• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 1995.11a
• /
• pp.281-284
• /
• 1995

A molecular photodiode was fabricated with hetero-Langmuir-Blodgett (LB) film consisting of an electron accepter(A) and sensitizer. N-Allyl-N-[3-propylamido-N\",N\"-야(n-octadecyl)]-4,4-bipyridum Dibromide and 7,8-dimethyl-10-dodecyl isoalloxan-zine were used as A and S units, respectively. By aligning hefter-LB film of A/S units on ITO glass with an aluminium thin film, a molecular photodiode with the structure of Metal/Insulator/Metal(MIM) was constructed. Due to excitation by irradiation with a 460nm monochromatic light source, the photo-induced unidirectional flow of electrons in the MIM device could be achieved and was detected as photocurrents. The direction of energy flow was in accordance with the energy level profile across the LB films. The photo switching function was achieved and the rectifying characteristics was obserbed in the molecular devise.

• Journal of Photoscience
• /
• v.9 no.1
• /
• pp.9-12
• /
• 2002

A porphyrin derivative covalently tinted to Ni aria-macrocycle complex has been prepared. Absorption spectrum of porphyrin-Ni aria-macrocycle dyad (λ$\^$max/$\sub$a/=227 nm) was observed to similar to a sum of those of tetratolylporphyrin (λ$\^$max/$\sub$a/=419 nm) and Ni aza-macrocycle (λ$\^$max/$\sub$a/=227 nm), indicating no electronic interaction between porphyrin and Ni aza-macrocycle moieties. Fluorescence quantum yield of dyad (${\Phi}$$\sub$f/= 0.10) was same to that of tetratolylporphyrin (${\Phi}$$\sub$f/= 0.10). Photoinduced intramolecular electron transfer or energy transfer from excited porphyrin moiety to Ni(II) aza-macrocycle moiety should be very inefficient in dyad.

• Rapid Communication in Photoscience
• /
• v.5 no.1
• /
• pp.1-7
• /
• 2016

Fluorescent receptors have gained much attention because of their usefulness in analysis and clarification of the roles of biomolecules in living systems. Molecular structures of the integrated type including that the receptor itself is fluorescent, and play an important role in having the functionality or selectivity of the fluorescent compounds. These spaced type fluorescent receptors are required to have special molecular design in order to transmit the information of molecular recognition to the fluorescent unit through the spacer unit. Compared with the spaced type fluorescent receptors, number of the integrated type receptors is limited due to the difficult molecular design and synthesis. Modification of alteration of the fluorophore frequently caused deterioration of the fluorescent property. Various spaced type and integrated type fluorescent receptors including switch on-off receptors are introduced in this article.

• Journal of Photoscience
• /
• v.11 no.1
• /
• pp.1-6
• /
• 2004

Molecular assembling is one of the current interests in the field of bottom-up nanotechnology. Self-assembled monolayers of sulfur-containing molecules or supramolecular assemblies via surface sol-gel processes formed on conductive supports are chemically robust and can be easily fabricated without sophisticated instruments. We have fabricated various types of molecular assemblies consisting of donor-acceptor pairs on the surfaces of gold and indium-tin-oxide electrodes. Build-up of three-dimensional multi structures consisting of thiol dyes and gold nanoparticles also has been successful. These assemblies showed clear photocurrent responses in photoelectro-chemical cells. In this article, we will describe recent progress on photoelectric conversion using molecular assemblies especially focused on our research results.

• Bulletin of the Korean Chemical Society
• /
• v.25 no.10
• /
• pp.1495-1498
• /
• 2004

A novel-type of structurally simple fluorescent chemosensor for oxalic acid was designed, synthesized, and evaluated to show that it detects oxalic acid in methanol with high selectivity over other anions including monoand dibasic carboxylic acids.

• Journal of the Korean Chemical Society
• /
• v.55 no.6
• /
• pp.932-935
• /
• 2011

Using tetrabutyl titanate as precursor, $Eu^{3+}$ doped $TiO_2$ nano-powder was prepared by sol-gel method, the nature of luminescence of nano-powder was studied. The interaction of chlorpyrifos with $Eu^{3+}$ doped $TiO_2$ was studied by absorption and fluorescence spectroscopy. The results indicated the fluorescence intensity of $Eu^{3+}$ doped $TiO_2$ was quenched by chlorpyrifos and the quenching rate constant ($k_q$) was $1.24{\times}10^{11}\;L/mol{\cdot}s$ according to the Stern-Volmer equation. The dynamics of photoinduced electron transfer from chlorpyrifos to conduction band of $TiO_2$ nanoparticle was observed and the mechanism of electron transfer had been confirmed by the calculation of free energy change (${\Delta}G_{et}$) by applying Rehm-Weller equation as well as energy level diagram. A new rapid method for detection of chlorpyrifos was established according to the fluorescence intensity of $Eu^{3+}$ doped $TiO_2$ was proportional to chlorpyrifos concentration. The range of detection was $5.0{\times}10^{-10}-2.5{\times}10^{-7}mol/L$ and the election limit ($3{\sigma}$) was $3.2{\times}10^{-11}$ mol/L.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.08a
• /
• pp.68-69
• /
• 2011

The process of charge transfer at the interface between two semiconductors or between a metal and a semiconductor plays an important role in many areas of technology. The optimization of such devices requires a good theoretical description of the interfaces involved. This, in turn, has motivated detailed mechanistic studies of interfacial charge-transfer reactions at metal/organic, organic/organic, and organic/inorganic semiconductor heterojunctions. Charge recombination of photo-induced electron with redox species such as oxidized dyes or triiodide or cationic HTM (hole transporting materials) at the heterogeneous interface of $TiO_2$ is one of main loss factors in liquid junction DSSCs or solid-state DSSCs, respectively. Among the attempts to prevent recombination reactions such as insulating thin layer and lithium ions-doped hole transport materials and introduction of co-adsorbents, although co-adsorbents retard the recombination reactions as hydrophobic energy barriers, little attention has been focused on the anchoring processes. Molecular engineering of heterogeneous interfaces by employing several co-adsorbents with different properties altered the surface properties of $TiO_2$ electrodes, resulting to the improved power conversion efficiency and long-term stability of the DSSCs. In this talk, advantages of the coadsorbent-assisted sensitization of N719 in preparation of DSSCs will be discussed.

• Journal of the Korean Ceramic Society
• /
• v.47 no.2
• /
• pp.169-176
• /
• 2010

The Fe-treated CNT/$TiO_2$ photocatalysts mixed with anatase and rutile phase have been developed for the decomposition of non-biodegradable different organic dyes like methylene blue (MB), rhodamine B (Rh.B), and methyl orange (MO) in two conditions as ultraviolet and visible light respectively. The results indicate that all the Fe-CNT/$TiO_2$ composites proved to be more efficient photocatalysts since degradation of MB at higher reaction rates, tthe decomposition rate of different dyes increases with an increase of $Fe^{3+}$ concentration in composites the highest rate of decomposition of different dyes was noted under UV irradiation. These results can indicate that the large CNT network is facilitate the electron transfer and strongly adsorb dye molecules on the texted photocatalysts, iron is reactive in the photo-Fenton process resulting in high production of OH radicals and also high activity of the photocatalyst. And Fe particles can generate more photoinduced electrons to conduction band of $TiO_2$ under visible light irradiation. The composites of Fe-CNT/$TiO_2$ photocatalysts synthesized by a sol-gel method were characterized by BET, TEM, SEM, XRD and EDX.

• Bulletin of the Korean Chemical Society
• /
• v.24 no.4
• /
• pp.446-452
• /
• 2003

Some new nanohybrid materials have been synthesized by intercalating the oxotitanium(IV) meso-tetrakis(4- sulfonatophenyl) porphyrin$(O=Ti^{(IV)} TSPP)$ into the Zn/Al layered double hydroxides (LDHs), and their structures and photophysical properties have been investigated by various laser spectroscopic techniques. According to the XRD pattern of the synthesized nanohybrid materials, the macrocycle plane of $O=Ti^{(IV)}$ TSPP are grafted perpendicular to the LDH layers. The $O=Ti^{(IV)}$ TSPP-intercalated LDH exhibits band broadening of the absorption spectrum and a blue shift of Q-band as compared to that observed in solution. Resonance Raman spectral measurements demonstrate that the positively charged LDHs give rise to a slight decrease of the electronic density of the porphyrin ring accompanying a small change of the electronic distribution of the $O=Ti^{(IV)}$ TSPP. Consequently the LDH environment affects the energies of the two highest occupied molecular orbitals (HOMOs) of the $O=Ti^{(IV)}$) TSPP, $a_{1u}$ and $a_{2u}$, producing a mixed orbital character. Being consistent with these electronic structural changes of $O=Ti^{(IV)}$ TSPP in LDH, both the fluorescence spectral change and the fsdiffuse reflectance transient measurements imply that the photoexcitation of the $O=Ti^{(IV)}$ TSPP intercalated into LDH undergoes fast relaxation to the O=Ti(IV) $TSPP^+-LDH^- $charge transfer (CT) state within a few picoseconds, followed by a photoinduced electron transfer between the O=Ti(IV) TSPP and LDHs with a rate constant greater than %1×10^{10}S^{-1}$. No evidence is found for back electron transfer. In conclusion, the $O=Ti^{(IV)}$ TSPP intercalated LDH seems to be a possible candidate for an artificial reaction center for an efficient solar energy conversion system.

• Rapid Communication in Photoscience
• /
• v.3 no.4
• /
• pp.70-72
• /
• 2014

Visible-light irradiation of MeCN solution containing di(hydroxo)metallo(tetraphenyl)porphyrin complex $(tppM(OH)_2$: 1a; $M=Sb(V)^+Br^-$, 1b; $M=P(V)^+Cl^-$, 1c; M=Ge(IV)) and 2-mercaptoethanol (2-ME) as a substrate under aerated condition gave bis(2-hydroxyethyl)disulfide (2-HEDS) as an oxidative product of 2-ME. It is indicated that the oxidation of 2-ME should proceed with a photocatalytic process by 1, because the turn over number (TON) for the formation of 2-HEDS was over unit. The TON was determined to be 642 as a maximum value when 1a was used as a sensitizer. The formation of 2-HDES was extremely slow under argon atmosphere. The fluorescence of 1 was not quenched by 2-ME at all, and the free energy change (${\Delta}G$) with electron transfer (ET) from 2-ME to excited triplet state of $1(^31^*)$ was estimated as a negative value. The quenching rate constant ($k_r$) of $^31^*$ by 2-ME, obtained by the kinetics for the formation of 2-HEDS, strongly depends on ${\Delta}G$. These findings indicate that 1-sensitized oxidation was initiated by photoinduced ET from 2-ME to $^31^*$ to generate both radical cation of 2-ME ($2-ME^{+\bulle}$) and porphyrin radical anion ($1^{-\bulle}$), resulting that the formation of 2-HEDS can be proceeded by the dimerization of $2-ME^{+\bulle}$, and through a catalytic cycle due to returning to 1 by the ET from $1^{-\bulle}$ to molecular oxygen.