Ti(Ⅳ)이온의 포집용 고분자 피막전극

차성극 경남대학교 환경문제연구소 2002 환경연구 Vol.25 No.-

3.4-dihydroxybenzoic acid(3,4-DHBA) was electropolymerized on glassy carbon electrode to give the GC/p-3,4-DHBA type electrode which was remodified with dopamine by the help of EDC acting as coupling agent. The -COOH sites on the polymeric surface of p-3,4-DHBA and amino group at the dopamine gave a QCA(Au)/p-3,4-DHBA-dopamine type of modified electrodes. The redox process of the electrode is hydroquinone = quinone + 2H^(+) + 2e^(-), which had two strong and two weak peaks at CV. The modified electrode can deposit Ti(IV) ions as much as 4.13 × 10^(-5) gcm^(-2).

Arterenol로 수식된 자기조립 단층막 전극의 pH영향과 NADH의 전기촉매 산화반응

차성극 경남대학교 환경문제연구소 2003 환경연구 Vol.26 No.-

Mercaptopropionic acid(mpa) containing thiol and carboxyl groups was employed to prepare SAMs electrode, which was coupled with arterenol(art) to give the type of Au/mpa-art electrode. The electrochemical behaviors of the modified electrodes influenced on the buffer solution at acidic, neutral and basic region. The electrodes exhibited very reversible 0.28V of formal potential and 0.06V of △E_(p) in 0.1 M phosphate buffer(pH=7.02). This electrode had surface coverage of Г= 1.10 × 10^(-10)mo1/㎠ and gave activity in reaction of electrocatalytic oxidation at NADH. The calibration curve for determination of NADH with the electrodes showed excellent linearty to 1.0 mM of (NADH) having correlationship of 1.0.

Oligopyridine류의 코발트 착체 내에서 전자전달

차성극 慶南大學校 附設 基礎科學硏究所 1999 硏究論文集 Vol.13 No.-

〔Co₂(terpy)₂(tppz)〕⁴+ and 〔Co₃(novi-py)₂〕6+ were synthesized. redox profiles and electron transfer rate from their characteristics in cyclic volmmetry and rotating disk voltammetry were quitely different. The former had two pairs of redox peaks at E˚' = 0.18V and 0.31V and isopotential point in rotating disk voltammograms at 0.05V where the rate constants of electron transfer were k₁= 4.68 x 10-5 and k₂= 3.29 x 10-5cm/s. In the case of Letter, three redox waves were observed at E˚' = -0.135V, 0.10V and 0.29V and their rate constants of electron transfer were k₁= 4.27 x10-³ , k₂= 1.21 x 10-³ and k₃= 1.04 x 10-³ cm/s. At simplest case of these series [Co(terpy)₂]²+ has k = 1.58 x 10-5 cm/s. From there results, it is obvious that increasing number of pyridine ring enhanced the rate. In the double stranded helical complex, the values were larger than that of another as a facter of 100 times, which resulted from the unstability of substituted pyridine and strain on the fairly excited state of helical molecules to give easy redox process.

3,4-디하이드록시벤조산으로 수식된 3,4-디하이드록시벤즈알데하이드 고분자 피막 전극

차성극 경남대학교 신소재연구소 2002 신소재연구 Vol.14 No.-

3,4-dihydroxybenzaldehyde(3,4-DHB)를 유리탄소 전극 상에 전기화학법으로 중합하여 GC/p-3,4-DHB형의 저극을 제작하고 이것을 3,4-dihydroxybenzoic acid(3,4-DHBA)로 재 수식한 전극을 0.1 MHCl 촉매 하에서 제작하였다. 이 반응은 고분자 피막상에 -OH기와 3,4-DHBA상에 -COOH기 사이에 에스테르화 반응에 의하여 연쇄반응으로 진행할 수 있다. 이 재 수식반응은 1차로 진행되며 그 속도상수는 초기 단계에서는 0.18 x 10^-1s^-1로 진행하며 그 이후에는 2.46 x 10^-2s^-1로 속도 상수 값이 다소 낮아진다. 재 수식하기 전후에 촉매능은 각각 0.11 and 3.18μAs^-1였다. 또 재 수식한 전극의 어드미턴스 값은 3배정도 증가하였다. 이 전극을 에탄올에서 6시간동안 정치해두면 잘 배열된 고분자 피막이 되고 그 결과 산화-환원 과정에서 피크전류가 배로 증가하였다. 3,4-dihydroxybenzaldehyde(3,4-DHB) was electropolymerized on glassy carbon electrode to give the GC/p-3,4-DHB type electrode which was remodified with 3,4-dihydroxybenzoic acid(3,4-DHBA) under 0.1M HCl of catalyst. These can be done as chain reaction at -OH sites on the polymeric surface of p-3,4-DHB and -COOH at the 3,4-DHBA. These reactions were first order having 1.18 x 10^-1s^-1 at initial step but being to 2.46 x 10^-2s^-1 after then as rate constant. The catalytic abilities of two electrodes were respectively. Electrical admittance of the remodified one was also triply increased. The resulted electrode was aligned into ethanol for 6 hours, which gave doubly enhanced redox procedure.

Diethyldithiocarbamate로 수식된 피롤 고분자 피막전극으로 U(VI)의 포집

차성극 경남대학교 공업기술연구소 2000 硏究論文集 Vol.18 No.-

전도성이 뛰어난 피롤고분자 피막을 전기화학적으로 중합하고 이를 Gr/ppy(polypyrrole), car(diethyldithiocarbamate)형의 수식된 전극을 제작하여 U(VI)의 포집에 이용하였다. 사전 피막제인 NBR(nitrile butadiene rubber)을 사용하였을 때 중합속도는 3.22 x 10□□□로 이를 사용하지 않았을 때 보다 1.6배 느린 반응이었다. 포집된 U(VI)의 양은 ppy 1.70Ccm□ 당에 5.56 x 10□개었으며, 인공해수 중에서 matrix효과는 8.28%로 나타났다. ppy전극이 Gr/ppy, car□, UO□형으로 수식됨에 따라서 피막자체의 임피던스가 증가하여 ppy만일 때의 확산에 지배적인 전도과정에서 피막자체의 전자전도와 이온도핑과정이 함께 영향을 받는 결과를 보였다. ppy전극을 car로 수식하여 U(VI)를 포집함에 따라 전기이중층의 용량은 각각 94와 135여 배로 증가하였다. Anodically polymerized conducting polypyrrole film electrode was employed to pick up uranyl ion with the type of Gr/ppy, diethyldithiocarbamate modified electrode. To have porous and oriented ppy film, NBR was applied as precoating agent. The rate constant of polymerization was 3.22 x 10□□□ which was 1.6 times smaller value than bare graphite surface. The deposited amount of uranyl ions on 1.70Ccm □ of ppy was 5.56 x 10□ions. The matrix effect in artifical seawater was 8.28%. The polymer film electrode has a diffusion controlled process in conduction, but the modified Gr/ppy, car.□ UO□ type was influenced on the ion doping and electronic conduction of film itself owing to increasing of impedance. The capacitance of electrical double layer was respectively enhanced to 94 and 135 times in Gr/ppy, car.□ and Gr/ppy, car.□, UO □ than Gr/ppy type electrode.

Dopamine으로 수식된 Au/mercaptopropionic acid 자기조립 단층 막 전극에서 반응성

차성극 慶南大學校 附設 工業技術硏究所 2003 硏究論文集 Vol.21 No.1

mercaptopropionic acid를 사용하여 금의 표면에 자기조립 단층 막을 만든 후 이를 dopamine과 반응시켜 Au/mpa-dopa형의 전극을 제작하였으며 이 전극을 에탄올에서 6시간 동안 정돈시켜 잘 배열된 피막 전극을 제작할 수 있었으며 이 전극의 형식전위는 0.25 V 그리고 ΔE_P는 0.06 V로 산호환원반응에서 가역성이 뛰어났다. 이 전극 반응은 전자전달에 지배적인 과정이고 산화과정에서만 ECcat의 반응기구를 나타냈다. 유사 일차반응으로 그 속도상수 값인 ks는 2.19 × 10^7 ㏖^-1 s^-1이었다. Self-assembled monolayers of mercaptopropionic acid(mpa) on gold electrodes were modified with dopamine (dopa) to give the Au/mpa-dopa type electrodes. Those were aligned in ethanol for 6 hours to have well oriented monolayers and better cyclic voltammograms, which gave very reversible in redox reaction as the formal potential of 0.25 V and ΔE_P of 0.06 V. The reaction was controlled by electron transfer and had reaction mechanism of ECcat. The rate constant for the pseudo first order reaction was 2.19 × 10^7 ㏖^-1 s^-1.

우라닐이온 포집용 수식된 피롤 고분자 피막전극의 전기화학

차성극 慶南大學校 附設 基礎科學硏究所 2000 硏究論文集 Vol.14 No.-

Anodically polymerized conducting polypyrrole film electrode has PF6- ion as dopant. The electrode was modified with diethyldithiocarbamate having pK=17.5 of stability constant for coordination of uranyl ion by ion exchange. This could give multiful use of uptaking uranyl ion in water from analytical signal with graphite/ppy.ligand.U(VI) type electrode. According to increased quantity of the exchanged ligand on electroactive sites, cyclic voltammetric area was greatly shrunk. But as this was deposited with uranyl ion that was also increased as much as adsorpted uranyl ions. The deposited quantity of U(VI) was 325 C/㎠ for 6.35 C/㎠ of polypyrrole film. From stripping voltammetry the procedure of deportion of them was controlled by diffusion.

주석산으로 수식된 [Ru(v-bpy)₃]^(2+) 고분자 피막전극을 이용한 UO₂^(2+)의 정량

車星極 경남대학교 환경문제연구소 1999 환경연구 Vol.22 No.-

Electrodes of the polycationic film with electropolymerized 〔Ru(v-bpy)₃〕(2+) having about 1:1 ratio of PF_(6-)/CIO₄^(-) as the doped counter ions, were modified with tartarate ion by ion exchange which had stability constant as 32.4. These electrodes were employed in the quantitative multiple determination of U(VI) in solution. The electrochemical cell type for the analytical signal was Pt/p-〔Ru(v-bpy)₃〕^(2+), ligand. U(VI)/1.0M HCIO₄(aq.)/Pt with Ag/AgCI referance electrode. In the stripping voltammetry, electrode process was electron transfer controlled one and calibration curves at the ranges of 10(-3)~10^(-7)M had excellent relationship as 0.98 and relative standard deviation as 8%.

[Ru(v-bpy)₃ ]^(2+) 고분자 피막내에서 전하전달

차성극 경남대학교 환경문제연구소 1997 환경연구 Vol.20 No.-

Poly[Ru(v-bpy)₃]^(2+) was anodically polymerized on platinum surface, which is polycationic polymer film containing PF_(6) ions counter ions on the polymer strands. These ions were exchanged with some amino acids as ligands. such as glycine. tyrosine, L-alanine. D-alanine and hippuic acid. These electrochemically modified electrodes were used to measure the rate constant for charge transfer by linear sweep voltammetry with rotating disk electrode. Those measured values were respectively 7.23. 7.45. 8.67. 9.01 및 14.78㎤/mol.s. which were bigger than PolypRu(v-bpy)₃]^(2+) doped with PF6-ion as a factor of 58 to 117 times. These results come from the incorporated amino acid to have structal advantage in the polymer network and electron donating at electrochemical active sites on the polymer film.

Mercaptopropionic acid와 Arterenol로 제작된 자기조립 단층 막 전극에서 조효소의 전기화학 반응

차성극 慶南大學校 附設 工業技術硏究所 2003 硏究論文集 Vol.21 No.2

Mercaptopionic acid(mpa)로 된 자기조립단층막(Self-assembled monolayers : SAMs)을 금 전극위에 만들고 이를 arterenol(arte)로 수식한 Au/mpa-arte형의 전극을 제작하였다. 이 전극을 에탄올내에서 6시간동안 담그어 두면 피막상에 SAMs가닥들이 잘 정돈된다. 그 결과로 순환 전압전류법(cyclic voltammetry)에서 0.1M 인산염 완충용액(pH=7.02)에서 형식전위가 0.22V 그리고 ΔEp가 0.05V로 크게 개선된 결과를 보였다. 이 전극을 사용하여 NADG를 전기화학적 산화반응하였을 때 촉매작용이 크고 그 반응기구가 ECcat로 나타났다. 또 이 전극을 이용한 NADH의 정량도 가능하였으며 정량의 가능한 범위도 3.06x10 mM로 높았다. Self-assembled monolayers(SAMs) of mercaptopropionic acid(mpa) on gold electrodes were modified with arterenol(arte) to give the Au/mpa-arte type electrodes. Those were annealed in ethanol for 6 hours to have the well oriented monolayers and better cyclic voltammograms, which gave very reversible in redox reaction as the formal potential of 0.22V and ΔEp of 0.05V in 0.1M phosphate buffer solution(pH=7.02). The reaction was controlle by electron transfer and had reaction mechanism of ECcat. The calibration curve of NADH at electrocatalytic oxidation reaction gave excellent linearty exhibiting corelationship of 0.99 to 3.06 x 10 mM