Chiral and Luminescent TiO<sub>2</sub> Nanoparticles

Cleary, O.; Purcell-Milton, Finn; Vandekerckhove, Aurélien; Gun’ko, Yurii K.

doi:10.1002/adom.201601000

Cited by 36 publications

(32 citation statements)

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“…For the T20VR, the room temperature PL QY is measured to be 5.76%, which is significantly higher than that reported in the literature for TiO 2 nanostructures (QY ≈ 0.05–3.5% or lower) The details of PL QY of our as‐grown and annealed samples are tabulated in Table . Figure a shows the variation of PL QY for the samples grown with various HF concentrations (10 × 10 −3 to 80 × 10 −3 m ) after 3 min vacuum RTA treatment, while Figure b exhibits the change in QY as a function of RTA duration for T20VR.…”

Section: Resultssupporting

confidence: 93%

“…This hinders its applicability in living cells and study for nontoxic analogues of these chiral luminescent nanomaterials is of great interest . Recently, Cleary et al reported on the highly luminescent TiO 2 nanoparticles (NPs) with chiral capping ligand having size 30–50 nm with a PL QY up to ≈3.5%. However, the reported PL yields were measured mostly in colloidal solution, where surface functionalization by the solvents may have contribution to the observed PL yield .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO₂ Quantum Dots on Fluorine Doped Mesoporous TiO₂ Flowers by Rapid Thermal Annealing

Paul

Jana

Giri

2018

Part & Part Syst Charact

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past few years for their high aspect ratio (surface-to-volume ratio), distinctive physicochemical properties compared to the conventional nanostructures. Under equilibrium, {001} facet dominated TiO 2 nanostructure is rarely observed as it has very high surface energy (average surface energy of {001} facet (0.90 J m −2 ) is double that of {101} facet (0.44 J m −2 )). [14] Thus, during the usual growth process, the less reactive {101} facet is dominated over the highly reactive {001} facet. However, several reports [14][15][16] have been published on the controlled growth of TiO 2 single crystals with exposed {001} facet after the breakthrough work by Yang et al. [17] that demonstrated the hydrothermal synthesis of anatase TiO 2 single crystals with 47% exposed {001} facet. Following this work, {001} facet dominated TiO 2 microcrystals are being extensively investigated with various doping and photocatalytic applications for environmental cleaning. Recently, mesoporous TiO 2 single crystals delivering enhanced mobility and optoelectronic device performance was reported by Crossland et al. [18] Ding et al. reported on mesoporous hollow TiO 2 microspheres with enhanced photoluminescence (PL). [19] However, most of these works were carried out using a mesoporous template method and the PL yield was not addressed in these works. To the best of our knowledge, there is no report on fluorine doping of mesoporous TiO 2 nanostructure and the extremely high PL quantum yield (QY) of self-grown anatase fluorine doped TiO 2 (F-TiO 2 ) nanocrystals (NCs) on mesoporous F-TiO 2 flowers. Thus, a detailed study on structural and optical properties of mesoporous F-TiO 2 nanostructures is warranted to explore its novel properties including high PL QY.With conventional semiconductor quantum dots, chiral quantum dots based cellular imaging, sensing, and biomedical applications are not so encouraging because of the involvement of toxic elements such as cadmium [20] in the chiral composition. This hinders its applicability in living cells and study for nontoxic analogues of these chiral luminescent nanomaterials is of great interest. [21] Recently, Cleary et al. [22] reported on the highly luminescent TiO 2 nanoparticles (NPs) with chiral capping ligand having size 30-50 nm with a PL QY up to ≈3.5%. However, the reported PL yields were measured mostly in colloidal solution, where surface functionalization by the solvents Herein a novel approach is reported to achieve tunable and high photoluminescence (PL) quantum yield (QY) from the self-grown spherical TiO 2 quantum dots (QDs) on fluorine doped TiO 2 (F-TiO 2 ) flowers, mesoporous in nature, synthesized by a simple solvothermal process. The strong PL emission from F-TiO 2 QDs centered at ≈485 nm is associated with shallow and deep traps, and a record high PL QY of ≈5.76% is measured at room temperature. Size distribution and doping of F-TiO 2 nanocrystals (NCs) are successfully tuned by simply varying the HF concentration during synthesis. During the post-growth rapid thermal annealing...

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Section: Resultssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO₂ Quantum Dots on Fluorine Doped Mesoporous TiO₂ Flowers by Rapid Thermal Annealing

Paul

Jana

Giri

2018

Part & Part Syst Charact

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“…[4] Intuitively,c hiral inorganic NCs with chirality transferred from chiral ligands that are bound to their surface are commonly studied, and the species of inorganic materials can vary from metallic nanoparticles (NPs) or clusters to av ariety of semiconductor NCs. Gunko and coauthors [6] reported that diphenylethylenediamine-capped TiO 2 NPs can express chiroptical activities at their band-edge region owing to the overlap of the chiral ligand highest-occupied molecular orbital (HOMOs) with the TiO 2 quantum-dot valence-band states.M ore recently,J . Gunko and coauthors [6] reported that diphenylethylenediamine-capped TiO 2 NPs can express chiroptical activities at their band-edge region owing to the overlap of the chiral ligand highest-occupied molecular orbital (HOMOs) with the TiO 2 quantum-dot valence-band states.M ore recently,J .…”

Section: Chiralinorganicnanocrystals(ncs)asanemergingareahasmentioning

confidence: 99%

“…[5] Among them, chiral metal oxide NPs with ligand induced chirality has triggered tremendous interests for their essential applications in chiral catalysis,b iomaterials,o ptics and understanding of light-matter interactions.T od ate,Y . Gunko and coauthors [6] reported that diphenylethylenediamine-capped TiO 2 NPs can express chiroptical activities at their band-edge region owing to the overlap of the chiral ligand highest-occupied molecular orbital (HOMOs) with the TiO 2 quantum-dot valence-band states.M ore recently,J . Yeom et al [7] synthesized Co 3 O 4 chiromagnetic NPs and their gels that can be used for real-time magnetic field modulation.…”

Section: Chiralinorganicnanocrystals(ncs)asanemergingareahasmentioning

confidence: 99%

Tunable Chiroptical Properties from the Plasmonic Band to Metal–Ligand Charge Transfer Band of Cysteine‐Capped Molybdenum Oxide Nanoparticles

Cheng

et al. 2018

Angewandte Chemie

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Understanding the interactions between as emiconducting nanocrystal surface and chiral anchoring molecules could resolve the mechanism of chirality induction in nanoscale and facilitate the rational design of chiral semiconducting materials for chiroptics.N ow,c hiral molybdenum oxide nanoparticles are presented in which chirality is transferred via abio-to-nano approach. With facile control of the amount of chiral cysteine molecules under redox treatment, circular dichroism (CD) signals are generated in the plasmon region and metal-ligand charge-transfer band. The obtained enhanced CD signals with tunable lineshapes illustrate the possibility of using chiral molybdenum oxide nanoparticles as potentials for chiral semiconductor nanosensors,optoelectronics,and photocatalysts. Figure 2. XPS spectra of different l-Cys capped NPs with deconvoluted Mo 3d peaks. Blue, orange, and green peak areas corresponds to three valence states of molybdenum with Mo VI ,M o V ,and Mo IV respectively.

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“…Arrested growth in a chiral environment, is a common method for synthesis of chiral nanoceramics. In this context, individual chiral ceramic NPs from TiO 2 , [37] tungsten oxide (WO 3−x ) [38] molybdenum oxide (MoO 3−x , MoO 2 ), [39] and zinc oxide (ZnO) [40] and Co 3 O 4 [22b] were reported. The atomic organization of ceramic NPs can be affected by chiral ligands inducing lattice distortion and crystal lattice displacement that may also be referred sometimes to as "chiral footprint."…”

Section: Surface Modificationmentioning

confidence: 99%

Chiral Nanoceramics

Fan

Kotov

2020

Advanced Materials

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Jinchen Fan received his Ph.D. degree from Shanghai Jiao Tong University in 2014. He is now an associate professor at Shanghai University of Electric Power, China. He joined Prof. Kotov's group as a visiting scholar from October 2017 to October 2019. His current research focus is on the fabrication of chiral nanoceramics and their applications in chiroptical activity and catalysis. 2.2. Chiral Assemblies and Soft Templates Most of organic amphiphiles can be assembled into chiral superstructures. [43] This series of superstructures can be used as soft templates in the preparation of helical ceramic nanomaterials including, SiO 2 , [44] Ta 2 O 5 , [45] TiO 2 , [46] ZrO 2 , [47] and poly(bi ssilsesquioxane) [48] via the sol-gel transcription approach. Similarly, bio-macromolecules, such as peptides and DNA can serve as templates for realizing chiral ZnO [49] and silica structures. [50] Chiral synthesis with sodium cholate (SC) also serves as a representative example of this method. Because of its amphiphilic character, SC self-assembles into a unique bilayer structure through the hydrogen bonding between hydroxyl groups. [51] Huang and co-workers [51b] used the SC assembled via coordination with calcium ions, well-defined helical nanoribbons for creating additional helical SiO 2 and ZnS by sol-gel process. Methods of chirality transfer from soft templates often include self-organization ceramic building blocks based on hydrogen bonding, van der Waals forces, π-π stacking, hydrophobic effect, electrostatic and Coulomb interactions, and metal coordination. [41] One of representative examples of chiral assembly is the preparation of chiral nanostructured silica that proceeds via Nicholas A. Kotov pioneered conceptual foundations and technical realizations of biomimetic nanostructures, which include chiral nanomaterials. Chiral ceramic nanostructures are being investigated in his laboratory for optical, magnetic, biological, and catalytic properties. His contribution to technology include nacremimetic nanocomposites including those from graphene oxide, 3D tissue replicas for drug-testing, chiral biosensors, and cartilage-like electrolytes for batteries. He is a founder of several start-up companies that commercialized bioinspired nanomaterials for biomedical, energy, and automotive technologies.

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Chiral and Luminescent TiO₂ Nanoparticles

Cited by 36 publications

References 36 publications

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO₂ Quantum Dots on Fluorine Doped Mesoporous TiO₂ Flowers by Rapid Thermal Annealing

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO₂ Quantum Dots on Fluorine Doped Mesoporous TiO₂ Flowers by Rapid Thermal Annealing

Tunable Chiroptical Properties from the Plasmonic Band to Metal–Ligand Charge Transfer Band of Cysteine‐Capped Molybdenum Oxide Nanoparticles

Chiral Nanoceramics

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Chiral and Luminescent TiO2 Nanoparticles

Cited by 36 publications

References 36 publications

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO2 Quantum Dots on Fluorine Doped Mesoporous TiO2 Flowers by Rapid Thermal Annealing

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO2 Quantum Dots on Fluorine Doped Mesoporous TiO2 Flowers by Rapid Thermal Annealing

Tunable Chiroptical Properties from the Plasmonic Band to Metal–Ligand Charge Transfer Band of Cysteine‐Capped Molybdenum Oxide Nanoparticles

Chiral Nanoceramics

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Chiral and Luminescent TiO₂ Nanoparticles

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO₂ Quantum Dots on Fluorine Doped Mesoporous TiO₂ Flowers by Rapid Thermal Annealing

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO₂ Quantum Dots on Fluorine Doped Mesoporous TiO₂ Flowers by Rapid Thermal Annealing