Solid-State Synthesis of Mixed-

Metal OxidesPaola G. Caballero León

Anthony Hernández Rivera

Dr. Lukasz Koscielski

RISE Program

University of Puerto Rico at Cayey

Introduction

Solid State Chemistry

Materials Science

Synthesis, structure, and properties of

solid materials

Solid State Synthesis

Production of a solid substance by

combining simpler substances through

a chemical process.

High Temperature

Reaction in Solvents

“Shake and Bake” Procedure Involves precipitating the solid

from a solvent

Technological Applications

• Solid State Electronics

– Semiconductors

• Transistors

• Silicon Chips

• Photocells

• Cooperative Magnetic Behavior

– Ferromagnetism and Antiferromagnetism

• Reactions

– Catalysts(Salamat et al. 2011)

Specific Aims

• Synthesize new mixed metal oxide

compounds that exhibit distinct properties

resulting in a variety of applications for a

wide range of fields.

• Synthesize a mixed metal oxide with the

pyrochloric structure of A2B2O7

(Salamat et al. 2011)

Problem and Hypothesis

• Problem

– Can novel mixed metal oxide crystals be

obtained from a high temperature reaction of

solid powder reactants?

• Hypothesis

– Due to the wide array of stoichiometric

proportions, novel mixed metal oxide crystals

can be obtained from a high temperature

reaction of solid powder reactants.

Solid State Synthesis

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Liquid 1000°C “solution”

Predicting Products

1. Choose Reactants: Sn and Pb

2. Stoichiometry: 3Sn: 5Pb

3. Oxidation States: Sn+2, Sn+4, Pb+2, Pb+4 ,

O-2

4. Possible Products:Reactants Products

3Sn+2, 5Pb+2 Sn3Pb5O8

3Sn+2, 5Pb+4 Sn3Pb5O11

3Sn+4, 5Pb+2 Sn3Pb5O13

3Sn+4, 5Pb+4 Sn3Pb5O16

MIXED METAL OXIDE

REACTIONS

Group 14/14

1. Reaction 1: Sn and Pb

2. Stoichiometry: 9Sn: 15Pb

3. Oxidation States: Sn+2, Sn+4, Pb+2, Pb+4 ,

O-2

4. Possible Products:Reactants Products

9Sn+2, 15Pb+2 Sn9Pb15O24

9Sn+2, 15Pb+4 Sn9Pb15O39

9Sn+4, 15Pb+2 Sn9Pb15O33

9Sn+4, 15Pb+4 Sn9Pb15O48

Group 14/14

1. Reaction 2: Sn and Pb

2. Stoichiometry: 13Sn: 6Pb

3. Oxidation States: Sn+2, Sn+4, Pb+2, Pb+4 ,

O-2

4. Possible Products:Reactants Products

13Sn+2, 6Pb+2 Sn13Pb6O19

13Sn+2, 6Pb+4 Sn13Pb6O25

13Sn+4, 6Pb+2 Sn13Pb6O32

13Sn+4, 6Pb+4 Sn13Pb6O38

Group 15/15

1. Reaction 3: Sb and Bi

2. Stoichiometry: 7Sb: 21Bi

3. Oxidation States: Sb+3, Sb+5, Bi+3, O-2

4. Possible Products:

Reactants Products

7Sb+3, 21Bi+3 Sb7Bi21O42

7Sb+5, 21Bi+3 Sb7Bi21O49

Group 15/15

1. Reaction 4: Sb and Bi

2. Stoichiometry: 11Sb: 3Bi

3. Oxidation States: Sb+3, Sb+5, Bi+3, O-2

4. Possible Products:

Reactants Products

11Sb+3, 3Bi+3 Sb11Bi3O21

11Sb+5, 3Bi+3 Sb11Bi3O32

Group 14/15

Reactants Products

7Bi+3 , 9Sn+2 Bi14Sn18O39

7Bi+3 , 9Sn+4 Bi14Sn18O57

Reaction #1

1. Chosen Reactants: Sn, Bi

2. Stoichiometry: 7Bi:9Sn

3. Oxidation States: Bi+3, Sn+2, Sn+4

4. Possible Products:

Group 14/15

Reactants Products

13Pb+2, 23Bi+3 Pb26Bi46O95

13Pb+4, 23Bi+3 Pb26Bi46O121

Reaction #2

1. Chosen Reactants: Pb, Bi

2. Stoichiometry: 13Pb:23Bi

3. Oxidation States: Pb+2, Pb+4, Bi+3

4. Possible Products

Group 14/15

Reactants Products

33Pb+2, 21Sb+3 Pb66Sb42O129

33Pb+2, 21Sb+5 Pb66Sb42O171

33Pb+4, 21Sb+3 Pb66Sb42O195

33Pb+4, 21Sb+5 Pb66Sb42O237

Reaction #3

1. Chosen Reactant: Pb, Sb

2. Stoichiometry: 33Pb:21Sb

3. Oxidation States: Pb+4, Pb+4, Sb+3, Sb+5

4. Possible Products

Group 14/15

Reactants Products

12Sn+2, 17Sb+3 Sn24Sb34O75

12Sn+2, 17Sb+5 Sn24Sb34O109

12Sn+4, 17Sb+3 Sn24Sb34O99

12Sn+4, 17Sb+5 Sn24Sb34O133

Reaction #4

1. Chosen Reactant: Sn, Sb

2. Stoichiometry: 12Sn: 17Sb

3. Oxidation States: Sn+2, Sn+4, Sb+3, Sb+5

4. Possible Products

Group 14/15

Reactants Products

2Sn+2, 2Bi+3 Bi2Sn2O5

2Sn+4, 2Bi+3 Bi2Sn2O7

Reaction #5

1. Chosen Reactant: Bi, Sn

2. Stoichiometry: 2Sn:2Bi

3. Oxidation States: Sn+2, Sn+4, Bi+3

4. Possible Products

Pyrochloric

Structure

Methodology

1. Silica tubes are used because

of its ability to withstand

extreme pressures (10atm)

2. Pairs of tubes are split in half

using a special acetylene

flame.

3. Using the acetylene flame,

the bottom side of the tube is

ideally molded so the

reactants don’t pour out.

4. 2-3 drops of acetone are

added to the tubes, and the

bottom part of the tube is

flamed using a Bunsen

burner.

5. This step is repeated on three

separate occasions, in order

to create a three carbon lining

layer.

6. Finely powdered starting

materials are individually

added to the tubes and then

place in an oven at 500˚C-

1000˚C for approximately 1-2

weeks.

Methodology

Silica Tube

Acetilene

Flame

Carbon

Lining

http://www.uruguaye

duca.edu.uy/UserFil

es/P0001/Image/ima

genes/Bunsen.jpg

http://www.ustudy.in/sites

/default/files/images/oxy-

acetylene_weld_torch.jpg

Methodology

Limitations

• Non-operational Ovens

• Limited time

http://www.carolroth.com/wp-content/uploads/2013/04/MP900400674.jpg

Future Work

• Load our respective reactions using finely

powdered starting materials available at

the laboratory, elements: Sn, Pb, Sb, and

Bi (groups 14/15, 14/14, and 15/15).

• Synthesize new mixed-metal oxide

compounds according to the established

reactions.

Acknowledgements

• Dr. Lukasz Koscielski

• Gerardo Ramos

• RISE Program

• University of Puerto Rico at Cayey

Solid-State Synthesis of Mixed-

Metal OxidesPaola G. Caballero León

Anthony Hernández Rivera

Dr. Lukasz Koscielski

RISE Program

University of Puerto Rico at Cayey