WO2011155669A1 - Spr sensor for fuel measurement of a fuel cell having a modified metal thin film surface, and manufacturing method therefor - Google Patents

Spr sensor for fuel measurement of a fuel cell having a modified metal thin film surface, and manufacturing method therefor Download PDF

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WO2011155669A1
WO2011155669A1 PCT/KR2010/006949 KR2010006949W WO2011155669A1 WO 2011155669 A1 WO2011155669 A1 WO 2011155669A1 KR 2010006949 W KR2010006949 W KR 2010006949W WO 2011155669 A1 WO2011155669 A1 WO 2011155669A1
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spr sensor
fuel
thin film
fuel cell
concentration
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French (fr)
Korean (ko)
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이혜진
심혜림
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경북대학교 산학협력단
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G01N21/553—Attenuated total reflection and using surface plasmons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0444—Concentration; Density
    • H01M8/04447—Concentration; Density of anode reactants at the inlet or inside the fuel cell
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N2021/258—Surface plasmon spectroscopy, e.g. micro- or nanoparticles in suspension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an SPR sensor for measuring fuel having a modified metal thin film surface and a method of manufacturing the same.
  • a fuel cell is a battery that directly converts chemical energy generated by oxidation of a fuel into electrical energy.
  • the fuel cell is characterized in that the reactants are continuously supplied from the outside and the reaction products are continuously removed out of the system.
  • Fuels mainly used in fuel cells include methanol, ethanol and formic acid. As fuel is consumed to generate electricity, continuous injection of fuel is essential. Accordingly, a system capable of real-time detection of fuel concentration is required for efficient utilization of fuel cells.
  • the SPR sensor refers to a sensor for measuring the concentration of a substance by Surface Plasmon Resonance (SPR), and has a characteristic of sensitively measuring the concentration of a fluid substance in contact with the surface of the sensor.
  • SPR Surface Plasmon Resonance
  • a gold thin film is generally used as the SPR sensor. When fuel comes into contact with the surface of the gold thin film, the concentration of the signal varies depending on the concentration, and thus the concentration of the fuel can be measured.
  • the SPR sensor if the fuel concentration is measured by the SPR sensor, the signal becomes unstable and its sensitivity is low. This is because the surface of the gold thin film is hydrophobic, whereas the fuel of the fuel cell is mostly hydrophilic, and thus the interaction at the interface is not smooth. Accordingly, there is a limit in measuring accurate fuel concentration due to bubble generation and signal instability on the surface of the gold thin film.
  • the present inventors while studying the surface treatment, which is the key in developing the fuel cell SPR sensor for efficient operation of the fuel cell system, by chemical treatment on the surface of the conventional gold thin film chip as a fuel cell sensor Confirmed that the usability of the can be improved and completed the present invention.
  • the present invention is to provide an SPR sensor for measuring the fuel concentration of the fuel cell that can not only accurately measure the fuel concentration of the fuel cell accurately and reproducibly, but also can be applied to an existing SPR sensor.
  • the present invention is to provide a method for manufacturing an SPR sensor for measuring the fuel concentration of the fuel cell that can improve the characteristics of the SPR sensor without undue increase of complex process and process cost.
  • the present invention is a SPR sensor for measuring the fuel concentration of the fuel cell, the SPR sensor comprises a gold thin film chip, the surface of the gold thin film chip is modified with a polymer having a hydrophilic group It provides an SPR sensor characterized in that.
  • SPR sensor used in the present invention means a sensor for measuring the concentration of a substance and the like by Surface Plasmon Resonance (SPR).
  • SPR Surface Plasmon Resonance
  • the SPR method can measure the interactions between molecules using optical principles without a separate label such as a fluorescent material.
  • Surface plasmons are quantized vibrations of free electrons that propagate along a conductor surface, such as a metal surface. These surface plasmons pass through a dielectric medium such as a prism and enter the metal film at an angle above the critical angle of the dielectric medium. It is excited by incident light and causes resonance at a certain angle. The angle of incidence, ie resonance angle, at which this resonance occurs is sensitive to the change in refractive index of the material in proximity to the thin metal film. Using this property, the SPR sensor can quantitatively analyze a sample from a change in refractive index of a material, that is, a sample close to a metal thin film, and apply the same to measure a fuel concentration of a fuel cell
  • Gold thin film In order to measure the fuel concentration of a fuel cell among the SPR sensors, a gold thin film is generally used.
  • Gold thin film has the advantage that it can be used stably because it does not cause additional chemical reactions such as fuel of a fuel cell such as methanol or ethanol.
  • the surface of the gold thin film is hydrophobic, the signal change is irregular due to problems such as surface tension or problems caused by a change in the interface generated when the fuel cell of the hydrophilic fuel cell contacts the surface of the gold thin film.
  • the present invention is to modify the surface of the gold thin film with a polymer having a hydrophilic group, thereby making the surface of the gold thin film hydrophilic to solve the above problems, it is possible to improve the accuracy and reproducibility of the SPR sensor.
  • the polymer having a hydrophilic group means a compound in which one end of the polymer has a reactor capable of bonding with a gold thin film, and the other end has a hydrophilic reactor.
  • 11-mercapto-undecylamine, 11-mercapto-undecanoic acid, 11-mercapto-undecanoic acid, 11-mercapto-1-undecanol (11- mercapto-1-undecanol), or poly-ethylene-glycol may be used.
  • the accuracy and reproducibility of the SPR sensor is increased, and in particular, the concentration of methanol, ethanol or formic acid can be measured very accurately. Can be.
  • step 1 the step of dissolving a polymer having a hydrophilic group in a solvent
  • step 2 Method of manufacturing an SPR sensor for measuring the fuel concentration of the fuel cell comprising the step of immersing the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell in a solution in which the polymer having the hydrophilic group dissolved (step 2) To provide.
  • Step 1 is a step of dissolving a polymer having a hydrophilic group in a solvent, the polymer means a compound having one end of the polymer can be combined with a gold thin film, the other end having a hydrophilic reactor.
  • the polymer means a compound having one end of the polymer can be combined with a gold thin film, the other end having a hydrophilic reactor.
  • 11-mercapto-undecylamine, 11-mercapto-undecanoic acid, 11-mercapto-undecanoic acid, 11-mercapto-1-undecanol (11- mercapto-1-undecanol), or poly-ethylene-glycol may be used.
  • methanol may be preferably used, but is not limited thereto.
  • Step 2 is a step for modifying a polymer having a hydrophilic group on the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell, the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell
  • the surface of the gold thin film may be modified by immersion in a solution in which a polymer having a group is dissolved. Immersion time is preferably 11 to 13 hours, so that the polymer can be sufficiently modified.
  • the SPR sensor and its manufacturing method for measuring the fuel concentration of the fuel cell according to the present invention has the following features.
  • the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can measure the fuel concentration of the fuel cell accurately and reproducibly.
  • the fuel cell is operated for a long time according to the supply of fuel, and it is important to accurately measure the concentration of the fuel during the long time of operation.
  • the SPR sensor for measuring the fuel concentration of a commonly used fuel cell uses a gold thin film chip, it is difficult to accurately measure the concentration due to the hydrophobicity of the surface of the gold thin film chip and the hydrophilicity of the fuel.
  • the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can be applied as it is to the SPR sensor used in the past.
  • the SPR sensor can be used as it is, and a simple method can increase the accuracy of the SPR sensor. Accordingly, it is possible to effectively improve the characteristics of a conventionally used fuel cell.
  • the manufacturing method of the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can be manufactured by a simple method of immersing the SPR sensor in a solution in which a hydrophilic polymer is dissolved. Accordingly, it is possible to improve the characteristics of the conventional SPR sensor used in a simple manner, it is possible to improve the characteristics of the SPR sensor without undue increase of complex process and process cost.
  • Figure 1 shows the signal change of the SPR sensor when injecting methanol.
  • Figure 2 shows the signal change of the SPR sensor when ethanol is injected.
  • Figure 3 shows the signal change of the SPR sensor when injecting formic acid.
  • Figure 4 shows the signal change of the SPR sensor according to the change in the concentration of formic acid.
  • Figure 5 shows the signal change of the SPR sensor according to the change in the concentration of formic acid.
  • FIG. 6 shows a calibration curve according to an embodiment of the present invention.
  • FIG. 7 illustrates a result of measuring an RU value for each time zone according to an embodiment of the present invention.
  • 11-mercapto-undecylamine (Dojindo), 11-mercapto-undecanoic acid (Aldrich), 11-mercapto-1-unde in ethanol Canol (11-mercapto-1-undecanol, Aldrich), and poly-ethylene-glycol (SH-poly-ethylene-glycol, Paraon), each of which was modified at a thiol group, were dissolved at a concentration of 1 mM.
  • a gold thin film chip (gold thin film chip manufactured by Kmac (gold thin film chip for microSPR) manufactured by Kmac) was used; BK7 glass substrate (1 cm width ⁇ 1 cm length ⁇ 0.5 cm Thin chromium thin film (approximately 1 nm) and then immersed a 45 nm gold thin film chip) to form a self-assembled monolayer to modify the surface of the gold thin film with a polymer. Immersion time was adjusted to 12 hours.
  • the gold thin film chip of the SPR sensor (using Kmac's microSPR equipment) whose surface was modified with MUAM showed the most sensitive signal change.
  • the gold thin film chip of the SPR sensor whose surface was modified with MUD when formic acid was injected showed the most sensitive signal change.
  • the signal change was shown quantitatively according to the concentration of formic acid, and in particular, since the exact signal change was reproducible according to each concentration, the Refractive Unit (RU) value corresponding to each concentration was changed. It could be confirmed that almost identical.
  • RU Refractive Unit
  • the SPR sensor for measuring the fuel concentration of a fuel cell is required for long-term sustainability at the same time as sensitive response.
  • the formic acid was maintained at a concentration of 2.5M, and the RU value was measured at each time zone, and the results are shown in FIG. 7.

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Abstract

The present invention relates to an SPR sensor for measuring the fuel concentration of a fuel cell, which can exactly and reproducibly measure the fuel concentration of a fuel cell and be applied to existing SPR sensors. The present invention also relates to a manufacturing method for the SPR sensor for measuring the fuel concentration of a fuel cell, which can enhance the properties of the SPR sensor without excessive increases in complicated processes and manufacturing costs.

Description

금속 박막 표면이 개질된 연료전지의 연료측정용 ＳＰＲ 센서 및 이의 제조방법SRP sensor for fuel measurement of fuel cell with modified metal thin film surface and manufacturing method thereof
본 발명은 금속 박막 표면이 개질된 연료측정용 SPR 센서 및 이의 제조방법에 관한 것이다.The present invention relates to an SPR sensor for measuring fuel having a modified metal thin film surface and a method of manufacturing the same.
연료전지는, 연료의 산화에 의해서 생기는 화학에너지를 직접 전기에너지로 변환시키는 전지로서, 반응물이 외부에서 연속적으로 공급되어 반응생성물이 연속적으로 계의 바깥으로 제거된다는 특징을 가지고 있다. 종래에는 연료전지의 크기가 매우 커야한다는 문제점이 있었으나 최근에는 소형화가 이루어지고 있으며, 이에 따라 일반 휴대용 건전지와 같이 휴대가 간편한 연료전지로 개발되는 추세에 있다. A fuel cell is a battery that directly converts chemical energy generated by oxidation of a fuel into electrical energy. The fuel cell is characterized in that the reactants are continuously supplied from the outside and the reaction products are continuously removed out of the system. Conventionally, there has been a problem that the size of a fuel cell must be very large, but in recent years, miniaturization has been made, and accordingly, there is a trend to be developed as a fuel cell that is easy to carry like a general portable battery.
연료전지에 주로 사용되는 연료로는, 메탄올, 에탄올 및 포름산 등이 있다. 이러한 연료가 소비됨으로서 전기가 생산되므로 연료의 지속적인 주입이 필수적이며, 이에 따라 연료전지의 효율적인 활용을 위해서 연료의 농도를 실시간으로 감지할 수 있는 시스템이 필요하다. Fuels mainly used in fuel cells include methanol, ethanol and formic acid. As fuel is consumed to generate electricity, continuous injection of fuel is essential. Accordingly, a system capable of real-time detection of fuel concentration is required for efficient utilization of fuel cells.
연료전지의 연료를 측정하기 위한 다양한 센서가 개발되고 있으며, 일반적으로 SPR법을 이용한 센서가 사용되고 있다. SPR 센서는, 표면 플라즈몬 공명법(Surface Plasmon Resonance; SPR)으로 물질의 농도 등을 측정하는 센서를 의미하는 것으로, 센서의 표면에 접촉하는 유체물질의 농도를 민감하게 측정할 수 있다는 특징이 있다. 이러한 SPR 센서로서 금 박막이 일반적으로 사용되고 있으며, 금 박막 표면에 연료가 접촉되면 그 농도에 따라 신호의 증폭정도가 달라 연료의 농도를 측정할 수 있다. Various sensors for measuring fuel of a fuel cell have been developed, and sensors using the SPR method are generally used. The SPR sensor refers to a sensor for measuring the concentration of a substance by Surface Plasmon Resonance (SPR), and has a characteristic of sensitively measuring the concentration of a fluid substance in contact with the surface of the sensor. As the SPR sensor, a gold thin film is generally used. When fuel comes into contact with the surface of the gold thin film, the concentration of the signal varies depending on the concentration, and thus the concentration of the fuel can be measured.
그러나, SPR 센서로 연료의 농도를 측정하게 되면, 신호가 불안정하고 그 민감도가 떨어지게 된다. 이는 금 박막 표면은 소수성의 성질을 띠는 반면, 연료전지의 연료는 대부분 친수성의 성질을 띠고 있기 때문에, 계면에서 상호작용이 원활하지 않기 때문이다. 이에 따라 금 박막 표면에서 기포의 발생, 신호의 불안정성 등의 이유로 정확한 연료의 농도를 측정하는데 한계가 있다. However, if the fuel concentration is measured by the SPR sensor, the signal becomes unstable and its sensitivity is low. This is because the surface of the gold thin film is hydrophobic, whereas the fuel of the fuel cell is mostly hydrophilic, and thus the interaction at the interface is not smooth. Accordingly, there is a limit in measuring accurate fuel concentration due to bubble generation and signal instability on the surface of the gold thin film.
이에 본 발명자는, 연료전지 시스템의 효율적인 작동을 위한 연료측정용 SPR센서를 개발함에 있어 핵심이 되는 표면처리를 연구하던 중, 기존에 사용되고 있는 일반 금 박막칩 표면에 화학적 처리를 함으로써 연료전지 센서로의 활용성을 높일 수 있음을 확인하고 본 발명을 완성하였다.The present inventors, while studying the surface treatment, which is the key in developing the fuel cell SPR sensor for efficient operation of the fuel cell system, by chemical treatment on the surface of the conventional gold thin film chip as a fuel cell sensor Confirmed that the usability of the can be improved and completed the present invention.
본 발명은, 연료전지의 연료 농도를 정확하고 재현성 있게 측정할 수 있을 뿐만 아니라, 기존에 사용되는 SPR 센서에 그대로 적용될 수 있는 연료전지의 연료 농도를 측정하기 위한 SPR 센서를 제공하기 위한 것이다. The present invention is to provide an SPR sensor for measuring the fuel concentration of the fuel cell that can not only accurately measure the fuel concentration of the fuel cell accurately and reproducibly, but also can be applied to an existing SPR sensor.
또한 본 발명은, 복잡한 공정 및 공정단가의 과도한 증가 없이 SPR 센서의 특성을 향상시킬 수 있는 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 제조방법을 제공하기 위한 것이다.In another aspect, the present invention is to provide a method for manufacturing an SPR sensor for measuring the fuel concentration of the fuel cell that can improve the characteristics of the SPR sensor without undue increase of complex process and process cost.
상기의 과제를 해결하기 위하여, 본 발명은 연료전지의 연료 농도를 측정하기 위한 SPR 센서에 있어서, 상기 SPR 센서는 금 박막 칩을 포함하고, 상기 금 박막 칩의 표면은 친수성 기를 가지는 고분자로 개질되어 있는 것을 특징으로 하는 SPR 센서를 제공한다. In order to solve the above problems, the present invention is a SPR sensor for measuring the fuel concentration of the fuel cell, the SPR sensor comprises a gold thin film chip, the surface of the gold thin film chip is modified with a polymer having a hydrophilic group It provides an SPR sensor characterized in that.
본 발명에서 사용되는 용어 "SPR 센서"는, 표면 플라즈몬 공명법(Surface Plasmon Resonance; SPR)으로 물질의 농도 등을 측정하는 센서를 의미한다. SPR 법은 형광물질과 같은 별도의 표지물질 없이 광학적 원리를 이용하여 분자들 간의 상호작용을 계측할 수 있다. 표면 플라즈몬(surface plasmon)이란 금속 표면과 같은 도체 표면을 따라서 전파하는 자유전자의 양자화 된 진동을 의미하는데, 이와 같은 표면 플라즈몬은 프리즘과 같은 유전매체를 지나 유전매체의 임계각 이상의 각도로 금속박막에 입사하는 입사광에 의해 여기 되며 일정한 각도에서 공명을 일으킨다. 이러한 공명이 일어나는 입사각, 즉 공명각은 금속박막에 근접한 물질의 굴절률 변화에 민감하다. SPR 센서는 이러한 성질을 이용하여 금속박막에 근접한 물질, 즉 시료의 굴절률 변화로부터 시료의 정량 분석이 가능하며, 이를 응용하여 연료전지의 연료 농도를 측정할 수 있다. The term "SPR sensor" used in the present invention means a sensor for measuring the concentration of a substance and the like by Surface Plasmon Resonance (SPR). The SPR method can measure the interactions between molecules using optical principles without a separate label such as a fluorescent material. Surface plasmons are quantized vibrations of free electrons that propagate along a conductor surface, such as a metal surface. These surface plasmons pass through a dielectric medium such as a prism and enter the metal film at an angle above the critical angle of the dielectric medium. It is excited by incident light and causes resonance at a certain angle. The angle of incidence, ie resonance angle, at which this resonance occurs is sensitive to the change in refractive index of the material in proximity to the thin metal film. Using this property, the SPR sensor can quantitatively analyze a sample from a change in refractive index of a material, that is, a sample close to a metal thin film, and apply the same to measure a fuel concentration of a fuel cell.
상기 SPR 센서 중 연료전지의 연료 농도를 측정하기 위해서, 일반적으로 금 박막이 사용되고 있다. 금 박막은 메탄올 또는 에탄올과 같은 연료전지의 연료 등과 부가적인 화학반응을 일으키지 않으므로 안정적으로 사용될 수 있다는 이점이 있다. 그러나, 금 박막의 표면은 소수성이므로, 친수성을 띄는 연료전지의 연료와 금 박막 표면의 접촉시 발생하는 계면의 변화로 인한 문제나 표면장력 등의 문제로 신호변화가 불규칙하다는 단점이 있다. In order to measure the fuel concentration of a fuel cell among the SPR sensors, a gold thin film is generally used. Gold thin film has the advantage that it can be used stably because it does not cause additional chemical reactions such as fuel of a fuel cell such as methanol or ethanol. However, since the surface of the gold thin film is hydrophobic, the signal change is irregular due to problems such as surface tension or problems caused by a change in the interface generated when the fuel cell of the hydrophilic fuel cell contacts the surface of the gold thin film.
이에 본 발명은, 상기 금 박막 표면을 친수성 기를 가지는 고분자로 개질한 것으로, 이에 따라 금 박막 표면이 친수성을 띄게 되어 상기 문제를 해결할 수 있을 뿐만 아니라, SPR 센서의 정확성 및 재현성이 향상시킬 수 있다. Accordingly, the present invention is to modify the surface of the gold thin film with a polymer having a hydrophilic group, thereby making the surface of the gold thin film hydrophilic to solve the above problems, it is possible to improve the accuracy and reproducibility of the SPR sensor.
상기 친수성 기를 가지는 고분자는, 고분자의 한 쪽 말단은 금 박막과 결합할 수 있는 반응기를 가지고, 다른 쪽 말단은 친수성 반응기를 가지는 화합물을 의미한다. 바람직하게는, 11-머캅토-운데실아민(11-mercapto-undecylamine), 11-머캅토-운데카노익 애시드(11-mercapto-undecanoic acid), 11-머캅토-1-운데카놀(11-mercapto-1-undecanol), 또는 폴리-에틸렌-글리콜(poly-ethylene-glycol)이 사용될 수 있다. The polymer having a hydrophilic group means a compound in which one end of the polymer has a reactor capable of bonding with a gold thin film, and the other end has a hydrophilic reactor. Preferably, 11-mercapto-undecylamine, 11-mercapto-undecanoic acid, 11-mercapto-undecanoic acid, 11-mercapto-1-undecanol (11- mercapto-1-undecanol), or poly-ethylene-glycol may be used.
상기 친수성 기를 가지는 고분자가, 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 금 박막 칩 표면에 개질될 경우, SPR 센서의 정확성 및 재현성이 높아지며, 특히 메탄올, 에탄올 또는 포름산의 농도를 매우 정확하게 측정할 수 있다. When the polymer having the hydrophilic group is modified on the surface of the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell, the accuracy and reproducibility of the SPR sensor is increased, and in particular, the concentration of methanol, ethanol or formic acid can be measured very accurately. Can be.
또한 본 발명은, 친수성 기를 가지는 고분자를 용매에 용해시키는 단계(단계 1); 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 금 박막 칩을 상기 친수성 기를 가지는 고분자가 용해된 용액에 침지시키는 단계(단계 2)를 포함하는 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 제조방법을 제공한다. In another aspect, the present invention, the step of dissolving a polymer having a hydrophilic group in a solvent (step 1); Method of manufacturing an SPR sensor for measuring the fuel concentration of the fuel cell comprising the step of immersing the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell in a solution in which the polymer having the hydrophilic group dissolved (step 2) To provide.
상기 단계 1은, 친수성 기를 가지는 고분자를 용매에 용해시키는 단계로서, 상기 고분자는 고분자의 한 쪽 말단은 금 박막과 결합할 수 있는 반응기를 가지고, 다른 쪽 말단은 친수성 반응기를 가지는 화합물을 의미한다. 바람직하게는, 11-머캅토-운데실아민(11-mercapto-undecylamine), 11-머캅토-운데카노익 애시드(11-mercapto-undecanoic acid), 11-머캅토-1-운데카놀(11-mercapto-1-undecanol), 또는 폴리-에틸렌-글리콜(poly-ethylene-glycol)이 사용될 수 있다. Step 1 is a step of dissolving a polymer having a hydrophilic group in a solvent, the polymer means a compound having one end of the polymer can be combined with a gold thin film, the other end having a hydrophilic reactor. Preferably, 11-mercapto-undecylamine, 11-mercapto-undecanoic acid, 11-mercapto-undecanoic acid, 11-mercapto-1-undecanol (11- mercapto-1-undecanol), or poly-ethylene-glycol may be used.
상기 고분자를 용해시키기 위하여 용매로, 바람직하게는 메탄올이 사용될 수 있으나, 이에 한정되지 않는다. As a solvent for dissolving the polymer, methanol may be preferably used, but is not limited thereto.
상기 단계 2는, 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 금 박막 칩에 친수성 기를 가지는 고분자를 개질하기 위한 단계로서, 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 금 박막 칩을 상기 친수성 기를 가지는 고분자가 용해된 용액에 침지시켜 금 박막의 표면을 개질할 수 있다. 침지시간은 고분자가 충분히 개질될 수 있도록, 11 내지 13시간이 바람직하다. Step 2 is a step for modifying a polymer having a hydrophilic group on the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell, the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell The surface of the gold thin film may be modified by immersion in a solution in which a polymer having a group is dissolved. Immersion time is preferably 11 to 13 hours, so that the polymer can be sufficiently modified.
본 발명에 따른 연료전지의 연료 농도를 측정하기 위한 SPR 센서 및 이의 제조방법은 다음과 같은 특징이 있다. The SPR sensor and its manufacturing method for measuring the fuel concentration of the fuel cell according to the present invention has the following features.
첫째, 본 발명에 따른 연료전지의 연료 농도를 측정하기 위한 SPR 센서는 연료전지의 연료 농도를 정확하고 재현성 있게 측정할 수 있다. 연료전지는 연료의 공급에 맞추어 장기간 운용되는 것으로, 장기간의 운용시간 동안 연료의 농도를 정확하게 측정하는 것이 중요하다. 그러나, 일반적으로 사용되는 연료전지의 연료 농도를 측정하기 위한 SPR 센서는 금 박막 칩을 사용하므로, 금 박막 칩 표면의 소수성과 연료의 친수성에 의하여 그 농도를 정확히 측정하기 힘들다. 반면, 본 발명의 경우, SPR 센서의 금 박막 칩 표면을 친수성 기를 가지는 고분자로 개질함으로서, 연료의 농도를 정확하게 측정할 수 있을 뿐만 아니라, 장기간의 사용에도 그 정확도를 그대로 유지할 수 있어, SPR 센서의 정확도를 높일 수 있다. First, the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can measure the fuel concentration of the fuel cell accurately and reproducibly. The fuel cell is operated for a long time according to the supply of fuel, and it is important to accurately measure the concentration of the fuel during the long time of operation. However, since the SPR sensor for measuring the fuel concentration of a commonly used fuel cell uses a gold thin film chip, it is difficult to accurately measure the concentration due to the hydrophobicity of the surface of the gold thin film chip and the hydrophilicity of the fuel. On the other hand, in the case of the present invention, by modifying the surface of the gold thin film chip of the SPR sensor with a polymer having a hydrophilic group, it is possible not only to accurately measure the concentration of the fuel, but also maintain the accuracy of the SPR sensor as it is for a long time use. You can increase the accuracy.
둘째, 본 발명에 따른 연료전지의 연료 농도를 측정하기 위한 SPR 센서는, 기존에 사용되는 SPR 센서에 그대로 적용될 수 있다. 일반적으로 사용되는 SPR 센서에서, 금 박막 칩 표면을 개질하는 것을 제외하고는 SPR 센서를 그대로 사용할 수 있는바, 간단한 방법으로 SPR 센서의 정확도를 높일 수 있다. 이에 따라 종래 사용되는 연료전지의 특성을 효과적으로 개선시킬 수 있다. Second, the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can be applied as it is to the SPR sensor used in the past. In the commonly used SPR sensor, except that the surface of the gold thin film chip is modified, the SPR sensor can be used as it is, and a simple method can increase the accuracy of the SPR sensor. Accordingly, it is possible to effectively improve the characteristics of a conventionally used fuel cell.
셋째, 본 발명에 따른 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 제조방법은, SPR 센서를 친수성 고분자가 용해되어 있는 용액에 침지시키는 간단한 방법으로 제조할 수 있다. 이에 따라, 종래 사용되는 SPR 센서를 간단한 방법으로 그 특성을 향상시킬 수 있는바, 복잡한 공정 및 공정단가의 과도한 증가 없이 SPR 센서의 특성을 향상시킬 수 있다. Third, the manufacturing method of the SPR sensor for measuring the fuel concentration of the fuel cell according to the present invention can be manufactured by a simple method of immersing the SPR sensor in a solution in which a hydrophilic polymer is dissolved. Accordingly, it is possible to improve the characteristics of the conventional SPR sensor used in a simple manner, it is possible to improve the characteristics of the SPR sensor without undue increase of complex process and process cost.
도 1은, 본 발명의 일 실시예에 따라, 메탄올을 주입할 경우 SPR 센서의 신호 변화를 나타낸 것이다. Figure 1, according to an embodiment of the present invention, shows the signal change of the SPR sensor when injecting methanol.
도 2는, 본 발명의 일 실시예에 따라, 에탄올을 주입할 경우 SPR 센서의 신호 변화를 나타낸 것이다. Figure 2, according to an embodiment of the present invention, shows the signal change of the SPR sensor when ethanol is injected.
도 3은, 본 발명의 일 실시예에 따라, 포름산을 주입할 경우 SPR 센서의 신호 변화를 나타낸 것이다. Figure 3, according to an embodiment of the present invention, shows the signal change of the SPR sensor when injecting formic acid.
도 4는, 본 발명의 일 실시예에 따라, 포름산의 농도 변화에 따른 SPR 센서의 신호 변화를 나타낸 것이다. Figure 4, according to an embodiment of the present invention, shows the signal change of the SPR sensor according to the change in the concentration of formic acid.
도 5는, 본 발명의 일 실시예에 따라, 포름산의 농도 변화에 따른 SPR 센서의 신호 변화를 나타낸 것이다. Figure 5, according to an embodiment of the present invention, shows the signal change of the SPR sensor according to the change in the concentration of formic acid.
도 6은, 본 발명의 일 실시예에 따라, Calibration curve를 나타낸 것이다. 6 shows a calibration curve according to an embodiment of the present invention.
도 7은, 본 발명의 일 실시예에 따라, 각 시간대별로 RU값을 측정한 결과를 나타낸 것이다.FIG. 7 illustrates a result of measuring an RU value for each time zone according to an embodiment of the present invention.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 더욱 쉽게 이해하기 위하여 제공되는 것일 뿐, 실시예에 의하여 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples.
실시예 : SPR 센서의 금 박막 표면의 개질Example: Modification of Gold Thin Film Surface of SPR Sensor
먼저, 에탄올에 11-머캅토-운데실아민(11-mercapto-undecylamine, Dojindo), 11-머캅토-운데카노익 애시드(11-mercapto-undecanoic acid, Aldrich), 11-머캅토-1-운데카놀(11-mercapto-1-undecanol, Aldrich), 및 말단이 티올기로 변형된 폴리-에틸렌-글리콜(SH-poly-ethylene-glycol, Paraon) 각각을 1 mM 농도로 용해시켰다. 상기 고분자가 용해된 용액 각각에, SPR 센서의 금 박막 칩(Kmac사에서 제작하여 판매하는 금 박막칩(microSPR용 금 박막 칩)을 사용; BK7 유리기판(1 cm 가로 × 1 cm 세로 × 0.5 cm 두께)에 얇은 크롬 박막(약 1 nm)를 증착한 후 45 nm의 금 박막을 증착한 칩)을 침지시켜 자기조립단막을 형성시켜, 금 박막 표면을 고분자로 개질 시켰다. 침지시간은 12시간으로 조정하였다. First, 11-mercapto-undecylamine (Dojindo), 11-mercapto-undecanoic acid (Aldrich), 11-mercapto-1-unde in ethanol Canol (11-mercapto-1-undecanol, Aldrich), and poly-ethylene-glycol (SH-poly-ethylene-glycol, Paraon), each of which was modified at a thiol group, were dissolved at a concentration of 1 mM. In each of the solutions in which the polymer is dissolved, a gold thin film chip (gold thin film chip manufactured by Kmac (gold thin film chip for microSPR) manufactured by Kmac) was used; BK7 glass substrate (1 cm width × 1 cm length × 0.5 cm Thin chromium thin film (approximately 1 nm) and then immersed a 45 nm gold thin film chip) to form a self-assembled monolayer to modify the surface of the gold thin film with a polymer. Immersion time was adjusted to 12 hours.
실험예 1 : 메탄올 주입에 따른 신호 측정Experimental Example 1 Signal Measurement According to Methanol Injection
실시예에서 제조된 다양한 SPR 센서의 금 박막 칩에 메탄올을 주입시켜 신호의 변화를 측정하였으며, 그 결과를 도 1에 나타내었다. The change of the signal was measured by injecting methanol into the gold thin film chip of the various SPR sensors manufactured in Examples, and the results are shown in FIG.
도 1에 나타난 바와 같이, 메탄올을 주입할 경우 MUAM으로 표면을 개질한 SPR 센서(Kmac사의 microSPR 장비 사용)의 금 박막 칩이 가장 민감한 신호 변화를 나타내었다. As shown in FIG. 1, when the methanol was injected, the gold thin film chip of the SPR sensor (using Kmac's microSPR equipment) whose surface was modified with MUAM showed the most sensitive signal change.
실험예 2 : 에탄올 주입에 따른 신호 측정Experimental Example 2 Signal Measurement According to Ethanol Injection
실험예 1과 동일한 방법으로 신호를 측정하되, 메탄올 대신 에탄올을 주입하였으며, 그 결과를 도 2에 나타내었다. Signal was measured in the same manner as in Experimental Example 1, ethanol was injected instead of methanol, the results are shown in FIG.
도 2에 나타난 바와 같이, 에탄올을 주입할 경우 MUAM으로 표면을 개질한 SPR 센서의 금 박막 칩이 가장 민감한 신호 변화를 나타내었다. As shown in FIG. 2, when the ethanol was injected, the gold thin film chip of the SPR sensor whose surface was modified with MUAM showed the most sensitive signal change.
실험예 3 : 포름산 주입에 따른 신호 측정Experimental Example 3 Signal Measurement by Formic Acid Injection
실험예 1과 동일한 방법으로 신호를 측정하되, 메탄올 대신 포름산을 주입하였으며, 그 결과를 도 3에 나타내었다. The signal was measured in the same manner as in Experimental Example 1, but formic acid was injected instead of methanol, and the results are shown in FIG. 3.
도 3에 나타난 바와 같이, 포름산을 주입할 경우 MUD로 표면을 개질한 SPR 센서의 금 박막 칩이 가장 민감한 신호 변화를 나타내었다. As shown in FIG. 3, the gold thin film chip of the SPR sensor whose surface was modified with MUD when formic acid was injected showed the most sensitive signal change.
실험예 4 : 연료의 농도별 민감도 및 정확성 측정Experimental Example 4 Measurement of Sensitivity and Accuracy by Fuel Concentration
연료를 주입하되, 일정하게 연료 농도를 변화시켜 그 변화에 따라 신호가 정확하게 변화하는지를 측정하였으며, 그 결과를 도 4에 나타내었다. The fuel was injected, but the fuel concentration was constantly changed, and the signal was accurately measured according to the change. The results are shown in FIG. 4.
도 4에 나타난 바와 같이, 포름산의 농도에 따라 정량적으로 그 신호의 변화가 나타났으며, 특히 각 농도에 따라 정확한 신호의 변화가 재현성 있게 나타나므로, 각 농도에 해당하는 Refractive Unit(RU)값이 거의 동일함을 확인할 수 있었다. As shown in FIG. 4, the signal change was shown quantitatively according to the concentration of formic acid, and in particular, since the exact signal change was reproducible according to each concentration, the Refractive Unit (RU) value corresponding to each concentration was changed. It could be confirmed that almost identical.
상기의 실험을 보다 구체화하여, 포름산의 농도를 0.01 M에서 7.5 M까지 변화시켰으며, 그 결과를 도 5에 나타내었다. In further detailing the above experiment, the concentration of formic acid was changed from 0.01 M to 7.5 M, and the results are shown in FIG. 5.
실험예 5 : Calibration curve 측정Experimental Example 5: Calibration curve measurement
Calibration curve를 측정하기 위하여, 실험예 4와 동일한 실험을 세 번 이상 진행하였고 그 결과를 도 6에 나타내었다. 도 6에 나타난 바와 같이, 선형(linear)의 calibration curve를 확인할 수 있었으며, error bar 결과를 확인하였을 때 도 그 민감성 부분은 상당히 우수함을 확인할 수 있었다. In order to measure the calibration curve, the same experiment as in Experiment 4 was performed three times or more, and the results are shown in FIG. 6. As shown in FIG. 6, the linear calibration curve was confirmed, and when the error bar result was confirmed, the sensitivity part was found to be quite excellent.
실험예 6 : 장기적 안정성 확인Experimental Example 6: Long-term stability confirmation
연료전지의 연료 농도를 측정하기 위한 SPR 센서는, 민감한 감응과 동시에 장기간 지속성이 요구된다. 이에 포름산을 2.5M 농도로 유지하고, 각 시간대별로 RU값을 측정하였으며, 그 결과를 도 7에 나타내었다. The SPR sensor for measuring the fuel concentration of a fuel cell is required for long-term sustainability at the same time as sensitive response. The formic acid was maintained at a concentration of 2.5M, and the RU value was measured at each time zone, and the results are shown in FIG. 7.
도 7에 나타난 바와 같이, 장기적으로 사용되는 경우(적어도 10 일 이상)에도, RU 값이 거의 일정하게 유지됨을 확인할 수 있다.As shown in FIG. 7, even when used for a long time (at least 10 days or more), it can be seen that the RU value remains almost constant.

Claims (7)

  1. 연료전지의 연료 농도를 측정하기 위한 SPR(Surface Plasmon Resonance) 센서에 있어서, 상기 SPR 센서는 금 박막 칩을 포함하고, 상기 금 박막 칩의 표면은 친수성 기를 가지는 고분자로 개질되어 있는 것을 특징으로 하는 SPR 센서. Surface Plasmon Resonance (SPR) sensor for measuring fuel concentration of a fuel cell, wherein the SPR sensor comprises a gold thin film chip, the surface of the gold thin film chip is SPR characterized in that the surface is modified with a polymer having a hydrophilic group sensor.
  2. 제1항에 있어서, 상기 친수성 기를 가지는 고분자는 11-머캅토-운데실아민(11-mercapto-undecylamine), 11-머캅토-운데카노익 애시드(11-mercapto-undecanoic acid), 11-머캅토-1-운데카놀(11-mercapto-1-undecanol), 또는 말단이 티올기로 변형된 폴리-에틸렌-글리콜(poly-ethylene-glycol)인 것을 특징으로 하는 SPR 센서.The method of claim 1, wherein the polymer having a hydrophilic group is 11-mercapto-undecylamine, 11-mercapto-undecanoic acid, 11-mercapto 11-mercapto-1-undecanol, or SPR sensor characterized in that the end is poly-ethylene-glycol (poly-ethylene-glycol) modified with a thiol group.
  3. 제1항에 있어서, 상기 SPR 센서는 메탄올, 에탄올 또는 포름산의 농도를 측정하기 위한 것을 특징으로 하는 SPR 센서.The SPR sensor according to claim 1, wherein the SPR sensor is for measuring the concentration of methanol, ethanol or formic acid.
  4. 친수성 기를 가지는 고분자를 용매에 용해시키는 단계;Dissolving a polymer having a hydrophilic group in a solvent;
    연료전지의 연료 농도를 측정하기 위한 SPR 센서의 금 박막 칩을 상기 친수성 기를 가지는 고분자가 용해된 용액에 침지시키는 단계를 포함하는 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 제조방법. A method of manufacturing an SPR sensor for measuring the fuel concentration of a fuel cell comprising immersing a gold thin film chip of the SPR sensor for measuring the fuel concentration of a fuel cell in a solution in which the polymer having the hydrophilic group is dissolved.
  5. 제4항에 있어서, 상기 친수성 기를 가지는 고분자는 11-머캅토-운데실아민(11-mercapto-undecylamine), 11-머캅토-운데카노익 애시드(11-mercapto-undecanoic acid), 11-머캅토-1-운데카놀(11-mercapto-1-undecanol), 또는 말단이 티올기로 변형된 폴리-에틸렌-글리콜(poly-ethylene-glycol)인 것을 특징으로 하는 SPR 센서의 제조방법.The method of claim 4, wherein the polymer having a hydrophilic group is 11-mercapto-undecylamine, 11-mercapto-undecanoic acid, 11-mercapto 11-mercapto-1-undecanol, or a method for producing an SPR sensor, characterized in that the terminal is poly-ethylene-glycol (poly-ethylene-glycol) modified with a thiol group.
  6. 제4항에 있어서, 상기 용매는 메탄올인 것을 특징으로 하는 SPR 센서의 제조방법. The method of claim 4, wherein the solvent is methanol.
  7. 제4항에 있어서, 상기 연료전지의 연료 농도를 측정하기 위한 SPR 센서의 금 박막 칩을 상기 친수성 기를 가지는 고분자가 용해된 용액에 11 내지 13시간동안 침지시키는 것을 특징으로 하는 SPR 센서의 제조방법. The method of claim 4, wherein the gold thin film chip of the SPR sensor for measuring the fuel concentration of the fuel cell is immersed in a solution in which the polymer having the hydrophilic group is dissolved for 11 to 13 hours.
PCT/KR2010/006949 2010-06-10 2010-10-11 Spr sensor for fuel measurement of a fuel cell having a modified metal thin film surface, and manufacturing method therefor WO2011155669A1 (en)

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US20030017579A1 (en) * 2001-07-10 2003-01-23 Corn Robert M. Surface plasmon resonance imaging of micro-arrays
US20030100127A1 (en) * 2001-07-10 2003-05-29 Corn Robert M. Fusion protein arrays on metal substrates for surface plasmon resonance imaging
JP2009042210A (en) * 2007-07-13 2009-02-26 Fujifilm Corp Chip for measuring surface plasmon resonance
KR20100041565A (en) * 2008-10-14 2010-04-22 강릉원주대학교산학협력단 A method for introducing a functional group on surface of material

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US20030017579A1 (en) * 2001-07-10 2003-01-23 Corn Robert M. Surface plasmon resonance imaging of micro-arrays
US20030100127A1 (en) * 2001-07-10 2003-05-29 Corn Robert M. Fusion protein arrays on metal substrates for surface plasmon resonance imaging
JP2009042210A (en) * 2007-07-13 2009-02-26 Fujifilm Corp Chip for measuring surface plasmon resonance
KR20100041565A (en) * 2008-10-14 2010-04-22 강릉원주대학교산학협력단 A method for introducing a functional group on surface of material

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