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    Local Structure of Bi Tao CL Nanophotocatalyst by Neutron Pair Distribution Function Analysis

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    linni123
    1) Neutron pair distribution function analysis was used to study the local structure of nano and bulk Bi4TaO8Cl photocatalyst. 2) Increased distortion of TaO6 octahedra was observed in the local structure of nano-Bi4TaO8Cl compared to bulk, leading to enhanced octahedral tilt. 3) The increased octahedral tilt influences the increased band gap of nano-Bi4TaO8Cl, improving its photocatalytic performance, as confirmed by density functional theory calculations.

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    Local Structure of Bi Tao CL Nanophotocatalyst by Neutron Pair Distribution Function Analysis

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    linni123
    31 views21 pages
    1) Neutron pair distribution function analysis was used to study the local structure of nano and bulk Bi4TaO8Cl photocatalyst. 2) Increased distortion of TaO6 octahedra was observed in the local structure of nano-Bi4TaO8Cl compared to bulk, leading to enhanced octahedral tilt. 3) The increased octahedral tilt influences the increased band gap of nano-Bi4TaO8Cl, improving its photocatalytic performance, as confirmed by density functional theory calculations.

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    IUCR 2017

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    1) Neutron pair distribution function analysis was used to study the local structure of nano and bulk Bi4TaO8Cl photocatalyst. 2) Increased distortion of TaO6 octahedra was observed in the local structure of nano-Bi4TaO8Cl compared to bulk, leading to enhanced octahedral tilt. 3) The increased octahedral tilt influences the increased band gap of nano-Bi4TaO8Cl, improving its photocatalytic performance, as confirmed by density functional theory calculations.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    31 views21 pages

    Local Structure of Bi Tao CL Nanophotocatalyst by Neutron Pair Distribution Function Analysis

    Uploaded by

    linni123
    1) Neutron pair distribution function analysis was used to study the local structure of nano and bulk Bi4TaO8Cl photocatalyst. 2) Increased distortion of TaO6 octahedra was observed in the local structure of nano-Bi4TaO8Cl compared to bulk, leading to enhanced octahedral tilt. 3) The increased octahedral tilt influences the increased band gap of nano-Bi4TaO8Cl, improving its photocatalytic performance, as confirmed by density functional theory calculations.

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    © All Rights Reserved
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    of 21

    Local Structure of Bi4TaO8Cl Nanophotocatalyst by

    Neutron Pair Distribution Function Analysis

    Dr. Nalini G Sundaram


    Assistant Professor
    Materials Science Division
    Poornaprajna Institute of Scientific Research
    Devanahalli, Bangalore

    August 21-28, 2017


    IUCr 2017
    Exploiting the Sun light by photocatalysis

    ➢Production of hydrogen by water splitting

    ➢Activating chemical processes ---- Organic transformations

    ➢Destroying undesired chemicals

    Mechanism

    Adv. Mater. 2012, 24, 229–251


    First Generation Photocatalyst : TiO2 a benchmark photocatalyst

    Band Gap – 3.2 eV

    Second Generation Photocatalysts


    ➢Doped TiO2 particularly with nonmetals
    Eg: TiO2-xN Optical absorption under visible ( wavelength < 500 nm )
    Low thermal stability
    ➢ Dopant free approach : Crystal facet engineering

    Third Generation Photocatalyst : Visible light active non-doped


    photocatalytic materials

    Bismuth based Photocatalyst Oxychlorides: BiOCl Eg=2.80 eV


    Phase Abs(nm) Eg (eV)
    Bi3O4Cl Eg=2.83 eV
    Bi12O17Cl2 524 2.60
    Bi3O4Cl 475 2.83 Anatase: TiO2 Eg=3.2 eV
    Bi24O31Cl10 463 2.90
    Bi12O15Cl 6 413 2.98
    BiOCl 480 2.82 Bismuth oxyhalides shows better catalytic performance
    Bi3O4Br 505 2.76 than Anatase
    Bi24O31Br10 494 2.79

    Science, 2001, 293, 269; Catalysis Today ., 2009 ,147 ,1–59; . Mater. Chem. A, 2014,2,2863–2884
    Third Generation Photocatalyst : Non-doped photocatalytic
    materials

    BiOBr Bi3O4Br

    TaO6 distortion decides the Layered structure enhances the


    photocatalytic activity photocatalytic activity

    Crystal Structure Matters!

    Jonathan Boltersdorf and Paul A. Maggard ACS Catal. 2013, 3, 2547-2555


    Influence of particle size and morphology on photocatalysis

    Substrate: RhB; UV: BiOCl > P25 Substrate: MO; visible: BiOI nanosheets Substrate: RhB; visible:
    > BiOI powders BiOBr> P25
    Environ. Sci.: Nano,2014,1,90–112
    Bismuth based Oxychlorides: Aurivillius-Sillen Phases

    ➢ [Bi2O2][An-1BnO3n+1][Clm] ;
    (n=1,m=1,B= Nb, Ta)

    ➢Sillen phase:[M2O2][Xm]
    ➢Aurivillius phase: [Bi2O2][An-1BnO3n+1]

    ➢Aurivillius-Sillen phase materials are


    important for ferroelectric, piezoelectric properties

    J. Mater. Chem.2001, 11, 1141–1145


    Bi4TaO8Cl nanoparticles synthesized by solution combustion technique

    ➢Size of the particles ranges from 30-80 nm for nano-Bi4TaO8Cl ;400-900 nm for bulk-Bi4TaO8Cl
    ➢ Forms nano structure with interconnected particle (Nano -Bi4TaO8Cl )
    N. Sundaram, et.al, RSC Advances, 2013, 3, 14371
    Band gap determination

    Band gap of bulk-Bi4TaO8Cl


    Eg=2.59 eV

    Band gap of nano-Bi4TaO8Cl


    Eg=2.80 eV

    Band gap for nano-Bi4TaO8Cl is larger than that of bulk-Bi4TaO8Cl


    Dye degradation(Congo Red) under UV irradiation
    Dye = 30 mg/L
    Catalyst = 0.2 g/100 mL

    Degradation profile for Congo Red dye under UV irradiation

    ➢ Nano Bi4TaO8Cl degrade the dye faster than the bulk


    Rietveld refinement of neutron data
    Bulk- Bi4TaO8Cl
    Nano- Bi4TaO8Cl

    ➢Neutron data were collected in spallation neutron source


    on NOMAD at Oak Ridge National Lab ()RNL), Oak Ridge
    Crystallographic data of nano-Bi4TaO8Cl and bulk -
    Bi4TaO8Cl obtained from Rietveld analysis

    Nano-Bi4TaO8Cl Bulk-Bi4TaO8Cl
    Space Group P 21cn P 21cn
    a (Å) 5.474(6) 5.459(2)
    b (Å) 5.431(7) 5.504(2)
    c (Å) 28.759(7) 28.699(9)
    α(degree) 90 90
    β (degree) 90 90
    γ (degree) 90 90
    Volume of unit cell(Å3) 855.19 (3) 862.37(1)
    Rf (%) 3.15 5.60
    Pair Distribution Function (PDF)

    a)

    b)

    Qmax = 36 Å-1
    a) nano- Bi4TaO8Cl PDF b) bulk- Bi4TaO8Cl
    ➢NPDF were collected in spallation neutron source
    on NOMAD, Oak Ridge National Lab (ORNL), Oak Ridge
    Pair distribution function pattern for a) nano- Pair distribution function indicating
    Bi4TaO8Cl PDF b) bulk- Bi4TaO8Cl PDF strain in TaO6 molecule.

    ➢ Broadened first peak in nano: wider distribution of Ta-O bond lengths

    ➢ signature of strain in TaO6 observed from the broadened peak at r


    range of 1.79 Å−2.21 Å for L-nano-Bi4TaO8Cl

    ➢ combination of particle size and strain: Shift of peak to lower ‘r’


    indicates presence of strain due to smaller particles
    PDF refinements using PDFgui from 1.5 to 5Å

    Pair distribution function fit for (a) nano-Bi4TaO8Cl and (b) bulk-Bi4TaO8Cl.
    Crystallographic data obtained from Rietveld analysis and PDF
    Structural representation along [010]

    TaO6 TaO6

    Bi2O2 Bi2O2

    Cl Cl

    nano-Bi4TaO8Cl bulk -Bi4TaO8Cl


    Octahedral Tilt

    The average Ta−O−Ta angle for L bulk- Bi4TaO8Cl tends more toward 180° than for L-nano-
    Bi4TaO8Cl
    Change in Ta−O−Ta angle enhanced tilt of TaO6 octahedra in local and average
    structures of nano-Bi4TaO8Cl

    TaO6 tilted octahedral shown with ball and stick model (a) A-nano-Bi4TaO8Cl (b) L-nano-Bi4TaO8Cl
    (TaO6 tilt is more for A-nano-Bi4TaO8Cl than L-nano-Bi4TaO8Cl).

    ➢Increase in tilt increases the band gap


    (a) Band structure of nano-Bi4TaO8Cl(Eg=1.48eV (b) Band
    structure of bulk-Bi4TaO8Cl (Eg=1.38eV)(c) DOS of nano-
    Bi4TaO8Cl (d) DOS of bulk-Bi4TaO8Cl The charge density plot of LUMO states in
    VB O 2p and Cl 3p orbitals (a) bulk-Bi4TaO8Cl and (b) nano-Bi4TaO8Cl
    (b) at 0.0015 electrons/Å3 isovalue
    CB Ta 5d and Bi 6p Orbitals

    ✓ Thestronger Bi−O pΠ−pΠ interactions within the Bi4O2 units are indicative
    of strong Bi−O bonds within the Bi4O2 units.

    ✓ The binding of Bi ions,connected with oxygens in TaO6 octahedra,


    weakens, which inturn is indicative of weak secondary structural distortion
    (second-order Jahn−Teller distortions
    Ta-O bond distances in (a) nano-Bi4TaO8Cl and (b) bulk-Bi4TaO8Cl

    Bi-O bond distances in (a) nano-Bi4TaO8Cl and (b) bulk-Bi4TaO8Cl


    Summary

    ➢ Increased distortion in TaO6 octahedra observed in the local


    structure of nano-Bi4TaO8Cl

    ➢ The corner-shared TaO6 octahedra were found to influence the


    photocatalytic performance.

    ➢ Increased octahedral tilt in local and average structure


    influence the increased band gap of nano-Bi4TaO8Cl which was
    further confirmed by DFT.

    ➢This study helps in identifying the key features in the crystal


    structure that controls the electronic structure and thereby the
    band gap.

    N. Sundaram, et.al, Inorg. Chem., 2017, 56 (10), pp 5525–5536.


    Acknowledgement
    ❖Dr. Swetha S.M., Former Research student, presently at Seoul
    National Unviersity, South Korea.
    ❖Dr. Mikhail Feygunson, Formerly Instrument scientist at NOMAD,
    ORNL, presently Scientific Staff at JCNS-1/ICS-1: Neutron Scattering
    ❖ Dr. Abhishek Mishra and Dr. Janardhan for DFT calclations
    ❖Prof. Chandrabhas Narayana JNCASR and Dr. Diptikanta, IISc
    ❖DST for funding
    ❖Dr. A.B.Halgeri, Director, PPISR, Bangalore

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