Structural analysis and characterization of layer perovskite oxynitrides made from Dion-Jacobson oxide precursors

Joshua A. Schottenfeld, Alan J. Benesi, Peter W. Stephens, Gugang Chen, Peter C. Eklund, Thomas E. Mallouk

Research output: Contribution to journalArticle

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Abstract

A three-layer oxynitride Ruddlesden-Popper phase Rb1+xCa2Nb3O10-xN x·yH2O (x=0.7-0.8, y=0.4-0.6) was synthesized by ammonialysis at 800 °C from the Dion-Jacobson phase RbCa2Nb 3O10 in the presence of Rb2CO3. Incorporation of nitrogen into the layer perovskite structure was confirmed by XPS, combustion analysis, and MAS NMR. The water content was determined by thermal gravimetric analysis and the rubidium content by ICP-MS. A similar layered perovskite interconversion occurred in the two-layer Dion-Jacobson oxide RbLaNb2O7 to yield Rb1+xLaNb2O7-xN x·yH2O (x=0.7-0.8, y=0.5-1.0). Both compounds were air- and moisture-sensitive, with rapid loss of nitrogen by oxidation and hydrolysis reactions. The structure of the three-layer oxynitride Rb 1.7Ca2Nb3O9.3N 0.7·0.5H2O was solved in space group P4/mmm with a=3.887(3) and c=18.65(1)Å, by Rietveld refinement of X-ray powder diffraction data. The two-layer oxynitride structure Rb1.8LaNb 2O6.3N0.7·1.0H2O was also determined in space group P4/mmm with a=3.934(2) and c=14.697(2)Å. GSAS refinement of synchrotron X-ray powder diffraction data showed that the water molecules were intercalated between a double layer of Rb+ ions in both the two- and three-layer Ruddlesden-Popper structures. Optical band gaps were measured by diffuse reflectance UV-vis for both materials. An indirect band gap of 2.51 eV and a direct band gap of 2.99 eV were found for the three-layer compound, while an indirect band gap of 2.29 eV and a direct band gap of 2.84 eV were measured for the two-layer compound. Photocatalytic activity tests of the three-layer compound under 380 nm pass filtered light with AgNO3 as a sacrificial electron acceptor gave a quantum yield of 0.025% for oxygen evolution.

Original languageEnglish (US)
Pages (from-to)2313-2321
Number of pages9
JournalJournal of Solid State Chemistry
Volume178
Issue number7
DOIs
StatePublished - Jul 1 2005

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oxynitrides
structural analysis
Structural analysis
Perovskite
Oxides
Energy gap
oxides
X ray powder diffraction
Nitrogen
Rubidium
Rietveld refinement
Gravimetric analysis
Optical band gaps
Quantum yield
Synchrotrons
Water content
Hydrolysis
Moisture
X ray photoelectron spectroscopy
Nuclear magnetic resonance

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Schottenfeld, J. A., Benesi, A. J., Stephens, P. W., Chen, G., Eklund, P. C., & Mallouk, T. E. (2005). Structural analysis and characterization of layer perovskite oxynitrides made from Dion-Jacobson oxide precursors. Journal of Solid State Chemistry, 178(7), 2313-2321. https://doi.org/10.1016/j.jssc.2005.05.012
Schottenfeld, Joshua A. ; Benesi, Alan J. ; Stephens, Peter W. ; Chen, Gugang ; Eklund, Peter C. ; Mallouk, Thomas E. / Structural analysis and characterization of layer perovskite oxynitrides made from Dion-Jacobson oxide precursors. In: Journal of Solid State Chemistry. 2005 ; Vol. 178, No. 7. pp. 2313-2321.
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title = "Structural analysis and characterization of layer perovskite oxynitrides made from Dion-Jacobson oxide precursors",
abstract = "A three-layer oxynitride Ruddlesden-Popper phase Rb1+xCa2Nb3O10-xN x·yH2O (x=0.7-0.8, y=0.4-0.6) was synthesized by ammonialysis at 800 °C from the Dion-Jacobson phase RbCa2Nb 3O10 in the presence of Rb2CO3. Incorporation of nitrogen into the layer perovskite structure was confirmed by XPS, combustion analysis, and MAS NMR. The water content was determined by thermal gravimetric analysis and the rubidium content by ICP-MS. A similar layered perovskite interconversion occurred in the two-layer Dion-Jacobson oxide RbLaNb2O7 to yield Rb1+xLaNb2O7-xN x·yH2O (x=0.7-0.8, y=0.5-1.0). Both compounds were air- and moisture-sensitive, with rapid loss of nitrogen by oxidation and hydrolysis reactions. The structure of the three-layer oxynitride Rb 1.7Ca2Nb3O9.3N 0.7·0.5H2O was solved in space group P4/mmm with a=3.887(3) and c=18.65(1){\AA}, by Rietveld refinement of X-ray powder diffraction data. The two-layer oxynitride structure Rb1.8LaNb 2O6.3N0.7·1.0H2O was also determined in space group P4/mmm with a=3.934(2) and c=14.697(2){\AA}. GSAS refinement of synchrotron X-ray powder diffraction data showed that the water molecules were intercalated between a double layer of Rb+ ions in both the two- and three-layer Ruddlesden-Popper structures. Optical band gaps were measured by diffuse reflectance UV-vis for both materials. An indirect band gap of 2.51 eV and a direct band gap of 2.99 eV were found for the three-layer compound, while an indirect band gap of 2.29 eV and a direct band gap of 2.84 eV were measured for the two-layer compound. Photocatalytic activity tests of the three-layer compound under 380 nm pass filtered light with AgNO3 as a sacrificial electron acceptor gave a quantum yield of 0.025{\%} for oxygen evolution.",
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Structural analysis and characterization of layer perovskite oxynitrides made from Dion-Jacobson oxide precursors. / Schottenfeld, Joshua A.; Benesi, Alan J.; Stephens, Peter W.; Chen, Gugang; Eklund, Peter C.; Mallouk, Thomas E.

In: Journal of Solid State Chemistry, Vol. 178, No. 7, 01.07.2005, p. 2313-2321.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structural analysis and characterization of layer perovskite oxynitrides made from Dion-Jacobson oxide precursors

AU - Schottenfeld, Joshua A.

AU - Benesi, Alan J.

AU - Stephens, Peter W.

AU - Chen, Gugang

AU - Eklund, Peter C.

AU - Mallouk, Thomas E.

PY - 2005/7/1

Y1 - 2005/7/1

N2 - A three-layer oxynitride Ruddlesden-Popper phase Rb1+xCa2Nb3O10-xN x·yH2O (x=0.7-0.8, y=0.4-0.6) was synthesized by ammonialysis at 800 °C from the Dion-Jacobson phase RbCa2Nb 3O10 in the presence of Rb2CO3. Incorporation of nitrogen into the layer perovskite structure was confirmed by XPS, combustion analysis, and MAS NMR. The water content was determined by thermal gravimetric analysis and the rubidium content by ICP-MS. A similar layered perovskite interconversion occurred in the two-layer Dion-Jacobson oxide RbLaNb2O7 to yield Rb1+xLaNb2O7-xN x·yH2O (x=0.7-0.8, y=0.5-1.0). Both compounds were air- and moisture-sensitive, with rapid loss of nitrogen by oxidation and hydrolysis reactions. The structure of the three-layer oxynitride Rb 1.7Ca2Nb3O9.3N 0.7·0.5H2O was solved in space group P4/mmm with a=3.887(3) and c=18.65(1)Å, by Rietveld refinement of X-ray powder diffraction data. The two-layer oxynitride structure Rb1.8LaNb 2O6.3N0.7·1.0H2O was also determined in space group P4/mmm with a=3.934(2) and c=14.697(2)Å. GSAS refinement of synchrotron X-ray powder diffraction data showed that the water molecules were intercalated between a double layer of Rb+ ions in both the two- and three-layer Ruddlesden-Popper structures. Optical band gaps were measured by diffuse reflectance UV-vis for both materials. An indirect band gap of 2.51 eV and a direct band gap of 2.99 eV were found for the three-layer compound, while an indirect band gap of 2.29 eV and a direct band gap of 2.84 eV were measured for the two-layer compound. Photocatalytic activity tests of the three-layer compound under 380 nm pass filtered light with AgNO3 as a sacrificial electron acceptor gave a quantum yield of 0.025% for oxygen evolution.

AB - A three-layer oxynitride Ruddlesden-Popper phase Rb1+xCa2Nb3O10-xN x·yH2O (x=0.7-0.8, y=0.4-0.6) was synthesized by ammonialysis at 800 °C from the Dion-Jacobson phase RbCa2Nb 3O10 in the presence of Rb2CO3. Incorporation of nitrogen into the layer perovskite structure was confirmed by XPS, combustion analysis, and MAS NMR. The water content was determined by thermal gravimetric analysis and the rubidium content by ICP-MS. A similar layered perovskite interconversion occurred in the two-layer Dion-Jacobson oxide RbLaNb2O7 to yield Rb1+xLaNb2O7-xN x·yH2O (x=0.7-0.8, y=0.5-1.0). Both compounds were air- and moisture-sensitive, with rapid loss of nitrogen by oxidation and hydrolysis reactions. The structure of the three-layer oxynitride Rb 1.7Ca2Nb3O9.3N 0.7·0.5H2O was solved in space group P4/mmm with a=3.887(3) and c=18.65(1)Å, by Rietveld refinement of X-ray powder diffraction data. The two-layer oxynitride structure Rb1.8LaNb 2O6.3N0.7·1.0H2O was also determined in space group P4/mmm with a=3.934(2) and c=14.697(2)Å. GSAS refinement of synchrotron X-ray powder diffraction data showed that the water molecules were intercalated between a double layer of Rb+ ions in both the two- and three-layer Ruddlesden-Popper structures. Optical band gaps were measured by diffuse reflectance UV-vis for both materials. An indirect band gap of 2.51 eV and a direct band gap of 2.99 eV were found for the three-layer compound, while an indirect band gap of 2.29 eV and a direct band gap of 2.84 eV were measured for the two-layer compound. Photocatalytic activity tests of the three-layer compound under 380 nm pass filtered light with AgNO3 as a sacrificial electron acceptor gave a quantum yield of 0.025% for oxygen evolution.

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