Seed-induced penetration: a new tool for the synthesis of core-shell nanoparticles using superfluid helium droplets

Lead Research Organisation: University of Leicester
Department Name: Chemistry

Abstract

Helium nanodroplets are very small drops of liquid helium, with diameters at 1/1000 ~ 1/100,000 of a human hair. They are extremely cold, with a temperature as low as 0.38 K. When molecules and atoms encounter helium droplets, they will be captured, and in most cases, migrate to the interior of helium droplets. Helium droplets are superfluid, and the bonding between helium atoms and the dopants are often very weak. Therefore, when more than one atom or molecule are picked up, molecular clusters will be formed. When more dopants are added to helium droplets molecule by molecule, or atom by atom, and different materials are added in sequence, core-shell nanoparticles (the nano-onions ), will be formed. Core-shell nanoparticles can have exotic properties depending on the size and compositions. The unique properties of helium droplets make it ideal for fabrication of nanoparticles because they allow almost any combination materials to be grown.However, not everything goes to the interior of helium droplets. For high-spin metal atoms, e.g., Na and K, they will reside on the surface of helium nanodroplets and will hinder the growth of sizeable nanoparticles using helium droplets. A seeding technique will be therefore introduced in this research to overcome this major difficulty for the formation of nanoparticles with high-spin metals. A number of core-shell and core-multiple shell nanoparticles will be synthesized which have potential for a number of applicatoins in material science, biomedical science, imaging and strorage devices.

Planned Impact

This is a ground-breaking research programme for the fabrication of novel core-shell nanoparticles using superfluid helium droplets. An innovative technique will be developed and applied to tackle major problems occurring in the synthesis of magnetic nanoparticles involving high-spin metals initially located on the surface of helium droplets. With this technique helium droplets will become uniquely powerful and versatile nano-reactors for the fabrication of core-shell nanoparticles, allowing almost a combination of any desired materials. Small metal clusters of a few metal atoms to large core and multi-shell magnetic nanoparticles (CMS-MNPs) of thousand metal atoms will be synthesized and investigated, from which the evolution of magnetism, and the size and composition-dependence of magnetic properties will all be investigated, hence will generate precious information for the understanding of nano-scale material science, theoretical modelling on magnetism and the design of functional nanoparticles in the future. The CMS-MNPs to be synthesized will possess unique magnetic properties, and will have the potential for a wide range of niche applications, such as MRI imaging, tumour hyperthermia therapy, digital storage devices, etc. The impact of this proposal to fundamental material science and nanotechnology is straight. From the point of view of physical chemistry, a new route to produce sizeable high-spin metal clusters inside helium droplets will be established by this research, and this will stimulate the investigation of metal clusters and their applications, for example, on nano-catalysis. Beyond the scientific impact, this research will also have the potential for positive societal impact because the unique CMS-MNPs could have the potential for technological innovation in biomedical and life science, which might contribute to the better quality of life for human being in the future. PUBLICATIONS AND PROFESSIONAL DISSEMINATION: through publication of our work in the high impact scientific literature. Given that the research project is original and innovative for both fundamental science and applied nanotechnology, it will be credible to seek publication in high-impact journals such as PRL, Nature Materials, Nano Letters, Science and Nature. Equally, the work will be presented at a wide range of conferences above and beyond specialist meetings. COMMUNICATIONS AND ENGAGEMENT: the unique capability and wide-range possibilities brought forward by this research will lend itself to a far wider audience within the international research community and this will be pursued in several meanss including: (i) a schools outreach programme, including a specific lecture and the production of articles for education journals; (ii) high quality web-based supporting materials, including a video resource that shows a movie on how to form nano-onions . Other source of publicity will be pursued, e.g., through press releases. EXPLOITATION: Some part of this research can be patentable, and this will be in contact with EBDO of the University of Leicester. In addition, industrial partners will be sought to commercialize the unique CMS-MNPs, such as imaging, tumor hyperthermia, etc, starting at 42nd month of the project. TRAINING IMPACT: Two young researchers would be trained in this project, one at the PDRA level and the other at PhD level. A wide range of trainings are involved in this project, e.g., design and operation of advanced instrumentation (such as UHV systems, helium droplet source, electronics and mass spectrometer, microscopes, etc.), characterization of core-shell structures and their magnetic properties. This will equip both the PDRA and the PhD student with skills that will be attractive to a variety of potential employers. They will be also required to contribute to impact-related activities, including public outreach, thereby providing a further layer of skills and expertise that would add to their employability.

Publications

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Boatwright A (2013) Helium droplets: a new route to nanoparticles. in Faraday discussions

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Spence D (2014) Formation of aluminium clusters in helium nanodroplets in International Journal of Mass Spectrometry

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Spence D (2014) Vortex-induced aggregation in superfluid helium droplets. in Physical chemistry chemical physics : PCCP

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Yang S (2013) Helium droplets: a chemistry perspective. in Chemical Society reviews

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Yang S (2013) Nanodroplets

 
Description We have now established superfluid helium nanodroplets as a uniquely powerful and highly versatile means for the synthesis of novel nanoparticles. This includes single-crystalline metal clusters such as Au, Ag and Ni, and core-shell nanoparticles such as Ni/Au and Ag/Si. For the Ni/Au core-shell nanoparticles, our investigation has shown a giant magnetism. More recently we have exploited new possibilities offered by superfluid helium, i.e., the direct preparation of one-dimensional nanowires using quantized vortices.

Discoveries have been recently made following the previous project, including

1) single Au atom catalyzed ion-molecule reactions, which is real-sense single-atom catalysis observed for the first time in absence of any surface contact;

2). Observation of full landscape of quantized vortex arrays by a particle deposition method and development of an enabling technology to control quantized vortices in superfluid helium.
Exploitation Route The Ni/Au magnetic nanoparticles can potentially be applied in biomedical applications such as MR imaging and hyperthermia treatment.

The Ag/Si nanoparticles will have the strong surface plasmon resonance, which will be shifted to the near infrared by the Si coating. In addition, the Si coating will also avoid the toxicity of Ag. Hence they are ideal candidates for the in vivo applications of Ag nanoparticles. We are looking forward to applications of Ag/Si nanoparticles in bio-diagnosis and photothermal treatment of cancer in the longer term. The Ni/Au nanoparticles have been found to have 7 time higher magnetism than those synthesised using wet-chemistry methods, which means a factor of 50 enhancement to the contrast in MR imaging, and a 7-times higher efficiency in the hyperthermia treatment of cancer. Currently we are seeking collaboration involving academic staff in the University Hospital of Leicester for in vitro tests.
Sectors Education,Energy,Other

 
Description We have made important discoveries in nanomagnetism, including 1) robust ferromagnetism in chromium nanoparticles, which is an antiferromagnetic material; 2) nickel nanoparticles have been formed with unprecedentedly high magnetic moments, e.g., 3.5 times higher than the bulk limit at room temperature, ~2.1 uB/atom) and approaching the atomic limit at 5 kelvin. We are currently continuing on this research and are preparing novel iron nanoparticles, aiming at ultrahigh moment magnetic nanoparticles for MRI and hyperthermia treatment of cancer.
Sector Education,Healthcare
Impact Types Policy & public services

 
Description Development of high-moment magnetic materials 
Organisation Clinical and Research Center, Rozzano
Department UOS/IRGB, Milan Unit, CNR
Country Italy 
Sector Academic/University 
PI Contribution We produced high-moment magnetic nanoparticles.
Collaborator Contribution The partner characterized the magnetic nanomaterials using SQUID and VSM.
Impact A paper was published on Advanced Materials.
Start Year 2008
 
Description Development of high-moment magnetic materials 
Organisation National Centre for Scientific Research (NCSR) Demokritos
Country Greece 
Sector Academic/University 
PI Contribution We produced high-moment magnetic nanoparticles
Collaborator Contribution Theoretical modeling
Impact A paper has been published in Advanced Materials.
Start Year 2010
 
Description Novel types of atropisomers in 1,3 benzoxazine family 
Organisation Jiangsu University
Country China 
Sector Academic/University 
PI Contribution We provided explanation on the atropisomeric mechanisms.
Collaborator Contribution His team synthesized the chemicals and characterized using NMR.
Impact New publications. A paper recently submitted to Science Advances.
Start Year 2015