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TEPTEP-CH

DESY

girls day

SINQ

PhD stud. day

PerovskitePerovskite-type photocatalysts
Anke Weidenkaff
www.empa.ch/abt.131
www.empa.ch/abt.131

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Materials Science & Technology

Laboratory for Solid State Chemistry and Catalysis


Weidenkaff, A.
Abteilungsleiterin
Hanselmann, K.
Sekretariat
Weidenkaff, A.
Solid State Chemistry
-Aguirre, M.
-Trottmann, M.
-Robert, R.
-Logvinovich,
Logvinovich, D.
-Shkabko,
Shkabko, A.
-Bocher,
Bocher, L.
-Tomes, P.
-Sch
Schuble, N.
-Hmmerli,
mmerli, A.
-Toggweiler,
Toggweiler, S.

Thermoelectric
materials
PerovskitePerovskite-type
oxynitrides

Ferri,
Ferri, D.
Heterogeneous Catalysis
-NN
-Hug,
Hug, P.
-Korsak,
Korsak, O.
-Eyssler,
Eyssler, A.
-Aglae,
Aglae, A.

Novel exhaust gas


catalysts
InIn-situ spectroscopy

N.N.
Solid State Analysis
-Lienemann,
Lienemann, P.
-Gfeller,
Gfeller, U.
-Bukowiecki,
Bukowiecki, N.

SRSR-XRF analysis
of trace elements
in ambient air

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Materials Science & Technology

Focal points of the laboratory


1. Solid State Materials Chemistry
Synthesis and characterization of tailortailor-made perovskiteperovskite-type functional materials
with improved properties for potential applications in energy conversion
conversion
technologies, such as thermoelectric converters, solar photocatalytic cells, and
exhaust gas treatment.
treatment.
2. Heterogeneous Catalysis
Improvement of present catalytic materials to reduce pollutants. Finding new
methods for the clarification of the nature, structure, sorptive and reactive
features of catalytic sites at the surface of catalysts and the behavior of the
catalyst components under reaction conditions.
conditions.
3. Inorganic Solid State Analysis
MacroMacro-, micromicro- and nanoscopic analysis of the chemical composition and structure
of solids, such as e.g. novel crystalline phases, functional materials,
materials, and particles
from synthetic and natural sources. The elemental and structural analysis is
performed by using Xray (synchrotron), electronelectron- and neutron probe techniques,
techniques,
i.e. XRD, ND, XRF, XPS, TEM and XAS.

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Materials Science & Technology

FKCh@empa:
FKCh@empa: tailoring
tailoring of functional materials
structurestructure-compositioncomposition-propertyproperty-relation
relation

Step 1: Definition of
Requirements
Function: e.g. transport
properties, reactivity,
stability

test
Step 4:
Characterisation

Structure and composition


Dynamic processes:

theory,
economy,
environment

Step 2: Choice of
Materials
e.g. perovskites AMX3

transport, reactivity
Step 3: Tailoring
synthesis methods:
e.g. chimie douce and
aerosol processes
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Materials Science & Technology

Synthesis methods
rotating cavity

Soft chemistry,
chemistry, microemulsion,
microemulsion,
SolSol-gel
Ultrasonic spray combustion
Microwave induced plasma
PLD at PSI
20 nm

USC

01-1

110
101

[-111]

Mesoporous (La,Sr)TiO3

MIP

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Materials Science & Technology

Characterisation of structure,
structure, composition,
composition, properties

TGATGA-MS Thermogravimetrie mit gekoppelter Massenspektroskopie Untersuchung


Untersuchung der thermischen
Eigenschaften (Reaktivit
(Reaktivitt und Stabilit
Stabilitt) von Materialien wie z.B. GasGas-FeststoffFeststoff-Reaktionen,
Reaktionen,
Phasenumwandlungen, Reaktionsuntersuchungen mit der Pulse TA

DSC Differential Scanning Calorimeter Dynamisches W


Wrmestrom Kalorimeter Wrmekapazit
rmekapazittstsMessungen (Cp)
Cp) Messung von Umwandlungsw
Umwandlungswrmen (H) in verschiedenen Atmosph
Atmosphren,
temperaturabh
temperaturabhngig bis 1400 C

XRD Phasenanalyse mit Rntgendiffraktionsmethoden/Rietveld

ND Phasenanalyse mit Neutronendiffraktionsmethoden/Rietveld

XRF Rntgenfluoreszenzspektroskopie, Ermittlung der Zusammensetzung diverser Proben.

XAS Rntgenabsorptionsspektroskopie, EXAFS, XANES

RamanRaman-Mikroskopie,
Mikroskopie, InIn-situ RamanRaman-Mikroskopie zur Phasenanalyse,
Phasenanalyse, Kristallinit
Kristallinitt, Bestimmung von
Oberfl
Oberflchenspezies.
chenspezies.

InfrarotInfrarot- Spektroskopie,
Spektroskopie, operando und inin-situ Untersuchungen chemischer Reaktionen.

REM EDX Rasterelektronenmikroskopie Energy Dispersive Xray Analysis

TEM Transmissionselektronenmikroskopie, Hochaufl


Hochauflsende Transmissionselektronenmikroskopie zur
Untersuchung des atomaren Aufbaus und -Ordnung von Festk
Festkrpern, Elektronendiffraktion zur
Phasenanalyse

BET Brunnauer Emmet Teller Methode GassorptionsGassorptions-Messungen zur Bestimmung der spezifischen
Oberfl
Oberflche (BET(BET-Oberfl
Oberflche) in m2/g, TPR (Temperature
(Temperature Programmed Reduction)
Reduction) TPD (Temperature
(Temperature
Programmed Desorption)TPO (Temperature Programmed Oxidation)Chemisorption

LFA Messungen der Wrmeleitf


rmeleitfhigkeit von Werkstoffen mit der LaserLaser-flash Methode bis 1100
1100C

Hochtemperaturtransportmessungen,
Hochtemperaturtransportmessungen, Bestimmung der elektrischen Leitf
Leitfhigkeit und
thermoelektrischen Eigenschaften von Materialien (elektrischer Widerstand, SeebeckSeebeck-Koeffizient,
Koeffizient, Figure
of merit)
merit) bis 1100
1100C.
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Materials Science & Technology

Development of nonnon-conventional thermoelectrics


New temperature stable nanostructured
thermoelectric materials
9 Best n-type thermoelectric perovskites
CaMn1-xNbxO3

p-type: GdCo0.95Ni0.05O3

9 Reduction of thermal conductivity

n-type: CaMn0.98Nb0.02O3

by > factor 3
9 First Perovskite Thermoelectric Oxide
Module (TOM)
9 Test stand: TT-,V,V-Measurement with
LABVIEWLABVIEW-logging unit
9 3D3D-Simulation: direct coupled thermal
electrical simulation finite elements
method (coop A. Bitschi,
Bitschi, ETHZ)

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Materials Science & Technology

Anionic substitutions:
substitutions: Oxynitride Perovskites
DOS_srmonU20
DOS / (eV, cell)

New compounds with interesting properties:


9 highly conductive material: SrMoO2N

DOS / (eV, atom)

9 Heterostructures with different NN-content show


giant Seebeck, resistivity switching and

total
Motot
Otot

2
1
0
-1
-2

Srtot

Moeg
Mot2g

0.5
0.0
-0.5

superconductivity
DOS / (eV, cell)

-8

9 potential new water splitting catalyst with


bandgap 1.7 eV : LaNbON2

-6

-4

-2

total
Motot
Otot

1
0
-1

-3

0.05

-2

-1

0
1
Energy (eV)

-2

-1

300 K
160 K
9K

0.04
0.03
0.02

Current, A

0.01
0.00
-0.01
-0.02
-0.03
-0.04
-0.05
-5

-4

-3

Voltage, V

E. Selli, et al Chem. Commun., 2007, 5022

LaNbON2
orthorhombic
Nb-(O,N)-Nb = 160

Pnma

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Materials Science & Technology

Oxynitride Perovskites challenges


H

He

Li Be

N O

Na Mg

Al Si P

F Ne

S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te J Xe
Cs Ba Ln Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
Structural investigations on
perovskiteperovskite-type oxynitrides are rare
Only polycrystalline samples are
described
Physical properties are inadequately
characterised until now

AB(O,N)3

A2B(O,N)4

A3B2(O,N)7

A4B3(O,N)10

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Materials Science & Technology

UVUV-Vis diffusive reflectance spectroscopy of (La,Ca)Ti(O,N)3

XRD

Intensity

Band gap [eV]

3.6

10

20

30

40

50

60

70

3.2

light green
green

2.8

2.4

dark green
red-violett
0.0

80

0.2

2 [ ]

band gap reduced

0.4

0.6

0.8

1.0

Ca content

B-N more covalent than B-O

blue

(La,Ca)Ti(O,N)3

M (nd)

M (nd)

9pigments
9photocatalysts

N (2p)
O (2p)

O (2p)

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Materials Science & Technology

Optical properties design


O/N content control by crosscross-substitution
Electronegativity and size of A and B site cations
E

M nd

M nd

M nd

E1
N 2p
O 2p

E3
N 2p
O 2p

Smaller M-O-M angles lead to an


decrease of the d-band width and an
increase of the band gap.
gap.

E2
N 2p
O 2p

E3
N 2p
O 2p

Decreasing EN of the transitiontransition-metal


leads to an increase of the band gap.
gap.

CaTaO2N

SrTaO2N

Cubic
TaTa-O-Ta = 180
180
Gap 1.8 eV

M nd

E1

N 2p
O 2p

BaTaO2N

M nd

M nd

E2
N 2p
O 2p

Orthorhombic
TaTa-O-Ta = 153
153
Gap 2.4 eV

Tetragonal
TaTa-O-Ta = 170
170
Gap 2.1 eV

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Dyes and Pigments, 76 (2007) 70-75.

Materials Science & Technology

Crystal structures, anionic composition, band gap


LaNbON2
orthorhombic
Nb-(O,N)-Nb = 160
Gap 1.7 eV

BaNbO2N

SrNbO2N

Cubic
Nb-(O,N)-Nb = 180
Gap 1.8 eV

Tetragonal
Nb-(O,N)-Nb = 173
Gap 1.9 eV

c
a

Pnma

Pm3m

orthorhombic
Nb-(O,N)-Nb = 153
Gap 2.1 eV

b
a

CaNbO2N

I4/mcm

Pnma

Ionic radii : Ba (1.61 A) > Sr (1.41 A) > La (1.18 A) > Ca (1.12 A)

Band gap can be tuned by changing the structure distortion and N-content

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Materials Science & Technology

Photocatalytic Screening
Photocatalyzed decomposition of simple organic molecules

Xe lamp

UV filter IR spectrometer

IR detector
Oxynitride
film

Reactor
vessel

KBr
window

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Ceramic Materials Research Trends 2007

Materials Science & Technology

Spectroscopy of photocatalysts (Davide


(Davide Ferri)
Ferri)
in situ ATRATR-IR spectroscopy of solidsolid-liquid interfaces

abs. units

photocatalyst

2000

1800

1600

1400

wavenumber (cm-1)

UV-vis light

Hydrogen production
water splitting
alcohol decomposition

Molecular mechanism @ surface


TiO2 and other representative photocatalysts
effect and role of noble metal (Pt, Pd, Au)

solution

dp

IRE
IRE, internal reflection element
Harrick, Internal reflection spectroscopy Interscience Publishers: New York (1967)
Brgi, Baiker Adv. Catal. 50 (2006) 227

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Materials
Science
& Technology
Materials
Science
& Technology