Unconventional synthesis methods for solid state...
Transcript of Unconventional synthesis methods for solid state...
Unconventional synthesis methodsfor solid state materials
Julia V. Zaikina
Chemistry Department, Iowa State University
Material discovery starts with synthesis...
steel plastic glass cement
solar panels superconductors QLED TV thermoelectrics
Structure
Synthesis
Properties
Properties
Synthesis
Structure
Material
Processing
Material
Chemistry
Materials Science
Theory
Structure
Synthesis
Properties
Properties
Synthesis
Structure
Material
Processing
Material
Chemistry
Materials Science
Theory
M. Jansen. Angew. Chem. Int. Ed. 2002, 41, 3746 ‐ 3766.
Solid State Synthesis is challenging...
Patnaik, S; Sadow, A. D. Angew. Chem. Int. Ed. 2019Walker, J. A.; Vickerman, K. L.; Humke, J. N.; Stanley, L. M.
J. Am. Chem. Soc. 2017, 30, 10228–10231.
R. Zhang, J. P. Peterson, L. J. Fischer , A. Ellern, A. H. Winter J. Am. Chem. Soc. 2018, 140, 43, 14308‐14313
Robole, Z.; Rahn, K.; Lampkin, B. J.; Anand, R. K.; VanVeller, B.Journal of Organic Chemistry 2018
End of XX century: Exploratory Solid State Synthesis
F. J. DiSalvo. Science, 1990, 247, 649‐655
A. Cheetham. Science, 1994, 264, 794‐795
J. D. Corbett. Inorg. Chem. 2010, 49, 13‐28 F. J. DiSalvo. Pure Appl. Chem., 2000, 72, 1799‐1807
From Exploratory Solid State Synthesis to Synthesis by Design
M. Jansen. Angew. Chem. Int. Ed. 2002, 41, 3746 ‐ 3766.
“Even the longest voyage begins with the first step”Lao‐tse 64, about 400 B.C.
M. Jansen. Adv. Mater. 2015, 27, 3229–3242.
M. Jansen. Adv. Mater. 2015, 27, 3229–3242.
M. Jansen. Adv. Mater. 2015, 27, 3229–3242.
Challenges
or she
M. G. Kanatzidis. Inorg. Chem. 2017, 56, 3158−3173
Panoramic Synthesis or in‐situ reaction monitoring by high‐temperature powder X‐ray diffraction
M. G. Kanatzidis. Inorg. Chem. 2017, 56, 3158−3173
D.P. Shoemaker, Y.‐J. Hu, D. Y. Chung, G. J. Halder, P.J. Chupas, L. Soderholm, J. F. Mitchell, M. G. Kanatzidis. PNAS, 2014, 111, 10922‐10927.
Cu + KSx ……..
V. Gvozdetskyi, B. Owens‐Baird, Sangki Hong, T. Cox, G. Bhaskar, J.V. Zaikina; manuscript in preparation. NaZn4Sb3
HT‐NaZn4Sb3
In‐situ reaction monitoring by high‐temperature powder X‐ray diffraction
An “easiest” task: a reproduction of published synthesis
Write your papers well
Read other’s papers well
Material Synthesis
Hans Georg von Schnering et al. Z. Anorg. Allgem. Chem. 2003, 629, 1256‐1264.
C
WCW6
Material Synthesis
An “easiest” task: a reproduction of published synthesis
Write your papers well
Report all and every details including The sources of starting materials Heating and cooling ratesAny postsynthetic treatments
Material Synthesis
H2Ti3O7 in KOH media:
TiO2 + KOH H2Ti3O7 + ???
Multiple reports of hydrothermal synthesis of H2Ti3O7 in
KOH solution at pH = 14
Not reproducible, expected K2Ti3O7 forms instead.
Authors “forgot” to report about washing samples with
HCl after synthesis.
Indeed, K2Ti3O7 + HCl H2Ti3O7 + KCl
Material Synthesis
GeP synthesis
“All discussed phases were synthesized in the temperature
range 600‐1000C.” No other details!T. Wadsten. Acta Chem. Scand. 1967, 21, 593‐594
Several attempts to synthesize GeP failed until (after multiple
attempts) the T and cooling rate were figured out.
Material Synthesis
Lee, K.; Synnestvedt, S.; Bellard, M.; Kovnir. J. Solid State Chem. 2015, 224, 62‐70.
SiP2 synthesis
Do I need to go crazy and report moon phase and ampoule length?
For synthesis involving gas phase, i.e. all pnictides,
chalcogenides, halogenides ampoule volume matters.
SiP2 syntheses in standard 10cm long ampoules failed.
SiP2 syntheses in 18cm long ampoules were successful.
Material Synthesis
An “easiest” task: a reproduction of published synthesisRead other papers well!
Not only main text but also supporting information
Pay attention to description of synthesis of different compounds, not all samples might have been produced in a similar way
Devil is in the details: if details, like heating/cooling rates, are not given, try several different heating rates or contact an author of original publication
Request students’ thesis – often helpful despite some might be not written in English
Material Synthesis
Material Synthesis
Dolyniuk, J.; Owens‐Baird, B.; Wang, J.; Zaikina, J.V.; Kovnir, K. Clathrate Thermoelectrics. Materials Science & Engineering R. 2016, 108, 1‐46.
Heat
Slow Cool
Spin
Dwell
• Seal under vacuum• Heat up• Cool down• Invert and Centrifuge• Harvest Crystals
Quartz Ampoule
Quartz Wool
Alumina Crucible
Layered Elements
Unconventinal Material SynthesisPart 1. Unconventional fluxes
M. G. Kanatzidis, R. Pöttgen, W. Jeitschko; Angew. Chem. Int. Ed. 2005, 44, 6996
P. Canfield. Solution Growth of Intermetallic Single Crystals: a Beginner’s Guide. In Properties and Application of Complex Intermetallics. 2010
Ga Ge
30°C 938°CTmelting
Unconventinal Material SynthesisPart 1. Unconventional fluxes
Good flux Not so good flux
Other low‐meting metals: Sn, In, Pb, Hg, Al, Bi, etc….
Unconventinal Material SynthesisPart 1. Unconventional fluxes
Binary Alloy Phase Diagrams, 2nd Ed., Ed. T.B. Massalski, ASM International, Materials Park, Ohio, 1990, 3, 2406‐2408
La‐Ni eutectic
+ B + C La2BC
+ Mn + CLa11[MnC6]3
LaRu2Al2B
+ Mn + C + ELa21Mn8E7C12 E = Ge, Sn, Sb, Te, Bi
+ Ru + B + Al
Mn + Al + SnLa11M13Sn4‐ (M = Mn/Ni/Al)
Unconventinal Material SynthesisPart 1. Unconventional fluxes
Synthesis from La/Ni eutectic flux
J.V. Zaikina, et. al. Inorg. Chem. 2010, 49, 2773‐2781 J.V. Zaikina, et. al. J. Solid State Chem. 2010, 183, 2987
J.V. Zaikina, et. al. Chem. Mater. 2010, 22, 1846‐1853
Prof. Susan E. Latturner
J.V. Zaikina, et. al. Inorg. Chem., 2017, 56, 15194–15202.
Synthesis from La/Ni eutectic flux
La‐Ni eutectic
+ B + C La2BC
+ Mn + CLa11[MnC6]3
+ Mn + C + ELa21Mn8E7C12 E = Ge, Sn, Sb, Te, Bi
Sn(1)@La9
Sn(2)@La12
AFM
Spin‐frustration
Unconventinal Material SynthesisPart 1. Unconventional fluxes
Synthesis from eutectic halide fluxes
Powders of LiCl and CsCl, elemental Fe and Se were added together with the flux into an alumina crucible andsealed under partial Ar atmosphere.The ampoule was heated to a homogenization temperature of 715C, where it was kept for 1 h and then removedinto a preheated furnace at 457C. After slow cooling to 300C, it was quenched in water.
R. Hu, H. Lei, M. Abeykoon, E. S. Bozin, S. J. L. Billinge, J. B. Warren, T. Siegrist, C. Petrovic. Phys. Rev. B 2011, 83, 224502
Unconventinal Material SynthesisPart 1. Unconventional fluxes
Synthesis from polysulphide fluxes
Cu + KSx ……..
M. G. Kanatzidis. Inorg. Chem. 2017, 56, 3158−3173
Standard ampoule synthesis: “shake and bake”
Temperature: check binary phase diagrams
Starting materials: Ru and Ge
Try to make RuGe, Tm > 1700 KRu + Ge good luck!
(Tm = 2607 K) (Tm = 1211 K)
Unconventinal Material SynthesisPart 2. Unconventional starting material
Unconventinal Material SynthesisPart 2. Unconventional starting material
Binary Alloy Phase Diagrams, 2nd Ed., Ed. T.B. Massalski, ASM International, Materials Park, Ohio, 1990, 3, 2406‐2408
Starting materials: not necessary elements
Try to make RuGe, Tm > 1700 KRu + Ge good luck
(Tm = 2607 K) (Tm = 1211 K)
What about…3Ru + 3GeCl2 3RuGe + 2RuCl3 ?
Unconventinal Material SynthesisPart 2. Unconventional starting material
Starting materials: not necessary elements
Try to make RuGe, Tm > 1700 KRu + Ge good luck
(Tm = 2607 K) (Tm = 1211 K)
What about…3Ru + 3GeCl2 3RuGe + 2RuCl3 ?
Unconventinal Material SynthesisPart 2. Unconventional starting material
Unconventinal Material SynthesisPart 2. Unconventional starting material
Y. Liu, L.‐M. Wu, L.‐H. Li, S.‐W. Du, J. D. Corbett, L. Chen. Angew. Chem. Int. Ed. 2009, 48, 5305 – 5308
Cs + Cd + Sb Cs8Cd18Sb28
Lu + Cd + Sb + CsClexcess Cs8Cd18Sb28 + LuCl3
Unconventinal Material SynthesisPart 2. Unconventional starting material
A. Kaltzoglou, S. Ponou, T. F. Fässler. Eur. J. Inorg. Chem. 2008, 538–542.
K + Hg + Sn K8Hg4Sn42
K + Hg + Ge
K4Ge9 + Hg K8Hg4Ge42 (powders)
K4Ge9 + HgO + WO3 K8Hg4Ge42 (crystals)
A. Kaltzoglou, S. Ponou, T. F. Fässler. Eur. J. Inorg. Chem. 2008, 4507‐4510.
NaH + Si Na4Si4 + H2KH + Ge K4Ge4 + H2Kauzlarich, S.M. and co‐workers, Dalton Trans., 2009, 10250
better mixing easy to work with lower synthesis temperaturefaster than traditional solid‐state methodsreducing atmosphere prevents formation of oxide layers
J. V. Zaikina, M. Batuk, A. M. Abakumov, A. Navrotsky, S.M. Kauzlarich J. Am. Chem. Soc. 2014, 136, 16932
Unconventinal Material SynthesisPart 2. Unconventional starting material
Hydride approach
Starting Materials Ball‐milled; for 30 min
Nb tube sealed with arc‐welder
KH + BaH2 + Fe + As Ba1‐xKxFe2As2 + H2
Hydride approach
Consolidate powder into dense pellet (>97%)
Applies pressure
Passes current through die & sample to raise temperaturePressure
Current
Spark‐Plasma Sintering (SPS)
Spark‐Plasma Sintering unit(upto 2200C and 20 kN)
In‐situ preparation and consolidation of BaFe2‐xCoxAs2via Spark‐Plasma Sintering (SPS)
J. V. Zaikina, M. Y. Kwong, B. Baccam, S.M. Kauzlarich. Chem. Mater. 2018, 30, 8883‐8890.
NaH + Si Na4Si4 + H2KH + Ge K4Ge4 + H2Kauzlarich, S.M. and co‐workers, Dalton Trans., 2009, 10250
better mixing easy to work with lower synthesis temperaturefaster than traditional solid‐state methodsreducing atmosphere prevents formation of oxide layers
Hydride approach toward synthesis of intermetallics
J. V. Zaikina, M. Y. Kwong, B. Baccam, S.M. Kauzlarich. Chem. Mater. 2018, accepted.
Hydride approach toward synthesis of intermetallics
T. Cox, V. Gvozdetskyi, B. Owens‐Baird, J. V. Zaikina. Chem. Mater., 2018, 30, 8707–8715.
V. Gvozdetskyi, M.P. Hanrahan, R.A. Ribeiro, T.H. Kim, L. Zhou, A.J.
Rossini, P.C. Canfield, J.V. Zaikina. Chem. Eur. J. 2019 Just Accepted.
LiH + Ni + B LiNi3B1.8 + H2
KH + Zn + Sb K8+xZn18+3xSb16 + H2
high‐temperature furnaces (up to 1200C) flow‐furnace
Unconventinal Material SynthesisPart 3. Unconventional heating
Spark‐Plasma Sintering unit(up to 2200C and 20 kN)
Unconventinal Material SynthesisPart 3. Unconventional heating
cold‐pressed bar shaped pellets
Ti + Ni + Sb TiNiSb
Ti + Co + Sb TiCoSb
evacuated quartz tubes
granular carbon as themicrowave susceptor inalumina insulation foam
Reactions were run at 100%power (700 W) for 1 min.After a ~ 2 sec. a purplish plasmawas observed through the gaps inthe housing surrounding thequartz tube which was followedby bright orange glow when thereaction was completed.
commercial microwave reactor(LG Goldstar)
No comparable reactiontakes place if no susceptormaterial is used
C.S. Birkel, W.G. Zeier, J.E. Douglas, B.R. Lettiere, C.E. Mills, G. Seward, A. Birkel, M.L. Snedaker, Y. Zhang, G. J. Snyder, T.M. Pollock, R. Seshadri, G.D. Stucky. Chem. Mater. 2012, 24, 2558–2565
Unconventinal Material SynthesisPart 3. Unconventional heating
cold‐pressed bar shaped pellets
Ti + Ni + Sb TiNiSb
Ti + Co + Sb TiCoSb
commercial microwave reactor(LG Goldstar)
• Energy‐saving preparative route• Faster (1 min vs. weeks)• No need for special setup
C.S. Birkel, W.G. Zeier, J.E. Douglas, B.R. Lettiere, C.E. Mills, G. Seward, A. Birkel, M.L. Snedaker, Y. Zhang, G. J. Snyder, T.M. Pollock, R. Seshadri, G.D. Stucky. Chem. Mater. 2012, 24, 2558–2565