Tag Archives: Wei-Li Li

Boron as a ‘buckyball’ or borospherene

First there was the borophene (like graphene but using boron rather than carbon) announcement from Brown University in my Jan. 28, 214 posting and now US (Brown University again) and Chinese researchers have developed a boron ‘buckyball’. Coincidentally, this announcement comes just after the 2014 World Cup final (July 13, 2014). Representations of buckyballs always resemble soccer balls. (Note: Germany won.)

From a July 14, 2014 news item on Azonano,

The discovery 30 years ago of soccer-ball-shaped carbon molecules called buckyballs helped to spur an explosion of nanotechnology research. Now, there appears to be a new ball on the pitch.

Researchers from Brown University, Shanxi University and Tsinghua University in China have shown that a cluster of 40 boron atoms forms a hollow molecular cage similar to a carbon buckyball. It’s the first experimental evidence that a boron cage structure—previously only a matter of speculation—does indeed exist.

“This is the first time that a boron cage has been observed experimentally,” said Lai-Sheng Wang, a professor of chemistry at Brown who led the team that made the discovery. “As a chemist, finding new molecules and structures is always exciting. The fact that boron has the capacity to form this kind of structure is very interesting.”

The researchers have provided an illustration of their borospherene,

The carbon buckyball has a boron cousin. A cluster for 40 boron atoms forms a hollow cage-like molecule. Courtesy Brown University

The carbon buckyball has a boron cousin. A cluster for 40 boron atoms forms a hollow cage-like molecule. Courtesy Brown University

A July 9, 2104 Brown University news release (also on EurekAlert), which originated the news item, describes the borosphene’s predecessor, the carbon buckyball, and provides more details about this new molecule,

Carbon buckyballs are made of 60 carbon atoms arranged in pentagons and hexagons to form a sphere — like a soccer ball. Their discovery in 1985 was soon followed by discoveries of other hollow carbon structures including carbon nanotubes. Another famous carbon nanomaterial — a one-atom-thick sheet called graphene — followed shortly after.

After buckyballs, scientists wondered if other elements might form these odd hollow structures. One candidate was boron, carbon’s neighbor on the periodic table. But because boron has one less electron than carbon, it can’t form the same 60-atom structure found in the buckyball. The missing electrons would cause the cluster to collapse on itself. If a boron cage existed, it would have to have a different number of atoms.

Wang and his research group have been studying boron chemistry for years. In a paper published earlier this year, Wang and his colleagues showed that clusters of 36 boron atoms form one-atom-thick disks, which might be stitched together to form an analog to graphene, dubbed borophene. Wang’s preliminary work suggested that there was also something special about boron clusters with 40 atoms. They seemed to be abnormally stable compared to other boron clusters.

Figuring out what that 40-atom cluster actually looks like required a combination of experimental work and modeling using high-powered supercomputers.

On the computer, Wang’s colleagues modeled over 10,000 possible arrangements of 40 boron atoms bonded to each other. The computer simulations estimate not only the shapes of the structures, but also estimate the electron binding energy for each structure — a measure of how tightly a molecule holds its electrons. The spectrum of binding energies serves as a unique fingerprint of each potential structure.

The next step is to test the actual binding energies of boron clusters in the lab to see if they match any of the theoretical structures generated by the computer. To do that, Wang and his colleagues used a technique called photoelectron spectroscopy.

Chunks of bulk boron are zapped with a laser to create vapor of boron atoms. A jet of helium then freezes the vapor into tiny clusters of atoms. The clusters of 40 atoms were isolated by weight then zapped with a second laser, which knocks an electron out of the cluster. The ejected electron flies down a long tube Wang calls his “electron racetrack.” The speed at which the electrons fly down the racetrack is used to determine the cluster’s electron binding energy spectrum — its structural fingerprint.

The experiments showed that 40-atom-clusters form two structures with distinct binding spectra. Those spectra turned out to be a dead-on match with the spectra for two structures generated by the computer models. One was a semi-flat molecule and the other was the buckyball-like spherical cage.

“The experimental sighting of a binding spectrum that matched our models was of paramount importance,” Wang said. “The experiment gives us these very specific signatures, and those signatures fit our models.”

The borospherene molecule isn’t quite as spherical as its carbon cousin. Rather than a series of five- and six-membered rings formed by carbon, borospherene consists of 48 triangles, four seven-sided rings and two six-membered rings. Several atoms stick out a bit from the others, making the surface of borospherene somewhat less smooth than a buckyball.

As for possible uses for borospherene, it’s a little too early to tell, Wang says. One possibility, he points out, could be hydrogen storage. Because of the electron deficiency of boron, borospherene would likely bond well with hydrogen. So tiny boron cages could serve as safe houses for hydrogen molecules.

But for now, Wang is enjoying the discovery.

“For us, just to be the first to have observed this, that’s a pretty big deal,” Wang said. “Of course if it turns out to be useful that would be great, but we don’t know yet. Hopefully this initial finding will stimulate further interest in boron clusters and new ideas to synthesize them in bulk quantities.”

The theoretical modeling was done with a group led by Prof. Si-Dian Li from Shanxi University and a group led by Prof. Jun Li from Tsinghua University. The work was supported by the U.S. National Science Foundation (CHE-1263745) and the National Natural Science Foundation of China.

Here’s a link to and a citation for the paper,

Observation of an all-boron fullerene by Hua-Jin Zhai, Ya-Fan Zhao, Wei-Li Li, Qiang Chen, Hui Bai, Han-Shi Hu, Zachary A. Piazza, Wen-Juan Tian, Hai-Gang Lu, Yan-Bo Wu, Yue-Wen Mu, Guang-Feng Wei, Zhi-Pan Liu, Jun Li, Si-Dian Li, & Lai-Sheng Wang. Nature Chemistry (2014) doi:10.1038/nchem.1999 Published online 13 July 2014

This paper is behind a paywall.

Borophene at Brown University (US)

It’s still theory at this point but researchers at Brown University (Rhode Island, US) have produced experimental proof that a single layer of boron atoms in a lattice reminiscent of  but not identical to a graphene layer is possible. A Jan. 28, 2014 news item on Azonano describes the research,

Researchers from Brown University have shown experimentally that a boron-based competitor to graphene is a very real possibility.

Graphene has been heralded as a wonder material. Made of a single layer of carbon atoms in a honeycomb arrangement, graphene is stronger pound-for-pound than steel and conducts electricity better than copper. Since the discovery of graphene, scientists have wondered if boron, carbon’s neighbor on the periodic table, could also be arranged in single-atom sheets. Theoretical work suggested it was possible, but the atoms would need to be in a very particular arrangement.

Boron has one fewer electron than carbon and as a result can’t form the honeycomb lattice that makes up graphene. For boron to form a single-atom layer, theorists suggested that the atoms must be arranged in a triangular lattice with hexagonal vacancies — holes — in the lattice.

“That was the prediction,” said Lai-Sheng Wang, professor of chemistry at Brown, “but nobody had made anything to show that’s the case.”

Wang and his research group, which has studied boron chemistry for many years, have now produced the first experimental evidence that such a structure is possible. In a paper published on January 20 in Nature Communications, Wang and his team showed that a cluster made of 36 boron atoms (B36) forms a symmetrical, one-atom thick disc with a perfect hexagonal hole in the middle.

Here’s an image that illustrates ‘borophene’,

Caption: This shows a 36-atom cluster of boron, left, arranged as a flat disc with a hexagonal hole in the middle, fits the theoretical requirements for making a one-atom-thick boron sheet, right, a theoretical nanomaterial dubbed "borophene." Credit: Wang Lab / Brown University

Caption: This shows a 36-atom cluster of boron, left, arranged as a flat disc with a hexagonal hole in the middle, fits the theoretical requirements for making a one-atom-thick boron sheet, right, a theoretical nanomaterial dubbed “borophene.”
Credit: Wang Lab / Brown University

The Jan. 27, 2014 Brown University news release (also on EurekAlert), which originated the news item, provides details about how the research was conducted,

The work required a combination of laboratory experiments and computational modeling. In the lab, Wang and his student, Wei-Li Li, probe the properties of boron clusters using a technique called photoelectron spectroscopy. They start by zapping chunks of bulk boron with a laser to create vapor of boron atoms. A jet of helium then freezes the vapor into tiny clusters of atoms. Those clusters are then zapped with a second laser, which knocks an electron out of the cluster and sends it flying down a long tube that Wang calls his “electron racetrack.” The speed at which the electron flies down the racetrack is used to determine the cluster’s electron binding energy spectrum — a readout of how tightly the cluster holds its electrons. That spectrum serves as fingerprint of the cluster’s structure.

Wang’s experiments showed that the B36 cluster was something special. It had an extremely low electron binding energy compared to other boron clusters. The shape of the cluster’s binding spectrum also suggested that it was a symmetrical structure.

To find out exactly what that structure might look like, Wang turned to Zachary Piazza, one of his graduate students specializing in computational chemistry. Piazza began modeling potential structures for B36 on a supercomputer, investigating more than 3,000 possible arrangements of those 36 atoms. Among the arrangements that would be stable was the planar disc with the hexagonal hole.

“As soon as I saw that hexagonal hole,” Wang said, “I told Zach, ‘We have to investigate that.'”

To ensure that they have truly found the most stable arrangement of the 36 boron atoms, they enlisted the help of Jun Li, who is a professor of chemistry at Tsinghua University in Beijing and a former senior research scientist at Pacific Northwest National Laboratory (PNNL) in Richland, Wash. Li, a longtime collaborator of Wang’s, has developed a new method of finding stable structures of clusters, which would be suitable for the job at hand. Piazza spent the summer of 2013 at PNNL working with Li and his students on the B36 project. They used the supercomputer at PNNL to examine more possible arrangements of the 36 boron atoms and compute their electron binding spectra. They found that the planar disc with a hexagonal hole matched very closely with the spectrum measured in the lab experiments, indicating that the structure Piazza found initially on the computer was indeed the structure of B36.

That structure also fits the theoretical requirements for making borophene, which is an extremely interesting prospect, Wang said. The boron-boron bond is very strong, nearly as strong as the carbon-carbon bond. So borophene should be very strong. Its electrical properties may be even more interesting. Borophene is predicted to be fully metallic, whereas graphene is a semi-metal. That means borophene might end up being a better conductor than graphene.

“That is,” Wang cautions, “if anyone can make it.”

Here’s a link to and a citation for the research paper,

Planar hexagonal B36 as a potential basis for extended single-atom layer boron sheets by Zachary A. Piazza, Han-Shi Hu, Wei-Li Li, Ya-Fan Zhao, Jun Li, & Lai-Sheng Wang. Nature Communications 5, Article number: 3113 doi:10.1038/ncomms4113 Published 20 January 2014

This paper is behind a paywall.