Chemists fabricate 'impossible' material

April 25, 2011 By Lisa Zyga feature
Chemists have synthesized an “impossible” material, mesoporous hydridosilica. Above 300 °C, the material transforms into a nanocomposite material embedded with photoluminescent silicon nanocrystallites. Image credit: Xie, et al. ©2011 American Chemical Society.

( -- When atoms combine to form compounds, they must follow certain bonding and valence rules. For this reason, many compounds simply cannot exist. But there are some compounds that, although they follow the bonding and valence rules, still are thought to not exist because they have unstable structures. Scientists call these compounds "impossible compounds." Nevertheless, some of these impossible compounds have actually been fabricated (for example, single sheets of graphene were once considered impossible compounds). In a new study, scientists have synthesized another one of these impossible compounds -- periodic mesoporous hydridosilica -- which can transform into a photoluminescent material at high temperatures.

The researchers, led by Professor Geoffrey Ozin of the Chemistry Department at the University of Toronto, along with coauthors from institutions in Canada, China, Turkey, and Germany, have published their study in a recent issue of the .

Like graphene, periodic mesoporous hydridosilica (meso-HSiO1.5) consists of a honeycomb-like . Theoretically, the structure should be so thermodynamically unstable that the mesopores (the holes in the honeycomb) should immediately collapse into a denser form, HSiO1.5, upon the removal of the template on which the material was synthesized.

In their study, the researchers synthesized the mesoporous material on an aqueous acid-catalyzed template. When they removed the template, they discovered that the impossible material remains stable up to 300 °C. The researchers attribute the stability to hydrogen bonding effects and steric effects, the latter of which are related to the distance between atoms. Together, these effects contribute to the material’s mechanical stability by making the mesopores resistant to collapse upon removal of the template.

“The prevailing view for more than 50 years in the massive field of micro-, meso-, or macroporous materials is that a four-coordinate, three-connected open framework material (called disrupted frameworks) should be thermodynamically unstable with respect to collapse of the porosity and therefore should not exist,” Ozin told “The discovery that this class of material can indeed exist with impressive stability is not a special effect related to the choice of the template, but rather that intrinsic hydrogen bonding between the silicon hydride O3SiH units and silanol O3SiOH that pervade the pore walls is strong enough to provide the meso-HSiO1.5 open-framework material with sufficient mechanical strength for it to be able to sustain the porosity intact in the as-synthesized template-containing and template-free material. This discovery is the big scientific surprise – so never say never when it comes to chemical synthesis.”

When raising the temperature above 300 °C, the researchers discovered that the mesoporous material undergoes a “metamorphic” transformation. This transformation eventually yields a silicon-silica nanocomposite material embedded with brightly photoluminescent silicon nanocrystals. Because the novel nanocomposite material retains its periodic mesoporous structure, the nanocrystals are evenly distributed throughout the structure. According to the researchers, the origin of the photoluminescence likely arises from quantum confinement effects inside the silicon nanocrystals.

In addition, the researchers found that they could control the photoluminescent properties of the nanocrystals by changing the thermal treatment. They predict that this ability could allow the bright nanocrystals to be used in the development of light-emitting devices, solar energy devices, and biological sensors.

“Now we have a periodic mesoporous hydridosilica in which we can exploit the chemistry of the silicon-hydride bonds that permeate the entire void space of the material,” Ozin said. “Every silicon in the structure has a Si-H bond to play creative synthetic games. This is a big deal in terms of it serving as a novel solid-state reactive host material within which one can perform novel chemistry limited only by one’s imagination, and a myriad new materials will emerge with a cornucopia of opportunities for creative discovery and invention.”

Explore further: First tri-continuous mesoporous Silica complex structure developed in Singapore

More information: Zhuoying Xie, et al. “Periodic Mesoporous Hydridosilica – Synthesis of an ‘Impossible’ Material and Its Thermal Transformation into Brightly Photoluminescent Periodic Mesoporous Nanocrystal Silicon-Silica Composite.” Journal of the American Chemical Society. DOI:10.1021/ja111495x


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5 / 5 (3) Apr 25, 2011
This is a far more important discovery than this article implies.
5 / 5 (3) Apr 25, 2011
This is a far more important discovery than this article implies.

Yes, it is. A breakthrough that allows many more 'impossibe meta-materials' to be considered and made. Chemistry was never so exiting :-)
4.6 / 5 (10) Apr 25, 2011
Who votes this type of discovery lower than five? Idiots, pardon my French. Go ahead and downvote me now...
5 / 5 (2) Apr 25, 2011
Perhaps ignorant, but teachable?
3 / 5 (1) Apr 25, 2011
I'm amazed that this is considered ground breaking work. Considering that chemists have known for quite some time that structures are often supported by the heat. Water changes from a liquid to a solid after cooling. And with that a new crystalline structure. They have also known for years that various compounds reorganize their crystalline structures at various temperatures, and also that at times when cooling has changed a particular lattice that to regain that lost lattice one must start from scratch. (Like how a dented fender is never quite the same shape even if you pull out the dent. (the lattice has been warped) The only way to fix it entirely is to reforge the fender.)
5 / 5 (2) Apr 26, 2011
I feel sorry for Impossible, big'ol Science has been beating him up for such a long time.
not rated yet Apr 26, 2011
...And I was getting all excited about LED bulbs. Next I know they'll be replaced by mesoporous photoluminescent impossible lights instead.
not rated yet Apr 28, 2011
I just love this science. No one knows where it will lead, but like the index of integration of negative one that drops through a hole into a new world of math, so can this.
3.7 / 5 (3) May 01, 2011
Who votes this type of discovery lower than five? Idiots, pardon my French. Go ahead and downvote me now...

Don't get too upset. There are a few people here who use the voting for personal reasons. They vote down posts because of what they think of the poster not the post. They don't realize how stupid they actually are. A careful look at their posts as well as their voting shows a pattern of ignorance on every subject.

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