Solid-State Metathesis Materials Synthesis

Richard G. Blair, Dr.1, Richard B. Kaner, Prof.2

1Materials and Device Technologies Division, Jet Propulsion Laboratory Pasadena, CA, 2Department of Chemistry & Biochemistry and California NanoSystems Institute, University of California, Los Angeles, CA

In the last two decades, a new method termed solid-state metathesis (SSM) has been developed to synthesize compounds that are often difficult to produce conventionally. Alkali or alkaline-earth metal main group compounds are combined with halides to form oxides,1–7 sulfides,3, 8 selenides,3, 8 tellurides,3 nitrides,9–15 phosphides,16–18 arsenides,17 antimonides,17 carbides,19, 20 silicides,21 borides,15, 22, 23 and aluminides.24 Additionally, nanostructured materials such as nanotubes,25 nanocrystals,26, 27 and high-surface-area materials28can be produced. These reactions provide a novel tool for preparing difficult-to-synthesize materials. Although the precursor is usually a halide, an oxide can be used as well. For example, we have shown that MgSiN2 can be synthesized by reacting SiO2 with Mg3N2.13Oxides have also been successfully used as precursors for hydroxyapatite29 and silicides.21

The driving force behind solid-state metathesis reactions is the formation of stable byproducts. For example, combining GaI3 with Li3N to produce GaN, as given in Scheme 1, has a ΔHrxn of –515 kJ.

Solid-state metathesis of gallium nitride

Scheme 1.Solid-state metathesis of gallium nitride

This is more than four times as energetic as the elemental reaction Ga + 0.5N2 > GaN (ΔH = –110 kJ).

SSM reactions can be initiated by flame, furnace, heated filament, ball mill, or microwave. The phase produced is often determined by the rate of the reaction.24 Similarly, the reaction rate can be tuned to control the crystallite size of the products formed.9 Diluents or fast reaction times can be used to produce nanoscale powders or materials with high surface areas.9

In a typical SSM reaction, an alkali or alkaline-earth metal compound with the desired anion is reacted with a metal halide or oxide. Reaction temperatures are controlled through the choice of halide, alkali or alkaline-earth metal,30 dilution, and vessel design. It is important to note that the driving force for these reactions is the heat released by the formation of alkali or alkaline-earth halides.

Alkali halides usually have lower heats of formation than alkalineearth halides, so reactions utilizing alkaline-earth metals will generally result in higher reaction temperatures. The upper limit of the reaction temperature is usually governed by the boiling point of the salt produced. Alkaline-earth salts have higher melting and boiling points, thereby increasing the upper limit of the reaction temperature.

The heavier the halogen used, generally the lower the reaction temperature. This can be useful for the synthesis of compounds that are unstable at high temperatures. For example, it is easier to obtain GaN from GaI3 than GaCl3 in a reaction with Li3N,10 due to the differences in heats of formation of LiI (ΔH = –270.4 kJ/mol) vs LiCl (ΔH = –408.5). Conversely, the synthesis of some materials is favored by high temperatures. The use of AlCl3 is a better choice than AlI3 when preparing AlN from the reaction with Ca3N2.9

Another effective method for lowering a reaction temperature is by using a diluent.31 This can be realized by adding inert salts, such as the byproduct salt itself, to the reaction mixture. This process can be improved for nitrides by adding low-melting or -vaporizing nitrogen containing compounds (like NH4Cl or LiNH2).10 Not only do these compounds act as a heat sink, but they can supply nitrogen to the reaction as well.

A final method for reducing a reaction temperature is by controlling the heat loss. In this way, these reactions can be effectively scaled up without producing destructive amounts of heat. This can be achieved by specifically designing the reaction vessel10 or by controlling the amount of heat produced by slow addition of precursors into the reactor. If a hotter reaction is desired, choose the starting materials carefully or begin these reactions at an elevated temperature.

In summary, solid-state metathesis (SSM) reactions have developed over the past two decades into an effective method for synthesizing materials that are difficult to make by conventional methods.31

Halides

Materials
Loading

References

1.
Gillan EG, Kaner RB. 2001. Rapid, energetic metathesis routes to crystalline metastable phases of zirconium and hafnium dioxide. J. Mater. Chem.. 11(7):1951-1956. http://dx.doi.org/10.1039/b102234m
2.
Wiley JB, Gillan EG, Kaner RB. 1993. Rapid solid state metathesis reactions for the synthesis of copper oxide and other metal oxides. Materials Research Bulletin. 28(9):893-900. http://dx.doi.org/10.1016/0025-5408(93)90035-c
3.
Parkin I, Rowley A. 1993. Metathesis routes to tin and lead chalcogenides. Polyhedron. 12(24):2961-2964. http://dx.doi.org/10.1016/s0277-5387(00)80046-7
4.
Hector A, Parkin I. 1993. Low-temperature solid-state routes to transition metal oxides via metathesis reactions involving lithium oxide. Polyhedron. 12(15):1855-1862. http://dx.doi.org/10.1016/s0277-5387(00)81423-0
5.
Hector AL, Parkin IP. 1994. Solid state metathesis preparations of group VIII metal oxide powders. J Mater Sci Lett. 13(3):219-221. http://dx.doi.org/10.1007/bf00278168
6.
Mandal TK, Gopalakrishnan J. 2004. From rocksalt to perovskite: a metathesis route for the synthesis of perovskite oxides of current interest. J. Mater. Chem.. 14(8):1273. http://dx.doi.org/10.1039/b315263d
7.
Parhi P, Ramanan A, Ray AR. 2004. A convenient route for the synthesis of hydroxyapatite through a novel microwave-mediated metathesis reaction. Materials Letters. 58(27-28):3610-3612. http://dx.doi.org/10.1016/j.matlet.2004.06.056
8.
Bonneau PR, Jarvis RF, Kaner RB. 1992. Solid-state metathesis as a quick route to transition-metal mixed dichalcogenides. Inorg. Chem.. 31(11):2127-2132. http://dx.doi.org/10.1021/ic00037a027
9.
Janes RA, Low MA, Kaner RB. 2003. Rapid Solid-State Metathesis Routes to Aluminum Nitride. Inorg. Chem.. 42(8):2714-2719. http://dx.doi.org/10.1021/ic026143z
10.
Cumberland RW, Blair RG, Wallace CH, Reynolds TK, Kaner RB. 2001. Thermal Control of Metathesis Reactions Producing GaN and InN?. J. Phys. Chem. B. 105(47):11922-11927. http://dx.doi.org/10.1021/jp0126558
11.
Wallace CH, Kim S, Rose GA, Rao L, Heath JR, Nicol M, Kaner RB. 1998. Solid-state metathesis reactions under pressure: A rapid route to crystalline gallium nitride. Appl. Phys. Lett.. 72(5):596-598. http://dx.doi.org/10.1063/1.120818
12.
Blair RG, Anderson A, Kaner RB. 2005. A Solid-State Metathesis Route to MgSiN2. Chem. Mater.. 17(8):2155-2161. http://dx.doi.org/10.1021/cm048234v
13.
Lacaze J. 2002. L'automobile et son monde. Annales des Ponts et Chaussées. 2002(101):85-86. http://dx.doi.org/10.1016/s0152-9668(02)80014-6
14.
Gibson K, Ströbele M, Blaschkowski B, Glaser J, Weisser M, Srinivasan R, Kolb H, Meyer H. 2003. Solid State Metathesis Reactions in Various Applications. Z. anorg. allg. Chem.. 629(10):1863-1870. http://dx.doi.org/10.1002/zaac.200300129
15.
Jarvis RF, Jacubinas RM, Kaner RB. 2000. Self-Propagating Metathesis Routes to Metastable Group 4 Phosphides. Inorg. Chem.. 39(15):3243-3246. http://dx.doi.org/10.1021/ic000057m
16.
Treece RE, Conklin JA, Kaner RB. 1994. Metathetical Synthesis of Binary and Ternary Antiferromagnetic Gadolinium Pnictides (P, As, and Sb). Inorg. Chem.. 33(25):5701-5707. http://dx.doi.org/10.1021/ic00103a016
17.
Rowley AT, Parkin IP. 1993. Convenient synthesis of lanthanide and mixed lanthanide phosphides by solid-state routes involving sodium phosphide. J. Mater. Chem.. 3(7):689. http://dx.doi.org/10.1039/jm9930300689
18.
Nartowski AM, Parkin IP, MacKenzie M, Craven AJ, MacLeod I. 1999. Solid state metathesis routes to transition metal carbides. J. Mater. Chem.. 9(6):1275-1281. http://dx.doi.org/10.1039/a808642g
19.
Nartowski AM, Parkin IP, Mackenzie M, Craven AJ. 2001. J. Mater. Chem.. 11(12):3116-3119. http://dx.doi.org/10.1039/b105352n
20.
Nartowski AM, Parkin IP. 2002. Solid state metathesis synthesis of metal silicides; reactions of calcium and magnesium silicide with metal oxides. Polyhedron. 21(2):187-191. http://dx.doi.org/10.1016/s0277-5387(01)00974-3
21.
Rao L, Gillan EG, Kaner RB. 1995. Rapid synthesis of transition-metal borides by solid-state metathesis. J. Mater. Res.. 10(2):353-361. http://dx.doi.org/10.1557/jmr.1995.0353
22.
Lupinetti AJ, Fife JL, Garcia E, Dorhout PK, Abney KD. 2002. Low-Temperature Synthesis of Uranium Tetraboride by Solid-State Metathesis Reactions. Inorg. Chem.. 41(9):2316-2318. http://dx.doi.org/10.1021/ic015607a
23.
Blair RG, Gillan EG, Nguyen NKB, Daurio D, Kaner RB. 2003. Rapid Solid-State Synthesis of Titanium Aluminides. Chem. Mater.. 15(17):3286-3293. http://dx.doi.org/10.1021/cm021829a
24.
McMillan PF, Gryko J, Bull C, Arledge R, Kenyon AJ, Cressey BA. 2005. Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route. Journal of Solid State Chemistry. 178(3):937-949. http://dx.doi.org/10.1016/j.jssc.2004.12.040
25.
McMillan PF, Gryko J, Bull C, Arledge R, Kenyon AJ, Cressey BA. 2005. Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route. Journal of Solid State Chemistry. 178(3):937-949. http://dx.doi.org/10.1016/j.jssc.2004.12.040
26.
Janes RA, Aldissi M, Kaner RB. 2003. Controlling Surface Area of Titanium Nitride Using Metathesis Reactions. Chem. Mater.. 15(23):4431-4435. http://dx.doi.org/10.1021/cm034629n
27.
Wen-yu S, Rong-hui Z, Qing-mei J. 2005. Catalyzed Oxidation of Tetrahydrofurfuryl Alcohol by Cerium(?) in Aqueous Sulphuric Acid Medium. 21(08):929-933. http://dx.doi.org/10.3866/pku.whxb20050821
28.
Parkin I, Nartowski A. 1998. Solid state metathesis routes to Group IIIa nitrides : comparison of Li3N, NaN3, Ca3N2 and Mg3N2 as nitriding agents. Polyhedron. 17(16):2617-2622. http://dx.doi.org/10.1016/s0277-5387(97)00454-3
29.
Gillan EG, Kaner RB. 1996. Synthesis of Refractory Ceramics via Rapid Metathesis Reactions between Solid-State Precursors. Chem. Mater.. 8(2):333-343. http://dx.doi.org/10.1021/cm950232a

Social Media

LinkedIn icon
Twitter icon
Facebook Icon
Instagram Icon

MilliporeSigma

Research. Development. Production.

We are a leading supplier to the global Life Science industry with solutions and services for research, biotechnology development and production, and pharmaceutical drug therapy development and production.

© 2021 Merck KGaA, Darmstadt, Germany and/or its affiliates. All Rights Reserved.

Reproduction of any materials from the site is strictly forbidden without permission.