[논문]고성능 전기 화학 pH 센서를 위한 유연한 3차원 다공성 폴리아닐린 필름 제조

박홍준; 박승화; 김호준; 이경균; 최봉길

doi:10.14478/ace.2020.1065

고성능 전기 화학 pH 센서를 위한 유연한 3차원 다공성 폴리아닐린 필름 제조
Preparation of Flexible 3D Porous Polyaniline Film for High-Performance Electrochemical pH Sensor 원문보기

공업화학 = Applied chemistry for engineering, v.31 no.5, 2020년, pp.539 - 544

박홍준 (강원대학교 화학공학과) , 박승화 (강원대학교 화학공학과) , 김호준 (강원대학교 화학공학과) , 이경균 (나노종합기술원) , 최봉길 (강원대학교 화학공학과)

초록
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본 연구에서는 넓은 면적의 나노필라 배열 필름을 기반으로 포토 및 소프트 리소그래피 기술과 화학적 희석 고분자 중합을 조절하여 3차원 다공성의 폴리아닐린 필름을 제조하였다. 3차원 폴리아닐린 필름은 계층 간 연결된 폴리아닐린 나노파이버들로 구성되어 있어, 넓은 표면적과 개방형의 다공성 구조를 가지는 3차원 계층형 나노웹 필름을 형성한다. 전기화학분석법을 기반으로 3차원 폴리아닐린 필름이 유연한 pH 센서 전극이 되는 것을 증명하였다. 3차원 폴리아닐린 필름은 이상적인 네른스트 거동과 근접한 60.3 mV/pH의 높은 민감도를 보였다. 또한, 3차원 폴리아닐린 전극은 10 min의 빠른 반응 속도, 우수한 반복성 그리고 높은 선택성을 나타내었다. 3차원 폴리아닐린 전극을 기계적으로 굽힌 상태에서 센서 특성을 측정하였을 때, 전극이 60.4 mV/pH의 높은 민감도를 보여줌으로써, 유연한 pH 센서 성능을 증명하였다.

Abstract ▼ AI-Helper

A three-dimensional (3D) porous polyaniline (PANI) film was fabricated by a combined photo-and soft-lithography technique based on a large-area nanopillar array, followed by a controlled chemical dilute polymerization. The as-obtained 3D PANI film consisted of hierarchically interconnected PANI nanofibers, resulting in a 3D hierarchical nanoweb film with a large surface and open porous structure. Using electrochemical measurements, the resulting 3D PANI film was demonstrated as a flexible pH sensor electrode, exhibiting a high sensitivity of 60.3 mV/pH, which is close to the ideal Nernstian behavior. In addition, the 3D PANI electrode showed a fast response time of 10 s, good repeatability, and good selectivity. When the 3D PANI electrode was measured under a mechanically bent state, the electrode exhibited a high sensitivity of 60.4 mV/pH, demonstrating flexible pH sensor performance.

주제어

표/그림 (6)

그림 Figure 1. (a) A schematic image for fabrication process of 3D PANI electrode and the SEM images of (b) Si mold, (c) PUN nanopillar, (d,e,f) top and (g) cross sectional views for 3D PANI structure.
그림 Figure 2. The OCP measurements recorded for increasing the pH level (a) and the calibration plot (b) of OCP versus pH in the pH 4.0~9.0 range.
그림 Figure 3. (a) The limit of detection curve of the 3D PANI electrode, conditioned in solution of pH 4.0, (b) the EMF responses for the 3D PANI electrode when changing from pH 4.0 to 6.0, (c) A repeatability for the 3D PANI electrode in pH 4~9, (d) long-term stability for the 3D PANI electrode for 15 h in pH 7.
그림 Figure 4. FT-IR spectra of the 3D PANI electrode.
그림 Figure 5. (a) Photography of a bent 3D PANI electrode, (b) OCP responses of 3D PANI electrode with different pH levels, and (c) calibration curve of bent 3D PANI electrode with increasing pH level.
표 Table 1. Selective Coefficients of 3D PANI Sensor Obtained by a Separation Solution Method (SSM) for Primary ion (H⁺) against Na⁺, K⁺, NH₄⁺, Ca²⁺, and Mg²⁺ (Interference Ions)

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문제 정의

This study demonstrated the application of a 3D porous film, composed of hierarchically interconnected PANI nanofibers, as a pH sensor electrode. The 3D PANI electrode was fabricated by a combined photo- and soft-lithography technique, followed by controlled dilute polymerization.

제안 방법

In this study, we developed a simple and scalable method for the fabrication of 3D porous PANI films with a hierarchical nanoweb morphology. The unique structure of the PANI film was prepared by a combined photo- and soft-lithography technique based on a large-area nanopillar array, followed by controlled dilute polymerization.
The selectivity coefficient of the pH sensor was investigated by the separate solution method (SSM) recommended by IUPAC. To evaluate the selectivity coefficients of the pH sensor, the OCP responses were measured for the primary ion (H⁺) in the solution and compared with the responses for interfering ions including Na⁺ , K⁺ , NH₄⁺ , Ca²⁺, and Mg²⁺. The selectivity coefficient (K) can be calculated by SSM using the following equation[39,40]:

대상 데이터

Ammonium persulfate (98%), aniline (99.5%), hydrochloric acid, calcium chloride, magnesium chloride, ammonium chloride, and potassium chloride were purchased from Sigma-Aldrich (USA). Perchloric acid (70%) was purchased from Junsei (Japan).
5%), hydrochloric acid, calcium chloride, magnesium chloride, ammonium chloride, and potassium chloride were purchased from Sigma-Aldrich (USA). Perchloric acid (70%) was purchased from Junsei (Japan). The pH buffer solutions (pH 4.

이론/모형

All electrochemical measurements were performed at room temperature, and the obtained data were within the error range of ± 1%. The sensitivity, limit of detection (LOD), response time, repeatability, selectivity, and durability test were performed using an open-circuit potential technique.

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