Chloroform Hydrodechlorination on Palladium Surfaces: A Comparative DFT Study on Pd(111), Pd(100), and Pd(211)

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Palladium has been shown to be an effective catalyst for chloroform hydrodechlorination, which serves as a promising treatment method for industrial chloroform waste. To investigate the structure sensitivity of this chemistry on Pd surfaces, we performed a density functional theory (DFT, GGA-PW91) study of the chloroform hydrodechlorination reaction on three distinct facets: Pd(111), Pd(100), and Pd(211). Based on the DFT results, the binding strengths of most surface intermediates generally increase in the following order: Pd(111) < Pd(100) < Pd(211). On all three Pd facets, methane is formed as the preferred reaction product through a pathway in which CHCl3* is fully dechlorinated to CH* first, and then hydrogenated to CH4. We constructed potential energy diagrams (PED) and compared the reaction energetics for chloroform hydrodechlorination on the three Pd facets. We propose that the competition between the desorption of chloroform and its initial dechlorination to form CHCl2* likely determines the hydrodechlorination activity of the catalyst. On Pd(111), the desorption of chloroform is energetically favored over its dechlorination while the dechlorination barriers are lower than the desorption barriers on Pd(100) and Pd(211). On the other hand, Pd(100) and Pd(211) bind atomic chlorine stronger and also catalyze the formation of atomic carbon effectively; both are potential site-blocking species. Our results suggest that the more open facets and step edge sites of a Pd nanoparticle may carry higher intrinsic activity towards chloroform hydrodechlorination than the close-packed facets, yet these under-coordinated sites are more prone to catalyst poisoning.

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  1. 1.

    Goldberg ED (1991) Halogenated hydrocarbons: past, present and near-future problems. Sci Total Environ 100:17–28

  2. 2.

    Kuhn TK, Hamonts K, Dijk JA et al (2009) Assessment of the intrinsic bioremediation capacity of an eutrophic river sediment polluted by discharging chlorinated aliphatic hydrocarbons: a compound-specific isotope approach. Environ Sci Technol 43:5263–5269

  3. 3.

    Moran MJ, Zogorski JS, Squillace PJ (2007) Chlorinated solvents in groundwater of the United States. Environ Sci Technol 41:74–81

  4. 4.

    Kovalchuk VI, d’Itri JL (2004) Catalytic chemistry of chloro- and chlorofluorocarbon dehalogenation: from macroscopic observations to molecular level understanding. Appl Catal A Gen 271:13–25

  5. 5.

    Linstrom PJ, Mallard WG (2017) NIST Chemistry WebBook, NIST Standard Reference Database Number 69.

  6. 6.

    Hsieh S-H, Horng J-J (2006) Deposition of Fe–Ni nanoparticles on Al2O3 for dechlorination of chloroform and trichloroethylene. Appl Surf Sci 253:1660–1665

  7. 7.

    Wang X, Chen C, Chang Y, Liu H (2009) Dechlorination of chlorinated methanes by Pd/Fe bimetallic nanoparticles. J Hazard Mater 161:815–823

  8. 8.

    Shin E-J, Keane MA (1998) Gas phase catalytic hydrodechlorination of chlorophenols using a supported nickel catalyst. Appl Catal B Environ 18:241–250

  9. 9.

    Ordóñez S, Sastre H, Díez FV (2000) Hydrodechlorination of aliphatic organochlorinated compounds over commercial hydrogenation catalysts. Appl Catal B Environ 25:49–58

  10. 10.

    Álvarez-Montero MA, Gómez-Sainero LM, Mayoral A et al (2011) Hydrodechlorination of chloromethanes with a highly stable Pt on activated carbon catalyst. J Catal 279:389–396

  11. 11.

    Prati L, Rossi M (1999) Reductive catalytic dehalogenation of light chlorocarbons. Appl Catal B Environ 23:135–142

  12. 12.

    Gómez-Sainero L (2002) Liquid-phase hydrodechlorination of CCl4 to CHCl3 on Pd/carbon catalysts: nature and role of pd active species. J Catal 209:279–288

  13. 13.

    Mori T, Hirose K, Kikuchi T, Morikawa Y (2002) Formation of higher hydrocarbons from chloromethanes via hydrodechlorination over Pd/SiO2 catalyst. J Japan Pet Inst 45:256–259

  14. 14.

    Chen N, Rioux RM, Barbosa LAMM, Ribeiro FH (2010) Kinetic and theoretical study of the hydrodechlorination of CH(4-x)Cl(x) (x = 1–4) compounds on palladium. Langmuir 26:16615–16624

  15. 15.

    Velázquez JC, Leekumjorn S, Nguyen QX et al (2013) Chloroform hydrodechlorination behavior of alumina-supported Pd and PdAu catalysts. AIChE J 59:4474–4482

  16. 16.

    Xu L, Yao X, Khan A, Mavrikakis M (2016) Chloroform Hydrodechlorination over palladium-gold catalysts: a first-principles dft study. ChemCatChem 8:1739–1746

  17. 17.

    Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54:11169–11186

  18. 18.

    Kresse G, Furthmüller J (1996) Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mater Sci 6:15–50

  19. 19.

    Blöchl P (1994) Projector augmented-wave method. Phys Rev B 50:17953–17979

  20. 20.

    Kresse G, Joubert D (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59:1758–1775

  21. 21.

    Perdew JP, Wang Y (1992) Accurate and simple analytic representation of the electron-gas correlation energy. Phys Rev B 45:244–249

  22. 22.

    Haynes WM (2014) CRC handbook of chemistry and physics, 94th edn. Taylor and Francis Group, Boca Raton

  23. 23.

    Neugebauer J, Scheffler M (1992) Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al (111). Phys Rev B 46:16067–16080

  24. 24.

    Bengtsson L (1999) Dipole correction for surface supercell calculations. Phys Rev B 59:12301–12304

  25. 25.

    Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13:5188–5192

  26. 26.

    Henkelman G, Jónsson H (2000) Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J Chem Phys 113:9978–9985

  27. 27.

    Mavrikakis M, Stoltze P, Nørskov J (2000) Making gold less noble. Catal Lett 64:101–106

  28. 28.

    Peterson AA, Grabow LC, Brennan TP et al (2012) Finite-size effects in O and CO adsorption for the late transition metals. Top Catal 55:1276–1282

  29. 29.

    Bonarowska M, Malinowski A, Juszczyk W, Karpiński Z (2001) Hydrodechlorination of CCl2F2 (CFC-12) over silica-supported palladium–gold catalysts. Appl Catal B Environ 30:187–193

  30. 30.

    Van De Sandt EJAX, Wiersma A, Makkee M et al (1997) Palladium black as model catalyst in the hydrogenolysis of CCl2F2 (CFC-12) into CH2F2 (HFC-32). Appl Catal A Gen 155:59–73

  31. 31.

    Bonarowska M, Kaszkur Z, Łomot D et al (2015) Effect of gold on catalytic behavior of palladium catalysts in hydrodechlorination of tetrachloromethane. Appl Catal B Environ 162:45–56

  32. 32.

    Gokhale AA, Kandoi S, Greeley JP et al (2004) Molecular-level descriptions of surface chemistry in kinetic models using density functional theory. Chem Eng Sci 59:4679–4691

  33. 33.

    Cortright RD, Dumesic JA (2001) Kinetics of heterogeneous catalytic reactions: Analysis of reaction schemes. Adv Catal 46:161–264

  34. 34.

    Rangarajan S, Maravelias CT, Mavrikakis M (2017) Sequential-optimization-based framework for robust modeling and design of heterogeneous catalytic systems. J Phys Chem C 121:25847–25863

  35. 35.

    Xu L, Stangland EE, Mavrikakis M (2018) A DFT study of chlorine coverage over late transition metals and its implication on 1,2-dichloroethane hydrodechlorination. Catal Sci Technol 8:1555–1563

  36. 36.

    Ojeda M, Nabar R, Nilekar AU et al (2010) CO activation pathways and the mechanism of Fischer-Tropsch synthesis. J Catal 272:287–297

  37. 37.

    Grabow LC, Mavrikakis M (2011) Mechanism of methanol synthesis on cu through CO2 and CO hydrogenation. ACS Catal 1:365–384

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This work was supported by the U.S. Department of Energy (DOE)-Basic Energy Sciences (BES), Office of Chemical Sciences, under Grant No. DE‐FG02‐05ER15731. Part of the computational work was conducted using supercomputing resources from the following institutions: the National Energy Research Scientific Computing Center (NERSC) and the Center for Nanoscale Materials (CNM) at Argonne National Laboratory (ANL). CNM and NERSC are supported by the U.S. Department of Energy, Office of Science, under contracts DE‐AC02‐06CH11357 and DE‐AC02‐05CH11231, respectively. We thank Jake Gold, Tibor Szilvási, and Sean Tacey for their helpful comments on this article.

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Correspondence to Manos Mavrikakis.

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Xu, L., Bhandari, S., Chen, J. et al. Chloroform Hydrodechlorination on Palladium Surfaces: A Comparative DFT Study on Pd(111), Pd(100), and Pd(211). Top Catal (2020) doi:10.1007/s11244-019-01218-6

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  • Chloroform
  • Hydrodechlorination
  • Density functional theory
  • Palladium
  • Structure sensitivity