• 대한화학회지
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• 제37권4호
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• pp.462-469
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• 1993

Cofacial bis-cobalt tetraphenylporphyrin 유도체 화합물들이 수식된 유리질 탄소 전극과 microelectrode에서 순환 전압 전류법 및 시간 전류법에 의해 산소의 환원 반응을 조사하였다. Microelectrode를 사용하여 시간-전류법에 의해 얻은 전자수 n값들은 유리질 탄소 전극을 사용하여 순환 전압 전류법들에 의해 얻은 결과들과 다소 다른 값으로 나타났다. 알카리성 용액에서 monomer인 cobalt tetraphenylporphyrin 화합물이 수식된 전극에서 산소의 호나원 반응 경로는 중간 생성물인 $H_2O_2$로 가는 2 전자반응으로 진행되었고, dimer인 cofacial bis-cobalt tetraphenylporphyrin 유도체 화합물들이 수식된 전극에서는 최종 생성물인 $H_2O$로 가는 4 전자 반응으로 진행되었다. 이와 같은 산소의 환원 반응은 전체적으로 비가역적으로 확산 지배적인 반응으로 주어졌다.

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3668-3674
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• 2010

Mesoporous SBA-15 was synthesized using tetraethylorthosilicate (TEOS) as the silica source and Pluronic (P123) as the structure-directing agent. The defective Si-OH groups present in SBA-15 were successively grafted with 3-chloropropyltrimethoxysilane (CPTMS) followed by tris-(2-aminoethyl) amine (TAEA) and/or tetraethylenepentamine (TEPA) for effective immobilization of silver nanoparticles. Grafting of TAEA and/or TEPA amine and immobilization of silver nanoparticles inside the channels of SBA-15 was verified by XRD, TEM, IR and BET techniques. The silver nanoparticles immobilized on TAEA and /or TEPA grafted SBA-15 was subjected for electrocatalytic reduction of hydrogen peroxide ($H_2O_2$). The TEPA stabilized silver nanoparticles show higher efficiency for reduction of $H_2O_2$ than that of TAEA, due to higher number of secondary amine groups present in TEPA. The amperometric analysis indicated that both the Ag/SBA-15/TAEA and Ag/SBA-15/TEPA modified electrodes required lower over-potential and hence possess high sensitivity towards the detection of $H_2O_2$. The reduction peak currents were linearly related to hydrogen peroxide concentration in the range between $3{\times}10^{-4}\;M$ and $2.5{\times}10^{-3}\;M$ with correlation coefficient of 0.997 and detection limit was $3{\times}10^{-4}\;M$.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.133-133
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• 2013

For both oxygen reduction (ORR) and hydrogen oxidation reactions (HOR) of proton electrolyte membrane fuel cells (PEMFCs), alloying Pt with another transition metal usually results in a higher activity relative to pure Pt, mainly due to electronic modification of Pt and bifunctional behaviour of alloy surface for ORR and HOR, respectively. However, activity and stability are closely related to the preparation of alloy nanoparticles. Preparation conditions of alloy nanoparticles have strong influence on surface composition, oxidation state, nanoparticle size, shape, and contamination, which result from a large difference in redox priority of metal precursors, intrinsic properties of metals, increasedreactivity of nanocrystallites, and interactions with constituents for the synthesis such as solvent, stabilizer, and reducing agent, etc. Carbon-supported Pt-Ni alloy nanoparticles were prepared by the borohydride reduction method in anhydrous solvent. Pt-Ru alloy nanoparticles supported on carbon black were also prepared by the similar synthetic method to that of Pt-Ni. Since electrocatalytic reactions are strongly dependent on the surface structure of metal catalysts, the atom-leveled design of the surface structure plays a significant role in a high catalytic activity and the utilization of electrocatalysts. Therefore, surface-modified electrocatalysts have attracted much attention due to their unique structure and new electronic and electrocatalytic properties. The carbon-supported Au and Pd nanoparticles were adapted as the substrate and the successive reduction process was used for depositing Pt and PtM (M=Ru, Pd, and Rh) bimetallic elements on the surface of Au and Pd nanoparticles. Distinct features of the overlayers for electrocatalytic activities including methanol oxidation, formic acid oxidation, and oxygen reduction were investigated.

• 한국광물학회지
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• 제18권1호
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• pp.1-9
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• 2005

몇 가지 점토광물과 메틸바이올로젠 또는 메틸렌블루를 함유시킨 점토수식전극을 이용하여 산소환원에 대한 전기화학적 촉매성을 검토하였다. 점토광물로는 Na-몬모릴로나이트, Ca-몬모릴로나이트, 카오리나이트를 사용하였다. 점토수식전극은 유리탄소전극 표면에 점토 현탁액을 입히고 메틸바이올로젠을 흡착시킨 것을 사용하였으며, 전기화학적 산소환원의 정도는 순환 전압전류법(cyclic voltammetry)으로 측정하였다. 실험결과, 다른 점토시료에 비하여 Na-몬모릴로나이트가 메틸바이올로젠의 흡착효과가 가장 크게 나타났고, 메틸바이올로젠을 흡착시킨 점토수식전극이 산소환원에 대한 촉매성이 월등히 우수하였다. 즉 촉매산소환원 피크가 242.6 mV 만큼 +방향으로 이동하였다. 메틸바이올로젠을 흡착시킨 점토수식전극이 메틸렌블루를 흡착시킨 점토수식전극보다 산소환원에 대한 촉매성이 더 높게 나타났다. Ca-몬모릴로나이트의 경우는 변화가 없었으나 Na-몬모릴로나이트의 구조는 메틸바이올로젠의 흡착으로 변화되었다. 메틸바이올로젠- Na-몬모릴로나이트 점토수식전극은 현탁액의 점토 농도가 약 0.87 g/10 mL이고. 메틸바이올로젠의 수용액의 농도가 대략 2.5 mM일 때 산소환원 촉매 효과가 가장 탁월하였다. 지지전해질의 pH에 따른 점토수식 전극의 산소 환원 촉매성은 중성의 pH 범위(6.3과 8.3)에서보다 산성인 pH 3.7과 알칼리성인 pH 12.7에서 월등히 크게 나타났다.

• 전기화학회지
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• 제13권4호
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• pp.251-255
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• 2010

We report on the electrocatalytic reduction of hydrogen peroxide at nanoporous gold (NPG) surfaces. Various NPG surfaces with different surface structure were prepared by changing the conditions of electrodeposition for Ag-Au layers such as the concentration ratios of $KAu(CN)_2$ over $KAg(CN)_2$ and deposition charges. The effects of different electrochemical conditions on the electrocatalysis of $H_2O_2$ reduction were investigated. The NPG surfaces exhibited sensitive amperometric responses for $H_2O_2$ reduction, from which calibration plots with higher sensitivity than a bare Au surface were obtained.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2004년도 춘계총회 및 학술발표회
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• pp.26-26
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• 2004

• Bulletin of the Korean Chemical Society
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• 제19권7호
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• pp.795-797
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• 1998

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 추계학술대회
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• pp.316-319
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• 2006

There is a worldwide interest in the development and commercialization of Polymer Electrolyte Membrane Fuel Cells (PEMFCs) for vehicular and stationary applications. One of the major objectives is the reduction of loaded electrode materials, which is comprise of the Pt-based noble metals. In this paper, a novel chemical strategy is described for the preparation and characterization of carbon-supported and surface-alloys, which were prepared by using a successive reduction process. After preparing Au colloid nanoparticles, the deposition of Au colloid nanoparticles occurred spontaneously in the carbon black-dispersed aqueous solution. Then nano-scaled active materials were formed on the surface of carbon-supported Au nanoparticles. The structural and electrochemical analyses indicate that the active materials were deposited on the surface of Au nanoparticles selectively and that an at toying process occurred during the successive reducing process The carbon-supported & surface-alloys showed the higher electrocatalytic activity than those of the particle-alloys and commercial one (Johnson-Matthey) for the reaction of methanol and formic acid oxidation. The increased electrocatalytic activity might be attributed to the effective surface structure of surface-alloys, which have a high utilization of active materials for the surface reaction of electrode.

• 신재생에너지
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• 제2권4호
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• pp.64-69
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• 2006

There is a worldwide interest in the development and commercialization of polymer electrolyte membrane fuel cells [PEMFCs] for vehicular and stationary applications. One of the major objectives is the reduction of loaded electrode materials, which is comprise of the Pt-based noble metals. In this paper, a novel chemical strategy is described for the preparation and characterization of carbon-supported and surface-alloys, which were prepared by using a successive reduction process. After preparing Au colloid nanoparticles, the supporting of Au colloid nanoparticles occurred spontaneously in the carbon black-dispersed aqueous solution. Then nano-scaled active materials were formed on the surface of carbon-supported Au nanoparticles. The structural and electrochemical analyses indicate that the active materials were deposited on the surface of Au nanoparticles selectively and that an alloying process occurred during the successive reducing process. The carbon-supported & surface-alloys showed the higher electrocatalytic activity than those of the particle-alloys and commercial one [Johnson-Matthey] for the reaction of methanol and formic acid oxidation. The increased electrocatalytic activity might be attributed to the effective surface structure of surface-alloys, which have a high utilization of active materials for the surface reaction of electrode.

• 전기화학회지
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• 제15권2호
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• pp.83-89
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• 2012

전기화학적 석출에 의해 Ag-Au 합금층을 전극표면에 형성한 후 진한 질산으로 Ag만을 녹여내는 기법으로 나노다공성 금(nanoporous gold, NPG) 구조를 만들어 전기화학적 산소환원에 대한 촉매현상을 관찰하였다. 석출과정의 전구체의 농도비를 달리하였을 때 나타나는 NPG 표면구조의 변화를 주사전자현미경으로 관찰하고 전기화학적 표면적을 측정하였다. 전기화학적 산소환원 촉매 효율은 NPG 표면의 구조에 따라 달라졌는데, Ag/Au 비율이 2.0에 해당하는 NPG 구조에서 가장 우수한 촉매 현상이 관찰 되었다. 표면구조의 변화에 따른 촉매 활성 변화에서 다공성 구조의 역할이 매우 큰 기여를 하는 반면 표면적의 변화는 큰 영향을 미치지 않았다. 최적 조건의 NPG 구조상의 전기화학적 산소환원 과정의 메커니즘을 회전원판전극 실험을 통해 관찰하였는데, 산성 조건에서 NPG 전극에서 전기화학적 산소환원은 과산화수소를 거쳐 물이 생성되는 2-단계 4-전자 환원 메커니즘으로 진행되었고 염기성 조건에서는 산소가 4개의 전자 전달을 통해 물로 직접적으로 환원 되었다.