prof. dr. claus feldmann at basf science symposium 2015
TRANSCRIPT
KIT – University of the State of Baden-Wuerttemberg and National Research Center of the Helmholtz Association
Prof. Dr. Claus Feldmann, Institut für Anorganische Chemie, Karlsruhe, Germany
www.kit.edu
Advanced Nanomaterials for a Sustainable Future
Karlsruhe Castle
150-Years-BASFSymposium on Smart Energy
08.03.–10.03.2015
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Advanced Nanomaterials for a Sustainable Future
I. Synthesis: Simple to Advanced
II. Materials: Controlling Composition, Size, Shape, Structure
III. Specific examples:
- Sensing
- Photocatalysis
- Less-noble Metals
C. Feldmann, KIT
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Polyol synthesisOxide nanoparticles
Aqueous precipitationInorganic-organic hybrids
Microemulsions / Liquid AmmoniaHollow Nanospheres, Less-noble Metals
Our Synthesis Strategies
CoAl2O4 ZnO:Co Fe2O3 CoO Cu2OTiO2 Ta2O5 Nb2O5 ZnO
Our reviews: Adv. Funct. Mater. 2003, 13, 101. Adv. Funct. Mater. 2003, 13, 511. Materials 2010, 3, 4355.Angew. Chem. Int. Ed. 2011, 50, 11050. Angew. Chem. Int. Ed. 2013, 52, 7610.
Ionic liquidsHalogen Compounds, Clusters
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Advanced Nanomaterials for a Sustainable Future
I. Synthesis: Simple to Advanced
II. Materials: Controlling Composition, Size, Shape, Structure
III. Specific examples:
- Sensing
- Photocatalysis
- Less-noble Metals
C. Feldmann, KIT
5Small 2007, 3, 1347. Nano Lett. 2007, 7, 3489. Adv. Mater. 2009, 21, 1586. Chem. Mater. 2010, 22, 4821. Nanoscale 2010, 2, 2223. Small 2010, 6, 1886. Nanoscale 2011, 3, 2544. Chem. Commun. 2012, 48, 844. Chem. Mater. 2013, 25, 4173.
Hollow Nanospheres
▪ Various materials▪ Outer diameter: 20 - 50 nm; Inner cavity size: 5 - 20 nm
6P. Leidinger, R. Popescu, D. Gerthsen, C. Feldmann, Chem. Mater. 2013, 25, 4173.
Hollow Nanosphere Superstructures: Ag2S
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In-Ag Janushead-likenanoparticles
Nanoscale Ag0
hollow spheresAg3In@In core-shell
nanoparticles
C. Kind, R. Popescu, E. Müller, R. Schneider, D. Gerthsen, C. Feldmann, RSC Adv. 2012, 2, 9473.
Nanoparticle Heterostructures: In-Ag Systema) b) c)
a) a) b) c) c)
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Controlled Shape: β-SnWO4
J. Ungelenk, C. Feldmann, Appl. Catal. B 2011, 102, 515.J. Ungelenk, C. Feldmann, Chem. Commun. 2012, 48, 7838.J. Ungelenk, C. Seidl, E. Zittel, S. Roming, U. Schepers, C. Feldmann, Chem. Commun. 2014, 50, 6600.Y.-C. Chen, J. Ungelenk, Y.-K. Hsu, Y.-G. Lin, C. Feldmann, in preparation.
▪ Nanoparticles(10 nm)
▪ Cubes(1 µm)
▪ Spike-Cubes(3 µm)
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Nanoparticle Composition: MWO4
J. Ungelenk, M. Speldrich, R. Dronskowski, C. Feldmann, Solid State Sci. 2014, 31, 62.
▪ Liquid phase synthesis of readily crystalline nanoparticles
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Structure: [BMIm]2[{Fe(CO)3}4{SnI}6I4]▪ Cluster compounds for thermal decomposition to nanoparticles
S. Wolf, F. Winter, R. Pöttgen, N. Middendorf, W. Klopper, C. Feldmann, Dalton Trans. 2012, 41, 10605.S. Wolf, F. Winter, R. Pöttgen, N. Middendorf, W. Klopper, C. Feldmann, Chem. Europ. J. 2012, 18, 13600.
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Advanced Nanomaterials for a Sustainable Future
I. Synthesis: Simple to Advanced
II. Materials: Controlling Composition, Size, Shape, Structure
III. Specific examples:
- Sensing
- Photocatalysis
- Less-noble Metals
C. Feldmann, KIT
12H. Goesmann, C. Feldmann, Angew. Chem. Int. Ed. 2010, 49, 1362 (Review).H. Gröger, C. Kind, P. Leidinger, M. Roming, C. Feldmann, Materials 2010, 3, 4355 (Review).
Water-in-oil microemulsion(w/o-ME)
Synthesis of Hollow Nanospheres
Advantages▪ Thermodynamically stable▪ Confined volume (nanoreactor)▪ Discrete reaction areas▪ Excellent colloidal stabilization▪ Standard technique
H2O
Dodecane
CTABhexanol
B
A
13D. H. M. Buchold, C. Feldmann, Nano Lett. 2007, 7, 3489.
Synthesis of Hollow NanospheresWater-in-oil microemulsion
(w/o-ME)
H2O
Dodecane
CTABhexanol
B
Al(Osec-Bu)3
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Hollow Nanospheres: γ-AlO(OH)
D. H. M. Buchold, C. Feldmann, Nano Lett. 2007, 7, 3489.
(120): 3.17 Å
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Pd@SnO2 core@shell structureSnO2@Pd core@shell structure
▪ 1-2 wt-% Pd for both samples▪ Different color of samples
Pd@SnO2 / SnO2@Pd for Sensing
Pd@SnO2 SnO2@PdF. Gyger, A. Sackmann, M. Hübner, P. Bockstaller, D. Gerthsen, H. Lichtenberg, J.-D. Grunwaldt, N. Barsan,U. Weimar, C. Feldmann, Part. Part. Syst. Charact. 2014, 31, 591.
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▪ Uniform fine distribution of Pd in SnO2
▪ Less uncovered Pd for Pd@SnO2
▪ Improved band-bending for Pd@SnO2
▪ Shielding against water for Pd@SnO2
Sensing: Pd@SnO2 / SnO2@Pd
F. Gyger, A. Sackmann, M. Hübner, P. Bockstaller, D. Gerthsen, H. Lichtenberg, J.-D. Grunwaldt, N. Barsan,U. Weimar, C. Feldmann, Part. Part. Syst. Charact. 2014, 31, 591.
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▪ Very good sensor performance with H2, CO▪ Best results for Pd@SnO2 at low temperature under humid conditions
Pd@SnO2 / SnO2@Pd for Sensing
F. Gyger, A. Sackmann, M. Hübner, P. Bockstaller, D. Gerthsen, H. Lichtenberg, J.-D. Grunwaldt, N. Barsan,U. Weimar, C. Feldmann, Part. Part. Syst. Charact. 2014, 31, 591.
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Advanced Nanomaterials for a Sustainable Future
I. Synthesis: Simple to Advanced
II. Materials: Controlling Composition, Size, Shape, Structure
III. Specific examples:
- Sensing
- Photocatalysis
- Less-noble Metals
C. Feldmann, KIT
19W. Jeitschko, A.W. Sleight, Acta Cryst. B 1972, 28, 3174. A. Walsh, Y. Yan, M. N. Huda, M. M. Al-Jassim, S. H. Wei, Chem. Mater. 2009, 21, 547.
β-SnWO4: A Promising Photocatalyst▪ β-SnWO4 claimed as promising photocatalyst▪ β-SnWO4 is a metastable high-temperature phase (>670 °C)
(Eg: 2.5-2.7 eV, yellow color)
α-SnWO4Red
1.6 eV
β-SnWO4Yellow2.5 eV
800 °CSnO + WO3
< 670 °C
▪ Quenching of β-SnWO4
→ defective, blackish, bulk material
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▪ Direct band gap (2.6 eV)▪ Mean particle diameter: 20 nm▪ Specific surface area: 71±1 m2 g−1
β-SnWO4: Nanoparticles
J. Ungelenk, C. Feldmann, Appl. Catal. B 2011, 102, 515.J. Ungelenk, C. Feldmann, Patent application, DE 102011012930.8, WO 2012031645.
β-SnWO4
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▪ Benchmarking of β-SnWO4 to other photocatalysts (TiO2, BiVO4)
J. Ungelenk, C. Feldmann, Chem. Commun. 2012, 48, 7838.J. Ungelenk, C. Seidl, E. Zittel, S. Roming, U. Schepers, C. Feldmann, Chem. Commun. 2014, 50, 6600.
β-SnWO4: Photocatalytic Evaluation▪ Degradation of methylene blue under simulated daylight
Methylene blue(most widely applied reference
for dye degradation)
22J. Ungelenk, C. Seidl, E. Zittel, S. Roming, U. Schepers, C. Feldmann, Chem. Commun. 2014, 50, 6600.
β-SnWO4: in-vitro Fluorescence▪ Transfection of β-SnWO4 in HepG2 cells (human liver carcinoma)
▪ Intrinsic fluorescence (optional detection)
23J. Ungelenk, C. Feldmann, Patent application, DE 102011012930.8, WO 2012031645.J. Ungelenk, C. Seidl, E. Zittel, S. Roming, U. Schepers, C. Feldmann, Chem. Commun. 2014, 50, 6600.
▪ Transfection of β-SnWO4 in HepG2 cells (human liver carcinoma)
▪ Acute phototoxicity at low dark and long-term toxicity
β-SnWO4: in-vitro Phototoxicity
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β-SnWO4: in-vivo Phototoxicity▪ HepG2 cells (human liver carcinoma) transfected with β-SnWO4
J. Ungelenk, C. Seidl, E. Zittel, S. Roming, U. Schepers, C. Feldmann, Chem. Commun. 2014, 50, 6600.C. Seidl, J. Ungelenk, E. Zittel, U. Schepers, C. Feldmann, 2015, submitted.
▪ Reduced size of primary tumor▪ Reduced metastasis
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Advanced Nanomaterials for a Sustainable Future
I. Synthesis: Simple to Advanced
II. Materials: Controlling Composition, Size, Shape, Structure
III. Specific examples:
- Sensing
- Photocatalysis
- Less-noble Metals
C. Feldmann, KIT
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Advantages▪ Standard technique▪ Thermodynamically stable▪ Confined volume (nanoreactor)▪ Excellent colloidal stabilization
Disadvantages▪ Phase stability (< 50°C)▪ Low yield▪ Water as polar phase
(MeOH, EtOH, EG, CH3CN)
N. M. Correa, J. J. Silber, R. E. Ritter, N. E. Levinger, Chem. Rev. 2012, 112, 4569 (Review).A. K. Ganguli, A. Ganguly, S. Vaidya, Chem. Soc. Rev. 2010, 39, 474 (Review).
Microemulsion Synthesis
Reactants
Alkane(oil-phase)
Surfactants
H2O
27F. Gyger, P. Bockstaller, D. Gerthsen, C. Feldmann, Angew. Chem. Int. Ed. 2013, 52, 12443.F. Gyger, P. Bockstaller, H. Gröger, D. Gerthsen, C. Feldmann, Chem. Commun. 2014, 50, 2939.
Advantages▪ Standard technique▪ Thermodynamically stable▪ Confined volume (nanoreactor)▪ Excellent colloidal stabilization
Disadvantages▪ Phase stability (< 50°C)▪ Low yield▪ Liquid ammonia as polar phase
… unknown in literature
Reactants
Alkane(oil-phase)
Surfactants
liquidNH3
Liquid-Ammonia-in-Oil Microemulsions
28F. Gyger, P. Bockstaller, D. Gerthsen, C. Feldmann, Angew. Chem. Int. Ed. 2013, 52, 12443.F. Gyger, P. Bockstaller, H. Gröger, D. Gerthsen, C. Feldmann, Chem. Commun. 2014, 50, 2939.
Synthesis of Less-Noble Metal Nanoparticles
▪ But: limited amount of nanoparticles from liquid-ammonia microemulsion
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Synthesis in Liquid Ammonia
C. Schöttle, P. Bockstaller, D. Gerthsen, C. Feldmann, 2014, 50, 4547.
▪ Easy to handle (except for -40 °C)
30C. Schöttle, P. Bockstaller, R. Popescu, D. Gerthsen, C. Feldmann, 2015, submitted.
Synthesis of Less-Noble Metal Nanoparticles
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Synthesis of Nanoscaled Nitrides: GaN
F. Gyger, P. Bockstaller, D. Gerthsen, C. Feldmann, Angew. Chem. Int. Ed. 2013, 52, 12443.F. Gyger, P. Bockstaller, H. Gröger, D. Gerthsen, C. Feldmann, Chem. Commun. 2014, 50, 2939.
d: 2.6 Å(β-GaN111: 2.60 Å)
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Summary
Hollow Nanospheres
Less-Noble Metal NanoparticlesNitride Nanoparticlesß-SnWO4 with different Shapes
C. Feldmann, KIT
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RG Feldmann – The Team
Metal-NPDr. Fabian GygerDr. Hailong DongLennart BrütschChristian SchöttleAlexander Egeberg
Solid State/Ionic LiquidsDr. Silke WolfDr. Dominic FreudenmannDavid HausmannNicola HerzbergFabian Altermann
Hollow Spheres/HybridsDr. Sara SimonatoJan Jung-KönigMarieke PoßDr. Witali BeichelViktor ReinLilly Neumeier
Luminescence/TCO/CatalysisJoachim HeckAna KuzmanoskiYing-Chu ChenDr. Qian LiuDorothee GößlMartin Röhr
C. Feldmann, KIT
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Cooperation / FundingAnalytical characterizationProf. Dagmar Gerthsen Laboratory for Electron Microscopy/KIT (TEM)Prof. Jörn Schmedt auf der Günne University of Siegen (NMR)Prof. Rainer Pöttgen University of Münster (Mößbauer)
Sensors / catalysis / solar cells:Dr. Nicolae Barsan, Prof. Udo Weimar University of TübingenProf. Jan-Dierk Grunwaldt Institute of Technical Chemistry and Polymer Sciences/KITDr. K. Schierle-Arndt, Dr. W. Hermes BASF LudwigshafenDr. Erik Ahlswede Center for Solar Energy and Hydrogen Research Stuttgart
Drug delivery:Prof. Frauke Alves MPI for Experimental Medicine GöttingenProf. Holger Reichardt University Hospital Göttingen, Institute of ImmunologyPD Ute Schepers Institute of Toxicology and Genetics/ KITDr. Kurt Dittmar, Dr. Heinrich Lünsdorf Helmholtz Center for Infection Research Braunschweig
Gas sorption/separation:Prof. Klaus Müller-Buschbaum University of WürzburgProf. Reiner Staudt University of Leipzig/University of OffenburgProf. Michael Türk Institute for Technical Thermodynamics and Refrigeration/KIT
C. Feldmann, KIT