当H
2S气体通过纳米MgO-Fe
2O
3表面时,被O
2催化氧化,产生化学发光(CL)。本文合成检测了五种不同配比催化材料,结果表明,当Fe
2O
3质量占比15%时,催化发光(CTL)强度高于其它不同配比的催化材料。由此,优化开发了一种优异的H
2S传感器。此CTL传感器具有高选择性,只有异丙醇引起14.54%的干扰,甲醇、乙醇、丙酮等均不干扰H
2S的测定。在温度为230℃,波长为400 nm,载气流速为200 ml/min的最佳实验条件下,催化发光强度与丙酮浓度在5~500 ppm内呈线性关系,检出限为2.8 ppm (S/N = 3),响应时间:3秒,恢复时间:6秒。
When the H
2S gas passes through the surface of the nano-MgO-Fe
2O
3, it is catalytically oxidized by O
2 to produce chemiluminescence (CL). In this paper, five different catalytic materials were syn-thesized and tested. The results show that when the mass of Fe
2O
3 is 15%, the intensity of catalytic luminescence (CTL) is higher than other different proportions of catalytic materials. As a result, an excellent H
2S sensor was optimized. The CTL sensor has high selectivity, only 14.54% interference caused by isopropanol, and methanol, ethanol, acetone and the like do not interfere with the de-termination of H
2S. Under the optimal experimental conditions of 230˚C, 400 nm, and carrier gas flow rate of 200 ml/min, the catalytic luminescence intensity is linear with acetone concentration within 5 to 500 ppm, and the detection limit is 2.8 ppm (S/N = 3), response time: 3 seconds, recov-ery time: 6 seconds.
论为了研究H2S在复合材料MgO-Fe2O3上的发光机理,实验收集尾气采用气相色谱-质谱进行分析测试。测试结果表明为尾气中的主要物质为SO2,根据所查文献,测试中光信号主要为被测物质所产生的中间体所产生 [21],H2S可能产生两种发光中间体 S 2 * 和 SO 2 * ,同时这两种中间体都在400 nm波长附近处有主峰的出现,经过查阅文献 [22], S 2 * 从激发态回到基态所产生的信号不与H2S的浓度成线性关系,而是呈2次方的关系,但是激发态的 SO 2 * 与H2S浓度呈线性关系,据此推测H2S催化发光机理如下,发光中间体为 SO 2 * ,但详尽的发光机理还需要进一步研究。
H 2 S + O 2 → Catalyst SO 2 * + H 2 O → SO 2 + H 2 O + h ν
成 栋,赵田园,张洪铭,黄飞飞,刘名扬. Mg/Fe纳米复合材料体系的催化发光性能研究Study on Cataluminescence Properties of Mg/Fe Nanocomposite System[J]. 材料化学前沿, 2019, 07(02): 19-27. https://doi.org/10.12677/AMC.2019.72003
参考文献ReferencesMoon, C.H., Zhang, M., Myung, N.V. and Haberer, E.D. (2014) Highly Sensitive Hydrogensulfide (H2S) Gas Sensors from Vi-ral-Templated Nanocrystalline Gold Nanowires. Nanotechnology, 25, 135-205.Asad, M. and Sheikhi, M.H. (2014) Surface Acoustic Wave Based H2S Gas Sensors Incorporating Sensitive Layers of Single Wall Carbon Nanotubes Decorated with Cu Nano-particles. Sensors and Actuators B: Chemical, 198, 134-141. https://doi.org/10.1016/j.snb.2014.03.024Yamazoe, N. (2005) Toward Innovations of Gas Sensor Technology. Sensors and Actuators B: Chemical, 108, 2-14. https://doi.org/10.1016/j.snb.2004.12.075Tanda, N., Washio, J., Ikawa, K., et al. (2007) A New Portable Sulfide Monitor with a Zinc-Oxide Semiconductor Sensor for Daily Use and Field Study. Journal of Dentistry, 35, 552-557. https://doi.org/10.1016/j.jdent.2007.03.003Sakai, G., Matsunaga, N., Shimanoe, K. and Yamazoe, N. (2001) Theory of Gas-Diffusion Controlled Sensitivity for Thin Film Semiconductor Gas Sensor. Sensors and Actuators B: Chemical, 80, 125-131. https://doi.org/10.1016/S0925-4005(01)00890-5Patil, L.A. and Patil, D.R. (2006) Heterocontact Type CuO-Modified SnO2 Sensor for the Detection of a ppm Level H2S Gas at Room Temperature. Sensors and Actuators B: Chemical, 120, 316-323. https://doi.org/10.1016/j.snb.2006.02.022Choi, S.W., Zhang, J., Akash, K. and Kim, S. (2012) H2S Sensing Performance of Electrospun CuO-Loaded SnO2 Nanofibers. Sensors and Actuators B: Chemical, 169, 54-60. https://doi.org/10.1016/j.snb.2012.02.054Jin, C., Yamazaki, T., Ito, K., Kikuta, T. and Nakatani, N. (2006) H2S Sensing Property of Porous SnO2 Sputtered Films Coated with Various Doping Films. Vacuum, 80, 723-725. https://doi.org/10.1016/j.vacuum.2005.11.002Liu, Y., Tang, F., Kang, C.J., et al. (2012) Detection of Hydrogen Sulphide Using Cataluminescence Sensors Based on Alkaline-Earth Metal Salts. Luminescence, 27, 274-278. https://doi.org/10.1002/bio.1345Liu, J., Yee, K.K., Lo, K.W., et al. (2014) Selective Ag(I) Binding, H2S Sensing, and White-Light Emission from an Easy-to-Make Porous Conjugated Polymer. Journal of the American Chemical Society, 136, 2818-2824. https://doi.org/10.1021/ja411067aMubeen, S., Zhang, T., Chartuprayoon, N., et al. (2010) Sensitive Detection of H2S Using Gold Nanoparticle Decorated Single-Walled Carbon Nanotubes. Analytical Chemistry, 82, 250-257. https://doi.org/10.1021/ac901871dZheng, W., Lu, X., Wang, W., et al. (2009) Assembly of Pt Nanoparticles on Electro-spun In2O3 Nanofibers for H2S Detection. Journal of Colloid and Interface Science, 338, 366-370. https://doi.org/10.1016/j.jcis.2009.06.041Liu, H., Gong, S.P., Hu, Y.X., Liu, J.Q. and Zhou, D.X. (2009) Properties and Mechanism Study of SnO2 Nanocrystals for H2S Thick-Film Sensors. Sensors and Actuators B: Chemical, 140, 190-195. https://doi.org/10.1016/j.snb.2009.04.027Zhang, F., Zhu, A., Luo, Y., et al. (2010) CuO Nanosheets for Sensitive and Selective Determination of H2S with High Recovery Ability. The Journal of Physical Chemistry C, 114, 19214-19219. https://doi.org/10.1021/jp106098zMai, L., Xu, L., Gao, Q., et al. (2010) Single β-AgVO3 Nanowire H2S Sensor. Nano Letters, 10, 2604-2608. https://doi.org/10.1021/nl1013184Wan, X., Wu, L., Zhang, L., et al. (2015) Novel Metal-Organic Frameworks-Based Hydrogen Sulfide Cataluminescence Sensors. Sensors & Actuators B: Chemical, 220, 614-621. https://doi.org/10.1016/j.snb.2015.05.125Cai, P., Wei, B., Zhang, L., et al. (2012) Hierarchical Hollow Microsphere and Flower-Like Indium Oxide: Controllable Synthesis and Application as H2S Cataluminescence Sensing Materials. Materials Research Bulletin, 47, 2212-2218. https://doi.org/10.1016/j.materresbull.2012.06.002Yuan, H., Li, L., Zhang, L. and Lv, Y. (2017) Dielectric Barrier Discharge Plasma-Assisted Fabrication of g-C3N4-Mn3O4 Composite for High-Performance Cataluminescence H2S Gas Sensor. Sensors & Actuators B: Chemical, 239, 1177-1184. https://doi.org/10.1016/j.snb.2016.08.082Wang, Q., Xie, L., Zhu, B., et al. (2013) Harmful Gas Recognition Exploiting a CTL Sensor Array. Sensors, 13, 13509-13520. https://doi.org/10.3390/s131013509Wang, C., Chu, X. and Wu, M. (2006) Detection of H2S Down to ppb Levels at Room Temperature Using Sensors Based on ZnO Nanorods. Sensors & Actuators B: Chemical, 113, 320-323. https://doi.org/10.1016/j.snb.2005.03.011Beauchamp, R.O., Bus, J.S., Popp, J.A., et al. (1984) A Critical Review of the Literature on Hydrogen Sulfide Toxicity. CRC Critical Reviews in Toxicology, 13, 25-97. https://doi.org/10.3109/10408448409029321Shearer, R.L. (1992) Development of Flameless Sulfur Chemiluminescence Detection: Application to Gas Chromatography. Analytical Chemistry, 64, 2192-2196. https://doi.org/10.1021/ac00042a030