Dongil Lee

This paper describes electrochemical and spectroscopic properties of a well-characterized, synthetically accessible, 1.1 nm diam Au nanoparticle, Au(38)(PhC(2)S)(24), where PhC(2)S is phenylethylthiolate. Properties of other Au(38) nanoparticles made by exchanging the monolayer ligands with different thiolate ligands are also described. Voltammetry of the Au(38) nanoparticles in CH(2)Cl(2) reveals a 1.62 V energy gap between the first one-electron oxidation and the first reduction. Based on a ch

Thiolate-protected metal nanoparticles containing a few to few hundred metal atoms are interesting materials exhibiting unique physicochemical properties. They encompass the bulk-to-molecule transition region, where discrete electronic states emerge and electronic band energetics yield to quantum confinement effects. Recent progresses in the synthesis and characterization of ultrasmall gold nanoparticles have opened up new avenues for the isolation of extremely monodispersed nanoparticles with a

Accurate identification of active sites is critical for elucidating catalytic reaction mechanisms and developing highly efficient and selective electrocatalysts. Herein, we report the atomic-level identification of active sites using atomically well-defined gold nanoclusters (Au NCs) Au₂₅ , Au₃₈ , and Au₁₄₄ as model catalysts in the electrochemical CO₂ reduction reaction (CO₂ RR). The studied Au NCs exhibited remarkably high CO₂ R

Development of efficient and selective electrocatalysts is a key challenge to achieve an industry-relevant electrochemical CO2 reduction reaction (CO2RR) to produce commodity chemicals. Here, we report that Au25 clusters with Au-thiolate staple motifs can initiate electrocatalytic reduction of CO2 to CO with nearly zero energy loss and achieve a high CO2RR current density of 540 mA cm–2 in a gas-phase reactor. Electrochemical kinetic investigations revealed that the high CO2RR activity of the Au

This paper describes the effects of doped metals on hydrogen evolution reaction (HER) electrocatalyzed by atomically controlled MAu₂₄ and M₂Au₃₆ nanoclusters, where M = Pt and Pd. HER performances, such as onset potential ( E_onset), catalytic current density, and turnover frequency (TOF), are comparatively examined with respect to the doped metals. Doping Pt or Pd into gold nanoclusters not only changes the electrochemical redox potentials of nanoclust

We report design strategies for the preparation of highly luminescent Au₂₂(SG)₁₈ clusters, where SG is glutathione, by the functionalization of the cluster shell. In these strategies, the cluster shell was covalently modified with small aromatic molecules and pyrene chromophores that led to a 5-fold PL enhancement by rigidifying the shell-gold. Highly luminescent water-soluble gold clusters with a PL quantum yield of 30% were obtained at room temperature. To further enhance

Gold nanoclusters are emerging as new materials for biomedical applications because of promises offered by their ultrasmall size and excellent biocompatibility. Here, the synthesis and optical and biological characterizations of a highly luminescent folate-functionalized Au₂₂ cluster (Au₂₂ -FA) are reported. The Au₂₂ -FA clusters are synthesized by functionalizing the surface of Au₂₂ (SG)₁₈ clusters, where SG is glutathione, with benzyl chlo

The metal-exchange reaction is a powerful means to generate atomically precise alloy nanoclusters. Both galvanic and antigalvanic exchange strategies have been devised to produce various doped metal nanoclusters with atomic precision. Here we report new insights into the metal-exchange synthesis of MAg24(SPhMe2)18 (M = Ni, Pd, Pt) nanoclusters. Based on the redox potential comparison of the Ag25 template with metal ion dopants, we reveal that the metal-exchange reaction is a redox potential-driv

A tailored PtAu₂₄ nanocluster mimicking the enzyme functions of hydrogenases can efficiently catalyze the hydrogen production.

2-Phenylethanethiolate (PET) and 4-tert-butylbenzenethiolate (TBBT) are the most frequently used ligands in the study of thiolate (SR)-protected metal clusters. However, the effect of difference in the functional group between these ligands on the fundamental properties of the clusters has not been clarified. We synthesized [Au24Pt(TBBT)18]0, which has the same number of metal atoms, number of ligands, and framework structure as [Au24Pt(PET)18]0, by replacing ligands of [Au24Pt(PET)18]0 with TBB

We report here the selective determination of dopamine (DA) using quantum-sized gold nanoparticles coated with charge selective ligands. Glutathione protected gold nanoparticles (GS-Au(25)) were synthesized and immobilized into a sol-gel matrix via thiol linkers. The GS-Au(25) modified sol-gel electrode was found to show excellent electrocatalytic activity towards the oxidation of DA but no activity towards the oxidation of ascorbic acid. The role of electrostatic charge in the selective electro

The first hydride-containing 2-electron palladium/copper alloys, [PdHCu₁₁ {S₂ P(Oⁱ Pr)₂ }₆ (C≡CPh)₄ ] (PdHCu₁₁ ) and [PdHCu₁₂ {S₂ P(Oⁱ Pr)₂ }₅ {S₂ PO(Oⁱ Pr)} (C≡CPh)₄ ] (PdHCu₁₂ ), are synthesized from the reaction of [PdH₂ Cu₁₄ {S₂ P(Oⁱ Pr)₂ }₆ (C≡CPh)<sub>

Syngas, a gaseous mixture of CO and H₂, is a critical industrial feedstock for producing bulk chemicals and synthetic fuels, and its production via direct CO₂ electroreduction in aqueous media constitutes an important step toward carbon-negative technologies. Herein, we report controlled syngas production with various H₂/CO ratios via the electrochemical CO₂ reduction reaction (CO₂RR) on specifically formulated Au₂₅ and PtAu<sub>2

Accurate measurements of intracellular pH are of crucial importance in understanding the cellular activities and in the development of intracellular drug delivery systems. Here we report a highly sensitive pH probe based on a fluorescein-conjugated Au₂₂ nanocluster. Steady-state photoluminescence (PL) measurements have shown that, when conjugated to Au₂₂, fluorescein exhibits more than 160-fold pH-contrasting PL in the pH range of 4.3-7.8. Transient absorption measurements

Abstract We report here the electrochemical behavior of quantum sized glutathione protected Au 25 nanoclusters and their use in electrochemical sensing. The Au 25 modified electrode was found to show excellent electrocatalytic activity towards the oxidation of ascorbic acid and dopamine over a wide linear range from 0.71 to 44.4 µM. The modified electrode exhibited pH dependent electrocatalytic activity, which was attributed to the consequence of electrostatic attraction/repulsion between the ch