X-ray absorption spectroscopic studies on nickel catalysts for epoxidation

M.C. Feiters, G.A. Metselaar, B.B. Wentzel, R.J.M. Nolte, S. Nikitenko, D.C. Sherrington, Y. Joly, G.Y. Smolentsev, A.N. Kravtsova, A.V. Soldatov

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

We have studied epoxidation catalysts based on complexes of nickel with acac (acetylacetonate) ligands in the solid state, in solution, and on a polymeric support by X-ray absorption spectroscopy. The EXAFS results show that the degree of association (monomer or trimer) of the Ni(acacR) complexes depends on the bulkiness of R. For R = H, trimers predominate both in the solid state and in solution, whereas for R = p-tBuBn, the monomers that are found in the solid state tend to associate to trimers in solution. The trimers are broken up by excess coreactant, i-butyraldehyde, which converts all Ni complexes to 6-coordinated species. The lower degree of association of the substituted Ni(acacR) complex accounts for its relatively high catalytic activity at low concentration. For the solid complexes, the EXAFS results, which provide one-dimensional structural information, are complemented by XANES simulations defining the three-dimensional structure around Ni. The benzimidazole and pyridine ligands of PBI and AMP-resin partially displace acac in the Ni ligand sphere upon grafting. For the rigid PBI this must result in vacancies in the Ni coordination sphere, which explains why this support gives an active catalyst whereas the AMP-resin does not.
LanguageEnglish
Pages8631-8640
Number of pages9
JournalIndustrial and Engineering Chemistry Research
Volume44
Issue number23
DOIs
Publication statusPublished - 9 Nov 2005

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Epoxidation
X ray absorption
Nickel
Catalysts
Ligands
Adenosine Monophosphate
Resins
Monomers
Association reactions
X ray absorption spectroscopy
Catalyst supports
Pyridine
Vacancies
Catalyst activity
acetyl acetonate

Keywords

  • CURVED-WAVE THEORY
  • MOLECULAR-STRUCTURE
  • EXAFS CALCULATIONS
  • CRYSTAL
  • COMPLEXES
  • XANES
  • REFINEMENT
  • ALKENES
  • EDGE

Cite this

Feiters, M. C., Metselaar, G. A., Wentzel, B. B., Nolte, R. J. M., Nikitenko, S., Sherrington, D. C., ... Soldatov, A. V. (2005). X-ray absorption spectroscopic studies on nickel catalysts for epoxidation. Industrial and Engineering Chemistry Research, 44(23), 8631-8640. https://doi.org/10.1021/ie050208z
Feiters, M.C. ; Metselaar, G.A. ; Wentzel, B.B. ; Nolte, R.J.M. ; Nikitenko, S. ; Sherrington, D.C. ; Joly, Y. ; Smolentsev, G.Y. ; Kravtsova, A.N. ; Soldatov, A.V. / X-ray absorption spectroscopic studies on nickel catalysts for epoxidation. In: Industrial and Engineering Chemistry Research. 2005 ; Vol. 44, No. 23. pp. 8631-8640.
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Feiters, MC, Metselaar, GA, Wentzel, BB, Nolte, RJM, Nikitenko, S, Sherrington, DC, Joly, Y, Smolentsev, GY, Kravtsova, AN & Soldatov, AV 2005, 'X-ray absorption spectroscopic studies on nickel catalysts for epoxidation' Industrial and Engineering Chemistry Research, vol. 44, no. 23, pp. 8631-8640. https://doi.org/10.1021/ie050208z

X-ray absorption spectroscopic studies on nickel catalysts for epoxidation. / Feiters, M.C.; Metselaar, G.A.; Wentzel, B.B.; Nolte, R.J.M.; Nikitenko, S.; Sherrington, D.C.; Joly, Y.; Smolentsev, G.Y.; Kravtsova, A.N.; Soldatov, A.V.

In: Industrial and Engineering Chemistry Research, Vol. 44, No. 23, 09.11.2005, p. 8631-8640.

Research output: Contribution to journalArticle

TY - JOUR

T1 - X-ray absorption spectroscopic studies on nickel catalysts for epoxidation

AU - Feiters, M.C.

AU - Metselaar, G.A.

AU - Wentzel, B.B.

AU - Nolte, R.J.M.

AU - Nikitenko, S.

AU - Sherrington, D.C.

AU - Joly, Y.

AU - Smolentsev, G.Y.

AU - Kravtsova, A.N.

AU - Soldatov, A.V.

PY - 2005/11/9

Y1 - 2005/11/9

N2 - We have studied epoxidation catalysts based on complexes of nickel with acac (acetylacetonate) ligands in the solid state, in solution, and on a polymeric support by X-ray absorption spectroscopy. The EXAFS results show that the degree of association (monomer or trimer) of the Ni(acacR) complexes depends on the bulkiness of R. For R = H, trimers predominate both in the solid state and in solution, whereas for R = p-tBuBn, the monomers that are found in the solid state tend to associate to trimers in solution. The trimers are broken up by excess coreactant, i-butyraldehyde, which converts all Ni complexes to 6-coordinated species. The lower degree of association of the substituted Ni(acacR) complex accounts for its relatively high catalytic activity at low concentration. For the solid complexes, the EXAFS results, which provide one-dimensional structural information, are complemented by XANES simulations defining the three-dimensional structure around Ni. The benzimidazole and pyridine ligands of PBI and AMP-resin partially displace acac in the Ni ligand sphere upon grafting. For the rigid PBI this must result in vacancies in the Ni coordination sphere, which explains why this support gives an active catalyst whereas the AMP-resin does not.

AB - We have studied epoxidation catalysts based on complexes of nickel with acac (acetylacetonate) ligands in the solid state, in solution, and on a polymeric support by X-ray absorption spectroscopy. The EXAFS results show that the degree of association (monomer or trimer) of the Ni(acacR) complexes depends on the bulkiness of R. For R = H, trimers predominate both in the solid state and in solution, whereas for R = p-tBuBn, the monomers that are found in the solid state tend to associate to trimers in solution. The trimers are broken up by excess coreactant, i-butyraldehyde, which converts all Ni complexes to 6-coordinated species. The lower degree of association of the substituted Ni(acacR) complex accounts for its relatively high catalytic activity at low concentration. For the solid complexes, the EXAFS results, which provide one-dimensional structural information, are complemented by XANES simulations defining the three-dimensional structure around Ni. The benzimidazole and pyridine ligands of PBI and AMP-resin partially displace acac in the Ni ligand sphere upon grafting. For the rigid PBI this must result in vacancies in the Ni coordination sphere, which explains why this support gives an active catalyst whereas the AMP-resin does not.

KW - CURVED-WAVE THEORY

KW - MOLECULAR-STRUCTURE

KW - EXAFS CALCULATIONS

KW - CRYSTAL

KW - COMPLEXES

KW - XANES

KW - REFINEMENT

KW - ALKENES

KW - EDGE

UR - http://pubs.acs.org/cgi-bin/article.cgi/iecred/2005/44/i23/pdf/ie050208z.pdf

UR - http://dx.doi.org/10.1021/ie050208z

U2 - 10.1021/ie050208z

DO - 10.1021/ie050208z

M3 - Article

VL - 44

SP - 8631

EP - 8640

JO - Industrial and Engineering Chemistry Research

T2 - Industrial and Engineering Chemistry Research

JF - Industrial and Engineering Chemistry Research

SN - 0888-5885

IS - 23

ER -

Feiters MC, Metselaar GA, Wentzel BB, Nolte RJM, Nikitenko S, Sherrington DC et al. X-ray absorption spectroscopic studies on nickel catalysts for epoxidation. Industrial and Engineering Chemistry Research. 2005 Nov 9;44(23):8631-8640. https://doi.org/10.1021/ie050208z