An Infrared Investigation on Surface Species over Iron-Based Catalysts: Implications for Oxygenates Formation
The nature of adsorbed species on catalytic surface
over an industrial precipitated iron-based high temperature catalyst
during FTS was investigated by in-situ DRIFTS and chemical
trapping. The formulation of the mechanism of oxygenates formation
and key intermediates were also discussed. Numerous oxygenated
precursors and crucial intermediates were found by in-situ DRIFTS,
such as surface acetate, acetyl and methoxide. The results showed that
adsorbed molecules on surface such as methanol or acetaldehyde
could react with basic sites such as lattice oxygen or free surface
hydroxyls. Adsorbed molecules also had reactivity of oxidizing.
Moreover, acetyl as a key intermediate for oxygenates was observed
by investigation of CH3OH + CO and CH3I + CO + H2. Based on the
nature of surface properties, the mechanism of oxygenates formation
on precipitated iron-based high temperature catalyst was discussed.
<p>[1] M.E. Dry, “Catalysis-Science and Technology”, vol. 1, Anderson and
Boudart, Ed. New York: Springer Verlag, 1981, pp. 159.
[2] A. Takeuchi, J.R. katzer, “Mechanism of methanol formation”, J. Phys.
Chem., vol. 85, pp. 937-939, Feb. 1981.
[3] D.G. Castner, R.L. Blackadar, G.A. Somorjai, “CO hydrogenation over
clean and oxidized rhodium foil and single crystal catalysts. Correlations
of catalyst activity, selectivity, and surface composition”, J. Catal., vol.
66, pp. 257-266, Dec. 1980.
[4] M. Ichikawa, T. Fukushima, “Mechanism of syngas conversion into
C2-oxygenates such as ethanol catalysed on a SiO2-supported Rh-Ti
catalyst”, J. Chem. Soc. Chem. Comm., vol. 1985, pp. 321-323, 1985.
[5] M. Pijolat, V. Perrichon, “Synthesis of alcohols from CO and H2 on a
Fe/A12O3 catalyst at 8-30 bars pressure”, Appl. Catal., vol. 13, pp.
321-333, Jan. 1985.
[6] A. Kiennemann, C. Diagne, J.P. Hindermann P. Chaumette, Ph. Courty,
“Higher alcohols synthesis from CO+2H2 on cobalt-copper catalyst: Use
of probe molecules and chemical trapping in the study of the reaction
mechanism”, Appl. Catal., vol. 53, pp. 197-216, Sep. 1989.
[7] J.L. Davis, M.A. Barteau, “Spectroscopic identification of alkoxide,
aldehyde, and acyl intermediates in alcohol decomposition on Pd(111)”,
Surf. Sci., vol. 235, pp. 235-248, Sep. 1990.
[8] C. Schild, A. Wokaun, A. Baiker, “On the mechanism of CO and CO2
hydrogenation reactions on zirconia-supported catalysts: a diffuse
reflectance FTIR study: Part II. Surface species on copper/zirconia
catalysts: implications for methanol synthesis selectivity”, J. Mol. Catal.,
vol. 63, pp. 243-254, Dec. 1990.
[9] R.G. Greenler, “An infrared investigation of xanthate adsorption by lead
sulfide”, J. Chem. Phys., vol. 66, pp. 879-883, May 1962.
[10] M. Domok, M. Toth, J. Rasko, A. Erdohelyi, “Adsorption and reactions
of ethanol and ethanol-water mixture on alumina-supported Pt catalysts”,
Appl. Catal. B, vol. 69, pp. 262-272, Jan. 2007.
[11] V. Zamboni, G. Zerbi, “Vibrational spectrum of a new crystalline
modification of polyoxymethylene”, J. Polym. Sci., vol. 7, pp. 153-161,
Mar. 1964.
[12] Y. Ei-Sayed, T J. Bandosz, “A Study of Acetaldehyde Adsorption on
Activated Carbons”, J. Coll. Interf. Sci., vol. 242, pp. 44-51, Oct. 2001.
[13] Y. He, J.H. Chin, “In-Situ DRIFTS Study on Catalytic Oxidation of
Formaldehyde over Pt/TiO2 under Mild Conditions”, Chin. J. Catal., vol.
31, pp. 171-175, Feb. 2010.
[14] G. Busca, V. Lorenzelli, “Infrared study of methanol, formaldehyde, and
formic acid adsorbed on hematite”, J. Catal., vol. 66, pp. 155-161, Nov.
1980.
[15] A.B. Anton, J.E. Parmeter, W.H. Weinberg, “Adsorption of
formaldehyde on the Ru(001) and Ru(001)-p(2 .times. 2)O surfaces”, J.
Am. Chem. Soc., vol. 108, pp. 1823-1833, April 1986.
[16] D. Demri, L. Chateau, J.P. Hindermann, A. Kiennemann, M.M. Bettahar,
“C1-oxygenated molecules adsorbed on rhodium containing catalysts.
Identification of a formyl species”, J. Mol. Catal., vol. 104, pp. 237-249,
Jan. 1996.
[17] H. Idriss, J.P. Hindermann, R. Kieffer, “Characterization of
dioxymethylene species over Cu-Zn catalysts”, J. Mol. Catal., vol. 42(2),
pp. 205-213, Oct. 1987.
[18] W.Y. Ying, F.H. Cao, D,Y, Fang, “Major products and technology in C1
Chemical industry”, vol. 1, Beijing: Chemical Industry Press, 2004, pp.
78.
[19] J.C. Lavalley, J. Saussey, J. Lamotte, “Infrared study of carbon monoxide
hydrogenation over rhodium/ceria and rhodium/silica catalysts”, J. Phys.
Chem., vol. 94, pp. 5941-5947, July 1990.
[20] A.B. Mark, S.C. Steven, A.H. Scott, “Dynamic and kinetic modeling of
isotopic transient responses for CO insertion on Rh and Mn–Rh
catalysts”, Catal. Today, vol. 44, pp. 151-163, Sep. 1998.
[21] D. Forster “Mechanistic Pathways in the Catalytic Carbonylation of
Methanol by Rhodium and Iridium Complexes”, Adv. Organomet.
Chem., vol. 17, pp. 255-267, 1979.
[22] L. Chateau, J.P. Hindermann, A. Kiennemann, E. Tempesti. “On the
mechanism of carbonylation in acetic acid and higher acid synthesis from
methanol and syngas mixtures on supported rhodium catalysts”, J. Mol.
Catal., vol. 107, pp. 367-378, May 1996.
[23] J.C. LAVALLEY, J. SAUSSEY, T. RAIS “Infrared study of the
interaction between CO and H2 on ZnO: Mechanism and sites of
formation of formyl species”, J. Mol. Catal., vol. 17(2-3), pp. 289-298,
Nov.-Dec. 1982.
[24] J. Saussey, J.C. Lavalley, T. Rais, A. Chakor-Alami, J.P. Hindermann, A.
Kiennemann, “The formation of formyl species from CO + H2 on ZnO:
evidence and comparative study using IR spectroscopy and chemical
trapping”, J. Mol. Catal., vol. 26(1), pp. 159-163, Feb. 1984.
[25] O. Johnston, R. Joyner, “Structure-Function Relationships in
Heterogeneous Catalysis: the Embedded Surface Molecule Approach and
Its Applications”, Stud. Surf. Sci. Catal., vol. 75, pp. 165-180, July 1993.
[26] G.A. Vedage, R.G. Herman, K. Klier, “Chemical trapping of surface
intermediates in methanol synthesis by amines”, J. Catal., vol. 95(2), pp.
423-434, Oct. 1985.</p>
<p>[1] M.E. Dry, “Catalysis-Science and Technology”, vol. 1, Anderson and
Boudart, Ed. New York: Springer Verlag, 1981, pp. 159.
[2] A. Takeuchi, J.R. katzer, “Mechanism of methanol formation”, J. Phys.
Chem., vol. 85, pp. 937-939, Feb. 1981.
[3] D.G. Castner, R.L. Blackadar, G.A. Somorjai, “CO hydrogenation over
clean and oxidized rhodium foil and single crystal catalysts. Correlations
of catalyst activity, selectivity, and surface composition”, J. Catal., vol.
66, pp. 257-266, Dec. 1980.
[4] M. Ichikawa, T. Fukushima, “Mechanism of syngas conversion into
C2-oxygenates such as ethanol catalysed on a SiO2-supported Rh-Ti
catalyst”, J. Chem. Soc. Chem. Comm., vol. 1985, pp. 321-323, 1985.
[5] M. Pijolat, V. Perrichon, “Synthesis of alcohols from CO and H2 on a
Fe/A12O3 catalyst at 8-30 bars pressure”, Appl. Catal., vol. 13, pp.
321-333, Jan. 1985.
[6] A. Kiennemann, C. Diagne, J.P. Hindermann P. Chaumette, Ph. Courty,
“Higher alcohols synthesis from CO+2H2 on cobalt-copper catalyst: Use
of probe molecules and chemical trapping in the study of the reaction
mechanism”, Appl. Catal., vol. 53, pp. 197-216, Sep. 1989.
[7] J.L. Davis, M.A. Barteau, “Spectroscopic identification of alkoxide,
aldehyde, and acyl intermediates in alcohol decomposition on Pd(111)”,
Surf. Sci., vol. 235, pp. 235-248, Sep. 1990.
[8] C. Schild, A. Wokaun, A. Baiker, “On the mechanism of CO and CO2
hydrogenation reactions on zirconia-supported catalysts: a diffuse
reflectance FTIR study: Part II. Surface species on copper/zirconia
catalysts: implications for methanol synthesis selectivity”, J. Mol. Catal.,
vol. 63, pp. 243-254, Dec. 1990.
[9] R.G. Greenler, “An infrared investigation of xanthate adsorption by lead
sulfide”, J. Chem. Phys., vol. 66, pp. 879-883, May 1962.
[10] M. Domok, M. Toth, J. Rasko, A. Erdohelyi, “Adsorption and reactions
of ethanol and ethanol-water mixture on alumina-supported Pt catalysts”,
Appl. Catal. B, vol. 69, pp. 262-272, Jan. 2007.
[11] V. Zamboni, G. Zerbi, “Vibrational spectrum of a new crystalline
modification of polyoxymethylene”, J. Polym. Sci., vol. 7, pp. 153-161,
Mar. 1964.
[12] Y. Ei-Sayed, T J. Bandosz, “A Study of Acetaldehyde Adsorption on
Activated Carbons”, J. Coll. Interf. Sci., vol. 242, pp. 44-51, Oct. 2001.
[13] Y. He, J.H. Chin, “In-Situ DRIFTS Study on Catalytic Oxidation of
Formaldehyde over Pt/TiO2 under Mild Conditions”, Chin. J. Catal., vol.
31, pp. 171-175, Feb. 2010.
[14] G. Busca, V. Lorenzelli, “Infrared study of methanol, formaldehyde, and
formic acid adsorbed on hematite”, J. Catal., vol. 66, pp. 155-161, Nov.
1980.
[15] A.B. Anton, J.E. Parmeter, W.H. Weinberg, “Adsorption of
formaldehyde on the Ru(001) and Ru(001)-p(2 .times. 2)O surfaces”, J.
Am. Chem. Soc., vol. 108, pp. 1823-1833, April 1986.
[16] D. Demri, L. Chateau, J.P. Hindermann, A. Kiennemann, M.M. Bettahar,
“C1-oxygenated molecules adsorbed on rhodium containing catalysts.
Identification of a formyl species”, J. Mol. Catal., vol. 104, pp. 237-249,
Jan. 1996.
[17] H. Idriss, J.P. Hindermann, R. Kieffer, “Characterization of
dioxymethylene species over Cu-Zn catalysts”, J. Mol. Catal., vol. 42(2),
pp. 205-213, Oct. 1987.
[18] W.Y. Ying, F.H. Cao, D,Y, Fang, “Major products and technology in C1
Chemical industry”, vol. 1, Beijing: Chemical Industry Press, 2004, pp.
78.
[19] J.C. Lavalley, J. Saussey, J. Lamotte, “Infrared study of carbon monoxide
hydrogenation over rhodium/ceria and rhodium/silica catalysts”, J. Phys.
Chem., vol. 94, pp. 5941-5947, July 1990.
[20] A.B. Mark, S.C. Steven, A.H. Scott, “Dynamic and kinetic modeling of
isotopic transient responses for CO insertion on Rh and Mn–Rh
catalysts”, Catal. Today, vol. 44, pp. 151-163, Sep. 1998.
[21] D. Forster “Mechanistic Pathways in the Catalytic Carbonylation of
Methanol by Rhodium and Iridium Complexes”, Adv. Organomet.
Chem., vol. 17, pp. 255-267, 1979.
[22] L. Chateau, J.P. Hindermann, A. Kiennemann, E. Tempesti. “On the
mechanism of carbonylation in acetic acid and higher acid synthesis from
methanol and syngas mixtures on supported rhodium catalysts”, J. Mol.
Catal., vol. 107, pp. 367-378, May 1996.
[23] J.C. LAVALLEY, J. SAUSSEY, T. RAIS “Infrared study of the
interaction between CO and H2 on ZnO: Mechanism and sites of
formation of formyl species”, J. Mol. Catal., vol. 17(2-3), pp. 289-298,
Nov.-Dec. 1982.
[24] J. Saussey, J.C. Lavalley, T. Rais, A. Chakor-Alami, J.P. Hindermann, A.
Kiennemann, “The formation of formyl species from CO + H2 on ZnO:
evidence and comparative study using IR spectroscopy and chemical
trapping”, J. Mol. Catal., vol. 26(1), pp. 159-163, Feb. 1984.
[25] O. Johnston, R. Joyner, “Structure-Function Relationships in
Heterogeneous Catalysis: the Embedded Surface Molecule Approach and
Its Applications”, Stud. Surf. Sci. Catal., vol. 75, pp. 165-180, July 1993.
[26] G.A. Vedage, R.G. Herman, K. Klier, “Chemical trapping of surface
intermediates in methanol synthesis by amines”, J. Catal., vol. 95(2), pp.
423-434, Oct. 1985.</p>
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:55558", author = "Wanyu Mao and Hongfang Ma and Haitao Zhang and WeixinQian and Weiyong Ying", title = "An Infrared Investigation on Surface Species over Iron-Based Catalysts: Implications for Oxygenates Formation", abstract = "The nature of adsorbed species on catalytic surface
over an industrial precipitated iron-based high temperature catalyst
during FTS was investigated by in-situ DRIFTS and chemical
trapping. The formulation of the mechanism of oxygenates formation
and key intermediates were also discussed. Numerous oxygenated
precursors and crucial intermediates were found by in-situ DRIFTS,
such as surface acetate, acetyl and methoxide. The results showed that
adsorbed molecules on surface such as methanol or acetaldehyde
could react with basic sites such as lattice oxygen or free surface
hydroxyls. Adsorbed molecules also had reactivity of oxidizing.
Moreover, acetyl as a key intermediate for oxygenates was observed
by investigation of CH3OH + CO and CH3I + CO + H2. Based on the
nature of surface properties, the mechanism of oxygenates formation
on precipitated iron-based high temperature catalyst was discussed.
", keywords = "Iron-based catalysts, intermediates, oxygenates,
in-situ DRIFTS, chemical trapping.", volume = "7", number = "7", pages = "531-5", }
