多面体双壳层 Co$_{\bf 3}$O$_{\bf 4}$-ZnO 及其 CO 传感性能

doi:10.12066/j.issn.1007-2861.2193

摘要/Abstract

摘要：

以甲醇为溶剂, 静置沉淀法合成 Co 掺杂的 ZIF(zeolitic imidazolate framework)-8, 将其在管式炉中空气氛围下退火得到多面体双壳层 Co$_{3}$O$_{4}$-ZnO. 通过 X 射线衍射仪(X-ray diffraction, XRD)、扫描电子显微镜(scanning electron microscope, SEM)、透射电子显微镜(transmission electron microscope, TEM)、热重分析仪(thermal gravimetric analyzer, TGA)手段对合成材料的组成、形貌和热稳定性进行了表征. 结果表明, 纯 ZIF-8 在较低的退火温度下保持稳定, 更高温度的退火使 ZIF-8 生成结构坍塌的 ZnO. 4% Co 掺杂的 ZIF-8 在较低温度下退火后得到多面体双壳结构的 Co$_{3}$O$_{4}$-ZnO(CZO-4), 表明 Co 在 ZIF-8 的氧化过程中提供了催化氧化的活性位点, 降低了 2-甲基咪唑的氧化反应能垒. 同时, 较低的退火温度给予 ZnO 充分的成型时间, 使其保持菱形十二面体结构而不坍塌. 由 Co 元素催化由外而内的氧化生长过程, 最终使 ZnO 生长为双壳层结构. 而将 Co 的载量提高到 8%, 得到的双壳层则变得不明显(CZO-8). 在对 CO 气敏测试结果分析中发现, 相对于 CZO-8 和 ZnO, CZO-4 具有更优异的 CO 传感性能, 具有高灵敏度($R_{\rm a}$/$R_{\rm g}$=21.8@100$\times $10$^{-6}$ CO)、高选择性(达到 H$_{2}$ 灵敏度的 8.7 倍)和长期稳定性(在42 d 测试中信号平稳). 这是由于 CZO-4 具有较大的比表面积和气体传输通道, 以及 Co 作为活性位点对 CO 催化氧化作用带来的气敏性能的提升.

关键词: ZIF-8, Co 掺杂, 催化氧化, 双壳层结构, 气敏性质, CO 传感

Abstract:

Herein, Co-doped ZIF (zeolitic imidazolate framework)-8 was synthesised via static precipitation method using methanol as solvent. The synthesised ZIF-8 was subsequently annealed under air atmosphere in a tubular furnace, yielding polyhedral bi-shell Co$_{3}$O$_{4}$-ZnO. The composition, morphology, and thermal stability of the synthesised materials were characterised via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermal gravimetric analyzer (TGA). Results show that the pure ZIF-8 remained stable at relatively low annealing temperature, whereas at higher annealing temperature, ZIF-8 transformed to a collapsed ZnO structure. The polyhedral bi-shell Co$_{3}$O$_{4}$-ZnO (CZO-4) was obtained by annealing 4% Co-doped ZIF-8 at a low temperature, suggesting that Co provides an active site for catalytic oxidation during the oxidation of ZIF-8 and reduces the oxidation barrier of 2-methylimidazole. Meanwhile, the low annealing temperature can provide sufficient forming process for ZnO to retain the rhombic dodecahedron structure. The oxidation growth process, catalysed by Co element, from outside to inside eventually results in the growth of ZnO into the bi-shell structure. When the Co loading is increased to 8%, the formation of bi-shell layer is not obvious (CZO-8). Compared with CZO-8 and ZnO, CZO-4 has better CO sensing performance, high sensitivity ($R_\mathrm a/R_\mathrm g = 21.8$@100$\times $10$^{-6}$ CO), high selectivity (up to 8.7 times of H$_{2}$ response), and long-term stability (stable signal in 42-day tests). This is because CZO-4 has a large specific surface area, gas transport channels, and Co as an active site for CO catalytic oxidation, resulting in an enhancement in gas sensing performance.

Key words: ZIF(zeolitic imidazolate framework)-8, Co doping, catalytic oxidation, bi-shell structure, gas sensing properties, CO sensing

中图分类号:

TP212.1

袁同伟, 张文爽, 马志恒, 徐甲强. 多面体双壳层 Co$_{\bf 3}$O$_{\bf 4}$-ZnO 及其 CO 传感性能[J]. 上海大学学报(自然科学版), 2021, 27(5): 866-878.

YUAN Tongwei, ZHANG Wenshuang, MA Zhiheng, XU Jiaqiang. Polyhedral bi-shell CO$_{\bf 3}$O$_{\bf 4}$-ZnO and its CO sensing performance[J]. Journal of Shanghai University（Natural Science Edition）, 2021, 27(5): 866-878.

图/表 15

图1

图2

图3

图4

图5

图6

图7

图8

图9

表1

图10

表2

图11

图12

图13

参考文献 43

[1]	Kida T, Doi T, Shimanoe K. Synjournal of monodispersed SnO$_{2}$ nanocrystals and their remarkably high sensitivity to volatile organic compounds[J]. Chemistry of Materials, 2010, 22(8): 2662-2667. doi: 10.1021/cm100228d
[2]	Broza Y Y, Vishinkin R, Barash O, et al. Synergy between nanomaterials and volatile organic compounds for non-invasive medical evaluation[J]. Chemical Society Reviews, 2018, 47(13): 4781-4859. doi: 10.1039/c8cs00317c pmid: 29888356
[3]	Lin H, Jang M, Suslick K S. Preoxidation for colorimetric sensor array detection of VOCs[J]. Journal of the American Chemical Society, 2011, 133(42): 16786-16789. doi: 10.1021/ja207718t
[4]	Gross P A, Jaramillo T, Pruitt B. Cyclic-voltammetry-based solid-state gas sensor for methane and other VOC detection[J]. Analytical Chemistry, 2018, 90(10): 6102-6108. doi: 10.1021/acs.analchem.8b00184
[5]	Ren F, Gao L, Yuan Y, et al. Enhanced BTEX gas-sensing performance of CuO/SnO$_{2}$ composite[J]. Sensors and Actuators B: Chemical, 2016, 223: 914-920. doi: 10.1016/j.snb.2015.09.140
[6]	Xue Z, Cheng Z, Xu J, et al. Controllable evolution of dual defect Zn$_{i}$ and V$_{\rm O}$ associate-rich ZnO nanodishes with (0001) exposed facet and its multiple sensitization effect for ethanol detection[J]. ACS Appl Mater Interfaces, 2017, 9(47): 41559-41567. doi: 10.1021/acsami.7b13370
[7]	Gao L, Cheng Z, Xiang Q, et al. Porous corundum-type In$_{2}$O$_{3}$ nanosheets: synjournal and NO$_{2}$ sensing properties[J]. Sensors and Actuators B: Chemical, 2015, 208: 436-443. doi: 10.1016/j.snb.2014.11.053
[8]	Shi J, Cheng Z, Gao L, et al. Facile synjournal of reduced graphene oxide/hexagonal WO$_{3}$ nanosheets composites with enhanced H$_{2}$S sensing properties[J]. Sensors and Actuators B: Chemical, 2016, 230: 736-745. doi: 10.1016/j.snb.2016.02.134
[9]	Xu J, Xue Z, Qin N, et al. The crystal facet-dependent gas sensing properties of ZnO nanosheets: experimental and computational study[J]. Sensors and Actuators B: Chemical, 2017, 242: 148-157. doi: 10.1016/j.snb.2016.09.193
[10]	Li G, Cheng Z, Xiang Q, et al. Bimetal PdAu decorated SnO$_{2}$ nanosheets based gas sensor with temperature-dependent dual selectivity for detecting formaldehyde and acetone[J]. Sensors and Actuators B: Chemical, 2019, 283: 590-601. doi: 10.1016/j.snb.2018.09.117
[11]	Ma J, Ren Y, Zhou X, et al. Pt nanoparticles sensitized ordered mesoporous WO$_{3}$ semiconductor: gas sensing performance and mechanism study[J]. Advanced Functional Materials, 2018, 28(6): 1705268. doi: 10.1002/adfm.v28.6
[12]	Li Y, Zhou X, Luo W, et al. Pore engineering of mesoporous tungsten oxides for ultrasensitive gas sensing[J]. Advanced Materials Interfaces, 2018, 6(1): 1801269. doi: 10.1002/admi.v6.1
[13]	Kou X, Wang C, Ding M, et al. Synjournal of Co-doped SnO$_{2}$ nanofibers and their enhanced gas-sensing properties[J]. Sensors and Actuators B: Chemical, 2016, 236: 425-432. doi: 10.1016/j.snb.2016.06.006
[14]	Li B, Liu J, Liu Q, et al. Core-shell structure of ZnO/Co$_{3}$O$_{4}$ composites derived from bimetallic-organic frameworks with superior sensing performance for ethanol gas[J]. Applied Surface Science, 2019, 475: 700-709. doi: 10.1016/j.apsusc.2018.12.284
[15]	Zhu Y, Zhao Y, Ma J, et al. Mesoporous tungsten oxides with crystalline framework for highly sensitive and selective detection of foodborne pathogens[J]. Journal of the American Chemical Society, 2017, 139(30): 10365-10373. doi: 10.1021/jacs.7b04221
[16]	Pan Y, Sun K, Liu S, et al. Core-shell ZIF-8@ZIF-67-derived CoP nanoparticle-embedded N-doped carbon nanotube hollow polyhedron for efficient overall water splitting[J]. Journal of the American Chemical Society, 2018, 140(7): 2610-2618. doi: 10.1021/jacs.7b12420
[17]	Hobday C L, Woodall C H, Lennox M J, et al. Understanding the adsorption process in ZIF-8 using high pressure crystallography and computational modelling[J]. Nature Communication, 2018, 9(1): 1429. doi: 10.1038/s41467-018-03878-6
[18]	Zhang R, Zhou T, Wang L, et al. Metal-organic frameworks-derived hierarchical Co$_{3}$O$_{4}$ structures as efficient sensing materials for acetone detection[J]. ACS Appl Mater Interfaces, 2018, 10(11): 9765-9773. doi: 10.1021/acsami.7b17669
[19]	Jo Y M, Kim T H, Lee C S, et al. Metal-organic framework-derived hollow hierarchical Co$_{3}$O$_{4 }$ nanocages with tunable size and morphology: ultrasensitive and highly selective detection of methylbenzenes[J]. ACS Appl Mater Interfaces, 2018, 10(10): 8860-8868. doi: 10.1021/acsami.8b00733
[20]	Hjiri M, el Mir L, Leonardi S G, et al. Al-doped ZnO for highly sensitive CO gassensors[J]. Sensors and Actuators B: Chemical, 2014, 196: 413-420. doi: 10.1016/j.snb.2014.01.068
[21]	Paliwal A, Sharma A, Tomar M, et al. Carbon monoxide (CO) optical gas sensor based on ZnO thin films[J]. Sensors and Actuators B: Chemical, 2017, 250: 679-685. doi: 10.1016/j.snb.2017.05.064
[22]	Hjiri M, el Mir L, Leonardi S G, et al. Al-doped ZnO for highly sensitive CO gas sensors[J]. Sensors and Actuators B: Chemical, 2014, 196: 413-420. doi: 10.1016/j.snb.2014.01.068
[23]	Paliwal A, Sharma A, Tomar M, et al. Carbon monoxide (CO) optical gas sensor based on ZnO thin films[J]. Sensors and Actuators B: Chemical, 2017, 250: 679-685. doi: 10.1016/j.snb.2017.05.064
[24]	Cheng Z, Huang C, Song L, et al. Electrospinning synjournal of CdIn$_{2}$O$_{4}$ nanofibers for ethanol detection[J]. Sensors and Actuators B: Chemical, 2015, 209: 530-535. doi: 10.1016/j.snb.2014.12.011
[25]	Gao L, Ren F, Cheng Z, et al. Porous corundum-type In$_{2}$O$_{3}$ nanoflowers: controllable synjournal, enhanced ethanol-sensing properties and response mechanism[J]. CrystEngComm, 2015(17): 3268-3276.
[26]	Saliba D, Ammar M, Rammal M, et al. Crystal growth of ZIF-8, ZIF-67 and their mixed-metal derivatives[J]. Journal of the American Chemical Society, 2018, 140(5): 1812-1823. doi: 10.1021/jacs.7b11589
[27]	Hu P, Long M. Cobalt-catalyzed sulfate radical-based advanced oxidation: a review on heterogeneous catalysts and applications[J]. Applied Catalysis B: Environmental, 2016, 181: 103-117. doi: 10.1016/j.apcatb.2015.07.024
[28]	Deng S, Liu X, Chen N, et al. A highly sensitive VOC gas sensor using p-type mesoporous Co$_{3}$O$_{4}$ nanosheets prepared by a facile chemical coprecipitation method[J]. Sensors and Actuators B: Chemical, 2016, 233: 615-623. doi: 10.1016/j.snb.2016.04.138
[29]	Wen Z, Zhu L, Zhang Z, et al. Fabrication of gas sensor based on mesoporous rhombus-shaped ZnO rod arrays[J]. Sensors and Actuators B: Chemical, 2015, 208: 112-121. doi: 10.1016/j.snb.2014.11.024
[30]	Li Y, Chen N, Deng D, et al. Formaldehyde detection: SnO$_{2}$ microspheres for formaldehyde gas sensor with high sensitivity, fast response/recovery and good selectivity[J]. Sensors and Actuators B: Chemical, 2017, 238: 264-273. doi: 10.1016/j.snb.2016.07.051
[31]	Pan X, Zhao X, Chen J, et al. A fast-response/recovery ZnO hierarchical nanostructure based gas sensor with ultra-high room-temperature output response[J]. Sensors and Actuators B: Chemical, 2015, 206: 764-771. doi: 10.1016/j.snb.2014.08.089
[32]	Shendage S S, Patil V L, Vanalakar S A, et al. Sensitive and selective NO$_{2}$ gas sensor based on WO$_{3}$ nanoplates[J]. Sensors and Actuators B: Chemical, 2017, 240: 426-433. doi: 10.1016/j.snb.2016.08.177
[33]	Vetter S, Haffer S, Wagner T, et al. Nanostructured Co$_{3}$O$_{4}$ as a CO gas sensor: temperature-dependent behavior[J]. Sensors and Actuators B: Chemical, 2015, 206: 133-138. doi: 10.1016/j.snb.2014.09.025
[34]	Patil D, Patil P, Subramanian V, et al. Highly sensitive and fast responding CO sensor based on Co$_{3}$O$_{4}$ nanorods[J]. Talanta, 2010, 81: 37-43. doi: 10.1016/j.talanta.2009.11.034
[35]	Wang Q, Wang C, Sun H, et al. Microwave assisted synjournal of hierarchical Pd/SnO$_{2}$ nanostructures for CO gas sensor[J]. Sensors and Actuators B: Chemical, 2016, 222: 257-263. doi: 10.1016/j.snb.2015.07.115
[36]	Mohammadi M, Fray D. Low temperature nanocrystalline TiO$_{2}$-Fe$_{2}$O$_{3}$ mixed oxide by a particulate sol-gel route: physical and sensing characteristics[J]. Physica E: Low-dimensional Systems and Nanostructures, 2012, 46: 43-51. doi: 10.1016/j.physe.2012.09.002
[37]	Basu A K, Chauhan P S, Awasthi M, et al. $\alpha $-Fe$_{2}$O$_{3}$ loaded rGO nanosheets based fast response/recovery CO gas sensor at room temperature[J]. Applied Surface Science, 2019, 465: 56-66. doi: 10.1016/j.apsusc.2018.09.123
[38]	Lu Z, Lü P, Liang Y, et al. CO oxidation catalyzed by the single Co atom embedded hexagonal boron nitride nanosheet: a DFT-D study[J]. Physical Chemistry Chemical Physics, 2016, 18(31): 21865-21870. doi: 10.1039/C6CP02221A
[39]	Amiinu I S, Liu X, Pu Z, et al. From 3D ZIF nanocrystals to Co-N$_{x}$/C nanorod array electrocatalysts for ORR, OER, and Zn-Air batteries[J]. Advanced Functional Materials, 2018, 28(5): 1704638. doi: 10.1002/adfm.v28.5
[40]	Li X, Fang Y, Lin X, et al. MOF derived Co$_{3}$O$_{4}$ nanoparticles embedded in N-doped mesoporous carbon layer/MWCNT hybrids: extraordinary bi-functional electrocatalysts for OER and ORR[J]. Journal of Materials Chemistry A, 2015, 3(33): 17392-17402. doi: 10.1039/C5TA03900B
[41]	Gao H, Wei D, Lin P, et al. The design of excellent xylene gas sensor using Sn-doped NiO hierarchical nanostructure[J]. Sensors and Actuators B: Chemical, 2017, 253: 1152-1162. doi: 10.1016/j.snb.2017.06.177
[42]	Fu D, Zhu C, Zhang X, et al. Two-dimensional net-like SnO$_{2}$/ZnO heteronanostructures for high-performance H$_{2}$S gas sensor[J]. Journal of Materials Chemistry A, 2016, 4(4): 1390-1398. doi: 10.1039/C5TA09190J
[43]	Yao F Z, Wang K, Jo W, et al. Diffused phase transition boosts thermal stability of high-performance lead-free piezoelectrics[J]. Advanced Functional Materials, 2016, 26(8): 1217-1224. doi: 10.1002/adfm.v26.8