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<\/p>\nArticle summary<\/p>\n
\nSuperatoms are atomically precise nanoclusters designed to mimic the chemistry of specific elements while avoiding drawbacks such as toxicity, rarity or high cost, potentially creating a \u2018third dimension\u2019 to the periodic table.
\nThe concept emerged from early nanocluster experiments showing certain \u2018magic number\u2019 clusters had unusual stability, with researchers discovering that aluminium clusters could behave like halogens depending on their electron configuration.
\nResearchers are now creating stable, ligand-protected superatoms for real-world applications including catalysis, light harvesting and energy materials, with gold and copper superatom clusters demonstrating enhanced selectivity, durability and efficiency.
\nSuperatoms are also being explored as replacements for problematic elements in technologies such as perovskite solar cells and batteries, where they can improve stability and performance while reducing reliance on toxic or precious materials.\u00a0
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This summary was generated by AI and checked by a human editor<\/p>\n
Across the periodic table\u2019s broad palette of chemical colour, each element is unique. Chemists artfully blend their distinct hues to create dazzling arrays of functional material masterpieces.<\/p>\n
Held up to the light, however, many elements have negative as well as positive aspects to their nature; characteristics that limit the real-world use of the materials they have been woven into. Next generation thin-film solar materials, for example, have been hampered by a reliance on toxic elements such as arsenic or lead. Palladium, platinum and rhodium often make exceptional catalysts, but their relative rarity and high cost prohibit many potential applications.<\/p>\n
From this perspective, the periodic table\u2019s elemental colour palette can seem very limited. Replacing the problematic element in a functional material with an alternative, even a near neighbour, often fundamentally changes the blend, altering the material\u2019s structure and compromising its function.<\/p>\n
What if we started making materials from building blocks whose properties were not so rigidly fixed? Could superatoms \u2013 small, tuneable clusters of atoms that can mimic aspects of the chemistry of particular elements, without containing a single atom of that element \u2013 fly to the rescue?<\/p>\n
Superatoms\u2019 origin story<\/p>\n
The concept that atomically precise nanoclusters could act as super-surrogates for specific chemical elements began as a theoretical pursuit, says Puru Jena, who came up with superatom science alongside Shiv Khanna at Virginia Commonwealth University in the US.<\/p>\n
\u2018Two experiments led us to the superatom concept,\u2019 Jena says. One involved an apparent magic trick, and the second centred on an aluminium cluster that thought it was a halogen.<\/p>\n
In the early 1990s, when Jena and Khanna proposed the superatom idea, nanocluster chemistry was in its infancy. Experimentalists worked mainly in the gas phase, producing nanoclusters in trace quantities from hot atomic plumes of one or more element in near-vacuum conditions.<\/p>\n
Walter Knight at the University of California, Berkeley, in the US had been using mass spectrometry to study sodium clusters created this way. \u2018They looked at the abundance of sodium clusters as a function of size, and found that clusters containing \u201cmagic\u201d numbers of atoms \u2013 including two, eight, 20 and 40 \u2013 were unusually stable, forming pronounced peaks in the mass spectra,\u2019 Jena says.<\/p>\n
This observation could be rationalised in the same way as noble gas stability, Knight showed. According to his \u2018jellium\u2019 model of spherical nanocluster electronic structure, each sodium atom contributes its single valance electron to a delocalised electron system. These electrons orbit the sodium ion cluster in shells akin to atomic orbitals. In magic number sodium clusters, these shells were filled. The eight-atom sodium cluster has its electrons arranged in a noble-gas-like 1s2 1p6 configuration, for example, while sodium-40 also has a filled shell set.<\/p>\n
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The size and composition of those superatoms could have almost infinite variation<\/p>\n
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The second experiment was led a few years later by Will Castleman at Pennsylvania State University, US. \u2018They found that if you take a cluster of 13 aluminium atoms \u2013 which has 39 delocalised electrons \u2013 and add one extra electron, then it becomes a stable 40 electron cluster just like sodium-40,\u2019 Jena says. With its stable closed shell electron arrangement, the Al13\u2013 cluster was inert to attack by oxygen, for example. Without the extra electron and one short of a closed shell, however, aluminium-13 was highly reactive \u2013 just like a halogen atom.<\/p>\n
By controlling the size and composition of a cluster, Jena realised, it should be possible to mimic the properties of atoms across the periodic table. He began to imagine a periodic table that was not flat like Mendeleev\u2019s, but featured a third dimension populated by superatoms. \u2018Because the size and composition of those superatoms could have almost infinite variation, that third dimension of the periodic table could be virtually unlimited,\u2019 he says.<\/p>\n
Superatoms also potentially offered enhancements over the elements they mimic. Toxic elements might be replaced by superatoms with the same chemistry but made only of atoms without environmental or health concerns. Rare and expensive elements could also be sidestepped. \u2018If I can mimic them with a superatom made of earth-abundant elements, I have found a way to circumvent the chemistry of the periodic table to eliminate some of the properties that are undesirable,\u2019 Jena says. As atomically precise cluster synthesis has developed, that vision is beginning to be realised.<\/p>\n
Moving from gas phase to solid state<\/p>\n
Cluster chemist Tatsuya Tsukuda from the University of Tokyo, Japan, makes solid-state superatom nanoclusters with real world functional promise. Tsukuda started his independent research group with the aim of testing whether superatom behaviours observed in clusters formed in near-vacuum gas phase conditions could be translated into solid phase materials. \u2018I wanted to bridge the gap between metal cluster research in vacuum and the metal clusters in the real world as materials,\u2019 Tsukuda says.<\/p>\n
Tsukuda focused on atomically precise gold nanocluster synthesis. The challenge with making nanoclusters outside of near-vacuum conditions is that, as soon as they come into contact, clusters want to aggregate to reduce their surface energy. \u2018To protect against aggregation, we cover the clusters with organic ligands, so the metal cores cannot contact each other and combine,\u2019 Tsukuda says.<\/p>\n
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The goal now is to make cluster-based materials with new properties\u00a0<\/p>\n
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The chemistry took a while to refine, but the effort to make these ligand-protected clusters was worth it. \u2018Once I achieved atomically precise synthesis of a series of clusters, I realised there was a common concept between free clusters in vacuum and the gold clusters protected by ligands \u2013 and that was the superatom concept,\u2019 Tsukuda says. Nanocluster electron-shell closure determined stability both in free clusters and ligand-protected clusters. \u2018The goal now is to make cluster-based materials with new properties that other materials cannot achieve,\u2019 he says.<\/p>\n
Catalysis is one promising application. Whereas bulk state gold is chemically inert, gold nanoparticles are famously active catalysts, able to oxidise organic substrates using oxygen from the air for example. Conventional synthesis typically generates gold nanoparticles with a range of sizes, however, and the nanoparticles are again prone to aggregation, curbing their catalytic performance.<\/p>\n
Tsukuda\u2019s superatom synthesis methods can overcome both limitations, generating atomically precise nanoclusters with a ligand coat that prevents aggregation. Engineering the ligand environment to enable substrate access to the gold surface while still preventing superatom aggregation has been a recent focus of his work.<\/p>\n
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In one surprise finding, the team showed that gold-25 clusters coated with long chain thiolate-capped ligands can make excellent heterogeneous catalysts. Ligands on the cluster\u2019s underside can stick the superatoms to solid carbon support through van der Waals interactions, and a controlled heat treatment then selectively strips ligands from the superatom\u2019s upper side to expose the gold surface. These anchored superatoms catalysed alcohol oxidation to carboxylic acids in air<\/a>.<\/p>\n \u2018We had initially tried removing all of the ligands, because thiolates are usually a catalyst poison,\u2019 Tsukuba says. \u2018But we found that when we intentionally left some ligands behind, their strong interaction with the support played a very important role, enhancing the catalyst\u2019s durability by suppressing superatom migration on the surface.\u2019<\/p>\n Engineered ligand environments also play a key role in the superatom catalysts recently reported by Quan-Ming Wang at Tsinghua University in Beijing, China, and his collaborators. The team made an unusual ligand-protected 40-atom gold cluster<\/a> in which the catalytically active core was a gold-26 superatom and the remaining gold atoms served as stabilising structural \u2018staples\u2019. Adhered to a titania support, this superatom was a 100% selective reduction catalyst for nitro groups in arenes with multiple other reducible groups.<\/p>\n More recently, Wang made a highly stable superatom catalyst from a copper-45 complex<\/a>. Copper has great appeal as a catalyst because it is abundant and inexpensive, but copper clusters are notoriously difficult to work with because they are inherently unstable, oxidising readily in the air. Stabilised by its 1S2 1P4 electron structure and strong ligand interactions, however, Wang\u2019s copper superatom set a new standard for the efficient electrocatalytic upcycling of carbon dioxide into ethylene<\/a>.<\/p>\n From molecules to materials<\/p>\n Single superatom catalysis is one aspect of these nanoclusters\u2019 promise. Tsukuda has also shown it is possible to bond superatoms together to make supermolecules. Again, the trick is to manipulate the superatom\u2019s ligand coating.<\/p>\n Inspired by Nobel-winning metal\u2013organic framework chemistry, the team synthesised gold superatoms with selectively removable ligands at the polar position. When the team chemically removed one polar ligand, then added a bridging linker ligand, superatom dimers formed. By removing both polar ligands, multiple superatoms can start to be strung together.<\/p>\n The team has also manipulated gold nanocluster ligand structure so that several superatoms can fuse in controlled fashion. The resulting thin gold rods possess tuneable light absorption; the longer the rod, the more red-shifted its light capture. Wrapped in the organic light emitter rubrene, these nanorods achieved efficient photon upconversion<\/a>, absorbing two near-infrared photons and combining their energy to emit a photon of visible light. Such materials could upconvert near-infrared light \u2013 a major component of the solar spectrum \u2013 into a form that solar cells or photocatalysts could use.<\/p>\n In Xavier Roy\u2019s lab at Columbia University in New York, US, the team has assembled superatoms into materials with properties that are not just unusual, but unique. Roy was drawn to the field to explore the possibility that by using superatoms to assemble functional materials, rather than using regular elements, their properties could be mixed and matched for the ideal blend of behaviour.<\/p>\n \u2018We started to think of them in terms of highly tuneable building blocks, where you can design the properties of each individual block using synthetic chemistry,\u2019 Roy recalls. \u2018We can tune their luminescence, their redox behaviour, introduce magnetism, control how they bind \u2026 All before their assembly into functional materials.\u2019<\/p>\n Roy initially worked on clusters synthesised from solution, where charge transfer between an electron-rich and electron-poor superatom could give rise to ionic superatomic materials. The team then transitioned to manipulating the chemistry of the superatom\u2019s capping ligands, using synthetic chemistry to control their bonding through covalent linkages.<\/p>\n \u2018We have developed methods where we can selectively decorate our superatoms with, for example, a set of bridging ligands, and then a set of capping ligands, and use these features to control the dimensionality of the lattice,\u2019 Roy says.<\/p>\n Light harvesting superatoms<\/p>\n Some of Roy\u2019s most intriguing results come from a well-known material only recently recognised as superatomic in nature. \u2018Rhenium selenium chloride is an old material that people have studied for decades, excising the clusters from these lattices to do chemistry on the individual superatoms,\u2019 Roy says. \u2018But we can grow these materials as large, crystalline, two-dimensional sheets of covalently bonded superatoms using high-temperature solid-state chemistry.\u2019<\/p>\n Strange things happen when these crystals are illuminated with light. Like many semiconductors, light exposure generates excited electron\u2013hole pairs known as excitons in the material. In rhenium selenium chloride, however, these excitons bind to vibrations in the lattice called acoustic phonons, forming a new quasi-particle called an acoustic polaron.<\/p>\n
<\/p>\n If you look at the edge of a typical crystal, there\u2019s a lot of defect sites\u00a0<\/p>\n
<\/p>\n \u2018These acoustic polarons travel across the material without any scattering, and so we see transport phenomena that have never been observed in any other material,\u2019 Roy says. These particles \u2013 which can only arise in superatomic materials \u2013 could be very useful for efficiently harnessing light, he says.<\/p>\n In traditional semiconductors, electron\u2013hole pairs frequently recombine before anything useful can be done with them. \u2018If you look at the edge of a typical crystal, there\u2019s a lot of defect sites where excitons get trapped and recombine, and you lose that energy,\u2019 Roy says. \u2018But because the acoustic polarons in our materials seem to be completely insensitive to this problem, we\u2019re thinking of ways that we can use these materials as antennas to funnel excitons to where we need them.\u2019 These light-energy-harvesting antennas could be used for low light energy generation or catalysis, delivering excitons directly to catalyst particles attached at specific sites on the material\u2019s surface.<\/p>\n Superatoms to the rescue in energy applications<\/p>\n For a concept once considered purely theoretical, superatom science has come a long way, Jena says. \u2018There are now many materials enhanced by replacing an atom with a superatom of the same chemistry,\u2019 he says.<\/p>\n Many early examples have involved swapping a halide for a superhalide. In hybrid perovskite solar cells such as methylammonium lead iodide, for example, lead\u2013iodide bonds\u2019 susceptibility to breakage contributes to the material\u2019s notorious instability to moisture and heat. Jena\u2019s computational modelling suggested that replacing some of the iodide with a superhalogen such as BH4\u2013, SCN\u2013 or SeCN\u2013 could stabilise the material by strengthening bonding.<\/p>\n Borohydride is a polyatomic species commonly used as a reducing agent in organic synthesis, and commercially available in bulk quantities. Just like a halogen, the neutral cluster is one electron short of a closed shell, Jena notes. In lab experiments, adding borohydride not only enhanced a photovoltaic perovskite\u2019s stability to humidity, heat and UV light, but boosted its solar power conversion efficiency from 18.43 to 21.10%<\/a>. Subsequent studies have confirmed the superhalide additive effect in a range of hybrid perovskite formulations. Modelling predicting that switching to superhalides in solid-state lithium-ion battery electrolytes could improve battery performance has also been borne out experimentally.<\/p>\n Jena has recently focused on finding cheap superatoms that mimic the performance of precious metal catalysts. In a 2025 computational study, he calculated that earth-abundant ZrO \u2013 a superatom with the same outer electron count as palladium \u2013 outperformed the precious metal as a catalyst, more strongly binding and activating small molecules such as H2 and CO2.<\/p>\n Compared to single atom catalysts, single superatom catalysts can offer the same chemistry but with multiple sites for substrate binding and reaction. \u2018Changing an atom with a superatom could lead to a new generation of catalysts,\u2019 Jena says. Experimentalist colleagues are already testing out the idea, he adds.<\/p>\n As the periodic table begins to sprout a superatomic third dimension, materials chemistry\u2019s colour palette looks increasingly bright.<\/p>\n James Mitchell Crow is a science writer based in Melbourne, Australia<\/p>\n","protected":false},"excerpt":{"rendered":"Article summary
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