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Functional Pd/reduced graphene oxide nanocomposites: effect of reduction degree and doping in hydrodechlorination catalytic activity

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Abstract

Pd catalysts supported on carbon have interesting features for chlorophenols-bearing water treatment by hydrodechlorination, including high stability, activity, and tunable support. In this work, a set of materials based on reduced graphene oxide (rGO) with different degrees of reduction, surface oxygen groups, nitrogen doping, and specific surface area were decorated with Pd nanoparticles, with diameter average size between 5 and 50 nm. Ethanol, hydrazine monohydrate, and sodium borohydride were used as reducing agents, and Pd(AcO)2 was used as a Pd precursor to obtain Pd/rGO nanocomposites in our developed one-pot synthesis approach. A thorough characterization revealed that a similar degree of reduction was obtained for sodium borohydride at 25 °C and hydrazine at 60 °C, although hydrazine also led to nitrogen doping. Pd nanoparticles were homogenously nucleated on the surface of the GO and the obtained nanocomposites were tested as catalysts for hydrodechlorination of 4-chlorophenol in the aqueous phase. The materials with a higher degree of reduction showed the best specific catalytic activity at 70 °C. However, the turnover frequency (TOF) only increased with the reduction degree for the N-doped Pd/rGO, indicating the important role of the nitrogenous functionalities in the catalytic activity. Therefore, the N doping of Pd/rGO catalysts is a feasible strategy to synthesize catalysts highly active for hydrodechlorination.

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References

  • Alonso-Morales N, Ruiz-Garcia C, Palomar J, Heras F, Calvo L, Rodriguez JJ, Gilarranz MA (2017) Hollow nitrogen- or boron-doped carbon submicrospheres with a porous shell: preparation and application as supports for hydrodechlorination catalysts. Ind Eng Chem Res 56:7665–7674

    CAS  Google Scholar 

  • Arrigo R, Schuster ME, Xie ZL, Yi YM, Wowsnick G, Sun LL, Hermann KE, Friedrich M, Kast P, Havecker M, Knop-Gericke A, Schlogl R (2015) Nature of the N-Pd interaction in nitrogen-doped carbon nanotube catalysts. ACS Catal 5:2740–2753

    CAS  Google Scholar 

  • Baeza JA, Calvo L, Gilarranz MA, Mohedano AF, Casas JA, Rodriguez JJ (2012) Catalytic behavior of size-controlled palladium nanoparticles in the hydrodechlorination of 4-chlorophenol in aqueous phase. J Catal 293:85–93

    CAS  Google Scholar 

  • Baeza JA, Alonso-Morales N, Calvo L, Heras F, Rodriguez JJ, Gilarranz MA (2015) Hydrodechlorination activity of catalysts based on nitrogen-doped carbons from low-density polyethylene. Carbon 87:444–452

    CAS  Google Scholar 

  • Bokobza L, Bruneel J-L, Couzi M (2014) Raman spectroscopy as a tool for the analysis of carbon-based materials (highly oriented pyrolitic graphite, multilayer graphene and multiwall carbon nanotubes) and of some of their elastomeric composites. Vib Spectrosc 74:57–63

    CAS  Google Scholar 

  • Calvo L, Gilarranz MA, Casas JA, Mohedano AF, Rodríguez JJ (2009) Hydrodechlorination of 4-chlorophenol in water with formic acid using a Pd/activated carbon catalyst. J Hazard Mater 161:842–847

    CAS  Google Scholar 

  • Chiou J-R, Lai B-H, Hsu K-C, Chen D-H (2013) One-pot green synthesis of silver/iron oxide composite nanoparticles for 4-nitrophenol reduction. J Hazard Mater 248–249:394–400

    Google Scholar 

  • Cruz-Silva R, Morelos-Gomez A, Kim H-I, Jang H-K, Tristan F, Vega-Diaz S, Rajukumar LP, Elias AL, Perea-Lopez N, Suhr J, Endo M, Terrones M (2014) Super-stretchable graphene oxide macroscopic fibers with outstanding knotability fabricated by dry film scrolling. ACS Nano 8:5959–5967

    CAS  Google Scholar 

  • Deng H, Fan G, Wang C, Zhang L (2014) Aqueous phase catalytic hydrodechlorination of 4-chlorophenol over palladium deposited on reduced graphene oxide. Catal Commun 46:219–223

    CAS  Google Scholar 

  • Diaz E, Casas JA, Mohedano AF, Calvo L, Gilarranz MA, Rodriguez JJ (2009) Kinetics of 4-chlorophenol hydrodechlorination with alumina and activated carbon-supported Pd and Rh catalysts. Ind Eng Chem Res 48:3351–3358

    CAS  Google Scholar 

  • Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) The chemistry of graphene oxide. Chem Soc Rev 39:228–240

    CAS  Google Scholar 

  • Gao X, Jang J, Nagase S (2010) Hydrazine and thermal reduction of graphene oxide: reaction mechanisms, product structures, and reaction design. J Phys Chem C 114:832–842

    CAS  Google Scholar 

  • Gomez-Sainero LM, Seoane XL, Fierro JLG, Arcoya A (2002) Liquid-phase hydrodechlorination of CCI4 to CHCl3 on Pd/carbon catalysts: Nature and role of Pd active species. J Catal 209:279–288

    CAS  Google Scholar 

  • Green AA, Hersam MC (2009) Solution phase production of graphene with controlled thickness via density differentiation. Nano Lett 9:4031–4036

    CAS  Google Scholar 

  • Grzyb B, Gryglewicz S, Sliwak A, Diez N, Machnikowski J, Gryglewicz G (2016) Guanidine, amitrole and imidazole as nitrogen dopants for the synthesis of N-graphenes. RSC Adv 6:15782–15787

    CAS  Google Scholar 

  • Guo S, Dong S (2011) Graphene nanosheet: synthesis, molecular engineering, thin film, hybrids, and energy and analytical applications. Chem Soc Rev 40:2644–2672

    CAS  Google Scholar 

  • Ham H., Tran Van K., Park N.-H., So D.S., Lee J.-W., Na H.G., Kwon Y.J., Cho H.Y., Kim H.W. (2014) Freeze-drying-induced changes in the properties of graphene oxides, Nanotechnology, 25:4830-4840.

    Google Scholar 

  • Hu B, Ding K, Wu T, Zhou X, Fan H, Jiang T, Wang Q, Han B (2010) Shape controlled synthesis of palladium nanocrystals by combination of oleylamine and alkylammonium alkylcarbamate and their catalytic activity. Chem.Comm. 46:8552–8554

    CAS  Google Scholar 

  • Jiang H (2011) Chemical preparation of graphene-based nanomaterials and their applications in chemical and biological sensors. Small 7:2413–2427

    CAS  Google Scholar 

  • Kim SK, Kim C, Lee JH, Kim J, Lee H, Moon SH (2013) Performance of shape-controlled Pd nanoparticles in the selective hydrogenation of acetylene. J Catal 306:146–154

    CAS  Google Scholar 

  • Krishnankutty N, Vannice MA (1995) The effect of pretreatment on Pd/C catalysts. I. Adsorption and absorption properties. J. Catal. 155:312–326

    CAS  Google Scholar 

  • Lan L, Du F, Xia C (2016) The reaction mechanism for highly effective hydrodechlorination of p-chlorophenol over a Pd/CNTs catalyst. RSC Adv 6:109023–109029

    CAS  Google Scholar 

  • Long D, Li W, Ling L, Miyawaki J, Mochida I, Yoon SH (2010) Preparation of nitrogen-doped graphene sheets by a combined chemical and hydrothermal reduction of graphene oxide. Langmuir 26:16096–16102

    CAS  Google Scholar 

  • López GP, Castner DG, Ratner BD (1991) XPS O 1s binding energies for polymers containing hydroxyl, ether, ketone and ester groups. Surf Interface Anal 17:267–272

    Google Scholar 

  • Mamtani K, Jain D, Co AC, Ozkan US (2017) Investigation of chloride poisoning resistance for nitrogen-doped carbon nanostructures as oxygen depolarized cathode catalysts in acidic media. Catal Lett 147:2903–2909

    CAS  Google Scholar 

  • Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z, Slesarev A, Alemany LB, Lu W, Tour JM (2010) Improved synthesis of graphene oxide. ACS Nano 4:4806–4814

    CAS  Google Scholar 

  • Navalon S, Dhakshinamoorthy A, Alvaro M, Garcia H (2016) Metal nanoparticles supported on two-dimensional graphenes as heterogeneous catalysts. Coord Chem Rev 312:99–148

    CAS  Google Scholar 

  • Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically thin carbon films. Science 306:666–669

    CAS  Google Scholar 

  • Park S, Ruoff RS (2009) Chemical methods for the production of graphenes. Nat Nanotechnol 4:217–224

    CAS  Google Scholar 

  • Park S, An J, Potts JR (2011) A. Ve200lamakanni, S. Murali, R.S. Ruoff, Hydrazine-reduction of graphite- and graphene oxide. Carbon 49:3019–3023

    CAS  Google Scholar 

  • Pei S, Cheng H-M (2012) The reduction of graphene oxide. Carbon 50:3210–3228

    CAS  Google Scholar 

  • Peng-Gang R, Ding-Xiang Y, Xu J, Tao C, Zhong-Ming L (2011) Temperature dependence of graphene oxide reduced by hydrazine hydrate. Nanotechnology 22:055705

    Google Scholar 

  • Pietrzak R (2009) XPS study and physico-chemical properties of nitrogen-enriched microporous activated carbon from high volatile bituminous coal. Fuel 88:1871–1877

    CAS  Google Scholar 

  • Rahul R, Singh RK, Bera B, Devivaraprasad R, Neergat M (2015) The role of surface oxygenated-species and adsorbed hydrogen in the oxygen reduction reaction (ORR) mechanism and product selectivity on Pd-based catalysts in acid media. Phys Chem Chem Phys 17:15146–15155

    CAS  Google Scholar 

  • Riedl C, Coletti C, Starke U (2010) Structural and electronic properties of epitaxial graphene on SiC(0 001): a review of growth, characterization, transfer doping and hydrogen intercalation. J Phys D Appl Phys 43:374009

    Google Scholar 

  • Ruan G, Sun Z, Peng Z, Tour JM (2011) Growth of graphene from food, insects, and waste. ACS Nano 5:7601–7607

    CAS  Google Scholar 

  • Ruditskiy A, Choi SI, Peng HC, Xia YN (2014) Shape-controlled metal nanocrystals for catalytic applications. MRS Bull 39:727–737

    CAS  Google Scholar 

  • Ruiz-Garcia C, Perez-Carvajal J, Berenguer-Murcia A, Darder M, Aranda P, Cazorla-Amoros D, Ruiz-Hitzky E (2013) Clay-supported graphene materials: application to hydrogen storage. Phys Chem Chem Phys 15:18635–18641

    CAS  Google Scholar 

  • Ruiz-Garcia C, Darder M, Aranda P, Ruiz-Hitzky E (2014) Toward a green way for the chemical production of supported graphenes using porous solids. J Mater Chem A 2:2009–2017

    CAS  Google Scholar 

  • Ruiz-García C, Heras F, Calvo L, Alonso-Morales N, Rodriguez JJ, Gilarranz MA (2018a) Platinum and N-doped carbon nanostructures as catalysts in hydrodechlorination reactions. Appl Catal B Environ 238:609–617

    Google Scholar 

  • Ruiz-Garcia C, Heras F, Alonso-Morales N, Calvo L, Rodriguez JJ, Gilarranz MA (2018b) Enhancement of the activity of Pd/C catalysts in aqueous phase hydrodechlorination through doping of carbon supports. Catal Sci Technol 8:2598–2605

    CAS  Google Scholar 

  • Ruiz-García C, Heras F, Gilarranz MA, Aranda P, Ruiz-Hitzky E (2018c) Sepiolite-carbon nanocomposites doped with Pd as improving catalysts for hydrodechlorination processes. Appl Clay Sci 161:132–138

    Google Scholar 

  • Ruiz-García C, Heras F, Calvo L, Alonso-Morales N, Rodriguez JJ, Gilarranz MA (2019) N-doped CMK-3 carbons supporting palladium nanoparticles as catalysts for hydrodechlorination. Ind Eng Chem Res 58:4355–4363

    Google Scholar 

  • She X, Yang Q, Yao F, Zhong Y, Ren W, Chen F, Sue J, Ma Y, Fe Z, Wang D (2019) Electrocatalytic hydrodechlorination of 4-chlorophenol on Pd supported multi-walled carbon nanotubes particle electrodes. Chem Eng J 358:903–911

    Google Scholar 

  • Sing KSW, Rouquerol F, Rouquerol J, Llewellyn P (2014) Adsorption by powders and porous solids (Second Edition). Academic Press, Oxford

    Google Scholar 

  • Stobinski L, Lesiak B, Malolepszy A, Mazurkiewicz M, Mierzwa B, Zemek J, Jiricek P, Bieloshapka I (2014) Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods. J Electron Spectros Relat Phenomena 195:145–154

    CAS  Google Scholar 

  • Terrones M (2009) Nanotubes unzipped. Nature 458:845–846

    CAS  Google Scholar 

  • Terrones M, Botello-Mendez AR, Campos-Delgado J, Lopez-Urias F, Vega-Cantu YI, Rodriguez-Macias FJ, Elias AL, Munoz-Sandoval E, Cano-Marquez AG, Charlier J-C, Terrones H (2010) Graphene and graphite nanoribbons: morphology, properties, synthesis, defects and applications. Nano Today 5:351–372

    Google Scholar 

  • Vu THT, Tran TTT, Le HNT, Tran LT, Nguyen PHT, Nguyen MD, Quynh BN (2016) Synthesis of Pt/rGO catalysts with two different reducing agents and their methanol electrooxidation activity. Mater Res Bull 73:197–203

    CAS  Google Scholar 

  • Wagner C.D., Riggs W.M., Davis L.E., Moulder J.F. (1979) Handbook of x-ray photoelectron spectroscopy, Perkin-Elmer

  • Yoon T, Kim J, Kim J, Lee J (2013) Electrostatic self-assembly of Fe3O4 nanoparticles on graphene oxides for high capacity lithium-ion battery anodes. Energies 6:4830

    CAS  Google Scholar 

  • Zhou J, Chen Q, Han Y, Zheng S (2015) Enhanced catalytic hydrodechlorination of 2,4-dichlorophenol over Pd catalysts supported on nitrogen-doped graphene. RSC Adv 5:91363–91371

    CAS  Google Scholar 

  • Zhu Y, Murali S, Cai W, Li X, Suk JW, Potts JR, Ruoff RS (2010) Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater 22:3906–3924

    CAS  Google Scholar 

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Acknowledgments

We are grateful to Kazunori Fujisawa, for technical assistance and useful discussions.

Funding

This work was supported by CTQ2015-65491_R and RTI2018-098431-B-I00 research grants. C. Ruiz-García also thanks for PhD and mobility grant (BES-2013-06608 5, EEBB-I-16-11722).

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  1. Cristina Ruiz-Garcia

    Present address: POR2E Group, CEMHTI (UPR 3079) CNRS, Univ. Orleans, Orleans, France

Authors and Affiliations

  1. Departamento de Ingeniería Química, Universidad Autónoma de Madrid, Madrid, Spain

    Cristina Ruiz-Garcia, Francisco Heras & Miguel A. Gilarranz

  2. Department of Materials Science and Engineering, The Pennsylvania State University, State College, USA

    Cristina Ruiz-Garcia, Yu Lei & Mauricio Terrones

  3. Department of Physics and Center for 2-Dimensional and Layered Materials, The Pennsylvania State University, State College, USA

    Ana Laura Elías & Mauricio Terrones

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  1. Cristina Ruiz-Garcia
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Correspondence to Cristina Ruiz-Garcia.

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Ruiz-Garcia, C., Lei, Y., Heras, F. et al. Functional Pd/reduced graphene oxide nanocomposites: effect of reduction degree and doping in hydrodechlorination catalytic activity. J Nanopart Res 21, 276 (2019). https://doi.org/10.1007/s11051-019-4696-x

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