| 研究生: |
言紹榮 SHAO-RONG YAN |
|---|---|
| 論文名稱: |
CZIS與BiVO4之電化學頻譜分析 Analysis of Electrochemical Impedance Spectroscopy for CZIS and BiVO4 |
| 指導教授: |
李岱洲
Tai-Chou Lee |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 化學工程與材料工程學系 Department of Chemical & Materials Engineering |
| 論文出版年: | 2019 |
| 畢業學年度: | 107 |
| 語文別: | 中文 |
| 論文頁數: | 124 |
| 中文關鍵詞: | 阻抗頻譜 、擬合 、電路模型 |
| 外文關鍵詞: | Impedance spectroscopt, fitting, circuit model |
| 相關次數: | 點閱:13 下載:0 |
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本研究以電化學阻抗譜(Electrochemical Impedance Spectroscopy)分析光化學於光反應與暗反應之行為,藉由擬合(fitting)以及電路圖了解光電化學反應系統,
以mott-schottky 方程式協助理解光陽極之各項參數。
材料以CIS、CZIS系列與BiVO4為主,分為暗反應與光反應兩種電化學機制,對於暗反應使用Randles cirsuit等效電路模型;對於光反應,經過fitting比較後選用以表面態傳輸電荷為主的等效電路模型。
由暗反應不同偏壓之測量,透過Mott-Schottky方程式繪製Mott-Schottky plot,藉此計算斜率與截距,進而推得實驗材料之平帶電位與載子濃度,配合霍爾測量交叉確認其值。
透過光暗反應之等效電路元件數值,Rct,trap(表面態電荷傳輸界面阻抗)相較於暗反應,其值大幅下降,Rtrapping(表面態再結合阻抗),確認實驗材料於光照下,電子與電洞的再結合率很低,且Rct的下降反映了電洞更易與電解液接觸且進行電荷傳遞、產生氧氣。
電荷傳輸阻抗、表面態電容變化曲線圖配合Mott-Schottky plot之平帶電位,表明當偏壓在平帶電位附近時,表面態有大量電荷累積而電容達到最大值,電荷不易擺脫電場束縛進行傳遞,表面態電荷轉移阻抗也達到最高;而加大偏壓後,電洞較易於抵達電解液而與界面上之陰離子結合且產氧,因此電荷累積情形下降,表面態電容與電荷轉移阻抗也對應下降。
In this study, we analyzed the photochemical behavior of light and dark reaction on Electrochemical Impedance Spectroscopy, by fitting (fitting) and circuit diagram to understand photoelectric chemical reaction system.
The mott-schottky equation was used to understand the parameters of photoanode.The materials are mainly CIS, CZIS series and BiVO4, which are divided into two electrochemical mechanisms: dark reaction and light reaction. Randles cirsuit equivalent circuit model is used for dark reaction.
For the light reaction, an equivalent circuit model dominated by surface state transfer charge is selected after the comparison of fitting.
Mott-schottky plot was plotted by using Mott-schottky equation to calculate slope and intercept, and then the horizontal band potential and carrier concentration of the experimental materials were obtained, and the values were cross-confirmed by hall measurement.
By Observing equivalent circuit element of light and dark reation, Rct,trap (surface charge transfer impedance interface) value has fallen dramatically which compared with dark reaction.
Confirmed that the recombination rate of electrons and holes is very low under illumination. The trop of Rct reflects the holes are more likely to be in contact with the electrolyte, and transfers charge, then produces oxygen.
The curve of charge transfer impedance and surface state capacitance change, combined with the flat band potential of mott-schottky plot, indicated that when the bias voltage was near the flat band potential, the surface state had a large amount of charge accumulation and the capacitance reached the maximum value, the charge was not easy to be transferred from the electric field, and the surface state charge transfer impedance also reached the highest level.
However, when the bias voltage is increased, the hole is easier to reach the electrolyte and combine with the anions on the interface to produce oxygen, so the charge accumulation situation decreases, and the surface state capacitance and charge transfer impedance also decrease correspondingly.
[1] 陳麗貞. 第三十三期電子月刊 取之不盡用之不竭的太陽能httpsrecord.epa.gov.twEpaper099333-3.html
[2] K.Fujishima, A., & Honda, “Electrochemical Photolysis of Water One and Two-dimensional Structure of Poly ( L-Alanine ) shown by Specific Heat Measurements at Low,” Nature, vol. 238, pp. 37–38, 1972.
[3] K. R.Tolod, S.Hernández, E. A.Quadrelli, andN.Russo, “Visible Light-Driven Catalysts for Water Oxidation: Towards Solar Fuel Biorefineries,” Stud. Surf. Sci. Catal., vol. 178, pp. 65–84, 2019.
[4] S. N.Basahel, T. T.Ali, M.Mokhtar, andK.Narasimharao, “Influence of crystal structure of nanosized ZrO2 on photocatalytic degradation of methyl orange,” Nanoscale Res. Lett., vol. 10, no. 1, 2015.
[5] G.Elango andS. M.Roopan, “Efficacy of SnO2 nanoparticles toward photocatalytic degradation of methylene blue dye,” J. Photochem. Photobiol. B Biol., vol. 155, pp. 34–38, 2016.
[6] X.Chen, Z.Wu, D.Liu, andZ.Gao, “Preparation of ZnO Photocatalyst for the Efficient and Rapid Photocatalytic Degradation of Azo Dyes,” Nanoscale Res. Lett., vol. 12, no. 1, pp. 4–13, 2017.
[7] W.Jiang, Z.Wu, X.Yue, S.Yuan, H.Lu, andB.Liang, “Photocatalytic performance of Ag 2 S under irradiation with visible and near-infrared light and its mechanism of degradation,” RSC Adv., vol. 5, no. 31, pp. 24064–24071, 2015.
[8] W.Gao et al., “In 2 S 3 nanomaterial as a broadband spectrum photocatalyst to display significant activity,” Appl. Catal. B Environ., vol. 176–177, pp. 83–90, 2015.
[9] E. S.Aazam, “Photocatalytic oxidation of cyanide under visible light by Pt doped AgInS2 nanoparticles,” J. Ind. Eng. Chem., vol. 20, no. 6, pp. 4008–4013, 2014.
[10] D.Chen andJ.Ye, “Photocatalytic H2 evolution under visible light irradiation on AgIn5S8 photocatalyst,” J. Phys. Chem. Solids, vol. 68, no. 12, pp. 2317–2320, 2007.
[11] G.Wang et al., “Cu2(OH)PO4, a near-infrared-activated photocatalyst,” Angew. Chemie - Int. Ed., vol. 52, no. 18, pp. 4810–4813, 2013.
[12] 吳錦貞,「I-III-VI/II-VI 族可見光應答光觸媒材料之光電化學分析與水分解產氫應用」,國立中正大學,博士論文,2009。
[13] A.Nylander, “Fabrication and reliability study of thermoelectric modules,” 2015.
[14] K.Rajeshwar, “Fundamentals of semiconductor electrochemistry and photoelectrochemistry,” Encycl. Electrochem., vol. 6, pp. 3–53, 2001.
[15] R. R.Chamberlin and J. S.Skarman, “Chemical Spray Deposition Process for Inorganic Films,” no. 1, pp. 86–89,1966
[16] F.Lisdat andD.Schäfer, “The use of electrochemical impedance spectroscopy for biosensing,” Anal. Bioanal. Chem., vol. 391, no. 5, pp. 1555–1567, 2008.
[17] D.Loveday, D.Loveday, P.Peterson, P.Peterson, B.Rodgers, andB.Rodgers, “Evaluation of organic coatings with electrochemical impedance spectroscopy. Part 2: application of EIS to coatings,” J. Coatings Technol., vol. 1, no. 10, pp. 88–93, 2004.
[18] T.Lopes, L.Andrade, H. A.Ribeiro, andA.Mendes, “Characterization of photoelectrochemical cells for water splitting by electrochemical impedance spectroscopy,” Int. J. Hydrogen Energy, vol. 35, no. 20, pp. 11601–11608, 2010.
[19] J.Ângelo, P.Magalhães, L.Andrade, andA.Mendes, “Characterization of TiO 2 -based semiconductors for photocatalysis by electrochemical impedance spectroscopy,” Appl. Surf. Sci., vol. 387, pp. 183–189, 2016.
[20] M. H.Habibi, N.Talebian, andJ. H.Choi, “Characterization and photocatalytic activity of nanostructured indium tin oxide thin-film electrode for azo-dye degradation,” Thin Solid Films, vol. 515, no. 4, pp. 1461–1469, 2006.
[21] S.States, B.Klahr, F.Fabregat-santiago, andT. W.Hamann, “Water Oxidation at Hematite Photoelectrodes : The role of the Surface States,” J. Am. Chem. Soc., vol. 134, no. October 2016, pp. 4294–4302, 2012.
[22] Bard, A. J.; Stratmann, M.; Licht, S., Semiconductor Electrodes and Photoelectrochemistry. Wiley-VCH: Weinheim, 2002.
[23] J. G. Webster, “Electrical Impedance Tomography”, Adam Hilger,Bristol, 1990.
[24] Simple circuits with resistors and capacitors,http://lacey.se/science/eis/simple-circuits/