DISCOVERY OF FULLERENE NANOTECHNOLOGY

For some, science can be boring, lacking emotions and adrenalin, but for the others it is an exciting journey, which can lead to the discovery of fullerene nanotechnology. The scientists are on the quest with uncertain results as their findings do not need to be accepted easily. It is not an easy occupation, but a breakthrough like this one can change the world as we know it and their work is forever remembered as the milestone in the human history.

“I am going to do something fantastic that no one else could have imagined.” Harry Kroto

Discovery of Fullerene – How It All Started

The first one who predicted fullerenes was David Edward Hugh Jones (1938 – 2017). He was British chemist and also the author. David Jones wrote under his pen name Daedalus and his columns were published in the New Scientist for 38 years.

The prediction of hollow carbon molecules was definitely his most significant contribution as Daedalus. It was published in 1966 long time before they were discovered, but unfortunately it remained unnoticed at this time.

In 1970 the Japanese professor of computational chemistry, Eiji Osawa predicted the molecule of C60, but as his studies were published in Japanese, it did not get much attention the same as the studies of the Soviet scientists from 1973.

And then came the year 1984. In this year the Exxon Corporate Research Science Laboratory (Annandale, New Jersey) scientists made experiments, where they used lasers to vaporize graphite to form carbon clusters. It is very interesting that they used a machine, which was very similar to the one, Smalley's team created at the Rice University. The Exxon team members were Eric Rohlfing, Donald Cox and Andrew Caldor. They discovered that the carbon clusters were even numbers never odd ones. But the Exxon team did not noticed that the majority of clusters have 60 atoms and therefore they did not realized that they had been observing fullerenes and not clusters.

Just one year later, in September 1985, the famous British chemist Harold Kroto decided to travel for a ten days stay to Houston. Kroto had been trying to model the formation of the molecules with a long carbon chain. Then he met R. F. Curl at one conference and he shared with him that they actually had ideal equipment for such purpose at the Rice University so he basically invited himself to experiment with carbon there.

Kroto, Smalley and Curl are the trio of scientists who discovered fullerenes. Their discovery was a revolutionary breakthrough, which established the foundation of fullerenes nanotechnology.

So Who Discovered the First Fullerene?

The beginning of Kroto's and Smalley's cooperation was not as enthusiastic as it looks as the studies of pure carbon are not very exciting for most scientists. However in 1984, Richard Smalley was addressed by Harold Kroto if he could use their equipment to study a carbon molecule, specifically a special type of carbon molecule. Smalley's agreement was the beginning of long-term, successful cooperation. Their hard work was recognized by the Royal Swedish Academy of Sciences, they were awarded the Nobel Prize in Chemistry in 1996.

Let's have a closer look at these three masterminds.

Sir Harold Walter Kroto (October 7, 1939 –  April 30, 2017)

Harry Kroto was an English chemist, who was born in Wisbech Cambridgeshire. His parents were war refugees who were escaping from Nazi Germany. He studied at Bolton School. As a child he was amazed by a Meccano set. He started to grow an interest in chemistry, physics and mathematics at secondary school and as his professor of chemistry recommended, he attended the University of Sheffield. His professor believed that they have the best chemistry department so he listened to his advice.

As expected he was an excellent student, who obtained a first-class honors BSc degree at Chemistry (1961) and a PhD in Molecular Spectroscopy (1964). After he spent two years in Ottawa, Canada at the postdoctoral position he started to research and teach at Sussex University in England. Here he concentrated mainly on the spectroscopic studies of new and novel unstable and semi-stable species. He became a full professor of Chemistry in 1975.

The year 1985 was a milestone in his career. It is the year the buckminsterfullerene was discovered. The team consisted not only of Kroto, Smalley and Curl, but also three graduate students, James Heath, Sean O'Brian and Yuan Liu.

Together with his colleagues he published a paper, which title was “C60 Buckminsterfullerine”. This paper was honored by the Citation for Chemical Breakthrough Award (Division of History of Chemistry of the American Chemical Society) in 2015.

In 2004, he left University of Sussex to become the Francis Eppes Professor of Chemistry at Florida State University.

He was known to be the real humanist and also a patron of the Biritsh Humanist Association.

Despite of the fact that he was devoted scientist, he was also very talented graphic designer, who designed for example the Noble UK Stamp for Chemistry.

Richard Errett Smalley, the Men, Who Discovered C60 Buckyballs

Richard Smalley (June 6, 1943 – October 28, 2005) was Professor of Chemistry and Professor of Physics and Astronomy at Rice University, in Houston, Texas. His most significant and famous achievement was undoubtedly the discovery of a new carbon form. It was named buckminsterfullerene and it is also known as buckyballs.

Since his early years, he was encouraged by his family, mainly father, mother, but also his aunt to be interested in science and his aunt suggested he should attend Hope College as they had great chemistry program there. He did attend Hope College, but after two years he transferred to the University of Michigan. Here he obtained his Bacherol of Science (1965). He got his PhD. from Princeton University in 1973. Smalley was a pioneer in the development of supersonic beam laser spectroscopy.

When Richard Met Harry

It was actually Robert Curl, who introduced Richard Smalley to Harry Kroto. He wanted them to research the constituents of astronomical dust.

It is important to mention that this fruitful collaboration consists of three articles.  First one was simply named “C60: Buckminsterfullerene”, the second one, which was more detail description of the discovery of the endohedral fullerenes was “Lanthanum Complexes of Spherodial Carbon Shells”. The third one was titled “Reactivity of Large Carbon Clusters: Spheroidal Carbon Shells and Their Possible Relevance to the Formation and Morphology of Soot”, this article was the announcement of the fullerene discovery.

Smalley was a true advocate of the nanotechnology. He devoted years for research and thanks to his outstanding findings and results, there was established the Rice's Center for Nanoscale Science and Technology. It was renamed The Richard E. Smalley Institute for Nanoscale Science and Technology after his death in 2015.

He was also passionate supporter of the clean energy as he believed it is one of the main issues that people will face to in 21^st century.

If we look at his personal life and beliefs, unlike Kroto, he rediscovered his Christian foundation in later life.

Robert Curl, One of the Trio Scientists, Who Discovered the Buckminsterfullerene

Robert Floyd Curl Jr. (born August 23, 1933) has received many honors and awards during his amazing career. He is a University Professor Emeritus, Pitzer-Schlumberger Professor of Natural Sciences Emeritus and Professor of Chemistry Emeritus at Rice University. As it was mentioned before he is also one of the three scientists who were awarded the Nobel Prize in Chemistry for their breakthrough discovery of buckminsterfullerene.

The same as his colleagues, he started to be interested in chemistry, when he was a child. He got his first chemistry set, when he was just nine and his first experiments took place in his mother's kitchen.

Curl obtained his BSc. at Rice Institute, today's Rice University (1954). He received his PhD. in chemistry from the University of California, Berkeley.

His Outstanding Career

Robert Curl made his postdoctoral studies at Harvard University. The subject of his work was the bond rotation barriers of molecules, with a use of microwave spectroscopy.

In 1967 he started to work at Rice University, where he continued in his research, which included both experiments and theory.

It was actually his work at the Rice University which attracted Richard E. Smalley, who wished to cooperate with Curl. Smalley joined him at the Rice University in 1976. And as we already know the trio was completed in 1985, when Kroto joined them as he needed Smalley's equipment to continue in his tests.

Although Curl and Smalley were not very willing to interrupt their work for Kroto's experiments on their equipment, in the end this decision led to an unexpected discovery of a carbon with 60 atoms.

Each of these three men took different path after they won the Nobel Prize. Curl chose the quieter one. As he once said: “Well, I enjoyed what I was doing, and I want to keep doing that.”

Today fullerenes are nanomaterials of great potential with a lot of possible applications. Thanks to Kroto's, Smalley's and Curl's discovery and research they are already successfully used and implemented in our lives and as the research proceeds to buy fullerenes is becoming more and more affordable.

1985, the Year When Was Buckminsterfullerene Discovered

Science can be tricky sometimes as the most amazing discoveries are unexpected and very often quite simple. The original research was to find the particles that could be found in space. Luckily the team who made the tests and work on this study was cautious enough to realize that they had actually observed something completely new. A new form of Carbon molecule with 60 atoms.

The Events, which Preceded

It might look like a happy coincidence. Two friends Harry Kroto and Robert Curl met at a conference in 1984. Robert Curl was already cooperating with Richard Smalley at the Rice University and Kroto was very interested in Smalley's AP2. This device was used for studying clusters of any element and Harry Kroto wanted to continue in his research of the atom clusters.

Kroto had the chance to check the instrument and saw the opportunity to use it for his studies. In the beginning Smalley did not want to leave his work for Kroto's experiments, but year later all of them three begun to work together.

1984 Could Also Be the Year When Was Fullerene Discovered

In this year the scientists from the Exxon Corporate Research Science Laboratory in Annandale, New Jersey made tests where they used lasers to vaporize graphite to form carbon clusters. In fact they used an equipment similar to Smalley's AP2. There was Eric Rohlfing, Donald Cox and Andrew Caldor in the Exxon team. During their experiments they observed that carbon clusters of more than 40 atoms were even numbers not odd. But they did not noticed the predominant clusters with 60 atoms and therefore they did not realized that they are in fact observing fullerenes and not clusters.

However, their progress was in some way the right push for Curl and Smalley who were rather cold to Kroto's request to perform his experiments using their equipment. As Smalley said: “Because we were trying to avoid needless overlap and competition with the Exxon group, their steady progress in the field was yet another disincentive to taking up work on carbon clusters at Rice.”

So Kroto, Curl and Smalley Were There, when Was C60 Discovered

All of them three were eventually in. First Curl offered Kroto that the Rice team could continue in his research, but that was out of the question as Kroto preferred to participate personally, so without a second thought, he flew to the USA.

The upcoming ten days were filled with experiments and during this exciting time they first found Kroto's long carbon chains and then unexpectedly an unknown molecule of pure carbon.

What followed can be described as the detective work which aim was to reveal the mystery of C60.

Buckyball Discovery – Three Articles that Paved the Way to the Nobel Prize

The research performed by these three geniuses’ scientists with three graduate students at their assistance, namely James R. Heath, Yuan Liu and Sean C. O'Brien, consists of three articles.

• C60: Buckminsterfullerene – This article was issued in Nature (November 14, 1985). The first one described the discovery of C
• Lanthanum Complexes of Spheroidal Carbon Shells – This is the second article. In this one, they spoke about the discovery of the endohedral fullerenes, which are also known as endofullerenes and it was published in the Journal of the American Chemical Society (1985).
• Reactivity of Large Carbon Clusters: Spheroidal Carbon Shells and Their Possible Relevance to the Formation and Morphology of Soot – This article was issued in the Journal of Physical Chemistry (1986) and was the third article which revealed the discovery of fullerenes.

What Was the First Fullerene Discovered?

We have already learned that the first fullerene discovered was C60 also known as buckminsterfullerene or buckyballs. It is a molecule of carbon which can have many shapes such as a hollow sphere, tube or ellipsoid.

The shape of buckyballs is very similar to the shape of football ball (soccer). And the buckminsterfullerene was named after Richard Buckminster “Bucky” Fuller (July 12, 1895 – July 1, 1983). This man was American architect, author, designer and futurist. He designed the famous geodesic dome, which resembles the shape of C60 molecule.

It might be interesting that there was a dispute between Smalley and Kroto about who came up with the idea of the structure and name first. The whole dispute is summarized the best by Robert Curl, who said: “Harry was convinced that it was his idea and Rick was convinced it was his idea and I'm convinced it wasn't my idea.”

Nevertheless, although the process of the discovery was not easy, it opened up the doors for the fullerene research and started the speculation of the possible applications in nanomaterials.

How Were Fullerenes Discovered? - The Method of Research

As it was mentioned before Harry Kroto desired to use Smalley's device to continue in his scientific research. He strongly believed this device would help him significantly and he was willing to wait till he finally got Smalley's permission and eventually also the invitation to join them at the Rice University. His patience paid off and AP2 really helped to discover something truly amazing.

What Is AP2 and How Does it Work?

AP2 is a machine designed and constructed by Richard E. Smalley. He was very proud of his creation, this device was pretty big, in fact it was 12 feet high and Smalley liked to joke about it saying: “We do things big in Texas.”

This laser vaporization cluster beam equipment, was able to vaporize metals and other refractory materials. This process produced aggregates of tens of atoms, which formed clusters.

Smalley's AP2 was a technical breakthrough in material science. The scientists could have only studied isolated metal atoms and diatomic molecules, but not very often.

Kroto wanted to use Smalley's laser-supersonic cluster beam apparatus to study the long linear carbon chain molecules - that was the original plan. He, together with Canadian radio astronomers had found them in interstellar space. He wanted to prove that these long molecules had been made in the atmosphere of the red giant stars. And Smalley's AP2 was the machine he was looking for.

But how does the AP2 work? Basically it fires an intense laser pulse at the target. This action produces a hot vapor above it. In order to achieve the desired results, the laser has to generate temperatures which can reach astonishing tens of thousands degrees. In fact the temperatures are even higher than the temperatures on the surface of most of the stars.

While the vapor starts to cool down, the clusters are formed. Then a high pressure burst of gas is used to push the vapor into a vacuum chamber. Here the clusters condensate as the vapor cools. This is the time for the second laser pulse, which ionizes the clusters and moves them to the spectrometer, where they can be analyzed.

Thanks to AP2 the group of scientists first found Kroto's long chain carbon molecules and then as Kroto described: “Something quite remarkable...taking place.” And that was till that time unknown molecule of C60.

And That's How Was C60 Discovered – Unexpected and Surprising Result

It had to be truly thrilling and exciting days at the Rice University lab as the students noticed something they did not expected at all. The molecule which consists of 60 carbon atoms was there and to their surprise it was also very stable.

It was even more interesting, because of the fact that this unknown molecule did not need hydrogen or any other element to strengthen the bonds. Till this particular day all known molecules which consist of carbon atoms have additional atoms of other elements.

But there was yet another mystery to unfold. They asked themselves an important question. What was the structure of C60?

The Structure of C60

They actually thought about two types of the structure.

1. Flatlander model – In this model the carbon was filled in the hexagonal sheets.
2. Spherical form – In this form the hexagonal graphite sheet was closed. That's where is the name coming from as well. Kroto remembered the architect, Buckminster Fuller who designed the spherical geodesic domes and whose work he saw at World Exposition in Montreal in 1967.

So there was a theory, but it was also necessary to try it in practice. Smalley did not hesitate. He was naturally curious if the shape which consists only of hexagons could actually closed. To be sure he had to build one. First he tried to make it on his computer, but in the end all he needed was paper, tape and scissors. To use only hexagons did not work, but when he added pentagons as Harry Kroto suggested it closed.

Winning the Nobel Prize in Chemistry

Harry Kroto, Richard Smalley and Robert Curl obtained many awards and honors during their successful careers including the most prestigious one. For their unexpected, but revolutionary discovery of a new form of carbon molecule, the buckminsterfullerene, they received the Nobel Prize in Chemistry in 1996.

How One Discovery Have Changed Everything

It has been already almost 33 years since C60 was discovered. The research of fullerene developed and progressed. Nowadays there are more than a thousand new compounds.

The scientists and nanomaterials companies  are studying and testing the possible applications of fullerenes in various fields such as: energy, improving the quality of materials, antibiotics, superconductors, optics etc.

How Was Buckminsterfullerene Discovered – The Summary

Fullerene discovery was one of that unexpected. The scientists gathered and joined forces to prove one’s theory. Harry Kroto, the British chemist, initiated the research and used Smalley's equipment the AP2 to continue in his work and it might not happened, if he did not meet Robert Curl at conference.  And although Smalley and Curl did not want to leave their work for Kroto's experiments, their decision to collaborate was the best they could have done as it led to the discovery of a new form of carbon molecule. Thankfully the group of passionate geniuses were aware enough to notice what great thing had happened in the lab.

Their findings and research was recognized by the Royal Swedish Academy of Sciences and the trio was awarded by the Nobel Prize in Chemistry in 1996, just eleven years after their surprising discovery.

Their contribution to the development of the nanomaterials and nanotechnology is priceless, fullerenes are materials with many possible applications, including those in biomedicine and cancer research, which could significantly improve our lives.

As Edward Teller once said: “The science of today is the technology of tomorrow.”