Ordered Mesoporous Alumina-Supported Metal Oxides

Transcription

1 American Chemical Society, J. Am. Chem. Soc., ja q, Supporting Information Page S1 Ordered Mesoporous Alumina-Supported Metal Oxides Stacy M. Morris, Pasquale F. Fulvio and Mietek Jaroniec Chemistry Department, Kent State University, Kent, Ohio Quantity Adsorbed (cm 3 /g STP) MA-400 MA Fractional Pore Volume (cm 3 g -1 nm -1 ) Relative Pressure (P/P o ) Pore Diameter, w (nm) Figure S1. Adsorption isotherms (left) and PSDs (right) for Al 2 O 3 calcined at different temperatures. The isotherms for MA-400, and were offset by 270, 90 and 20 cm 3 /g STP, respectively. PSDs for MA-400 and were offset by 0.35 and 0.13 cm 3 g -1 nm -1, respectively. PSD for is not shown due to the structural collapse of this sample. To whom the correspondence should be addressed: Phone: ; jaroniec@kent.edu

2 American Chemical Society, J. Am. Chem. Soc., ja q, Supporting Information Page S MA-400 Intensity (a.u.) θ (degrees) Figure S2. Small angle XRD patterns for the Al 2 O 3 samples studied θ (degrees) Figure S3. Powder XRD patterns for the Al 2 O 3 samples studied. The XRD patterns for and show the presence of η-alumina (JCPDS ) and α-alumina (JCPDS ), respectively.

3 American Chemical Society, J. Am. Chem. Soc., ja q, Supporting Information Page S3 Figure S4. TEM image for MA-10Ni-700. Figure S5. TEM image for.

4 American Chemical Society, J. Am. Chem. Soc., ja q, Supporting Information Page S4 A B C Figure S6. EDX measurements for MA-10Ni-700. Panel A displays a measurement over the entire sample, panel B refers to an ordered domain of the sample and panel C refers to a disordered domain of the sample. Since all EDX spectra show the presence of Ni, this indicates an uniform distribution of this element in the sample.

5 American Chemical Society, J. Am. Chem. Soc., ja q, Supporting Information Page S5 Figure S7. 27 Al NMR Spectra for MA samples (left) and MA-10Ni samples (right) calcined from C (top to bottom). MA samples show a gradual change from tetrahedral (IV), pentahedral (V) and octahedral (VI) coordinated aluminum for MA-400 to tetrahedral and octahedral coordinated aluminum for. This change indicates a transition to crystalline γ-alumina as the calcination temperature increases (JACS 130, 3465, 2008). NMR spectra for MA-10Ni samples indicate the presence of pentahedral and octahedral coordination, which suggests nickel replacing the tetrahedrally coordinated aluminum to form nickel aluminate. The presence of symmetrical side bands complicates the spectra and there may be a slight percentage of tetrahedrally coordinated aluminum.

6 American Chemical Society, J. Am. Chem. Soc., ja q, Supporting Information Page S6 MA-50Ni-1100 MA-33Ni-1100 MA-20Ni-1100 MA-10Ni-1100 MA-5Ni θ (degrees) Figure S8. Powder XRD patterns for pure alumina and nickel-containing aluminum oxide samples calcined at 1100 C. XRD patterns for the samples calcined at 1100 C were assigned as follows: MA (αalumina, JCPDS ), MA-5Ni (α-alumina, JCPDS and NiAl 2 O 4, JCPDS ), MA- 10Ni (γ-alumina, JCPDS and NiAl 2 O 4, JCPDS ), MA-20Ni (NiAl 2 O 4, JCPDS ), MA-33Ni (NiAl 2 O 4, JCPDS ) and MA-50Ni (NiAl 2 O 4, JCPDS and NiO, JCPDS ). Although MA-10Ni-1100 shows a strong match to γ-alumina there is also evidence, to a lesser degree, of the presence of α-alumina (JCPDS ).

7 American Chemical Society, J. Am. Chem. Soc., ja q, Supporting Information Page S7 Table S1. Adsorption parameters evaluated from nitrogen adsorption isotherms for Ti, Mg, Ca and Crcontaining alumina samples calcined at 700 o C. a Sample S BET (m 2 /g) V sp (cm 3 /g) V c (cm 3 /g) w KJS (nm) MA-10Ti MA-10Ti MA-10Ti MA-10Mg MA-10Mg MA-10Mg MA-10Cr MA-10Cr MA-10Cr MA-10Ca MA-10Ca MA-10Ca a S BET - BET specific surface area obtained from adsorption data in range of relative pressures; V sp - single-point pore volume calculated from adsorption isotherm at P/P o = 0.98; V c - complementary pore volume obtained by integration of the PSD curve up to 3 nm; w KJS - pore width at the maximum of PSD. Figure S9. Photograph of titanium, magnesium, chromium and calcium-containing aluminum oxide samples.