Abstract
Oscillatory behavior during CO oxidation over a Ni foil in a continuous-flow catalytic reactor has been discovered in the reaction mixture containing CO excess at atmospheric pressure in the temperature range of 500–630 °C. The oscillations are accompanied by propagation of the oxidation and reduction fronts which were recorded by a photo–video camera. Dark fronts of the oxidized state appear periodically in the upstream part of the catalyst and propagate to the downstream region in the direction of the gas flow. Reduction fronts move in the opposite direction. A mathematical model has been developed to simulate the oscillatory dynamics. The developed model simulates experimental data almost quantitatively. The origin of oscillations is connected with periodic oxidation and reduction of the nickel surface. It is shown that a precursor-mediated adsorption of CO on Ni surface is required to simulate the oscillations under reducing conditions.
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References
Engel T, Ertl G (1979) Elementary steps in the catalytic oxidation of carbon monoxide on platinum metals. Adv Catal 28:1–78
Freund H-J, Meijer G, Scheffler M, Schlögl R, Wolf M (2011) CO oxidation as a prototypical reaction for heterogeneous processes. Angew Chem Int Ed 50:10064–10094
Slinko MM, Jaeger NI (1994) Oscillatory heterogeneous catalytic systems Studies in surface sciences and catalysis. Elsevier, Amsterdam
Imbihl R, Ertl G (1995) Oscillatory kinetics in heterogeneous catalysis. Chem Rev 95:697–733
Eiswirth M, Ertl G (1994) In: Kapral R, Showalter K (eds) Chemical waves and patterns. Kluwer, Dordrecht
Luss D, Sheintuch M (2005) Spatiotemporal patterns in catalytic systems. Catal Today 105:254–274
Imbihl R (2008) Nonlinear dynamics in catalytic reactions. In: Hasselbrink E, Lundqvist B (eds) Handbook of surface science, vol 3. Elsevier, Amsterdam, pp 341–428
Bychkov VYu, Tulenin YuP, Slinko MM, Gordienko YuA, Korchak VN (2018) New oscillating system: CO oxidation over Ni. Catal Lett 148:653–659
Bychkov VYu, Tulenin YuP, Slinko MM, Gorenberg AY, Shashkin DP, Korchak VN (2020) Spatial and temporal self-organization during CO oxidation over Co. Reaction kinetics, mechanisms and catalysis (to be published)
Belyaev VD, Slinko MM, Slinko MG (1976) In: Proceedings of the 6th international congress on catalysis, London
Kurtanjek Z, Sheintuch M, Luss D (1980) Surface state and kinetic oscillations in the oxidation of hydrogen on nickel. J Catal 66:11–27
Bychkov VY, Tyulenin YP, Korchak VN, Aptekar EL (2006) Study of nickel catalyst in oscillating regime of methane oxidation by means of gravimetry and mass-spectrometry. Appl Catal A 3042:21–29
Bychkov VY, Tyulenin YP, Slinko MM, Korchak VN (2009) Nonlinear behavior during methane and ethane oxidation over Ni, Co and Pd catalysts. Surf Sci 603:1680–1689
Kaichev VV, Saraev AA, Gladky AYu, Prosvirin IP, Blume R, Teschner V, Hävecker V, Knop-Gericke A, Schlögl R, Bukhtiyarov VI (2017) Reversible bulk oxidation of Ni foil during oscillatory catalytic oxidation of propane: a novel type of spatiotemporal self-organization. Phys Rev Lett 119:026001
Lobban L, Luss D (1989) Spatial temperature oscillations during hydrogen oxidation on a nickel foil. J Phys Chem 93:6530–6533
van Rijn R, Balmes O, Felici R, Gustafson J, Wermeille D, Westerström R, Lundgren E, Frenken JWM (2010) Comment on “CO oxidation on Pt-group metals from ultrahigh vacuum to near atmospheric pressures. 2. Palladium and platinum”. J Phys Chem C 114:6875–6876
Gao F, Wang Y, Goodman DW (2010) Reply to Comment on “CO oxidation on Pt group metals from ultrahigh vacuum to near atmospheric pressures II Palladium and platinum”. J Phys Chem C 114:6874
Gao F, Wang Y, Cai Y, Goodman DW (2009) CO oxidation on Pt-group metals from ultrahigh vacuum to near atmospheric pressures. 2. Palladium and platinum. J Phys Chem C 113:174–181
Makeev AG, Slinko MM, Luss D (2019) Mathematical modeling of oscillating CO oxidation on Pt-group metals at near atmospheric pressure: activity of metallic and oxidized surfaces. Appl Catal A 57:127–136
Hendriksen BLM, Bobaru SC, Frenken JWM (2005) Bistability and oscillations in CO oxidation studied with scanning tunnelling microscopy inside a reactor. Catal Today 105:234–243
Knudsen J, Merte LR, Peng GW, Vang RT, Resta A, Lægsgaard E, Andersen JN, Mavrikakis M, Besenbacher F (2010) Low-temperature CO oxidation on Ni(111) and on a Au/Ni(111) surface alloy. ACS Nano 4:4380–4387
Peng GW, Merte LR, Knudsen J, Vang RT, Lægsgaard E, Besenbacher F, Mavrikakis M (2010) On the mechanism of low-temperature CO oxidation on Ni(111) and NiO(111) surfaces. J Phys Chem C 114:21579–21584
Slinko MM (2010) Oscillating reactions in heterogeneous catalysis: what new information can be obtained about reaction mechanisms? Catal Today 153:38–45
McAdam DJ, Geil GW (1942) Rate of oxidation of typical nonferrous metals as determined by interference colors of oxide films. J Res Natl Bur Stand 28:593–635
Stuckless JT, Wartnaby CE, Al-Sarraf N, StJB D-W, Kovar M, King DA (1997) Oxygen chemisorption and oxide film growth on Ni{100}, {110}, and {111}: sticking probabilities and microcalorimetric adsorption heats. J Chem Phys 106:2012–2030
Sales BC, Turner JE, Maple MB (1982) Oscillatory oxidation of CO over Pt, Pd and Ir catalysts: theory. Surf Sci 114:381–394
Stuckless JT, Al-Sarraf N, Wartnaby C, King DA (1993) Calorimetric heats of adsorption for CO on nickel single crystal surfaces. J Chem Phys 99:2202–2212
Feigerle CS, Desai SR, Overbury SH (1990) The kinetics of CO desorption from Ni(110). J Chem Phys 93:787–794
Kisliuk P (1957) The sticking probabilities of gases chemisorbed on the surfaces of solids. J Phys Chem Solids 3:95–101
Yang WS, Xiang HW, Li YW, Sun YH (2000) Micro-kinetic analysis and Monte Carlo simulation in methane partial oxidation into synthesis gas. Cat Today 61:237–242
Monnerat B, Kiwi-Minsker L, Renken A (2003) Mathematical modelling of the unsteady-state oxidation of nickel gauze catalyst. Chem Eng Sci 58:4911–4919
Munôz-Marquez MA, Tanner RE, Woodruff DP (2004) Surface and subsurface oxide formation on Ni(100) and Ni(111). Surf Sci 565:1–13
Makeev AG, Peskov NV, Semendyaeva NL, Slinko MM, Bychkov VYu, Korchak VN (2019) Mathematical modeling of oscillations during CO oxidation on Ni under reducing conditions. Chem Eng Sci 207:644–652
Behm RJ, Ertl G, Penka V (1985) Adlayer geometry and structural effects in the CO/Ni(110) system. Surf Sci 160:387–399
Labohm F, Gijzeman OLJ, Geus JW (1983) The interaction of oxygen with Ni(111) and the reduction of the surface oxide by carbon monoxide and by hydrogen. Surf Sci 135:409–427
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This study was funded by the Russian Science Foundation (Grant N 17-13-01057).
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Makeev, A.G., Peskov, N.V., Slinko, M.M. et al. Spatial and Temporal Self-organization During CO Oxidation Over Ni. Top Catal 63, 49–57 (2020). https://doi.org/10.1007/s11244-019-01214-w
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DOI: https://doi.org/10.1007/s11244-019-01214-w