硼掺杂Co3O4海胆状微球的制备及其乙醇气敏强化机制

doi:10.16085/j.issn.1000-6613.2020-1671

摘要/Abstract

摘要：

四氧化三钴（Co₃O₄）是一种p型半导体，可作为气体传感材料。非金属硼（B）具有吸电子特性，将其与p型半导体气敏材料进行掺杂，可增加材料的空穴载流子浓度，从而提高材料的气敏性能。本文以六水合硝酸钴[Co(NO₃)₂·6H₂O]、硼酸（H₃BO₃）和尿素[CO(NH₂)₂]为原料，采用低温一步水热法成功制备了B掺杂Co₃O₄海胆状微球。通过X射线衍射仪（XRD）、扫描电镜（SEM）、透射电镜（TEM）、X射线光电子能谱仪（XPS）和拉曼光谱仪（Raman）对掺杂B前后的Co₃O₄进行结构表征，探究B掺杂对其气敏性能的影响。结果表明：B掺杂对Co₃O₄材料的气敏性能有明显的强化作用。当掺杂摩尔比为Co∶B=8∶1时，B-Co₃O₄对1×10⁵μg/L乙醇的最佳工作温度为180℃，灵敏度响应达到26.8，是相同条件下纯Co₃O₄的4.4倍。B-Co₃O₄在较低的工作温度下，具有良好的灵敏度、选择性和稳定性，是一种性能优良的气敏材料。

关键词: 四氧化三钴, 硼掺杂, 乙醇传感, 气敏特性, 气敏机制

Abstract:

Cobalt oxide (Co₃O₄) is a typical p-type semiconductor and can be used as a gas sensing material. The gas-sensing properties of Co₃O₄ can be improved by doping non-metallic boron (B) due to the absorbing electron characteristics of boron(B) that makes hole concentration of Co₃O₄ increase. In this paper, B-doped Co₃O₄ microspheres with sea urchin morphology were successfully prepared by low-temperature one-step hydrothermal method using cobalt nitrate hexahydrate [Co(NO₃)₂·6H₂O], boric acid (H₃BO₃) and urea [Co(NH₂)₂] as raw materials. The structures and morphologies of Co₃O₄ before and after boron doping were characterized by various spectra, and the gas sensing properties to ethanol were examined. The results show that boron doping significantly enhances the gas sensing properties of Co₃O₄. When the doped molar ratio is Co∶B=8∶1, the doped Co₃O₄ not only exhibits high response of 26.8 in 1×10⁵μg/L ethanol, which is 4.4 times higher than that of pure Co₃O₄, but also good selectivity and stability at the optimal working temperature of 180℃. So, the B doped Co₃O₄ is a promising gas sensing material for detection of VOCs.

Key words: cobalt oxide, boron doping, ethanol sensor, gas-sensing properties, gas sensing mechanism

中图分类号:

O649

孙舒, 孙丽霞, 文晓慧, 张郝为, 廖丹葵, 孙建华. 硼掺杂Co₃O₄海胆状微球的制备及其乙醇气敏强化机制[J]. 化工进展, 2021, 40(3): 1537-1544.

SUN Shu, SUN Lixia, WEN Xiaohui, ZHANG Haowei, LIAO Dankui, SUN Jianhua. Preparation of boron doped Co₃O₄ sea urchin-like microspheres and its gas sensing enhancement mechanism for ethanol[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1537-1544.

图/表 13

图1 Co3O4和不同B掺杂量的B-Co3O4的XRD谱图

表1 Co3O4和不同B掺杂量的B-Co3O4的晶粒尺寸和晶格常数

样品名称	晶粒尺寸/nm	晶格常数（1?=0.1nm）/?
Co₃O₄	23.53	8.0347
1B-Co₃O₄	18.13	8.0351
2B-Co₃O₄	20.66	8.0547
3B-Co₃O₄	17.85	8.0391
4B-Co₃O₄	18.96	8.0473
5B-Co₃O₄	18.05	8.0504

图2 样品的微观形貌图

图3 样品的Raman光谱图

图4 样品的XPS谱图

表2 Co3O4和2B-Co3O4的不同元素价态相对含量

样品名称	元素价态	相对含量/%	Co³⁺/Co相对含量/%
Co₃O₄	Co³⁺	29.7	44.4
	Co²⁺	37.2
	O_L	51.6
	O_C	48.4
2B-Co₃O₄	Co³⁺	37.1	45.7
	Co²⁺	44.1
	O_L	47.7
	O_C	52.3

图5 Co3O4和2B-Co3O4在180℃下对1×105μg/L不同气体的灵敏度

图6 Co3O4和不同B掺杂量的B-Co3O4在不同工作温度下对1×105μg/L乙醇的灵敏度

图7 2B-Co3O4在180℃下对1×105μg/L乙醇的动态响应曲线

图8 Co3O4和2B-Co3O4在180℃下对不同浓度乙醇的动态响应曲线图和线性拟合图（内插图）

图9 2B-Co3O4对1×105μg/L乙醇的稳定性

表3 不同Co3O4复合材料气敏性能的比较

气敏材料	气体种类	工作温度 /℃	灵敏度	气体浓度 /×10³μg?L^-1	参考文献
Co₃O₄	乙醇	200	5.3	200	[27]
rGO-Co₃O₄	乙醇	180	13.5	100	[28]
Co₃O₄/N-rGO	乙醇	200	24.5	100	[29]
TiO₂/Co₃O₄	乙醇	150	16.7	150	[9]
B-Co₃O₄	乙醇	180	26.8	100	本研究

图10 B-Co3O4气体传感机理示意图

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硼掺杂Co₃O₄海胆状微球的制备及其乙醇气敏强化机制

Preparation of boron doped Co₃O₄ sea urchin-like microspheres and its gas sensing enhancement mechanism for ethanol

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