New boron nanomaterial may be possible

Graphene, a sheet of carbon one atom thick, may soon have a new nanomaterial partner. In the lab and on supercomputers, chemical engineers have determined that a unique arrangement of 36 boron atoms in a flat disc with a hexagonal hole in the middle may be the preferred building blocks for “borophene.” Findings are reported in Nature Communications.

PROVIDENCE, R.I. [Brown University] — 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.”

Lai-Sheng Wang
“We haven’t made borophene yet, but this work suggests that this structure is more than just a calculation.”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.

“It’s beautiful,” Wang said. “It has exact hexagonal symmetry with the hexagonal hole we were looking for. The hole is of real significance here. It suggests that this theoretical calculation about a boron planar structure might be right.”

It may be possible, Wang said, to use B₃₆ basis to form an extended planar boron sheet. In other words, B₃₆ may well be the embryo of a new nanomaterial that Wang and his team have dubbed “borophene.”

“We still only have one unit,” Wang said. “We haven’t made borophene yet, but this work suggests that this structure is more than just a calculation.”

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.”

In light of this work, that prospect seems much more likely.

Source: http://news.brown.edu/pressreleases/2014/01/borophene

Swiss cheese crystal, or high-tech sponge?

Created by chemists at the University at Buffalo and Penn
State Hazleton, this sponge-like crystal contains many
pores that change shape when exposed to ultraviolet (UV) light.
Credit: Ian M. Walton

The remarkable properties of a new, porous material could lead to advances in microscopic sponging

The sponges of the future will do more than clean house.

Picture this, for example: Doctors use a tiny sponge to soak up a drug and deliver it directly to a tumor. Chemists at a manufacturing plant use another to trap and store unwanted gases.

These technologies are what University at Buffalo Assistant Professor of Chemistry Jason Benedict, PhD, had in mind when he led the design of a new material called UBMOF-1. The material — a metal-organic framework, or “MOF” — is a hole-filled crystal that could act as a sponge, capturing molecules of specific sizes and shapes in its pores.

Swiss cheese-like MOFs are not new, but Benedict’s has a couple of remarkable qualities:

• The crystal’s pores change shape when hit by ultraviolet light. This is important because changing the pore structure is one way to control which compounds can enter or exit the pores. You could, for instance, soak up a chemical and then alter the pore size to prevent it from escaping. Secure storage is useful in applications like drug delivery, where “you don’t want the chemicals to come out until they get where they need to be,” Benedict says.
  
• The crystal also changes color in response to ultraviolet light, going from colorless to red. This suggests that the material’s electronic properties are shifting, which could affect the types of chemical compounds that are attracted into the pores.

Benedict’s team reported on the creation of the UBMOF on Jan. 22 in the journal Chemical Communications. The paper’s coauthors include chemists from UB and Penn State Hazleton.

“MOFs are like molecular sponges — they’re crystals that have pores,” Benedict said.

“Typically, they are these passive materials: They’re static. You synthesize them, and that’s the end of the road,” he added. “What we’re trying to do is to take these passive materials and make them active, so that when you apply a stimulus like light, you can make them change their chemical properties, including the shape of their pores.”

Benedict is a member of UB’s New York State Center of Excellence in Materials Informatics, which the university launched in 2012 to advance the study of new materials that could improve life for future generations.

To force UBMOF-1 respond to ultraviolet light, Benedict and colleagues used some clever synthetic chemistry.

MOF crystals are made from two types of parts — metal nodes and organic rods — and the researchers attached a light-responsive chemical group called a diarylethene to the organic component of their material.

Diarylethene is special because it houses a ring of atoms that is normally open but shuts when exposed to ultraviolet light.

In the UBMOF, the diarylethene borders the crystal’s pores, which means the pores change shape when the diarylethene does.

The next step in the research is to determine how, exactly, the structure of the holes is changing, and to see if there’s a way to get the holes to revert to their original shape.

Rods containing diarylethene can be forced back into the “open” configuration with white light, but this tactic only works when the rods are alone. Once they’re inserted into the crystal, the diarylethene rings stay stubbornly closed in the presence of white light.

Source: http://www.buffalo.edu/news/releases/2014/01/031.html

Engineers make golden breakthrough to improve electronic devices based on molybdenum disulfide

A Kansas State University chemical engineer has discovered that a new member of the ultrathin materials family has great potential to improve electronic and thermal devices.

Vikas Berry, William H. Honstead professor of chemical engineering, and his research team have studied a new three-atom-thick material -- molybdenum disulfide -- and found that manipulating it with gold atoms improves its electrical characteristics. Their research appears in a recent issue of Nano Letters.

The research may advance transistors, photodetectors, sensors and thermally conductive coatings, Berry said. It could also produce ultrafast, ultrathin logic and plasmonics devices.

Berry's laboratory has been leading studies on synthesis and properties of several next-generation atomically thick nanomaterials, such as graphene and boron-nitride layers, which have been applied for sensitive detection, high-rectifying electronics, mechanically strong composites and novel bionanotechnology applications.

"Futuristically, these atomically thick structures have the potential to revolutionize electronics by evolving into devices that will be only a few atoms thick," Berry said.

For the latest research, Berry and his team focused on transistors based on molybdenum disulfide, or MoS2, which was isolated only two years ago. The material is made of three-atom-thick sheets and has recently shown to have transistor-rectification that is better than graphene, which is a single-atom-thick sheet of carbon atoms.

When Berry's team studied molybdenum disulfide's structure, they realized that the sulfur group on its surface had a strong chemistry with noble metals, including gold. By establishing a bond between molybdenum disulfide and gold nanostructures, they found that the bond acted as a highly coupled gate capacitor.

Berry's team enhanced several transistor characteristics of molybdenum disulfide by manipulating it with gold nanomaterials.

"The spontaneous, highly capacitive, lattice-driven and thermally-controlled interfacing of noble metals on metal-dichalcogenide layers can be employed to regulate their carrier concentration, pseudo-mobility, transport-barriers and phonon-transport for future devices," Berry said.

The work may greatly improve future electronics, which will be ultrathin, Berry said. The researchers have developed a way to reduce the power that is required to operate these ultrathin devices.

"The research will pave the way for atomically fusing layered heterostructures to leverage their capacitive interactions for next-generation electronics and photonics," Berry said. "For example, the gold nanoparticles can help launch 2-D plasmons on ultrathin materials, enabling their interference for plasmonic-logic devices."

The research also supports the current work on molybdenum disulfide-graphene-based electron-tunneling transistors by providing a route for direct electrode attachment on a molybdenum disulfide tunneling gate.

"The intimate, highly capacitive interaction of gold on molybdenum disulfide can induce enhanced pseudo-mobility and act as electrodes for heterostructure devices," said T.S. Sreeprasad, a postdoctoral researcher in Berry's group.

The researchers plan to create further complex nanoscale architectures on molybdenum disulfide to build logic devices and sensors.

"The incorporation of gold into molybdenum disulfide provides an avenue for transistors, biochemical sensors, plasmonic devices and catalytic substrate," said Phong Nguyen, a doctoral student in chemical engineering, Wichita, Kan., who is part of Berry's research team.

Namhoon Kim, master's student in grain science and industry, Korea,worked on the research as an undergraduate in chemical engineering.

http://www.k-state.edu/media/newsreleases/sept13/berry9513.html