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The Structure of Mixed Mn–Co Oxide Catalysts for CO Oxidation

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A series of Mn5Co1Ox catalysts calcined at different temperatures in the range of 400–800 °C were synthesized by coprecipitation of manganese and cobalt nitrates and tested in the oxidation of CO. The specific surface area, structure, and chemistry of the catalysts were studied. In addition, the reduction of the catalysts by hydrogen was studied using in situ X-ray diffraction and temperature-programmed reduction techniques. It was found that the low-temperature catalyst calcined at 400 °C displays the best catalytic activity, which is attributed to its high surface area, low-temperature reducibility, and a high surface content of Mn4+. The formation of highly disperse and active CoMnO3 species and excess oxygen in a Mn3−xCoxO4+δ spinel leads to excellent low-temperature redox properties. The elevated temperature calcination results in a decline in the catalytic activity in CO oxidation due to formation of a well crystalline Mn3−xCoxO4 spinel, a decrease in the surface area and reducibility.

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  1. 1.

    Tomatis M, Xu HH, He J, Zhang XD (2016) Recent development of catalysts for removal of volatile organic compounds in flue gas by combustion: a review. J Chem 2016:8324826

  2. 2.

    Kamal MS, Razzak SA, Hossain MM (2016) Catalytic oxidation of volatile organic compounds (VOCs)—a review. Atmos Environ 140:117–134

  3. 3.

    Huang H, Xu Y, Feng Q, Leung DYC (2015) Low temperature catalytic oxidation of volatile organic compounds: a review. Catal Sci Technol 5:2649–2669

  4. 4.

    Liotta LF (2010) Catalytic oxidation of volatile organic compounds on supported noble metals. Appl Catal B 100:403–412

  5. 5.

    Royer S, Duprez D (2011) Catalytic oxidation of carbon monoxide over transition metal oxides. ChemCatChem 3:24–65

  6. 6.

    Fedorov AV, Tsapina AM, Bulavchenko OA, Saraev AA, Odegova GV, Ermakov DY, Zubavichus YV, Yakovlev VA, Kaichev VV (2018) Structure and chemistry of Cu–Fe–Al nanocomposite catalysts for CO oxidation. Catal Lett 148:3715–3722

  7. 7.

    Shi J (2013) On the synergetic catalytic effect in heterogeneous nanocomposite catalysts. Chem Rev 113:2139–2181

  8. 8.

    Xu H, Yan N, Qu Z, Liu W, Mei J, Huang W et al (2017) Gaseous heterogeneous catalytic reactions over Mn-based oxides for environmental applications: a critical review. Environ Sci Technol 51:8879–8892

  9. 9.

    Tian ZY, Tchoua Ngamou PH, Vannier V, Kohse-Höinghaus K, Bahlawane N (2012) Catalytic oxidation of VOCs over mixed Co-Mn oxides. Appl Catal B 117–118:125–134

  10. 10.

    Zhang X, Junhui Y, Jing Y, Ting C, Bei X, Zhe L et al (2018) Excellent low-temperature catalytic performance of nanosheet Co-Mn oxides for total benzene oxidation. Appl Catal A 566:104–112

  11. 11.

    Tang W, Wu X, Li S, Li W, Chen Y (2014) Porous Mn–Co mixed oxide nanorod as a novel catalyst with enhanced catalytic activity for removal of VOCs. Catal Commun 56:134–138

  12. 12.

    Qu Z, Gao K, Fu Q, Qin Y (2014) Low-temperature catalytic oxidation of toluene over nanocrystal-like Mn–Co oxides prepared by two-step hydrothermal method. Catal Commun 52:31–35

  13. 13.

    Lamonier JF, Boutoundou AB, Gennequin C, Pérez-Zurita MJ, Siffert S, Aboukais A (2007) Catalytic removal of toluene in air over Co-Mn-Al nano-oxides synthesized by hydrotalcite route. Catal Lett 118:165–172

  14. 14.

    Kovanda F, Rojka T, Dobešová J, Machovič V, Bezdička P, Obalová L et al (2006) Mixed oxides obtained from Co and Mn containing layered double hydroxides: preparation, characterization, and catalytic properties. J Solid State Chem 179:812–823

  15. 15.

    Aguilera DA, Perez A, Molina R, Moreno S (2011) Cu-Mn and Co-Mn catalysts synthesized from hydrotalcites and their use in the oxidation of VOCs. Appl Catal B 104:144–150

  16. 16.

    Faure B, Alphonse P (2015) Co-Mn-oxide spinel catalysts for CO and propane oxidation at mild temperature. Appl Catal B 180:715–725

  17. 17.

    Liu C, Gong L, Dai R, Lu M, Sun T, Liu Q et al (2017) Mesoporous Mn promoted Co3O4 oxides as an efficient and stable catalyst for low temperature oxidation of CO. Solid State Sci 71:69–74

  18. 18.

    Wu M, Zhan W, Guo Y, Guo Y, Wang Y, Wang L et al (2016) An effective Mn-Co mixed oxide catalyst for the solvent-free selective oxidation of cyclohexane with molecular oxygen. Appl Catal A 523:97–106

  19. 19.

    Scofield JH (1976) Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV. J Electron Spectrosc Relat Phenom 8:129–137

  20. 20.

    Shirley DA (1972) High-resolution X-ray photoemission spectrum of the valence bands of gold. Phys Rev B 5:4709–4714

  21. 21.

    Venediktova OS, Bulavchenko OA, Afonasenko TN, Tsyrul’nikov PG, Vinokurov ZS, Chesalov YA et al (2017) Synthesis and characterization of mixed manganese-gallium oxides Mn3-xGaxO4 (x = 1–2) with the spinel structure. J Alloys Compd 725:496–503

  22. 22.

    Bulavchenko OA, Venediktova OS, Afonasenko TN, Tsyrul’nikov PG, Saraev AA, Kaichev VV et al (2018) Nonstoichiometric oxygen in Mn-Ga-O spinels: reduction features of the oxides and their catalytic activity. RSC Adv 8:11598–11607

  23. 23.

    Regan E, Groutso T, Metson JB, Steiner R, Ammundsen B, Hassell D et al (1999) Surface and bulk composition of lithium manganese oxides. Surf Interface Anal 27:1064–1068

  24. 24.

    Oku M, Hirokawa K, Ikeda S (1975) X-ray photoelectron spectroscopy of manganese–oxygen systems. J Electron Spectrosc Relat Phenom 7:465–473

  25. 25.

    Castro VD, Polzonetti G (1989) XPS study of MnO oxidation. J Electron Spectrosc Relat Phenom 48:117–123

  26. 26.

    Bondi JF, Oyler KD, Ke X, Schiffer P, Schaak RE (2008) Chemical synthesis of air-stable manganese nanoparticles. J Am Chem Soc 131:9144–9145

  27. 27.

    Han Y-F, Chen F, Zhong Z, Ramesh K, Chen L, Widjaja E (2006) Controlled synthesis, characterization, and catalytic properties of Mn2O3 and Mn3O4 nanoparticles supported on mesoporous silica SBA-15. J Phys Chem B 110:24450–24456

  28. 28.

    Han Y-F, Chen L, Ramesh K, Zhong Z, Chen F, Chin J et al (2008) Coral-like nanostructured a-Mn2O3 nanocrystals for catalytic combustion of methane part I. Preparation and characterization. Catal Today 131:35–41

  29. 29.

    Yang X, Wang X, Zhang G, Zheng J, Wang T, Liu X et al (2012) Enhanced electrocatalytic performance for methanol oxidation of Pt nanoparticles on Mn3O4-modified multi-walled carbon nanotubes. Int J Hydrogen Energy 37:11167–11175

  30. 30.

    Ramesh K, Chen L, Chen F, Liu Y, Wang Z, Han Y-F (2008) Re-investigating the CO oxidation mechanism over unsupported MnO, Mn2O3 and MnO2 catalysts. Catal Today 131:477–482

  31. 31.

    Liu Y, Li J, Li W, Li Y, Chen Q, Zhan F (2015) Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction. J Power Sources 299:492–500

  32. 32.

    Kong W, Gao B, Jiang C, Chang A (2015) Influence of the oxygen pressure on the preferred orientation and optical properties of the pulsed-laser deposited Mn1.56Co0.96Ni0.48O4±δ thin films. J Alloys Compd 650:305–310

  33. 33.

    Zhang L, Tang Z, Wang S, Ding D, Chen M, Wan H (2012) Growth and vibrational properties of MnOx thin films on Rh(111). Surf Sci 606:1507–1511

  34. 34.

    Jadhav PR, Suryawanshi MP, Dalavi DS, Patil DS, Jo EA, Kolekar SS et al (2015) Design and electro-synthesis of 3-D nanofibers of MnO2 thin films and their application in high performance supercapacitor. Electrochim Acta 176:523–532

  35. 35.

    Kostowskyj MA, Kirk DW, Thorpe SJ (2010) Ag and Ag–Mn nanowire catalysts for alkaline fuel cells. Int J Hydrogen Energy 35:5666–5672

  36. 36.

    Hishida T, Ohbayashi K, Saitoh T (2013) Hidden relationship between the electrical conductivity and the Mn 2p core-level photoemission spectra in La1−xSrxMnO3. J Appl Phys 113:043710

  37. 37.

    Khassin AA, Yurieva TM, Kaichev VV, Bukhtiyarov VI, Budneva AA, Paukshtis EA et al (2001) Metal–support interactions in cobalt-aluminum co-precipitated catalysts: XPS and CO adsorption studies. J Mol Catal A 175:189–204

  38. 38.

    Biesinger MC, Payne BP, Grosvenor AP, Lau LWM, Gerson AR, Smart RSC (2011) Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl Surf Sci 257:2717–2730

  39. 39.

    Venezia AM, Murania R, Pantaleo G, Deganello G (2007) Nature of cobalt active species in hydrodesulfurization catalysts: combined support and preparation method effects. J Mol Catal A 271:238–245

  40. 40.

    Kosova NV, Devyatkina ET, Kaichev VV (2007) Optimization of Ni2+/Ni3+ ratio in layered Li (Ni, Mn, Co) O2 cathodes for better electrochemistry. J Power Sources 174:965–969

  41. 41.

    Liu B, Chai Y, Li Y, Wang A, Liu Y, Liu C (2014) Effect of sulfidation atmosphere on the performance of the CoMo/γ-Al2O3 catalysts in hydrodesulfurization of FCC gasoline. Appl Catal A 471:70–79

  42. 42.

    Guan Q, Cheng J, Li X, Wang B, Huang L, Nie F et al (2015) Low temperature vacuum synthesis of triangular CoO nanocrystal/graphene nanosheets composites with enhanced lithium storage capacity. Sci Rep 5:10017

  43. 43.

    Stobbe ER, De Boer BA, Geus JW (1999) The reduction and oxidation behaviour of manganese oxides. Catal Today 47:161–167

  44. 44.

    Christel L, Pierre A, Abel DAMR (1997) Temperature programmed reduction studies of nickel manganite spinels. Thermochim Acta 306:51–59

  45. 45.

    Arnoldy P, Moulijn JA (1985) Temperature-programmed reduction of CoO Al2O3 catalysts. J Catal 93:38–54

  46. 46.

    Garces LJ, Hincapie B, Zerger R, Suib SL (2015) The effect of temperature and support on the reduction of cobalt oxide: an in situ X-ray diffraction study. J Phys Chem C 119:5484–5490

  47. 47.

    Bulavchenko OA, Cherepanova SV, Malakhov VV, Dovlitova LS, Ishchenko AV, Tsybulya SV (2009) In situ XRD study of nanocrystalline cobalt oxide reduction. Kinet Catal 50:192–198

  48. 48.

    Bulavchenko OA, Gerasimov EY, Afonasenko TN (2018) Reduction of double manganese-cobalt oxides: in situ XRD and TPR study. Dalton Trans 47:17153–17159

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The authors were grateful to the Ministry of Science and Higher Education of the Russian Federation (Project AAAA-A17-117041710079-8). O.A.B. and G.E.Yu. acknowledge support from the Russian Foundation for Basis Research (Project No. 18-33-00542). The authors acknowledge Diamond Light Source for time on I11 Beamline, and Dr. V.A. Rogov for the TPR-H2 measurements.

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Correspondence to O. A. Bulavchenko.

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Bulavchenko, O.A., Afonasenko, T.N., Sigaeva, S.S. et al. The Structure of Mixed Mn–Co Oxide Catalysts for CO Oxidation. Top Catal (2020).

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  • Heterogeneous catalysts
  • CO oxidation
  • Mn oxide
  • Co oxide
  • Solid solution
  • Mn–Co mixed oxides