Tag Archives: van der Waals force

Change the shape of water with nanotubes

An August 24, 2018 news item on ScienceDaily describes a ‘shapeshifting’ water technique,

First, according to Rice University engineers, get a nanotube hole. Then insert water. If the nanotube is just the right width, the water molecules will align into a square rod.

Rice materials scientist Rouzbeh Shahsavari and his team used molecular models to demonstrate their theory that weak van der Waals forces between the inner surface of the nanotube and the water molecules are strong enough to snap the oxygen and hydrogen atoms into place.

Shahsavari referred to the contents as two-dimensional “ice,” because the molecules freeze regardless of the temperature. He said the research provides valuable insight on ways to leverage atomic interactions between nanotubes and water molecules to fabricate nanochannels and energy-storing nanocapacitors.

An August 24, 2018 Rice University news release (also on EurekAlert and received via email), which originated the news item, delves further,

Shahsavari and his colleagues built molecular models of carbon and boron nitride nanotubes with adjustable widths. They discovered boron nitride is best at constraining the shape of water when the nanotubes are 10.5 angstroms wide. (One angstrom is one hundred-millionth of a centimeter.)

The researchers already knew that hydrogen atoms in tightly confined water take on interesting structural properties. Recent experiments by other labs showed strong evidence for the formation of nanotube ice and prompted the researchers to build density functional theory models to analyze the forces responsible.

Shahsavari’s team modeled water molecules, which are about 3 angstroms wide, inside carbon and boron nitride nanotubes of various chiralities (the angles of their atomic lattices) and between 8 and 12 angstroms in diameter. They discovered that nanotubes in the middle diameters had the most impact on the balance between molecular interactions and van der Waals pressure that prompted the transition from a square water tube to ice.

“If the nanotube is too small and you can only fit one water molecule, you can’t judge much,” Shahsavari said. “If it’s too large, the water keeps its amorphous shape. But at about 8 angstroms, the nanotubes’ van der Waals force [if you’re not familiar with the term, see below the link and citation for my brief explanation] starts to push water molecules into organized square shapes.”

He said the strongest interactions were found in boron nitride nanotubes due to the particular polarization of their atoms.

Shahsavari said nanotube ice could find use in molecular machines or as nanoscale capillaries, or foster ways to deliver a few molecules of water or sequestered drugs to targeted cells, like a nanoscale syringe.

Lead author Farzaneh Shayeganfar, a former visiting scholar at Rice, is an instructor at Shahid Rajaee Teacher Training University in Tehran, Iran. Co-principal investigator Javad Beheshtian is a professor at Amirkabir University, Tehran.

Supercomputer resources were provided with support from the [US] National Institutes of Health and an IBM Shared Rice University Research grant.

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

First Principles Study of Water Nanotubes Captured Inside Carbon/Boron Nitride Nanotubes by Farzaneh Shayeganfar, Javad Beheshtian, and Rouzbeh Shahsavari. Langmuir, DOI: 10.1021/acs.langmuir.8b00856 Publication Date (Web): August 23, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

For the purposes of the posting, van der Waals force(s) are weak adhesive forces measured at the nanoscale. Humans don’t feel them (we’re too big) but gecko lizards can exploit those forces which is why they are able to hang from the ceiling by a single toe.  There’s a more informed description here in the van der Waals force entry on Wikipedia.

Legos, geckos (van der Waals force), and single-atom sheets at the University of Kansas (US)

A Nov. 25, 2014 news item on Nanowerk describes the achievement,

Physicists at the University of Kansas have fabricated an innovative substance from two different atomic sheets that interlock much like Lego toy bricks. The researchers said the new material — made of a layer of graphene and a layer of tungsten disulfide — could be used in solar cells and flexible electronics. …

Hsin-Ying Chiu, assistant professor of physics and astronomy, and graduate student Matt Bellus fabricated the new material using “layer-by-layer assembly” as a versatile bottom-up nanofabrication technique. Then, Jiaqi He, a visiting student from China, and Nardeep Kumar, a graduate student who now has moved to Intel Corp., investigated how electrons move between the two layers through ultrafast laser spectroscopy in KU’s Ultrafast Laser Lab, supervised by Hui Zhao, associate professor of physics and astronomy.

“To build artificial materials with synergistic functionality has been a long journey of discovery,” Chiu said. “A new class of materials, made of the layered materials, has attracted extensive attention ever since the rapid development of graphene technology. One of the most promising aspects of this research is the potential to devise next-generation materials via atomic layer-level control over its electronic structure.”

A Nov. 25, 2014 University of Kansas news release (also on EurekAlert), which originated the news item, describes the problems and the new technique in more detail,

According to the researchers, the approach is to design synergistic materials by combining two single-atom thick sheets, for example, acting as a photovoltaic cell as well as a light-emitting diode, converting energy between electricity and radiation. However, combining layers of atomically thin material is a thorny task that has flummoxed researchers for years.

“A big challenge of this approach is that, most materials don’t connect together because of their different atomic arrangements at the interface — the arrangement of the atoms cannot follow the two different sets of rules at the same time,” Chiu said. “This is like playing with Legos of different sizes made by different manufacturers. As a consequence, new materials can only be made from materials with very similar atomic arrangements, which often have similar properties, too. Even then, arrangement of atoms at the interface is irregular, which often results in poor qualities.”

Layered materials such as those developed by the KU researchers provide a solution for this problem. Unlike conventional materials formed by atoms that are strongly bound in all directions, the new material features two layers where each atomic sheet is composed of atoms bound strongly with their neighbors — but the two atomic sheets are themselves only weakly linked to each other by the so-called van der Waals force, the same attractive phenomenon between molecules that allows geckos to stick to walls and ceilings.

“There exist about 100 different types of layered crystals — graphite is a well-known example,” Bellus said. “Because of the weak interlayer connection, one can choose any two types of atomic sheets and put one on top of the other without any problem. It’s like playing Legos with a flat bottom. There is no restriction. This approach can potentially product a large number of new materials with combined novel properties and transform the material science.”

Chiu and Bellus created the new carbon and tungsten disulfide material with the aim of developing novel materials for efficient solar cells. The single sheet of carbon atoms, known as graphene, excels at moving electrons around, while a single-layer of tungsten disulfide atoms is good at absorbing sunlight and converting it to electricity. By combining the two, this innovative material can potentially perform both tasks well.

The team used scotch tape to lift a single layer of tungsten disulfide atoms from a crystal and apply it to a silicon substrate. Next, they used the same procedure to remove a single layer of carbon atoms from a graphite crystal. With a microscope, they precisely laid the graphene on top of the tungsten disulfide layer. To remove any glue between the two atomic layers that are unintentionally introduced during the process, the material was heated at about 500 degrees Fahrenheit for a half-hour. This allowed the force between the two layers to squeeze out the glue, resulting in a sample of two atomically thin layers with a clean interface.

Doctoral students He and Kumar tested the new material in KU’s Ultrafast Laser Lab. The researchers used a laser pulse to excite the tungsten disulfide layer.

“We found that nearly 100 percent of the electrons that absorbed the energy from the laser pulse move from tungsten disulfide to graphene within one picosecond, or one-millionth of one-millionth second,” Zhao said. “This proves that the new material indeed combines the good properties of each component layer.”

The research groups led by Chiu and Zhao are trying to apply this Lego approach to other materials. For example, by combining two materials that absorb light of different colors, they can make materials that react to diverse parts of the solar spectrum.

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

Electron transfer and coupling in graphene–​tungsten disulfide van der Waals heterostructures by Jiaqi He, Nardeep Kumar, Matthew Z. Bellus,     Hsin-Ying Chiu, Dawei He, Yongsheng Wang, & Hui Zhao. Nature Communications 5, Article number: 5622 doi:10.1038/ncomms6622 Published 25 November 2014

This paper is behind a paywall but there is a few preview available through ReadCube Access.