• Bulletin of the Korean Chemical Society
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• 제26권11호
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• pp.1795-1802
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• 2005

Potential energy curves and internuclear (M-X) distance variations for dissociation reactions of $[MX_4]^{2-}$ into ($[MX_3]^-$ + $X^-$) have been calculated using ab initio Hartree-Fock (HF), second order M$\ddot{o}$ller-Plesset perturbation (MP2), and Density Functional Theory (DFT) methods with a triple zeta plus polarization (TZP) basis set. The equilibrium geometrical structures of $[MX_4]^{2-}$ are optimized to tetrahedral geometry for $[NiX_4]^{2-}$ and square planar geometry for ($[PdX_4]^{2-}$ and $[PtX_4]^{2-}$). The bond (M-X) distances of $[NiCl_4]^{2-}$, $[NiBr_4]^{2-}$, $[PdCl_4]^{2-}$, $[PdBr_4]^{2-}$, $[PtCl_4]^{2-}$, and $[PtBr_4]^{2-}$ at the DFT level are 2.258, 2.332, 2.351, 2.476, 2.367, and 2.493 $\AA$, respectively. The dissociation energies for the bond dissociation of ($[MX_3]^-$${\cdot}{\cdot}{\cdot}$$X^-$) at the DFT level are found to be 4.73 eV for $[NiCl_4]^{2-}$, 4.89 eV for $[NiBr_4]^{2-}$, 4.93 eV for $[PdCl_4]^{2-}$, 5.57 eV for $[PdBr_4]^{2-}$, 5.44 eV for $[PtCl_4]^{2-}$, and 5.87 eV for $[PtBr_4]^{2-}$. As the (M${\cdot}{\cdot}{\cdot}$X) distance of ($[MX_3]^-$${\cdot}{\cdot}{\cdot}$$X^-$) increases, the distance variation (Rt) of trans (M-X) bond at the trans-position is shorter than those (Rc) of two cis (M-X) bonds at the cisposition. Simultaneously the atomic charge variation of trans-X atom is more positive than those of equilibrium $[MX_4]^{2-}$ structures, while the variation of leaving X group is more positive.

• 전기화학회지
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• 제7권4호
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• pp.201-205
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• 2004

본 연구에서는 Pt-Ru 촉매를 $H_2PtCI_6$ 및 $RuCl_3$ 용액을 화학적 환원에 의해 전도성 고분자인 폴리피롤을 중합시킨 Nafion 막위에 직접 침적시켰다 EDS 분석 결과 Pt 및 Ru 촉매는 Ppy/Nafion 표면에 주로 분포하는 것을 알 수 있었다. 또한 폴리피롤이 중합된 Nanon 위에 침적시킨 Pt-Ru 촉매의 메탄올에 대한 전기화학적 산화특성을 CV로 평가하였다. 메탄을 산화 개시 전위는 Ru촉매에 사용이 증가함에 따라 음전위 방향으로 전이되었다. 따라서 폴리피롤이 중합된 Nafion표면에 Pt-Ru촉매를 직접 함침할 수 있었고. 메탄올 산화 특성을 나타내는 전극을 제작할 수 있었다.

• 한국수소및신에너지학회논문집
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• 제20권3호
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• pp.194-201
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• 2009

The e1ectrocatalytic properties of heteropolyacids(HPAs) entrapped in covalently cross-linked sulfonated polyetheretherketone(CL-SPEEK/HPA) membranes have been studied for water electrolysis. The HPAs, including tungstophosphoric acid(TPA), molybdophosphoric acid(MoPA), and tungstosilicic acid(TSiA) were used as additives in the composite membranes. The MEA was prepared by a non-equilibrium impregnation-reduction(I-R) method, using reducing agent, sodium borohydride(NaBH4) and tetraamineplatinum(II) chloride(pt(NH$_3$)$_4$Cl$_2$). The electrocatalytic properties of composite membranes such as the cell voltage were in the order of magnitude CL-SPEEKlMoPA40 (wt%) > /TPA30 > /TSiA40. In the optimum cell applications for water electrolysis, the cell voltage of PtlPEM/Pt-Ru MEA with CL-SPEEKlTPA30 membrane was 1.75 V at 80$^{\circ}$C and I A/cm$^2$ and this voltage carried lower than that of 1.81 V of Nafion 117. Consequently, in regards of electrochemical and mechanical characteristics and oxidation durability, the newly developed CL-SPEEKITPA30 composite membrane exhibited a better performance than the others, but CLSPEEKlMoPA40 showed the best electrocatalytic activity (1.71 Vat 80$^{\circ}$C and 1 A/cm$^2$) among the composite membranes.

• Carbon letters
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• 제14권2호
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• pp.117-120
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• 2013

In this study, an electro-catalyst of Pt nanoparticles supported by polypyrrole-functionalized graphene (Pt/PPy-reduced graphene oxide [RGO]) is reported. The Pt nanoparticles are deposited on the PPy-RGO composite by chemical reduction of H2PtCl6 using NaBH4. The presence of graphene (RGO) caused higher activity. This might have been due to increased electro-chemically accessible surface areas, increased electronic conductivity, and easier charge-transfer at polymer-electrolyte interfaces, allowing higher dispersion and utilization of the deposited Pt nano-particles. Microstructure, morphology and crystallinity of the synthesized materials were investigated using X-ray diffraction and transmission electron microscopy. The results showed successful deposition of Pt nano-particles, with crystallite size of about 2.7 nm, on the PPy-RGO support film. Catalytic activity for methanol electro-oxidation in fuel cells was investigated using cyclic voltammetry. The fundamental electrochemical test results indicated that the electro-catalytic activity, for methanol oxidation, of the Pt/PPy-RGO combination was much better than for commercial catalyst.

• 대한화학회지
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• 제32권5호
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• pp.495-500
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• 1988

trans-[$PtNH_3Cl_2L$] (L = $H_2O$, $NH_3$, $Cl^-$, $Br^-$, $I^-$, $CH_3$ 및 $PH_3$)형 백금(Ⅱ)착물계열의 트란스효과를 설명하기 위해 필자들이 수정한 확장 Huckel MO법을 사용했다. 계산에 의하면 L이 보다 좋은 트란스배향리간드일수록 L의 트란스자리에 있는 Pt-N의 결합의 reduced overlap population(ROP)은 감소했다. 즉 이 사실은 보다 좋은 트란스배향리간드 일수록 트란스 효과가 증대되었다. 따라서 일반적인 trans-[$PtTL_2X$] 착물의 트란스효과를 양자화학적으로 설명할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3077-3083
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• 2010

The electrochemical detection of As(III) was investigated on a platinum-iron(III) nanoparticles modified multiwalled carbon nanotube on glassy carbon electrode(nanoPt-Fe(III)/MWCNT/GCE) in 0.1 M $H_2SO_4$. The nanoPt-Fe(III)/MWCNT/GCE was prepared via continuous potential cycling in the range from -0.8 to 0.7 V (vs. Ag/AgCl), in 0.1 M KCl solution containing 0.9 mM $K_2PtCl_6$ and 0.6 mM $FeCl_3$. The Pt nanoparticles and iron oxide were co-electrodeposited into the MWCNT-Nafion composite film on GCE. The resulting electrode was examined by cyclic voltammetry (CV), scanning electron microscopy (SEM), and anodic stripping voltammetry (ASV). For the detection of As(III), the nanoPt-Fe(III)/MWCNT/GCE showed low detection limit of 10 nM (0.75 ppb) and high sensitivity of $4.76\;{\mu}A{\mu}M^{-1}$, while the World Health Organization's guideline value of arsenic for drinking water is 10 ppb. It is worth to note that the electrode presents no interference from copper ion, which is the most serious interfering species in arsenic detection.

• 자원리싸이클링
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• 제28권2호
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• pp.46-53
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• 2019

본 연구에서는 백금족 금속의 분리회수 가능성을 알아보기 위해 백금족 금속 혼합물로부터 이온성액체 기반의 용매에서 백금족 금속의 추출과 전해 환원거동을 조사하였다. 촉매조성인 10:1:0.5 M의 비로 $PdCl_2$, $PtCl_4$, $RhCl_3$가 용해되어 있는 혼합액으로부터 이온성액체인 $[C_4mim]PF_6$를 이용하여 백금(Pt)을 선택적으로 추출한 후 수계 전해액인 1 M $HNO_3$으로 역추출하고 -0.8 V (vs. Pt-QRE)의 전압과 금을 작동전극으로 사용하여 백금을 우선적으로 회수하였다. 잔류하는 팔라듐과 로듐은 $[C_4mim]Cl$ 용액으로 추출한 다음 비수계 전해법으로 환원회수하였다. 전극물질과 전압에 따른 두 금속의 환원거동을 조사하였으며, 작동전극을 탄소, 금과 STS304를 이용하여 각각 팔라듐과 로듐을 순차적으로 회수할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제20권11호
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• pp.1295-1298
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• 1999

Novel platinum(IV) complexes with asymmetric chiral diamine ligands cis,cis,trans-A2PtCl2(X)2 (X = OH, OCOCH3, OCOC2H5, A2 =NH2CH(CH3)CH2NH(c-C6H11)(apcha), NH2CH(CH3)CH2NH(c-C5H9)(apcpa)) have been prepared. One of the platinum(IV) complexes, (apcpa)PtCl2(OCOC2H5)2(6), was subjected to X-ray crystallographic analysis. The crystal structure of (apcpa)PtCl2(OCOC2H5)2 (monoclinic, P21 (No. 4), a = 9.1391(1), b = 22.2517(1), c = 10.0687(1)Å, β= 109.105(1)。 , V = 1934.80(3)Å3 , Z = 4, R1 = 0.0532) exhibits that the platinum atom achieves a typical octahedral arrangement with two nitrogen atoms in cis positions and two carboxylato group in trans positions. The spectroscopic data disclose that these platinum(IV) complexes are stable and their molecular structures are retained in aqueous solution. The title complexes are highly cytotoxic in vitro but do not exhibit oral anticancer activity in vivo.

• Bulletin of the Korean Chemical Society
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• 제30권5호
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• pp.1157-1163
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• 2009

Complexes of Pd(btnbmtp)$Cl_2$ and Pt(btnbmptp)$Cl_2$ (btnbmtp = 2,5-bis(thiophen)-1-nonyl-3,4-bis(methylthio)- pyrrole) were prepared and their crystal structures were determined at room temperature. In the structures, the two thiophene moieties lie in cis form with an average dihedral angle of $55.26^{\circ}$ to the pyrrole frame. The luminescence properties of the free ligand and the complexes were investigated in solution and solid states. The luminescence of the compounds were not favored by substituting thiophene moieties to the pyrrole frame, compared to the unsubstituted nbmptp (nbmptp = 1-nonyl-3,4-bis(methylthio)pyrrole). In particular, thiophene substitution quenched the emission from the complexes dissolved in ,$CH_2Cl_2$ and reduced the charge transfer transitions from S atoms of the thio moieties to Pt in crystalline state, which was very characteristic of Pt(nbmptp)$Cl_2$.

• Korean Chemical Engineering Research
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• 제46권4호
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• pp.727-731
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• 2008

계면활성제(P123)를 주형물질로 사용하여 메조포러스 구조의 Pt-Au 합금박막을 전기화학적 증착법에 의해 ITO가 코팅된 유리 위에 합성하였다. 전해질은 각각 10 mM의 $H_2PtCl_6$와 $HAuCl_4$의 혼합용액에 일정량의 계면활성제를 첨가하여 사용하였다. TEM(Transmission Electron Microscopy) 분석을 통하여 기공구조를 확인하였고, SEM(Scanning Electron Microscopy) 분석을 통하여 합성된 박막의 표면입자의 형태를 확인하였다. 합성된 메조포러스 구조의 Pt-Au 합금박막의 입자 함량비는 EDS(Energy Dispersive X-ray Spectroscopy) 분석으로 조사하였다. 메탄올 산화에 대한 전기화학적 촉매활성과 박막의 안정성을 평가한 결과 메조포러스 구조일 때, 넓은 표면적으로 인해 산화전류밀도가 월등히 증가함을 알 수 있었으며, 순수한 Pt박막과 비교하였을 때 소량의 Au입자의 첨가로 촉매적 안정성이 향상됨을 확인하였다.