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Coating Nanodiamonds with Silica Shell: Unraveling the Bonding Mechanism

Coating something rare ÔÇô tiny shards of diamond ÔÇô with the main ingredient in sand might sound unusual, but the end result turns out to have a number of valuable applications. The trick is, nobody knows for sure how the two materials bond.

Today, researchers from San Jose State University (SJSU) report in the journal ACS Nanoscience Au that alcohol chemical groups on a diamondÔÇÖs surface are responsible for usefully uniform silica shells, a result that could help them to create better silica-coated nanodiamonds ÔÇô tiny tools with applications from biolabeling of cancer cells to quantum sensing.

The team unraveled the bonding mechanism thanks to powerful X-rays generated by the Stanford Synchrotron Radiation Lightsource (SSRL) at the DOEÔÇÖs SLAC National Accelerator Laboratory. ÔÇ£Now that we know these finer details ÔÇô how the bond works instead of just guessing ÔÇô we can better explore new diamond hybrid systems,ÔÇØ said Abraham Wolcott, the studyÔÇÖs principal investigator and an SJSU professor.

Much of Wolcott’s work concerns nanodiamonds, synthetic diamonds shattered into pieces so tiny that youÔÇÖd need 40,000 of them to span the width of a single human hair. Theoretically, nanodiamonds have perfect carbon lattices, but occasionally a nitrogen atom sneaks in and replaces a carbon atom next to a missing carbon atom. ItÔÇÖs technically a defect, but itÔÇÖs useful ÔÇô the defect responds to magnetic fields, electric fields and light, all at room temperature, meaning nanodiamonds have many applications. They can be used as qubits, the basic unit for a quantum computer. Hit them with green light, and they glow red, so biologists can put them in living cells and track them as they move. But scientists canÔÇÖt easily program nanodiamonds to go where they want, and diamond edges are pointy and can rupture cell membranes.

Coating them with silica solves both problems. Silica forms a smooth, uniform shell that covers the sharp edges. It also creates a modifiable surface, which scientists can decorate with tags to direct the particles toward specific cells, like cancer cells or neurons. ÔÇ£The diamond with silica shell becomes a controllable system,ÔÇØ Wolcott said.

But for some time, Wolcott said, scientists have disagreed on how that shell forms. His team showed that ammonium hydroxide with ethanol, chemicals normally included in the coating process, produces many alcohol groups on the nanodiamond surface, and those alcohols facilitate the growth of the shell.

ÔÇ£Nobody was able to explain it for over 10 years,ÔÇØ Wolcott said, ÔÇ£but we were able to tease out that information.ÔÇØ

After studying the particles with transmission electron microscopes at the DOEÔÇÖs Lawrence Berkeley National Laboratory Molecular Foundry, the researchers shot SSRL X-rays at nanodiamonds to explore the surfaces hidden below the silica coating.

SSRLÔÇÖs transition edge sensor ÔÇô a super-sensitive thermometer that collects temperature changes and converts them to X-ray energies ÔÇô revealed which chemical groups were present on the nanodiamondsÔÇÖ surfaces.

Using a second technique ÔÇô X-ray absorption spectroscopy (XAS) ÔÇô the team generated mobile electrons on the nanodiamond surface, then caught them as they traveled through the silica shell and escaped. The thicker the coating, the fewer electrons made it to the surface. The signals acted like a tiny measuring tape, showing the thickness of the silica coating on the nanometer scale.

ÔÇ£XAS is powerful because you can detect something that is submerged, that’s hidden ÔÇô like diamond underneath a silica shell,ÔÇØ Wolcott said. ÔÇ£Folks have never done this with nanodiamonds before, so in addition to figuring out the bonding mechanism, weÔÇÖve also shown that XAS is useful for material scientists and chemists.ÔÇØ

In the future, Wolcott, who is known for providing hands-on research opportunities, wants to put students to work coating nanodiamonds with other materials. Titanium, zinc and other metal oxides, for example, could open new avenues in quantum sensing and biological labeling applications.

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Reference: Sandoval PJ, Lopez K, Arreola A, et al. Quantum diamonds at the beach: Chemical insights into silica growth on nanoscale diamond using multimodal characterization and simulation. ACS Nanosci Au. 2023. doi: 10.1021/acsnanoscienceau.3c00033

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