• Bulletin of the Korean Chemical Society
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• 제27권9호
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• pp.1405-1417
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• 2006

The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum $(PtY_2L_2\;:\;Y,\;L=Cl^-,\;OH^-,\;OH_2,\;NH_3)$ complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of $(PtCl_4\;+\;H_2O)^{^\ast_\ast}\;to\;[PtCl_3(H_2O)\;+\;Cl^-]$ and $[Pt(NH_3)_2Cl_2\;+\;H_2O]$$[Pt(NH_3)_2Cl_2\;+\;H_2O]$ to $[Pt(NH_3)_2Cl(H_2O)\;+\;Cl^-] $ were investigated in detail. For these two exchange reactions, the transition states $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime])^{^\ast_\ast} $ correspond to complexes such as $(PtCl_4{\cdot}{\cdot}{\cdot}H_2O)^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$, respectively. In the transition state, $([PtCl_4{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]]^{^\ast_\ast})$ have a kind of 6-membered $(Pt-Cl{\cdot}{\cdot}{\cdot}HOH{\cdot}{\cdot}{\cdot}Cl)$ and $(Pt-OH{\cdot}{\cdot}{\cdot}Cl{\cdot}{\cdot}{\cdot}HN)$ interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving $Cl^-$ and an entering $H_2O$. Simultaneously, the entering $H_2O$ interacts with a leaving $Cl^-$. No vertical one metal-ligand interactions $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime]) $ are found at the axial positions of the square planar $(PtY_2L_2)$ complexes, which were formed via a vertically associative mechanism leading to $D_{3h}$ or $C_{2v}$-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtCl4(H2O)n(n=2,4)} into {$PtCl_3(H_2O)_{(n-2)}\;+\;Cl^-(H_2O)_2$} and the binding energies {$PtCl_4(H_2O)_n$(n = 1-5)} of $PtCl_4$ with water molecules are drawn.

• 대한화학회지
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• 제51권4호
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• pp.339-345
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• 2007

Urea는 높은 온도(60~80 °C)의 수용액 상태에서 PtCl2, H2[PtCl6]·6H2O, H2[IrCl6] Ni(CH3CO2)2 와 반응해서 각각 (1)[PtCl2(Urea)]·2H2O, (2)(NH4)2[PtCl6], (3)(NH4)2[IrCl6]·H2O, (4)[Ni2(OH)2(NCO)2(H2O)2]의 complexes를 생성 한다. complexe 1에서 urea는 중성 bidentate 리간드로써 Pt(II)와 배위한다. complexe 2,3,4에서는 높은 온도에서 반 응하는 동안 배위 urea분자들이 분해되고 다양한 반응생성물들을 얻을 수 있다. 모든 complexes은 각각 적당한 수득률 로 dark green(1) yellow(2), pale brown (3) faint green(4)의 침전물로 분리된다. 반응생성물은 열분석, IR, 1H and 13C NMR spectra에 의해 측정 되었다. 이 complexes의 구성을 설명하는 일반적인 매카니즘이 제시되었다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2008년도 추계학술대회 논문집 Vol.21
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• pp.435-436
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• 2008

Dye-sensitized Solar Cells(DSSCs) which convert incident sun light into electricity were expected to overcome global warming and depletion of fossil fuels. And it is one of study that is lately getting into the spotlight because manufacturing method is more simple and inexpensive than existing silicon solar cells. In this respect, DSSCs are in the limelight as the next generation solar cells. DSSCs are generally composed of a dye-modified $TiO_2$ photoelectrode, a Pt counter electrode, and an electrolytes containing a redox couple$(I^-/I_3^-)$. Among these elements, pt electrode were prepared by applying electric potential to FTO substrate in the $H_2PtCl_6$ solution. In this study, we report the solar cell efficiency depending on $PtCl_4$ concentration change. $PtCl_4$ concentration was 1mM, 5mM, 10mM, and 20mM, and adhered on FTO glass substrate by sintering process. When applied each $PtCl_4$ counter electrode on DSSC, the best efficiency was found at 10mM of $PtCl_4$ concentration. The catalyst promotes the movement of electron from the counter electrode to the electrolyte the higher the molarity, the better the efficiency. However, in case of 20mM, it is estimated that over-deposited $PtCl_4$ tends to restrict the movement of electron due to its bundle formation.

• 자원리싸이클링
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• 제18권1호
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• pp.30-37
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• 2009

염산농도 0.001에서 10 M사이의 범위에서 백금(IV)과 팔라듐(II) 및 로듐(III)의 착물형성반응과 물질수지를 고려하여 각 금속의 분배곡선을 구했다. 염산농도가 0.1 M이상인 조건에서는 백금과 팔라듐의 대부분은 $PtCl_6^{2-}$와 $PdCl_2^{2-}$로 존재하였다. 로듐의 농도분포는 염산농도에 큰 영향을 받는다. 염산농도가 0.1에서 10 M로 증가함에 따라 로듐의 주 화학종이 $PhCl_5^{2-}$에서 $PhCl_6^{3-}$로 변했다. 문헌에 발표된 백금과 팔라듐의 용매추출자료로부터 $PtCl_6^{2-}$ 및 $PtCl_4^{2-}$와 수소이온간의 매개변수를 추산했다.

• 대한화학회지
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• 제37권8호
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• pp.717-722
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• 1993

물에서 [PtCl$_4$]^{2-}$의 백금(II)에 결합된 클로로리간드를 디티오카바메이트로 치환시켜 [Pt(A)], [Pt(B)$_2$]Cl$_2$, [Pt(C)$_2$] 및 [Pt(D)(CH$_2$=CH$_2$)Cl]Cl를 합성하였다. 백금 착물은 원소분석, 적외선 및 자외선-가시광선 스펙트럼과 전도도 측정을 하여 이들의 성질을 조사하였따. 이들 백금(II)의 디티오카바메이트류 착물은 물, 알코올, 디메틸술폭시드 및 티메틸포름아미드와 같은 극성용매에 잘 녹았다. 이들 백금(II) 착물의 원소분석과 물리적 측정결과에서부터 그 가능한 구조를 제시하였다.

• Bulletin of the Korean Chemical Society
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• 제10권5호
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• pp.443-447
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• 1989

The mechanism on the oxidative addition reaction of $(TBA)_2\;Pt(CN)_4$ with $Cl_2$ has been studied by means of extended Huckel calculations. Among two possible mechanisms, computational calculations demonstrated that the linear approach of $Cl_2$ to a $Pt(CN)_4$ moiety is more favourable than three-centered transition state. From our calculations, the most stable process is that a $Pt(CN)_4$ moiety interacts with $Cl_2$ in the linear transition state and the cleavage of Cl-Cl bond in a coordinated halogen occurred spontaneously, giving rise to a trans product by back-attacking a $Pt(CN)_4Cl$ moiety by Cl. The process consists of the comparison in the stability of each intermediate with use of bonding and potential energy.

• Bulletin of the Korean Chemical Society
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• 제17권11호
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• pp.1061-1065
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• 1996

The charge transfer compounds of tetrathiafulvalene (TTF) with the general formula of (TTF)mMCln, (M=Au, Pt, Ir, Os) were prepared by the direct reaction using excess HAuCl4·3H2O, H2PtCl6·xH2O, H2IrCl6·xH2O and H2OsCl6 respectively. The powdered electrical conductivities (σrt) at room temperature are given as follows; (TTF)3AuCl2, 4.53×10-3; (TTF)3.5AuCl2, 6.37×10-3; (TTF)3PtCl4, 5.51×10-4; (TTF)2IrCl4, 2.40×10-5; (TTF)OsCl4·1/2C2H5OH, 4.46×10-7 Scm-1. Magnetic susceptibility, electronic (UV-Vis.), vibrational (IR) and EPR spectroscopic evidences indicate that there is incomplete charge transfer from the TTF donor to gold, platinum, and iridium respectively, and that there is essentially complete charge transfer to osmium, thereby resulting a relatively low electrical conductivity in osmium compound. The EPR and magnetic susceptibility data reflect that the metals are in diamagnetic Au(Ⅰ), Pt(Ⅱ), Ir(Ⅲ), and Os(Ⅱ) oxidation states, and the odd electrons are extensively delocalized over the TTF lattices in each compound.

• Bulletin of the Korean Chemical Society
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• 제6권4호
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• pp.214-217
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• 1985

Platinum(II) complexes of R-2,2'-diaminobinaphthyl (R-dabn), [Pt(R-dabn)(H2O)2]Cl2, [Pt(R-dabn)(R-Pn)]Cl2, [Pt(R-dabn)(R-bn)]Cl2, and platinum(II) complexes of S-2,2'-diaminobinaphthyl (S-dabn), [Pt(S-dabn)(H2O)2]Cl2, [Pt(S-dabn)(S-Pn)]Cl2, and [(Pt(S-dabn)(S-bn)]Cl2 have been prepared. (R-Pn and S-Pn are, respectively R- and S isomer of 2,3-diaminobutane). R-Pn and S-bn are, respectively R and S isomer of 2,3-diaminopropane). In the vicinity of the B-absorption band region of dabn, the circular dichroism spectra of platinum(Ⅱ) complexes of R-dabn series show a positive B-band followed by a negative higher energy A-band, which is generally understood as the splitting pattern for a ${\lambda}$ conformation, while the circular dichroism spectra of platinum(Ⅱ) complexes of S-dabn series show a negative B-band followed by a positive higher energy A-band in the long-axis polarized absorption region as expected for a $\delta$ conformation.

• 자원리싸이클링
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• 제16권5호
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• pp.36-40
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• 2007

백금은 물리화학적 특성에 기인하여 많은 분야에서 중요한 역할을 하고 있으며, 이러한 분야에서는 아주 미세한 백금의 사용을 요구하고 있다. 그러므로 본 연구에서는 액상에서 환원제를 사용하여 백금염을 환원시킴으로서 나노크기의 백금을 제조하는 방법에 대하여 알아보았다. 수용액상에서 C14TABr과 $H_2[PtCl_6]$ 상호작용은 $[C1_4TA]_2[PtCl_6]$의 유기백금염 화합물을 형성한다. 단분산 나노 백금입자를 얻기 위해서는 $C1_4TABr$과 $H_2[PtCl_6]$ 농도가 각각 cmc와 0.32 mM 이상이 되어야 한다. $H_2[PtCl_6]$와 C14TABr 농도가 증가함에 따라 백금입자 크기가 증가하였으며, 백금입자의 형태는 C14RABr농도 증가에 따라 제어가 가능하였다.

• 한국전기전자재료학회논문지
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• 제11권10호
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• pp.804-808
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• 1998

The inductively coupled plasma(ICP) etching of platinum with BCl$_3$/Cl$_2$ gas chemistry has been studied. X-ray photoelectron spectroscopy (XPS) was used to investigate the chemical binding states of the etched surface. The plasma characteristics was extracted from optical emission spectroscopy (OES) and a single Langmuir probe. In this case of Pt etching using BCl$_3$/Cl$_2$ gas chemistries, the result of OES and Langmuir probe showed the increase of Cl radicals and ion current densities in the plasmas with increasing Cl$_2$ gas ratio. At the same time, XPS results indicated that the intensities of Pt 4f decreased with increasing Cl$_2$ gas ratio. The decrease of Pt 4f intensities implies the increase of residue layer thickness on the etched Pt surface.