Ionic Liquids for Inorganic and Materials Synthesis

Peter Nockemann, Rostock 2015 Ionic Liquids for Inorganic and Materials Synthesis Workshop Rostock 20. February 2015 . Peter Nockemann . Queen‘s Unive...

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Ionic Liquids for Inorganic and Materials Synthesis Workshop Rostock 20. February 2015 Peter Nockemann Queen‘s University of Belfast E-mail: [email protected] Peter Nockemann, Rostock 2015

Introduction to Ionic Liquids Applications of ILs in inorganic & materials chemistry

Metal-organic frameworks

Zeolithe synthesis

Catalysis Shaped nanoparticles

Coordination chemistry Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry

Outline 1. Coordination Chemistry in Ionic Liquids 2. Ionic Liquids for Materials Synthesis 3. Metal-Containing Ionic Liquids 4. Ionic Liquid Applications 5. Conclusions

Peter Nockemann, Rostock 2015

Spectroscopy in ionic liquids

Lanthanide & actinide spectroscopy in ionic liquids

Ionogels: hybrid materials consisting of an ionic liquid confined inside the nano-sized pores of a silica matrix

Chem. Commun., 2005, 34, 4354-4356. Inorganic Chemistry, 2007, 46, 11335-11344. Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry

O

N+

COOH

S

UCST

CF3

O NO S O CF3

Betainium ionic liquid [Hbet][Tf2N]

“Catalytic Hydrogenolysis of Aromatic Ketones in Mixed CholineBetainium Ionic Liquids“, ChemSusChem, 2008, 1, 997-1005. Stripping of metal ions from the ionic liquid

[Hbet][Tf2N] can solubilize large quantities of metal oxides J. Phys. Chem. B, 2006, 110, 20978 – 20992. Inorg. Chem., 2008, 47, 9987 - 9999. Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry Solubility of metal oxides in the task-specific ionic liquid [Hbet][Tf2N] [Cu3(bet)8(H2O)4][Tf2N]6

[Ni5(bet)12(H2O)6][Tf2N]10 formation of pentameric Ni-clusters potential magnetic material P. Nockemann et al., Crystal Growth & Design, 2008, 8, 1353 – 1363.

high solubility of the complexes in ionic liquids

Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry Pathway provides access to new classes of compounds and materials Co

Metal oxides dissolved in a taskspecific ionic liquid Mn

Ni

Zn Pb

Indication for the high potential of synthesis from ionic liquids Crystal Growth & Design, 2008, 8, 1353 – 1363. Inorg. Chem., 2008, 47, 9987 - 9999. Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry Coordination Chemistry in Ionic Liquids • Coordination of a cobalt(II) salt in a nitrile functionalised ionic liquid • Example for tunable coordinating abilities and solvent interaction • Cationic ‘solvent coordination’

F3C S

O

CF3

N

S

O

O

H

H

C

O

N

N

Chemistry – A European Journal 2010, 16, 1849-1858. Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry Nitrile functionalized ionic liquids – ionic analogues of organic solvents

• Thermally robust

F3C

• Large electrochemical window

O

N

• High conductivity

m

• high solubilizing power for metal salts

2A

3A

4A N

N

N N

N

(m = 1,2,3,5)

“ionic” analogue of acetonitrile

•„Tuning“ of the coordinating abilities possible 1A

O

N

• Low vapor pressure

S

N

N N

1B

2B

3B

N

N

4B N

N

Peter Nockemann, Rostock 2015

N

N

acetonitrile

CF3 S O

O

Coordination Chemistry in Ionic Liquids

F 3C

O S

N F3C O O

S

N

O CF3 S

O

Co

N O

O

S F3C O

O

N

O S O

CF3

S CF3

O S

Peter Nockemann, Rostock 2015

O

2+

N

2

S O

F 3C

O

O CF3

Coordination Chemistry in Ionic Liquids

Tf2N C

N

Tf2N Co

N

N NTf2

Peter Nockemann, Rostock 2015

N

Tf2N

C

Coordination Chemistry in Ionic Liquids

+8

N

N C

C N C

N

N

N

Peter Nockemann, Rostock 2015

Co N

C

N N N

N

C

C N

Coordination Chemistry in Ionic Liquids Hydration of a solvate – but reversible! F3 C

F3 C O

O N

S

O

S O

H2O C

N

Tf2N Co

N N

C

N NTf2

Tf2N

Crystal structure of [Co(Tf2N)3(H2O)(C2NMPyr)2](Tf2N)

Chemistry – A European Journal 2010, 16, 1849-1858. Peter Nockemann, Rostock 2015

Ionic liquids for extraction / separation of lanthanides Phosphine Oxide Functionalised Ionic Liquids • Tuning of the spacer length of these ion-tagged phosphine oxides affects the donor properties of the functional group

Chem. Commun., 2012, 48, 6115. Peter Nockemann, Rostock 2015

Ionic liquids for extraction / separation of lanthanides Phosphine oxide functionalised imidazolium ionic liquids as tuneable ligands for Lanthanide complexation 31

31P

NMR shift

P NMR shifts in a complexometric titration

molar ratio of IL Chem. Commun., 2012, 48, 6115. Peter Nockemann, Rostock 2015

1-hexyl-diphenylphosphine-oxide-2,3-dimethylimidazolium [Tf2N]-

Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry

Coordination Chemistry in Ionic Liquids • Coordination in an ionic liquid with a strongly coordinating anion • Dissolved metal complexes form anionic species • Conceptually suitable for extraction of metals

O N

O

N F3C

CF3

H. Mehdi et al., Chem. Commun., 2010, 113, 234-236. Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry Neodymium extraction using an ionic liquid Aqueous solution of Nd(Tf2N)3

O N

O

N F3C

CF3

[BMIM][hfac]

+

(a) (b)

(b) Ionic liquid

(a) Nd(Tf2N)3 in H2O H. Mehdi et al., Chem. Commun., 2010, 113, 234-236. Peter Nockemann, Rostock 2015

Peter Nockemann

Ionic Liquids for Inorganic and Materials Chemistry Structure of a neodymium(II) complex obtained after extraction Nd(Tf2N)3,aq + 4[C4mim][hfac]org -> [C4mim][Nd(hfac)4]org + 3[C4mim][Tf2N]org

[C4mim][Nd(hfac)4] Crystallised from a concentrated solution Chem. Commun., 2010, 113, 234-236. Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry

Outline 1. Coordination Chemistry in Ionic Liquids 2. Ionic Liquids for Materials Synthesis 3. Metal-Containing Ionic Liquids 4. Ionic Liquid Applications 5. Conclusions

Peter Nockemann, Rostock 2015

Ionic Liquid Based Nanofluids metal oxide NPs formation Cu2(OAc)4∙2H2O + 2 [P8 8 8 12][OAc] → [P8 8 8 12]2[Cu2(OAc)4(OH)2] + 2 HOAc → 2 CuO + 2 [P8 8 8 12][OAc] + 4 HOAc Heating a solution of Cu2(OAc)4∙2H2O in [P8 8 8 12][OAc]

In-situ synthesis of a copper(II)oxide dispersion Dalton Trans, 2012, 41, 219 (Hot Paper). Peter Nockemann, Rostock 2015

TEM - EDX

Facile in situ synthesis of nanofluids based on ionic liquids and copper oxide clusters and nanoparticles

Dalton Trans, 2012, 41, 219 (Hot Paper). Peter Nockemann, Rostock 2015

Ionic Liquid Based Nanofluids: In-Situ Synthesis and Physical Properties of Stable and Liquid Nanocomposite Materials

[Emim][Cu3(OAc)5(H2O)(OH)2]H2O Peter Nockemann, Rostock 2015

Ionothermal Synthesis of Polynuclear Metal Clusters in Acetate Ionic Liquids [C2mim]4[Ni6(OAc)13(OH)2(H2O)2](OAc)(HOAc)

µ-η2:η2 acetate binding mode

Peter Nockemann, Rostock 2015

Ionothermal Synthesis of Polynuclear Metal Clusters in Acetate Ionic Liquids

Peter Nockemann, Rostock 2015

Ionothermal Synthesis of Polynuclear Metal Clusters in Acetate Ionic Liquids

[C4mim]2[Co3(OAc)8]

[C4mim]{Mn3(OAc)7}n

Peter Nockemann, Rostock 2015

Ionothermal, Microwave-Assisted Synthesis of Indium(III) Selenide

J. Mat. Chem. A, 2014, accepted. Peter Nockemann, Rostock 2015

Ionothermal Syntheses of Nano- and Microstructured Ternary Copper-Indium-Chalcogenides

Overview of the reaction pathways and methods used

Peter Nockemann, Rostock 2015

Ionothermal Syntheses of Nano- and Microstructured Ternary Copper-Indium-Chalcogenides

Crystal structure of [C8mim]3{CuICl2CuIIOCl8}n Peter Nockemann, Rostock 2015

Ionothermal Syntheses of Nano- and Microstructured Ternary Copper-Indium-Chalcogenides Formed by the reaction of [C2mim][CuCl2], Ph2Se2 and [C2mim][InCl4]

Part of the crystal structure of the polymeric [CuCl(Se2Ph2)2]n Peter Nockemann, Rostock 2015

Ionothermal Syntheses of Nano- and Microstructured Ternary Copper-Indium-Chalcogenides

Peter Nockemann, Rostock 2015

Ionothermal Syntheses of Nano- and Microstructured Ternary Copper-Indium-Chalcogenides

SEM for CuInSe2

PXRD for CuInSe2

Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry

Outline 1. Coordination Chemistry in Ionic Liquids 2. Ionic Liquids for Materials Synthesis 3. Metal-Containing Ionic Liquids 4. Ionic Liquid Applications 5. Conclusions

Peter Nockemann, Rostock 2015

Chlorostannate(II) Ionic Liquids: Speciation, Lewis Acidity, and Oxidative Stability

119Sn

NMR spectra (186.48 MHz, 80 °C, neat liquid.

Inorg. Chem. 2013, 52, 1710−1721. Peter Nockemann, Rostock 2015

Validation of Speciation Techniques • • • •

Chlorozincate ionic liquids with imidazolium cations Chlorometallate ionic liquids are lewis acidic catalysts Tunable – control of the catalytic activity Applications in catalysis, electrodeposition and batteries

Peter Nockemann, Rostock 2015

+

Why is speciation so important? Lewis acidity





depends on a metal



increases with increasing χMClx: • Cl- is a Lewis base • polynuclear species, e.g. [Al2Cl7]-, are Lewis acids

Coordination environment of metal affects its:

• •

catalytic properties



redox potential Peter Nockemann, Rostock 2015

Bibliography

Critical review of the existing literature

Looking for a hint

bibliographic study on chlorozincates, including molten salts

speciation technique

FAB-MS ESI-MS Raman 1H and 13C NMR 35Cl NMR 1H and 13C solid state NMR X-Ray diffraction powder XRD EXAFS XANES cyclic voltammetry Freezing point DSC DSC POM

Peter Nockemann, Rostock 2015

phase

model

ionised gas ionised gas neat liquid solution neat supercooled liquid neat solid neat solid neat solid neat solid or liquid neat solid or liquid neat liquid neat solid/liquid neat solid/liquid neat solid/liquid neat solid

A A B A A A B A A A A A B A A

Guttmann Acceptor numbers

How we investigated...

Methodology

The acidity of these compounds were determined by measuring their Guttmann acceptor numbers (AN) via 31P NMR

Which means:

• A probe P(O)Et3 (tepo) is used and reacts with Lewis acid as follows: OO H55CC22 H

PP

H55 CC22H C C22HH55

OO + L.A.

H H55CC22

L.A.

PP

H55 CC22H CC2 HH5 2 5

• The chemical shift of the probe is measured on 31PNMR and directly proportional to their AN • Concentration effect eliminated by extrapolation to infinite dilution • Comparable to “classical” organic acids as AN are known for many acids or solvents

Peter Nockemann, Rostock Inorganic chemistry, 2011, 50,2015 5258-71.

Acidity of chlorozincate(II) ionic liquids 50 45

ZnCl3-

Zn2Cl5-

Zn2Cl5-

[Zn2Cl7]3-

GaCl4-

Ga2Cl7-

Ga2Cl7-

Ga3Cl10-

31P NMR

chemical shift (ppm)

40 35 30 25 20 15 10 5 0,30

0,40

0,50

0,60 χMClx

Peter Nockemann, Rostock Inorganic chemistry, 2011, 50,2015 5258-71.

0,70

Acidity of chlorozincate(II) ionic liquids - range of acidity Our enlarged acidity scale

Results obtained for chlorozincate(II) ILs have been compared to others ILs

As expected, chlorozincate(II) ionic liquids possess a medium Lewis acidity. Peter Nockemann, Rostock Inorganic chemistry, 2011, 50,2015 5258-71.

One technique in the liquid phase: Raman spectroscopy [ZnCl4]2

[Zn2Cl6]2-

[Zn3Cl8]2[Zn4Cl10]2[ZnnCl2n+2]2-

This Raman study confirms the results observed for the AN Both of these techniques are carried out on the liquid phase Peter Nockemann, Rostock Inorganic chemistry, 2011, 50,2015 5258-71.

The solid phase - A crystallographic study Single crystal have been obtained for different composition of [C2mim]Cl-ZnCl2

χZnCl2 = 0.33

χZnCl2 = 0.50

Crystal structures give results equivalent to what is observed with Raman. Here, speciation in the liquid and the solid states are equivalent. Peter Nockemann, Rostock Inorganic chemistry, 2011, 50,2015 5258-71.

The solid phase - A crystallographic study

Crystallography of [C2mim]Cl-ZnCl2

Single crystal have been obtained for different composition of [C2mim]Cl-ZnCl2

χZnCl2 = 0.33

χZnCl2 = 0.75

• First example of this type of zinc coordination • Here, obvious difference of speciation in the liquid and the solid states Inorganic chemistry, 2011, 50, 5258-71. Peter Nockemann, Rostock 2015

Suggested liquid-phase speciation of chlorozincate(II) ionic liquids:

Inorganic chemistry, 2011, 50, 5258-71.

Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry

Outline 1. Coordination Chemistry in Ionic Liquids 2. Ionic Liquids for Materials Synthesis 3. Metal-Containing Ionic Liquids 4. Ionic Liquid Applications 5. Conclusions

Peter Nockemann, Rostock 2015

+

WO/2012/046057

An ionic liquid process for mercury removal from natural gas

Peter Nockemann, Rostock 2015

An ionic liquid process for mercury removal from natural gas

Dalton Trans. 2015, DOI: 10.1039/c4dt03273j Peter Nockemann, Rostock 2015

+

WO/2012/046057

An ionic liquid process for mercury removal from natural gas

Dalton Trans. 2015, DOI: 10.1039/c4dt03273j Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry

Towards low temperature solid state chemistry in ILs A „temperature gap“ „Ionothermal Synthesis“ Solvent chemistry

Coordination chemistry

Solvothermal

Solid-state chemistry

Temperature

Novel inorganic synthetic pathways in coordination & materials chemistry Peter Nockemann, Rostock 2015

Ionic Liquids for Inorganic and Materials Chemistry Advantages of ionic liquids for materials chemistry: • Tuneable chemical and physical properties • Negligible vapour pressure – e.g. water can be reversibly removed • Large electrochemical window (some -4 V to +4 V) & chemical stability • High temperature stability (for some up to 400°C) • Stabilisation of new species, oxidation states etc. Limitations of ionic liquids: • Product separations / crystallisation • High viscosities • High manufacturing costs • Purity of ionic liquids is crucial Peter Nockemann, Rostock 2015

Acknowledgement •

Queen’s University Belfast • Dr. Małgorzata (Gosia) Swadźba-Kwaśny • Dr. Nimal Gunaratne • Collaborators: Dr. Johan Jacquemin, Dr John Holbrey, Prof. Martin Atkins, Prof. Ken Seddon • • •

Jorge Alvarez Vicente, Sophie Tyrrell, Claire Boudie, Anne Schmidt Sabine Möhle, Agata Mlonka, Stephen Osborne Lisa Shearer, Matthew Currie, Ke Wang, Yiwen Xu



Collaboration with Prof. Rik Van Deun, Prof. Kristof Van Hecke, UGhent; Prof. Koen Binnemans, K.U. Leuven



Funding: EPSRC, Umicore, Petronas, DAAD, IAESTE, InvestNI Peter Nockemann, Rostock 2015

Northern Ireland & Belfast

Peter Nockemann, Rostock 2015