Tag Archives: black gold

Climate change and black gold

A July 3, 2019 news item on Nanowerk describes research coming from India and South Korea where nano gold is turned into black nanogold (Note: A link has been removed),

One of the main cause of global warming is the increase in the atmospheric CO2 level. The main source of this CO2 is from the burning of fossil fuels (electricity, vehicles, industry and many more).

Researchers at TIFR [Tata Institute of Fundamental Research] have developed the solution phase synthesis of Dendritic Plasmonic Colloidosomes (DPCs) with varying interparticle distances between the gold Nanoparticles (AU NPs) using a cycle-by-cycle growth approach by optimizing the nucleation-growth step. These DPCs absorb the entire visible and near-infrared region of solar light, due to interparticle plasmonic coupling as well as the heterogeneity in the Au NP [gold nanoparticle] sizes, which transformed golden gold material to black gold (Chemical Science, “Plasmonic colloidosomes of black gold for solar energy harvesting and hotspots directed catalysis for CO2 to fuel conversion”).

A July 3, 2019 Tata Institute of Fundamental Research (TIFR) press release on EurekAlert, which originated the news item, provides more technical detail,

Black (nano)gold was able to catalyze CO2 to methane (fuel) conversion at atmospheric pressure and temperature, using solar energy. They also observed the significant effect of the plasmonic hotspots on the performance of these DPCs for the purification of seawater to drinkable water via steam generation, temperature jump assisted protein unfolding, oxidation of cinnamyl alcohol using pure oxygen as the oxidant, and hydrosilylation of aldehydes.

This was attributed to varying interparticle distances and particle sizes in these DPCs. The results indicate the synergistic effects of EM and thermal hotspots as well as hot electrons on DPCs performance. Thus, DPCs catalysts can effectively be utilized as Vis-NIR light photo-catalysts, and the design of new plasmonic nanocatalysts for a wide range of other chemical reactions may be possible using the concept of plasmonic coupling.

Raman thermometry and SERS (Surface-enhanced Raman Spectroscopy) provided information about the thermal and electromagnetic hotspots and local temperatures which was found to be dependent on the interparticle plasmonic coupling. The spatial distribution of the localized surface plasmon modes by STEM-EELS plasmon mapping confirmed the role of the interparticle distances in the SPR (Surface Plasmon Resonance) of the material.

Thus, in this work, by using the techniques of nanotechnology, the researchers transformed golden gold to black gold, by changing the size and gaps between gold nanoparticles. Similar to the real trees, which use CO2, sunlight and water to produce food, the developed black gold acts like an artificial tree that uses CO2, sunlight and water to produce fuel, which can be used to run our cars. Notably, black gold can also be used to convert sea water into drinkable water using the heat that black gold generates after it captures sunlight.

This work is a way forward to develop “Artificial Trees” which capture and convert CO2 to fuel and useful chemicals. Although at this stage, the production rate of fuel is low, in coming years, these challenges can be resolved. We may be able to convert CO2 to fuel using sunlight at atmospheric condition, at a commercially viable scale and CO2 may then become our main source of clean energy.

Here’s an image illustrating the work

Caption: Use of black gold can get us one step closer to combat climate change. Credit: Royal Society of Chemistry, Chemical Science

A July 3, 2019 Royal Society of Chemistry Highlight features more information about the research,

A “black” gold material has been developed to harvest sunlight, and then use the energy to turn carbon dioxide (CO2) into useful chemicals and fuel.

In addition to this, the material can also be used for applications including water purification, heating – and could help further research into new, efficient catalysts.

“In this work, by using the techniques of nanotechnology, we transformed golden gold to black gold, by simply changing the size and gaps between gold nanoparticles,” said Professor Vivek Polshettiwar from Tata Institute of Fundamental Research (TIFR) in India.

Tuning the size and gaps between gold nanoparticles created thermal and electromagnetic hotspots, which allowed the material to absorb the entire visible and near-infrared region of sunlight’s wavelength – making the gold “black”.

The team of researchers, from TIFR and Seoul National University in South Korea, then demonstrated that this captured energy could be used to combat climate change.

Professor Polshettiwar said: “It not only harvests solar energy but also captures and converts CO2 to methane (fuel). Synthesis and use of black gold for CO2-to-fuel conversion, which is reported for the first time, has the potential to resolve the global CO2 challenge.

“Now, like real trees which use CO2, sunlight and water to produce food, our developed black gold acts like an artificial tree to produce fuel – which we can use to run our cars,” he added.
Although production is low at this stage, Professor Polshettiwar (who was included in the RSC’s 175 Faces of Chemistry) believes that the commercially-viable conversion of CO2 to fuel at atmospheric conditions is possible in the coming years.

He said: “It’s the only goal of my life – to develop technology to capture and convert CO2 and combat climate change, by using the concepts of nanotechnology.”

Other experiments described in the Chemical Science paper demonstrate using black gold to efficiently convert sea water into drinkable water via steam generation.

It was also used for protein unfolding, alcohol oxidation, and aldehyde hydrosilylation: and the team believe their methodology could lead to novel and efficient catalysts for a range of chemical transformations.

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

Plasmonic colloidosomes of black gold for solar energy harvesting and hotspots directed catalysis for CO2 to fuel conversion by Mahak Dhiman, Ayan Maity, Anirban Das, Rajesh Belgamwar, Bhagyashree Chalke, Yeonhee Lee, Kyunjong Sim, Jwa-Min Nam and Vivek Polshettiwar. Chem. Sci., 2019, Advance Article. DOI: 10.1039/C9SC02369K First published on July 3, 2019

This paper is freely available in the open access journal Chemical Science.

Creating cheap, small carbon nanotubes

The excitement fairly crackles off the video,

A May 24, 2018 news item on Nanowerk announces the research,

Imagine a box you plug into the wall that cleans your toxic air and pays you cash.

That’s essentially what Vanderbilt University researchers produced after discovering the blueprint for turning the carbon dioxide into carbon nanotubes with small diameters.

Carbon nanotubes are supermaterials that can be stronger than steel and more conductive than copper. The reason they’re not in every application from batteries to tires is that these amazing properties only show up in the tiniest nanotubes, which are extremely expensive. Not only did the Vanderbilt team show they can make these materials from carbon dioxide sucked from the air, but how to do this in a way that is much cheaper than any other method out there.

I’m not sure what ‘small’ means in this context. I’ve heard of long and short carbon nanotubes (CNTs) and also of single-walled, multi-walled, and double-walled CNTs. I wish there’d been an an explanation and measurements for ‘small diameter CNTs’. That nitpick aside, a May 23, 2018 Vanderbilt University news release by Heidi Hall adds a few more technical details,

These materials, which Assistant Professor of Mechanical Engineering Cary Pint calls “black gold,” could steer the conversation from the negative impact of emissions to how we can use them in future technology.

“One of the most exciting things about what we’ve done is use electrochemistry to pull apart carbon dioxide into elemental constituents of carbon and oxygen and stitch together, with nanometer precision, those carbon atoms into new forms of matter,” Pint said. “That opens the door to being able to generate really valuable products with carbon nanotubes.

“These could revolutionize the world.”

In a report published today in ACS [American Chemical Society] Applied Materials and Interfaces, Pint, interdisciplinary material science Ph.D. student Anna Douglas and their team describe how tiny nanoparticles 10,000 times smaller than a human hair can be produced from coatings on stainless steel surfaces. The key was making them small enough to be valuable.

“The cheapest carbon nanotubes on the market cost around $100-200 per kilogram,” Douglas said. “Our research advance demonstrates a pathway to synthesize carbon nanotubes better in quality than these materials with lower cost and using carbon dioxide captured from the air.”

But making small nanotubes is no small task. The research team showed that a process called Ostwald ripening — where the nanoparticles that grow the carbon nanotubes change in size to larger diameters — is a key contender against producing the infinitely more useful size. The team showed they could partially overcome this by tuning electrochemical parameters to minimize these pesky large nanoparticles.

side-by-side photos showing stainless steel plate becoming covered in carbon nanotubes (which look like lumps of ash or mud)
Small diameter carbon nanotubes grown on a stainless steel surface. (Pint Lab/Vanderbilt University)

This core technology led Pint and Douglas to co-found SkyNano LLC, a company focused on building upon the science of this process to scale up and commercialize products from these materials.

“What we’ve learned is the science that opens the door to now build some of the most valuable materials in our world, such as diamonds and single-walled carbon nanotubes, from carbon dioxide that we capture from air through our process,” Pint said.

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

Toward Small-Diameter Carbon Nanotubes Synthesized from Captured Carbon Dioxide: Critical Role of Catalyst Coarsening by Anna Douglas, Rachel Carter, Mengya Li, and Cary L. Pint. ACS Appl. Mater. Interfaces, Article ASAP DOI: 10.1021/acsami.8b02834 Publication Date (Web): May 1, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Regarding the start-up, SkyNano, which Douglas and Pint have co-founded, it looks to be at a  very early stage.

Black gold: ultralight, high density nanoporous gold

South Korean researchers have found a way to fabricate a new kind of gold nanoparticle according to a March 28, 2016 news item on ScienceDaily,

A new material is more solid and 30 percent lighter than standard gold, scientists report. In their study, the team investigated grain boundaries in nanocrystalline np-Au and found a way to overcome the weakening mechanisms of this material, thereby suggesting its usefulness.

A March 28, 2016 Ulsan National Institute of Science and Technology (UNIST) press release (also on EurekAlert) by Chorok Oh, which originated the news item, provides more information,

A team of Korean research team, led by Professor Ju-Young Kim (School of Materials Science and Engineering) of Ulsan National Institute of Science and Technology (UNIST), South Korea has recently announced that they have successfully developed a way to fabricate an ultralight, high-dense nanoporous gold (np-Au).

In a new paper, published in Nano Letters on March 22, the team reported that this newly developed material, which they have dubbed “Black Gold” is twice more solid and 30% lighter than standard gold.

According to Prof. Kim, “This particular nanoporous gold has a 100,000 times wider surface when compared to standard gold. Moreover, due to its chemically stablity, it is also harmless to humans.”

The surfaces of np-Au are rough and the metal loses its shine and eventually turns black when they are at sizes less than 100 nanometres (nm). This is the reason that they are called “Black Gold”.

In their study, the team investigated grain boundaries in nanocrystalline np-Au and found a way to overcome the weakening mechanisms of this material, thereby suggesting its usefulness.

The team used a ball milling technique to increase the flexural strength of the three gold-silver precursor alloys. Then, using free corrosion dealloying of silver from gold-silver alloys, they were able to achieve the nanoporous surface. According to the team, “The size of the pores can be controlled by the temperature and concentration of nitrate.” Moreover, they also note that this crack-free nanoporous gold samples are reported to exhibit excellent durability in three-point bending tests.

Prof. Kim’s team notes, “Ball-milled np-Au has a much greater density of two-dimensional defects than annealed and prestrained np-Au, where intergranular fracture is preferred.” They continue, “Therefore, the probable existence of grain boundary opening in the highest tensile region is attributed to the flexural strength of np-Au.”

They suggest that this newly developed technique can be also applied to many other metal, as the np-Au produced by this technique have shown increased strength and durability while still maintaining the good qualities of standard gold.

This means that this technique can be also used in other technologies, like catalytic-converting as observed by platinum, the automobile catalyst and palladium, the hydrogen sensor catalyst.

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

Weakened Flexural Strength of Nanocrystalline Nanoporous Gold by Grain Refinement by Eun-Ji Gwak and Ju-Young Kim. Nano Lett., Article ASAP DOI: 10.1021/acs.nanolett.6b00062 Publication Date (Web): March 16, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

There’s more than one black gold

‘Black gold’ is a phrase I associate with oil, signifying its importance and desirability. These days, this analogic phrase can describe a material according to a July 24, 2015 news item on Nanowerk,

If colloidal gold [gold in solution] self-assembles into the form of larger vesicles, a three-dimensional state can be achieved that is called “black gold” because it absorbs almost the entire spectrum of visible light. How this novel intense plasmonic state can be established and what its characteristics and potential medical applications are is explored by Chinese scientists and reported in the journal Angewandte Chemie …

A July 24, 2015 Wiley (Angewandte Chemie) press release, which originated the news item, provides more details,

Metal nanostructures can self-assemble into superstructures that offer intriguing new spectroscopic and mechanical properties. Plasmonic coupling plays a particular role in this context. For example, it has been found that plasmonic metal nanoparticles help to scatter the incoming light across the surface of the Si substrate at resonance wavelengths, therefore enhancing the light absorbing potential and thus the effectivity of solar cells.

On the other hand, plasmonic vesicles are the promising theranostic platform for biomedical applications, a notion which inspired Yue Li and Cuncheng Li of the Chinese Academy of Science, Hefei, China, and the University of Jinan, China, as well as collaborators to prepare plasmonic colloidosomes composed of gold nanospheres.

As the method of choice, the scientists have designed an emulsion-templating approach based on monodispersed gold nanospheres as building blocks, which arranged themselves into large spherical vesicles in a reverse emulsion system.

The resulting plasmonic vesicles were of micrometer-size and had a shell composed of hexagonally close-packed colloidal nanosphere particles in bilayer or, for the very large superspheres, multilayer arrangement, which provided the enhanced stability.

“A key advantage of this system is that such self-assembly can avoid the introduction of complex stabilization processes to lock the nanoparticles together”, the authors explain.

The hollow spheres exhibited an intense plasmonic resonance in their three-dimensionally packed structure and had a dark black appearance compared to the brick red color of the original gold nanoparticles. The “black gold” was thus characterized by a strong broadband absorption in the visible light and a very regular vesicle superstructure. In medicine, gold vesicles are intensively discussed as vehicles for the drug delivery to tumor cells, and, therefore, it could be envisaged to exploit the specific light-matter interaction of such plasmonic vesicle structures for medical use, but many other applications are also feasible, as the authors propose: “The presented strategy will pave a way to achieve noble-metal superstructures for biosensors, drug delivery, photothermal therapy, optical microcavity, and microreaction platforms.” This will prove the flexibility and versatility of the noble-metal nanostructures.

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

Black Gold: Plasmonic Colloidosomes with Broadband Absorption Self-Assembled from Monodispersed Gold Nanospheres by Using a Reverse Emulsion System by Dilong Liu, Dr. Fei Zhou, Cuncheng Li, Tao Zhang, Honghua Zhang, Prof. Weiping Cai, and Prof. Yue Li. Angewandte Chemie International Edition Article first published online: 25 JUN 2015 DOI: 10.1002/anie.201503384

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This article is behind a paywall.

There is an image illustrating the work but, sadly, the gold doesn’t look black,


© Wiley-VCH

That’s it!