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