EDTA辅助合成Co3O4纳米材料及其气敏性能

doi:10.15541/jim20200025

摘要/Abstract

摘要： 以有机化合物作为助剂合成纳米材料, 可调控材料的形貌和结构, 进而影响材料的催化和电化学性能。以乙二胺四乙酸二钠盐(EDTA-2Na)为助剂, 乙酸钴为钴源, 利用水热法合成Co₃O₄纳米材料, 测定材料的结构和气敏性能, 研究其结构与气敏性能的关系, 并探讨EDTA-2Na在材料合成中的作用机制。结果表明, Co²⁺与EDTA^2-形成的配合物调控Co₃O₄晶核的生长方向, 形成了边长约为50 nm的六边形介孔纳米片。在205 ℃下, 利用该材料构筑的气敏传感器对100×10^-6甲苯响应值约为104, 在225 ℃下对100×10^-6丙酮的响应值约为70。该传感器对甲苯和丙酮等挥发性有机化合物(VOCs)的高响应性能是由于EDTA-2Na辅助合成的Co₃O₄表面存在的大量缺陷, 提高了吸附氧含量。另外, 介孔结构和较大的比表面积有利于VOCs的吸附、表面反应和扩散。本研究提供了一种添加EDTA-2Na辅助合成Co₃O₄纳米材料并获得高响应VOCs气体传感器的有效方法。

关键词: Co₃O₄乙二胺四乙酸二钠, 水热, VOCs传感器

Abstract: Organic compounds can be used as additives to regulate the morphology and structure of materials in the process of nanomaterial synthesis, thereby affecting the catalytic and electrochemical properties of the materials. In this paper, the nanomaterial Co₃O₄ was synthesized by hydrothermal method using disodium ethylenediamine tetraacetate (EDTA-2Na) as the additives and cobalt acetate as the cobalt source, and its structure and gas sensing properties were measured. The relationship between structure and gas sensitive properties was studied, and the mechanism of EDTA-2Na in the synthesis of materials was discussed. The results show that the complex formed by Co²⁺ and EDTA^2- regulates the growth direction of Co₃O₄ nuclei to generate the hexagonal nanosheets of Co₃O₄ with a side length of about 50 nm and a mesoporous structure. The response values of gas sensors fabricated by the Co₃O₄nanomaterials to 100×10^-6 toluene and 100×10^-6 acetone are approximately 104 at 205 ℃ and 70 at 225 ℃, respectively. The high response of the gas sensor to volatile organic compounds (VOCs) is attributed to a large number of defects on the surface of Co₃O₄ synthesized by EDTA-2Na, which improve the adsorbed oxygen content. In addition, the mesoporous structure and large specific surface area are conducive to the adsorption, surface reaction and diffusion of VOCs. In this study, an effective method is proposed to obtain a highly responsive VOCs gas sensor by adding EDTA-2Na to synthesize Co₃O₄ nanomaterials.

Key words: Co₃O₄, EDTA-2Na, hydrothermal, VOCs gas sensing

中图分类号:

O614

汤丹蕾, 贾丽华, 赵振龙, 杨瑞, 王欣, 郭祥峰. EDTA辅助合成Co₃O₄纳米材料及其气敏性能[J]. 无机材料学报, 2020, 35(11): 1214-1222.

TANG Danlei, JIA Lihua, ZHAO Zhenlong, YANG Rui, WANG Xin, GUO Xiangfeng. EDTA Assistant Preparation and Gas Sensing Properties of Co₃O₄ Nanomaterials[J]. Journal of Inorganic Materials, 2020, 35(11): 1214-1222.

参考文献

[1] ZHANG R, GAO S, ZHOU T,et al. Facile preparation of hierarchical structure based on p-type Co₃O₄ as toluene detecting sensor. Applied Surface Science, 2020, 503: 144-167.
[2] ZHANG C, LI L, HOU L,et al. Fabrication of Co₃O₄ nanowires assembled on the surface of hollow carbon spheres for acetone gas sensing. Sensors and Actuators B: Chemical, 2019, 291: 130-140.
[3] LI Y, HUA Z, WU Y,et al. Modified impregnation synthesis of Ru-loaded WO₃ nanoparticles for acetone sensing. Sensors and Actuators B: Chemical, 2018, 265: 249-256.
[4] MIRZAEI A, LEONARDI S G, NERI G.Detection of hazardous volatile organic compounds (VOCs) by metal oxide nanostructures-based gas sensors: a review.Ceramics International, 2016, 42(14): 15119-15141.
[5] ANSARI M O, ANSARI S A, CHO M H,et al. Conducting polymer nanocomposites as gas sensors. Functional Polymers, 2019: 911-940.
[6] PIRSA S, ALIZADEH N.A selective DMSO gas sensor based on nanostructured conducting polypyrrole doped with sulfonate anion.Sensors and Actuators B: Chemical, 2012, 168: 303-309.
[7] WANG X, CHEN F, YANG M,et al. Dispersed WO₃ nanoparticles with porous nanostructure for ultrafast toluene sensing. Sensors Actuators B: Chemical, 2019, 289: 195-206.
[8] SHANKAR P, RAVAPPAN J B B. Gas sensing mechanism of metal oxides: the role of ambient atmosphere, type of semiconductor and gases-a review.Science Letters Journal, 2015, 4(4): 126-144.
[9] LIANG J R, ZHANG Y, YANG R,et al. Room-temperature NH₃ gas sensing property of VO₂(B)/ZnO hierarchical heterogeneous composite with nanorod structure. Journal of Inorganic Materials, 2018, 33(12): 1323-1329.
[10] DU H Y, PENG Y J, WANG J,et al. Preparation and gas sensing property of SnO₂/ZnO composite hetero-nanofibers using two-step method. Journal of Inorganic Materials, 2018, 33(4): 453-461.
[11] TANG Y F, XIE G W, ZHAO K, et al. Fabrication and gas sensing properties of aligned vanadium pentoxide micro-nano fiber membranes by electrospinning. Journal of Inorganic Materials, 2014, 29(3): 315-320.
[12] KIM H J, LEE J H.Highly sensitive and selective gas sensors using p-type oxide semiconductors: overview.Sensors Actuators B: Chemical, 2014, 192: 607-627.
[13] QUANG P L, CUONG N D, HOA T T,et al. Simple post-synthesis of mesoporous p-type Co₃O₄ nanochains for enhanced H₂S gas sensing performance. Sensors Actuators B: Chemical, 2018, 270: 158-166.
[14] DENG S, LIU X, CHEN N,et al. A highly sensitive VOC gas sensor using p-type mesoporous Co₃O₄ nanosheets prepared by a facile chemical coprecipitation method. Sensors Actuators B: Chemical, 2016, 233: 615-623.
[15] XU J M, CHENG J P.The advances of Co₃O₄ as gas sensing materials: a review.Journal of Alloys and Compounds, 2016, 686: 753-768.
[16] DENG J, ZHANG R, WANG L,et al. Enhanced sensing performance of the Co₃O₄ hierarchical nanorods to NH₃ gas. Sensors Actuators B: Chemical, 2015, 209: 449-455.
[17] ZHANG Z, ZHU L, WEN Z,et al. Controllable synthesis of Co₃O₄ crossed nanosheet arrays toward an acetone gas sensor. Sensors and Actuators B: Chemical, 2017, 238: 1052-1059.
[18] LIN Y, JI H, SHEN Z,et al. Enhanced acetone sensing properties of Co₃O₄ nanosheets with highly exposed (111) planes. Journal of Materials Science: Materials in Electronics, 2016, 27(2): 2086-2095.
[19] JIANG R, JIA L, GUO X,et al. Dimethyl sulfoxide-assisted hydrothermal synthesis of Co₃O₄-based nanorods for selective and sensitive diethyl ether sensing. Sensors Actuators B: Chemical, 2019, 290: 275-284.
[20] ZHOU H, KANG M, WU D,et al. Synthesis and catalytic property of facet-controlled Co₃O₄ structures enclosed by (111) and (113) facets. CrystEngComm, 2016, 18(29): 5456-5462.
[21] TONG F, ZHAO Y, QU X,et al. EDTA-complexing Sol-Gel synthesis of LaFeO₃ nanostructures and their gas-sensing properties. Journal of Electronic Materials, 2019, 48(2): 982-990.
[22] ZHANG Z, WEN Z, YE Z,et al. Synthesis of Co₃O₄/Ta₂O₅ heterostructure hollow nanospheres for enhanced room temperature ethanol gas sensor. Journal of Alloys and Compounds, 2017, 727: 436-443.
[23] LU J, JIANG Y, ZHANG Y,et al. Preparation of gas sensing CoTiO₃ nanocrystallites using EDTA as the chelating agent in a Sol-Gel process. Ceramics International, 2015, 41(3): 3714-3721.
[24] XIONG S, CHEN J S, LOU X W,et al. Mesoporous Co₃O₄ and CoO@C topotactically transformed from chrysanthemum-like Co(CO₃)_0.5(OH)·0.11H₂O and their lithium-storage properties. Advanced Functional Materials, 2012, 22(4): 861-871.
[25] XU K, YANG L, ZOU J,et al. Fabrication of novel flower-like Co₃O₄ structures assembled by single-crystalline porous nanosheets for enhanced xylene sensing properties. Journal of Alloys and Compounds, 2017, 706: 116-125.
[26] ZHOU T, LU P, ZHANG Z,et al. Perforated Co₃O₄ nanoneedles assembled in chrysanthemum-like Co₃O₄ structures for ultra-high sensitive hydrazine chemical sensor. Sensors Actuators B: Chemical, 2016, 235: 457-465.
[27] JOSHI N, DA SILVA L F, JADHAV H S,et al. Yolk-shelled ZnCo₂O₄ microspheres: surface properties and gas sensing application. Sensors and Actuators B: Chemical, 2018, 257: 906-915.
[28] HU L, PENG Q, LI Y.Selective synthesis of Co₃O₄ nanocrystal with different shape and crystal plane effect on catalytic property for methane combustion.Journal of the American Chemical Society, 2008, 130(48): 16136-16137.
[29] GAO C, MENG Q, ZHAO K,et al. Co₃O₄ hexagonal platelets with controllable facets enabling highly efficient visible-light photocatalytic eeduction of CO₂. Advanced Materials, 2016, 28(30): 6485-6490.
[30] ZHOU T, ZHANG C, LU P,et al. Morphology controlled synthesis of Co₃O₄ nanostructures for hydrazine chemical sensor. Nanoscience and Nanotechnology Letters, 2016, 8(8): 634-640.
[31] NI C, CAROLAN D, ROCKS C,et al. Microplasma-assisted electrochemical synthesis of Co₃O₄ nanoparticles in absolute ethanol for energy applications. Green Chemistry, 2018, 20(9): 2101-2109.
[32] NASSAR M Y.Size-controlled synthesis of CoCO₃ and Co₃O₄ nanoparticles by free-surfactant hydrothermal method.Materials Letters, 2013, 94: 112-115.
[33] BAI S, DU L, SUN J,et al. Preparation of reduced graphene oxide/ Co₃O₄ composites and sensing performance to toluene at low temperature. RSC Advances, 2016, 6(65): 60109-60116.
[34] NAVALE S T, LIU C, GAIKAR P S,et al. Solution-processed rapid synthesis strategy of Co₃O₄ for the sensitive and selective detection of H₂S. Sensors Actuators B: Chemical, 2017, 245: 524-532.
[35] ZHANG J, LIANG Y, MAO J,et al. 3D microporous Co₃O₄-carbon hybrids biotemplated from butterfly wings as high performance VOCs gas sensor. Sensor Actuators B: Chemical, 2016, 235: 420-431.
[36] LUO F, LI J, LEI Y,et al. Three-dimensional enoki mushroom-like Co₃O₄ hierarchitectures constructed by one-dimension nanowires for high-performance supercapacitors. Electrochimica Acta, 2014, 135: 495-502.
[37] ZHANG X, ZHONG H, XU L,et al. Fabrication of Co₃O₄/PEI-GO composites for gas-sensing applications at room temperature. Materials Research Bulletin, 2018, 102: 108-115.
[38] CHEN G, SI X, YU J,et al. Doping nano-Co₃O₄ surface with bigger nanosized Ag and its photocatalytic properties for visible light photodegradation of organic dyes. Applied Surface Science, 2015, 330: 191-199.
[39] DEORI K, UJJAIN S K, SHARMA R K,et al. Morphology controlled synthesis of nanoporous Co₃O₄ nanostructures and their charge storage characteristics in supercapacitors. ACS Applied Materials & Interfaces, 2013, 5(21): 10665-10672.
[40] YU T, CHENG X L, ZHANG X,et al. Highly sensitive H₂S detection sensors at low temperature based on hierarchically structured NiO porous nanowall arrays. Journal of Materials Chemistry A, 2015, 3(22): 11991-11999.

EDTA辅助合成Co₃O₄纳米材料及其气敏性能

EDTA Assistant Preparation and Gas Sensing Properties of Co₃O₄ Nanomaterials

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	姚仪帅, 郭瑞华, 安胜利, 张捷宇, 周国治, 张国芳, 黄雅荣, 潘高飞. 原位负载Pt-Co高指数晶面催化剂的制备及其电催化性能[J]. 无机材料学报, 2023, 38(1): 71-78.
[2]	张弦, 张策, 姜文君, 冯德强, 姚伟. 四元BiMnVO₅的合成、电子结构与可见光催化性能研究[J]. 无机材料学报, 2022, 37(1): 58-64.
[3]	王婷婷, 史书梅, 柳晨媛, 朱万诚, 张恒. 多级多孔硅酸镍微球的合成及其对碱性品红的高效吸附[J]. 无机材料学报, 2021, 36(12): 1330-1336.
[4]	宋可可, 黄浩, 鲁梦婕, 杨安春, 翁杰, 段可. 水热制备锌、硅、镁、铁等元素掺杂羟基磷灰石及其表征[J]. 无机材料学报, 2021, 36(10): 1091-1096.
[5]	肖昱旻, 李彬, 覃礼钊, 林华, 李庆, 廖斌. 用CuCl₂为铜源高效制备形貌可控CuGeO₃的研究[J]. 无机材料学报, 2021, 36(1): 69-74.
[6]	王举汉,文雄,刘成超,张煜华,赵燕熹,李金林. 多级孔Co/Al-SiO₂催化剂制备及其费-托合成催化性能[J]. 无机材料学报, 2020, 35(9): 999-1004.
[7]	张东硕,蔡昊,高凯茵,马子川. Zn₂SiO₄-ZnO-生物炭复合物的制备及其可见光催化H₂O₂降解甲硝唑[J]. 无机材料学报, 2020, 35(8): 923-930.
[8]	王志虎,张菊梅,白力静,张国君. AZ31镁合金微弧氧化陶瓷层表面Mg(OH)₂膜层的制备及耐蚀性[J]. 无机材料学报, 2020, 35(6): 709-716.
[9]	张志宾, 周润泽, 董志敏, 曹小红, 刘云海. 偕胺肟水热碳对U(VI)-CO₃/Ca-U(VI)-CO₃的吸附性能研究[J]. 无机材料学报, 2020, 35(3): 352-358.
[10]	王金敏, 于红玉, 马董云. 纳米二氧化锰的制备及其应用研究进展[J]. 无机材料学报, 2020, 35(12): 1307-1314.
[11]	李孟夏, 陆越, 王利斌, 胡先罗. Mn₃O₄@ZnO核壳结构纳米片阵列的可控合成及其在水系锌离子电池中的应用[J]. 无机材料学报, 2020, 35(1): 86-92.
[12]	许云青,王海增. EDTA辅助水热法制备不同形貌的氟化镁钠[J]. 无机材料学报, 2019, 34(9): 933-937.
[13]	苟生莲, 乃学瑛, 肖剑飞, 叶俊伟, 董亚萍, 李武. 碱式氯化镁晶须制备纳米氧化镁热分解动力学研究[J]. 无机材料学报, 2019, 34(7): 781-785.
[14]	刘伟, 郑凯, 王东红, 雷忆三, 范怀林. Co₃O₄纳米线阵列@活性炭纤维复合材料的水热合成及电化学应用[J]. 无机材料学报, 2019, 34(5): 487-492.
[15]	王伟, 罗世阶, 鲜聪, 肖群, 杨洋, 欧云, 刘运牙, 谢淑红. 水热合成BiCl₃/Bi₂S₃复合材料的热电性能[J]. 无机材料学报, 2019, 34(3): 328-334.