correa  C. Catalytic hydrodechlorination of tetrachloroethylene over Pd/TiO2 minimonoliths. Industrial & Engineering Chemistry Research, 2010, 49(2): 490–497
27 Thompson  C D, Rioux  R M, Chen  N, Ribeiro  F H. Turnover rate, reaction order, and elementary steps for the hydrodechlorination of chlorofluorocarbon compounds on palladium catalysts. Journal of Physical Chemistry B, 2000, 104(14): 3067–3077
28 Lee  A F, Carr  P, Wilson  K. Direct observation of extremely low temperature catalytic dehydrochlorination of 1,1,1-trichloroethane over platinum. Journal of Physical Chemistry B, 2004, 108(39): 14811–14814
29 Yang  M X, Sarkar  S, Bent  B E, Bare  S R, Holbrook  M T. Degradation of multiply-chlorinated hydrocarbons on Cu(100). Langmuir, 1997, 13(2): 229–242
30 Barbosa  L, Sautet  P. Trichloroethene dechlorination reactions on the PdCu(110) alloy surface: A periodical density functional theory study of the mechanism. Journal of Catalysis, 2002, 207(1): 127–138
Full text