Pore size dependent geochemistry...• Controlled Pore Glass (SiO 2(am)) –Macroporous (300 nm):...

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Joey M. Nelson 1 , John R. Bargar 2 , Gordon E. Brown, Jr. 1,2,3 , Kate Maher 1 1 Department of Geological and Environmental Sciences, Stanford University 2 Department of Photon Science and Stanford Synchrotron Radiation Lightsource, SLAC 3 Department of Chemical Engineering, Stanford University Pore size dependent geochemistry Global Climate & Energy Project Distinguished Student Lecture October 8, 2013

Transcript of Pore size dependent geochemistry...• Controlled Pore Glass (SiO 2(am)) –Macroporous (300 nm):...

  • Joey M. Nelson1, John R. Bargar2, Gordon E. Brown, Jr.1,2,3, Kate Maher1

    1 Department of Geological and Environmental Sciences, Stanford University 2 Department of Photon Science and Stanford Synchrotron Radiation Lightsource, SLAC 3 Department of Chemical Engineering, Stanford University

    Pore size dependent geochemistry

    Global Climate & Energy Project Distinguished Student Lecture October 8, 2013

  • EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    2

    Motivation: CO2 sequestration and engineering subsurface reactivity

  • 3

    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    Data from Brantley and Mellott (Am. Min., 2000), and Mayer (Chem. Geol., 1994)

    1 nm

    1 µm

    m

    m

    m

    m

    m

    m

    m

    m

    m

    m

    Macro

    po

    res (> 5

    0 n

    m)

    Micro

    po

    res (< 2

    nm

    ) M

    eso

    po

    res

    (2-5

    0 n

    m)

    IUPAC pore size ranges

    Stubbs et al., GCA, 2009 Velbel and Baker, CCM, 2008 Smith et al., PNAS, 1999

  • Effects of Mesopores

    Enhanced Adsorption Capacity

    4

    Diffusion Limited Transport

    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    (Zn adsorbed to alumina data from Wang et al., JCIS, 2002)

    Equilibration Time (s)

    Macroporous

    Mesoporous

    pH

    (U adsorbed to alumina data from Sun et al., Separ. Purif. Tech., 2011)

    Ad

    sorp

    tio

    n C

    apac

    ity

    (ml/

    g)

    pH

    Macroporous

    Mesoporous

  • Hypotheses 1. Meso-confinement phenomena result from unique

    geochemical processes, not transport limitations.

    2. The chemical mechanisms of sorption differ between macropores and mesopores, which could significantly impact CO2 sequestration.

    5

    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    Objectives 1. Quantify sorption rates and capacities with respect

    to pore size.

    2. Determine molecular structure of sorption complexes in macropores and mesopores.

  • Zn Adsorption on Silica

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    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    Batch Adsorption Experiments • Controlled Pore Glass (SiO2(am))

    – Macroporous (300 nm): 8.58 m2 g-1

    – Mesoporous (13.9 nm): 174 m2 g-1

    – Each batch contained equivalent amounts of substrate surface area

    Choice of Experimental System

    • Molecular geometry of sorbed CO2 is difficult to observe with XAFS

    • Zn exists in various complexes and is easily observed with XAFS

    • Silica is a simple substrate and the dominant mineral in saline aquifers

  • Geochemical Modeling

    • Diffusion-Reaction Model – Rate coefficient, k = 10-6 mol s-1

    – Diffusivity, Deff = 10-7 cm2 s-1

    • Batch reaction is well-mixed (i.e., not diffusion-limited)

    • Meso-confinement effects are due to unique geochemistry 7

    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    Reaction vs. Transport

    𝜕𝐶

    𝜕𝑡= 𝐷𝑒𝑓𝑓

    𝜕2𝐶

    𝜕𝑥2− 𝑘𝐶

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    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    Zn Adsorption Results

    • Zn adsorption capacity is enhanced by mesopores.

    • Indirect evidence that mesopores promote inner-sphere complexation (i.e., stronger binding).

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    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    • Extended X-ray absorption fine structure spectroscopy at BL 11-2 at SSRL, SLAC

    • Spectra unique to molecular environment of Zn in sample

    (Roberts et al., JCIS, 2003)

    C.N. 6

    4.6

    4

    4

    6.6

    4

    4

    4

    6

    Molecular Fingerprinting with EXAFS

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    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

    Zn EXAFS Results

    • Zn is dominantly 6-fold coordinated in macropores.

    • Zn is dominantly 4-fold coordinated in mesopores.

  • • Pore size is a tunable parameter for environmental remediation and chemical separations.

    • More accurate reactive transport models

    • Induce or enhance subsurface mineralization

    Conclusions

    • Zn adsorption capacity is enhanced and molecular configuration is altered in mesoporous silica.

    • Sorption of CO2 molecules in meso-confined pore volumes may also differ from less confined spaces.

    • Future study of CO2 sorption geometries with ATR-FTIR spectroscopy and quantum calculations.

    Implications

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    EXPERIMENTATION CONCLUSIONS INTRODUCTION SPECTROSCOPY

  • Acknowledgements

    Kate Maher, Gordon E. Brown Jr., Jen Wilcox, Scott Fendorf, Mike Massey, Adam Jew, Caroline Harris, Karrie Weaver, John Bargar, Noemie Janot

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    PORE SIZE DEPENDENT GEOCHEMISTRY GCEP RESEARCH SYMPOSIUM 2013

    Thank you! Questions? Poster 59: Enhanced Sorption of Zn in Mesoporous Silica


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