havana varadero photoprocesses · (koh + dmso + luminol) ... chemoluminescence color by...
TRANSCRIPT
Michael W. Tausch
Havana
VaraderoJune, 2015
Photoprocessesin Chemical Education
Scientific Talk: Towards Photocatalytic CO2 Reduction
University Chemistry
of Wuppertal Education
Program
Curriculum Innovation
I: Why photoprocesses?
II: Didactical Credo
III: Experiments & Concepts
Outline:
Innovative Contents ► Experiments ► Teaching Concepts ► Printed and Eletronic Media
Photoprocesses in
Science Education
„It is now clear that electronically excited states of molecules
are the heart of all photoprocesses.The excited state is in fact
an electronic isomer of the ground state.“N. J. Turro, Modern Molecular Photochemistry. Benjamin/Cummings, N.Y. (1978)
Chemical education … deals with the metamorphosis of how to teach chemistry
„A pretty Experiment quite often is more precious than twenty
equations bred in the thinking retort.“A. Einstein, 1955
„Chemistry … deals with the metamorphosis of matter“A. F. Kekulé, 1855
E = mc2
Photoprozesse in der Lehre
der Naturwissenschaften
Light
S1→S0T1→S0
Luminescence: F, P, CL, EL, ECL
Energy transfer
Elektron transferFurther reaction
types
Isomerization
Photovoltaics
Photoprocesses in
Science Education
Requirements for a „pretty“ Experiment: ►appealing & beautiful ► instant & inexpansive
►secure & clean ► innovative & grean ► …
►didactically concise & scientifically consistent
Photoprocesses in
Science Education
Paradigm: Atomic and molecular systems can exist in the electronic ground state
as well as (even for a short time) in electronically excited states.
M.Tausch, M. v. Wachtendonk , C. Bohrmann-Linde, S. Krees (Hrsg.), CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2014)
The energy level model for molecules – A core concept in chemistry
excited state T1
τ = 10-2 – 102 s
excited state S1
τ = 10-9 – 10-8 s
Fluorescence
Phosphorescence
Exchange
of heat
lowest
unoccupied
energy level
highest
occupied
energy level
ground state So
M.T., D. Paterkiewicz, PdN-Chemie 36, 14 (1988); M.T., A. Grolmuss, M. Woock, PdN-Physik 47, 10 (1998); M.T., F.Gärtner, PdN-ChiS, 53, 20 (2004)
Photoprocesses in
Science Education
www.chemiedidaktik.uni-wuppertal.de > Vorträge; oder > Teaching Photochemistry
Photoprocesses in
Science Education
Melting 5 g
of tartric acid
Adding 5 mg
of Aesculene
Mixing and distributing
the melted mass
Testing the photo-
luminescence
Fluorescence at
room temperaturePhosphorescence at
room temperature
Video
Leuchtendes Scherblatt
Leuchtende Elektroden
with C. Bohrmann, ChiuZ 36 (3), 164 (2002) ; with J. Ibanez, C. Bohrmann -Linde u.a. J. Chem. Educ.. , 90 (4), 470 (2013)
(KOH + DMSO + Luminol)
www.chemiedidaktik.uni-wuppertal.de
Generation of the excited state
Chemical
reaction
Ground
state
Excided
state
Photoprocesses in
Science Education
The Glowing Razor Foil
Self made-OLED‘s
• Basic-OLED
• Flexi-OLED
• Easy-OLED
• Quick-OLED
Photoprocesses in
Science Education
with A. Banerji, U. Scherf, M. T., Chemkon, 19 (1), 7 (2012); with A. Banerji, U. Scherf , M. T. , Educ. Quimica , 24 (1), 17 (2013)
with C. Bohrmann, ChiuZ 36 (3), 164 (2002) ; with J. Ibanez, C. Bohrmann -Linde u.a. J. Chem. Educ.. , 90 (4), 470 (2013)
www.chemiedidaktik.uni-wuppertal.de
Chemoluminescence
Color by absorp-
tion of light
LB
VB e-
LB
VB
angeregter Zustand
e-
e-
e-
e-
h
Grundzustand
Pluspol
Minuspol
E
Electroluminescence
Chemical Core Concept
Ground State
and
Electronically Excited
States
Photoprozesse in der Lehre
der Naturwissenschaften
Photoluminescence
Fluorescence
Photoprocesses in
Science Education
Phosphorescence
non radiative
deactivation
DIN A5 ca. 4 €
E.D.Bergmann, A.Weizmann, E.Fischer, JACS, 72, 5009 (1950), M. T., Chemkon, 3, 123 (1996)
S. Krees, PdN-ChiS, 62 (8), 35 (2013); M. T., PdN-ChiS, 64 (1) 5 (2015)
Polystyrol
Toluol
PET-Folie
Light
Heat
Spiropyrane C19H18O3N2 Merocyanine C19H18O3N2
10
Non Polar
Nano-Enviroment
(Polystyrene)
Polar
Nano-Environment
(Nitrocellulose)
Mero SpiroSpiro Mero1 Basic Experiment
2 Wavelength
3 Temperature
4 Thin Layer
5 Matrix / Solvent
Photoprocesses in
Science Education
Chemie 2000+ , C.C. Buchner, Bamberg (2002..2014)
S. Spinnen, M. Essers, S. Krees, M. T., PdN-ChiS, 63, (2) 35 (2014);
S. Spinnen, M. T. PdN-ChiS 64 … (2015)
Photoprocesses in
Science Education
Beng Zhing Tang et al. „Aggregation-Induced Emission:
The Whole Is More Brilliant than the Parts“, Adv. Mat. DOI 10.1002 (2014)
S. Spinnen, M. Essers, S. Krees, M. T., PdN-ChiS, 63, (2) 35 (2014);
S. Spinnen, M. T. PdN-ChiS 64 … (2015)
Photoprocesses in
Science Education
S. Spinnen, M. T. PdN-ChiS 64 in press (2015)
Stokes Shift: 120 nm
Stokes Shift: 120 nm
Photoprocesses in
Science Education
Angeregter
Zustand
Grundzustand
Thermische Reaktion vs. photochemische Reaktion
M. W.Tausch, Chemkon, 3, 123 (1996)
Thermischer
Reaktionsweg
Photochemischer
Reaktionsweg
M.Tausch, M.v.Wachtendonk (Hrsg.), CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2010)
E.D.Bergmann, A.Weizmann, E.Fischer, JACS, 72, 5009 (1950)
Photochemical
Reaction
Pathway
Thermal
Reaction
Pathway
Reaction Coordinate
Photosteady
State
Photoprocesses in
Science Education
S. Shinkai et al. Bull. Chem. Soc. Jap., 60, 1819, (1987)
V. Ramamurthy, Photochemistry in Organized and Constrained Media, VCH, (1991)
D. Wöhrle, M.W. Tausch, W.-D. Stohrer, Photochemie, Wiley-VCH, (1998)
… a Molecular
Trojan Horse
… a Molecular „Vise“
(„Screw Matrix“)
Photoprocesses in
Science Education
M. Tausch, M.von Wachtendonk, C. Bohrmann-Linde, S. Krees (Hrsg.) Chemie 2000+ , C.C. Buchner, Bamberg (2002..2014)
K. Palczewski et al. „Crystal Structure of Rhodopsin...“. SCIENCE 289, 739 (2000)
M. T, M. Woock, A. Grolmuss: „Vom Lichtquant zum Sehreiz“, PdN (Physik), 47, 26 (1998)
… the photoswitch
in eye rhodopsine3 Millions of Retinal Cones
+ 100 Millions of Retinal Rods
Photoprocesses in
Science Education
„Viviamo sul fondo
di un oceano d‘aria“Evanghelista Torricelli, 1640
Satellite Photograph: Narrows of Gibraltar, 1995
Photoprocesses in
Science Education
poco despues de
la creation del Universo ...
Y dios dijo:
„Hagase la luz.“
Y la luz fue hechaBiblia, 1. Mose, Vers 4
…un requisito indispensable
para la vida en la tierra.
Y dios vio que
la luz era buena.Biblia, 1. Mose, Vers 4
Photosynthesis in numbers700.000.000.000 t Biomass/a 3.000.000.000.000.000.000.000 J/a 0,15%
Photoprocesses in
Science Education
yellow
solution
blue
solution
+hνλ < 450 nm
+O2
Silke Korn
Silke Korn
Shake
1. a light driven reduction
2. an oxygen consuming oxidation
3. the need of a light absorbing species
the natural cycle of
photosynthesis and respiration
M. T. , D. Wöhrle „“Photokatalyse“ PdN-Chemie 38 (3), 37 (1989); M.T. „Photo-Blue-Bottle …“ . PdN-Chemie 43 (3), 13 (1994)
S .Korn, M. T., J. Chem. Educ. 78 (9), 1238 (2001); … M. Heffen, M. T., PdN-ChiS, 64 (2), 45 (2015)
D. Wöhrle. M.Tausch, W.-D. Stohrer, Photochemie – Konzepte, Methoden, Experimente, Wiley-VCH, Weinheim (1998)
Photoprocesses in
Science Education
Photoprocesses in
Science Education
c ≈ 5.10-5 mol/l
c ≈5. 10-3 mol/l
excessM. T., S .Korn, J. Chem. Educ. 78 (9), 1238 (2001); M. T., M. Heffen, R. Krämer, N. Meuter, PdN-ChiS, 64 (2), 45 (2015)
Sacrificial
DonorPhotocatalyst Substrate
Oxidizing
Agent
c = 5.10-3 mol/Lc = 5.10-5 mol/LExcess
Supply
Light
Model-Sugar
Model-CO2
Photoprocesses
in Science Education
M. W. Tausch, PdN-ChiS 43 (3), 13 (1994)
EV2+
EV+
EthylviologeneProflavine
or TiO2
E
Electronically excited state
Highest occupied
energy level (HOMO)
Lowest unoccupied
energy level (LUMO)
AA
A
Endergonic
Reduction
Photoprocesses in
Science Education
Photosynthesis
Apparatus
C- and O-
cycles
Respiratory
Apparatus
Light
Mechanical, thermic
and other Energies
Energy
Photoprocesses
in Science Education
M. Tausch, M.von Wachtendonk, C. Bohrmann-Linde, S. Krees (Hrsg.) Chemie 2000+ , C.C. Buchner, Bamberg (2002..2014)
Shake
Light
Model-Sugar
Model-CO2
Energy
EV++
EV+Energy
Ethylviologene
EV2+ + e- EV+
C. Bohrmann-Linde, F. Posala, D. Nietz, M. T., PdN-ChiS 62 (5), 25 (2013)S .Korn, M. T., J. Chem. Educ. 78 (9), 1238 (2001);
M. Heffen, M. T. PdN-ChiS; in press
- +
X Light on
X Light off
● Air on
Air off
Time [min]
Vo
lta
ge
[mV
]
Conclusion:Light is converted
into chemical energy and
stored in the reduced substrate.
Photoprocesses
in Science Education
1LED
400 nm
3LED
530 nm
4LED
630 nm
100 nm
Nano-TiO2
REM
M.T., D. Wöhrle: PdN (Chemie) 38, 37 (1998); …M.T.., M. Heffen, PdN-ChiS 64 in press (2015)
M.Tausch, M. v. Wachtendonk , C. Bohrmann-Linde, S. Krees (Hrsg.), CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2014))
Photoprocesses in
Science Education
1LED
400 nm
3LED
530 nm
4LED
630 nm
Photoprocesses in
Science Education
388 nm
(3,1 eV)
Eg = 3,1 eV
EV++
EV+
TEA
TEAox
TiO2-Particle
Conduction Band
Valence Band
M.T., D. Wöhrle: PdN (Chemie) 38, 37 (1998); …M.T.., M. Heffen, PdN-ChiS 64 in press (2015)
M.Tausch, M. v. Wachtendonk , C. Bohrmann-Linde, S. Krees (Hrsg.), CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2014))
Photosynthesis-
apparatus
C- and O-
Cycles
Respiratory-
apparatus
Light
Mechanical, Thermic
and other Energies
Energye
Light
Modll-Shugar
Model-CO2
Energy
M. T., M. Heffen, PdN-ChiS; eingereicht, M. Tausch, M.von Wachtendonk, C. Bohrmann-Linde, S. Krees (Hrsg.) Chemie 2000+ … (2002..2014)
Ein starkes Paar
EV++
EV+
h∙ν
+O2
Ethylviologene
TiO2
TiO2 *
TiO2+
TEA
TEAox
Photoprocesses in
Science Education
Shake
Light
Model-H3COH … Energy
EV++
EV+
Model-CO2
Ethylviologene
Green
Fuel
Connected MediaOnline-Supplements for Textbooks:
Model Animations, Videos,
Interactive Worksheets etc.
Chemistry & Chem. Educ.
Michael W. Tausch
Dr. Claudia Bohrmann-
Linde
Prof. Dr. Simone Krees
Dr. Amitabh Banerji
Dr. Ralf-Peter Schmitz
Dr. Bernd Rohe
Rebecca Roggendorf
Heidrun Geller
René Krämer
Nico Meuter
Maria Heffen
Melanie Zepp
Heiko Hoffmann
Sebastian Spinnen
Ibeth Rendón Enríquez
Ingrid Reisewitz-Swertz
Renate Gärtig
David Nietz
Frederic Posalla
Saskia Ruckebier
u.v.a.