Abstract
Functional materials impact every area of our lives, from electronic and computing devices to transportation and health. Here we examine the relationship between synthetic discoveries and the scientific breakthroughs that they have enabled. By tracing the development of some important examples, we explore how and why the materials were initially synthesized and how their utility was subsequently recognized. Three common pathways to materials breakthroughs are identified. In a small number of cases, such as the aluminosilicate zeolite catalyst ZSM-5, an important advance is made by using design principles based on earlier work. There are also rare cases of breakthroughs that are serendipitous, such as the buckyball and Teflon. Most commonly, however, the breakthrough repurposes a compound that is already known and was often made out of curiosity or for a different application. Typically, the synthetic discovery precedes the discovery of functionality by many decades; key examples include conducting polymers, topological insulators and electrodes for lithium-ion batteries.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Kokotailo, G. T., Lawton, S. L. & Olson, D. H. Structure of synthetic zeolite ZSM-5. Nature 272, 437–438 (1978).
Wilson, S. T., Lok, B. M., Messina, C. A., Cannon, T. R. & Flanigen, E. M. Aluminophosphate molecular-sieves—a new class of microporous crystalline inorganic solid. J. Am. Chem. Soc. 104, 1146–1147 (1982).
Capaca, E. et al. Synthesis and structure of a 22 × 12 × 12 extra-large pore zeolite ITQ-56 determined by 3D electron diffraction. J. Am. Chem. Soc. 143, 8713–8719 (2021).
Kresge, C. T., Leonowicz, M. E. & Beck, J. S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359, 710–712 (1992).
Wudl, F., Smith, G. M. & Hufnagel, E. J. Bis-1,3 dithiolium chloride: an unusually stable organic radical cation. Chem. Commun. 1970, 1453–1454 (1970).
Wudl, F. From organic metals to superconductors: managing conduction electrons in organic solids. Acc. Chem. Res. 17, 227–232 (1984).
Martín, N. Tetrathiafulvalene: the advent of organic metals. Chem. Commun. 49, 7025–7027 (2013).
Haywang, G. & Jonas, F. Poly(alkylenedioxythiophene)s—new, very stable conducting polymers. Adv. Mater. 4, 116–118 (1992).
Jonas, F. & Schrader, L. Conductive modifications of polymers with polypyrroles and polythiophenes. Synth. Met. 41–43, 831–836 (1991).
Kim, G. H., Shao, L., Zhang, K. & Pipe, K. P. Engineered doping of organic semiconductors for enhanced thermoelectric efficiency. Nat. Mater. 12, 719–723 (2013).
Worfolk, B. J. et al. Ultrahigh electrical conductivity in solution-sheared polymeric transparent films. Proc. Natl Acad. Sci. USA 112, 14138–14143 (2015).
Plunkett, R. J. in High Performance Polymers, their Origin and Development (eds Seymour, R. B. & Kirshenbaum, G. S.) 261–266 (Springer, 1986).
Sicard, A. J. & Baker, R. T. Fluorocarbon refrigerants and their syntheses: past to present. Chem. Rev. 120, 9164–9303 (2020).
Jones, D. E. H. Hollow molecules. New Sci. 32, 245 (1966).
Osawa, E. The evolution of the football structure for the C60 molecule: a retrospective. Phil. Trans. R. Soc. A 343, 1–8 (1993).
Rohlfing, E. A., Cox, D. M. & Kaldor, A. Production and characterization of supersonic carbon cluster beams. J. Chem. Phys. 81, 3322–3330 (1984).
Kroto, H. W., Heath, J. R., O’Brien, S. C., Curl, R. F. & Smalley, R. E. C60: buckminsterfullerene. Nature 318, 162–164 (1985).
Kratschmer, W., Lamb, L. D., Fostirapoulos, K. & Huffman, D. R. Solid C60: a new form of carbon. Nature 347, 354–358 (1990).
Hebard, A. F. et al. Superconductivity at 18 K in potassium-doped C60. Nature 350, 600–601 (1991).
Campbell, E. K., Holz, M., Gerlich, D. & Maier, J. P. Laboratory confirmation of C60+ as carrier of two diffuse interstellar bands. Nature 523, 322–323 (2015).
Rasmussen, S. C. Conjugated polymers and conducting polymers: the first 150 years. ChemPlusChem 85, 1412–1429 (2020).
Natta, G., Mazzanti, G. & Corradini, P. Stereospecific polymerization of acetylene. Atti Accad. Naz. Lincei Mem. Cl. Sci. Fis. Mat. Na. 25, 3–12 (1958).
Shirakawa, H., Lewis, E. J., MacDiarmid, A. J., Chiang, C. K. & Heeger, A. J. Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH)x. J. Chem. Soc. J. Chem. Soc. 1977, 578–580 (1977).
Ito, T., Shirakawa, H. & Ikeda, S. Simultaneous polymerization and formation of polyacetylene film on the surface of a concentrated soluble Ziegler-type catalyst solution. J. Poly. Sci. Polym. Chem. Ed. 12, 11–20 (1974).
Burroughes, J. H. et al. Light emitting diodes based on conjugated polymers. Nature 347, 539–541 (1990).
Wudl, F. & Srdanov, G. Conducting polymer formed of poly(2-methoxy-5-(2′-ethylhexyloxy)-p-phenylenevinylene). US patent 5,189,136 (1993).
Sariciftci, N. S., Smilowitz, L., Heeger, A. J. & Wudl, F. Photoinduced electron transfer from conducting polymer to buckminsterfullerene. Science 258, 1474–1476 (1992).
Perrot, S., Pawla, F., Pechev, S., Hadziioannou, G. & Fleury, G. PEDOT:Tos electronic and thermoelectric properties: lessons from two polymerization processes. J. Mater. Chem. C 9, 7417–7425 (2021).
Lee, G.-H. et al. Multifunctional materials for implantable and wearable photonic healthcare devices. Nat. Rev. Mater. 5, 149–165 (2020).
Weber, D. CH3NH3PbX3, ein Pb(II)-System mit kubischer Perowskitstruktur/CH3NH3PbX3, a Pb(II)-system with cubic perovskite structure. Z. Naturforsch. B 33, 1443–1445 (1978).
Wasylishen, R. E., Knop, O. & Macdonald, J. B. Cation rotation in methylammonium lead halides. Solid State Commun. 56, 581–582 (1985).
Poglitsch, A. & Weber, D. Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter-wave spectroscopy. J. Chem. Phys. 87, 6373–6378 (1987).
Yamada, K., Kawaguchi, H. & Matsui, T. Bull. Chem. Soc. Jpn 63, 2521–2525 (1990).
Koutselas, I. B., Ducasse, L. & Papavassiliou, G. C. Electronic properties of three- and low-dimensional semiconducting materials with Pb halide and Sn halide units. J. Phys. Condens. Matter. 8, 1217–1227 (1996).
Mitzi, D. B., Feild, C. A., Harrison, W. T. A. & Guloy, A. M. Conducting tin halides with a layered organic-based perovskite structure. Nature 369, 467–469 (1994).
Kagan, C. R., Mitzi, D. B. & Dimitrakopoulos, C. D. Organic–inorganic hybrid materials as semiconducting channels in thin-film field-effect transistors. Science 286, 945–947 (1999).
Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 6050–6051 (2009).
Jeong, J. et al. Pseudo-halide anion engineering for α-FAPbI3 perovskite solar cells. Nature 592, 381–385 (2021).
Al-Ashourim, A. et al. Monolithic perovskite/silicon tandem solar cell with >29% efficiency by enhanced hole extraction. Science 370, 1300–1309 (2020).
Wei, F. et al. Lead-free hybrid double perovskite (CH3NH3)2AgBiBr6: synthesis, electronic structure, optical and mechanical properties. Chem. Mater. 29, 1089–1094 (2017).
Vishnoi, P., Seshadri, R. & Cheetham, A. K. Why are double perovskites iodides so rare? J. Phys. Chem. C 125, 11756–11764 (2021).
Moore, J. E. The birth of topological insulators. Nature 464, 194–198 (2010).
Kane, C. L. & Mele, E. J. Z2 topological order and the quantum spin Hall effect. Phys. Rev. Lett. 95, 146802 (2005).
Bernevig, B. A., Hughes, T. A. & Zhang, S. C. Quantum spin Hall effect and topological phase transition in HgTe quantum wells. Science 314, 1757–1761 (2006).
Lange, P. W. Ein Vergleich zwischen Bi2Te3 und Bi2Te2S. Naturwissenschaften 27, 133–135 (1939).
Mönkmeyer, K. Über Tellur-Wismut. Z. Anorg. Chem. 46, 415–422 (1905).
Zhang, H. et al. Topological insulators in Bi2Se3, Bi2Te3 and Sb2Te3 with a single Dirac cone on the surface. Nat. Phys 5, 438–442 (2009).
Chen, Y. L. et al. Experimental realization of a three-dimensional topological insulator, Bi2Te3. Science 325, 178–181 (2006).
Boller, H. & Parthé, E. The transposition structure of NbAs and of similar monophosphides and arsenides of niobium and tantalum. Acta Crystallogr. 16, 1095–1101 (1963).
Weng, H., Fang, C., Fang, Z., Bernevig, B. A. & Dai, X. Weyl semimetal phase in noncentrosymmetric transition-metal monophosphides. Phys. Rev. X 5, 011029 (2015).
Lv, B. Q. et al. Experimental discovery of Weyl semimetal TaAs. Phys. Rev. X 5, 031013 (2015).
Huang, S.-M. et al. A Weyl fermion semimetal with surface Fermi arcs in the transition metal monopnictide TaAs class. Nat. Commun. 6, 7373 (2015).
Johnston, W. D., Heikes, R. R. & Sestrich, D. The preparation, crystallography and magnetic properties of the LixCo(1 − x)O system. J. Phys. Chem. Solids 7, 1–13 (1958).
Whittingham, M. S. The role of ternary phases in cathode reactions. J. Electrochem. Soc. 123, 315–320 (1976).
Mizushima, K., Jones, P. C., Wiseman, P. J. & Goodenough, J. B. LixCoO2 (0 < x < 1): a new cathode material for batteries of high energy density. Mater. Res. Bull. 15, 783–789 (1980).
Nishizawa, M., Yamamura, S., Itoh, T. & Uchida, I. Irreversible conductivity change of Li1-xCoO2 on electrochemical lithium insertion/extraction, desirable for battery applications. Chem. Commun. 1998, 1631–1632 (1998).
Chebiam, R. V., Kannan, A. M., Prado, F. & Manthiram, A. Comparison of the chemical stability of the high energy density cathodes of lithium-ion batteries. Electrochem. Commun. 3, 624–627 (2001).
Manthiram, A. A reflection on lithium-ion battery cathode chemistry. Nat. Commun. 11, 1550 (2020).
Li, W., Erickson, E. & Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy 5, 26–24 (2020).
Griffith, K. J. et al. Titanium niobium oxide: from discovery to application in fast-charging lithium-ion batteries. Chem. Mater. 33, 4–18 (2021).
Roth, R. S. & Coughanour, L. W. Phase equilibrium relations in the systems titania-niobia and zirconia-niobia. J. Res. Natl Bur. Stand. 55, 209–213 (1955).
Han, J.-T. & Goodenough, J. B. 3-V full cell performance of anode framework TiNb2O7/spinel LiNi0.5Mn1.5O4. Chem. Mater. 23, 3404–3407 (2011).
Danielson, E. et al. A combinatorial approach to the discovery and optimization of luminescent materials. Nature 389, 944–948 (1997).
Jandeleit, B., Schaefer, D. J., Powers, T. S., Turner, H. W. & Weinberg, W. H. Combinatorial materials science and catalysis. Angew. Chem. Int. Ed. 38, 2495–2532 (1999).
Banerjee, R. et al. High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture. Science 319, 939–943 (2008).
Corey, E. J. & Wipke, W. T. Computer-assisted design of complex organic syntheses. Science 166, 178–192 (1969).
Davies, I. W. The digitization of organic synthesis. Nature 570, 175–181 (2019).
Shields, B. J. et al. Bayesian reaction optimization as a tool for chemical synthesis. Nature 590, 89–96 (2021).
Kim, E. et al. Materials synthesis insights from scientific literature via text extraction and machine learning. Chem. Mater. 29, 9436–9444 (2017).
Raccuglia, P. et al. Machine-learning-assisted materials discovery using failed experiments. Nature 533, 73–76 (2016).
Schön, J. C. & Jansen, M. First step towards planning of syntheses in solid-state chemistry: determination of promising structure candidates by global optimization. Angew. Chem. Int. Ed. 35, 1286–1304 (1996).
Chen, B.-R. et al. Understanding crystallization pathways leading to manganese oxide polymorph formation. Nat. Commun. 9, 2553 (2018).
Jóhannesson, G. H. et al. Combined electronic structure and evolutionary search approach to materials design. Phys. Rev. Lett. 88, 255506 (2002).
Hautier, G., Fischer, C. C., Jain, A., Mueller, T. & Ceder, G. Finding nature’s missing ternary oxide compounds using machine learning and density functional theory. Chem. Mater. 22, 3762–3767 (2010).
Oliynyk, A. O. et al. High-throughput machine-learning-driven synthesis of full-Heusler compounds. Chem. Mater. 28, 7324–7331 (2016).
Burger, B. et al. A mobile robotic chemist. Nature 583, 237–241 (2020).
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. The Cambridge structural database. Acta Crystallogr. B 72, 171–179 (2016).
Bergerhoff, G., Hundt, R., Sievers, R. & Brown, I. D. The inorganic crystal structure data base. J. Chem. Inf. Comput. Sci. 23, 66–69 (1983).
Chung, Y. G. et al. Computation-ready, experimental metal–organic frameworks: a tool to enable high-throughput screening of nanoporous crystals. Chem. Mater. 26, 6185–6192 (2014).
Jain, A. et al. Commentary. The Materials Project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).
Ortiz, B. R. et al. New Kagome prototype materials: discovery of KV3Sb5, RbV3Sb5 and CsV3Sb5. Phys. Rev. Mater. 3, 094407 (2019).
Ortiz, B. R. et al. CsV3Sb5: a Z2 topological Kagome metal with a superconducting ground state. Phys. Rev. Lett. 125, 247002 (2020).
Sun, S. et al. Synthesis, crystal structure, and properties of a perovskite-related bismuth phase, (NH4)3Bi2I9. APL Mater. 4, 031101 (2016).
Zhuang, R. et al. Highly sensitive X-ray detector made of layered perovskite-like (NH4)3Bi2I9 single crystal with anisotropic response. Nat. Photon. 13, 602–608 (2019).
Hagman, L. & Kierkegaard, P. The crystal structure of NaMeIV2(PO4)3; MeIV = Ge, Ti, Zr. Acta Chem. Scand. 22, 1822–1832 (1968).
Chen, S. et al. Challenges and perspectives for NaSICON-type electrode materials for advanced sodium-ion batteries. Adv. Mater. 29, 1700431 (2017).
Acknowledgements
A.K.C. thanks the Ras al Khaimah Centre for Advanced Materials for financial support. R.S. gratefully acknowledges the US Department of Energy, Office of Science, Basic Energy Sciences, for support under award no. DE-SC-0012541.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Synthesis thanks Linda Nazar, Michael Hayward and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
References for Fig. 2.
Rights and permissions
About this article
Cite this article
Cheetham, A.K., Seshadri, R. & Wudl, F. Chemical synthesis and materials discovery. Nat. Synth 1, 514–520 (2022). https://doi.org/10.1038/s44160-022-00096-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s44160-022-00096-3
This article is cited by
-
A robotic platform for the synthesis of colloidal nanocrystals
Nature Synthesis (2023)
-
Combinatorial synthesis for AI-driven materials discovery
Nature Synthesis (2023)