基于机械化学的高比表面积CoxMn1-xOy催化剂合成及其VOCs燃烧研究

引用本文: 鲍佳锋, 陈皓, 杨是赜, 张鹏飞. 基于机械化学的高比表面积Co_xMn_1-xO_y催化剂合成及其VOCs燃烧研究[J]. 催化学报, 2020, 41(12): 1846-1854. doi: 10.1016/S1872-2067(20)63635-X shu

Citation: Jiafeng Bao, Hao Chen, Shize Yang, Pengfei Zhang. Mechanochemical redox-based synthesis of highly porous Co_xMn_1-xO_y catalysts for total oxidation[J]. Chinese Journal of Catalysis, 2020, 41(12): 1846-1854. doi: 10.1016/S1872-2067(20)63635-X shu

基于机械化学的高比表面积Co_xMn_1-xO_y催化剂合成及其VOCs燃烧研究

a 上海交通大学化学与化工学院, 上海 200240, 中国;
b 诺克斯维尔大学化学系, 田纳西州, 美国;
c 布鲁克海文国家实验室功能纳米材料中心, 纽约, 美国
基金项目:
国家自然科学基金（21776174）；海洋工程国家重点实验室开放基金（1809）；上海交通大学重点前瞻布局基金（2019QYB06）；中船重工集团委托项目；浙江新安化工集团委托项目.

摘要: 碳氢化合物的催化燃烧在控制挥发性有机化合物（VOCs）和汽车尾气方面非常重要.目前，商用催化剂通常是燃烧温度低且催化剂寿命长的贵金属基材料.相反，过渡金属氧化物催化剂价格便宜，而它们的活性和稳定性却较低，阻碍了它们的商业化.实际上，具有多重氧化还原循环的钴锰氧化物（CoMnO_x）在烃类的催化氧化中有不错的性能.在影响燃烧催化剂性能的参数中，孔隙率和表面活性氧物种是关键，目前已经有多种钴锰氧化物的合成方法.
Co_xMn_1-xO_y传统的合成方法是共沉淀法，溶胶-凝胶法和溶液氧化还原法等湿化学的工艺.从合成的角度来看，仍存在一些改善的空间.例如，溶液法合成过程中，金属前驱体必须是液体或可溶性固体原料；而且需要几个操作单元，包括金属前体的溶解和液-液混合.同时，钴锰物种的良好分散是合成高效催化剂的关键.由于液体环境下Co²⁺和Mn²⁺离子具有不同的平衡常数，利用共沉淀方法合成时，经常观察到钴和锰氧化物的局部分离.因此，开发一种有效的合成Co_xMn_1-xO_y催化剂的方法非常重要.
最近，机械化学重新引起了人们的兴趣，已有大量文献报道用来合成多孔材料.本文提出了一种通过球磨法简单合成Co_xMn_1-xO_y催化剂的机械化学氧化还原工艺.众所周知，在溶液中钴（II）盐与KMnO₄进行氧化还原反应可以合成Co_xMn_1-xO_y催化剂，但反应的进行程度取决于KMnO₄浓度，这可能会影响Co_xMn_1-xO_y内高价物种和孔道的形成.出乎意料的是，采用机械化学氧化还原法合成的Co_xMn_1-xO_y催化剂的表面积高达479m² g^-1.
在丙烯的催化燃烧反应中，使用机械化学氧化还原法合成的Co_xMn_1-xO_y时，丙烯在200℃时被完全氧化，远低于共沉淀法（450℃）和溶胶-凝胶法（400℃）合成的.此外，该催化剂还具有良好的抗水性（4.2% H₂O，>65h）和抗硫性（20-100ppm SO₂）.同时，该催化剂可以扩展到其他VOCs底物的低温催化燃烧，如一氧化碳、甲烷、乙醇、丙酮、甲苯.此外，机械化学氧化还原法可放大制备催化剂.目前，实验室已经完成公斤级制备，有望替代传统方法.

关键词:

English

Mechanochemical redox-based synthesis of highly porous Co_xMn_1-xO_y catalysts for total oxidation

a School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;
b Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, USA;
c Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY11973, USA
Received Date: 21 March 2020
Revised Date: 23 April 2020
Fund Project:
This work was supported by the National Natural Science Foundation of China (21776174), the Open Foundation of the State Key Laboratory of Ocean Engineering (Shanghai Jiao Tong University of China) (1809), Shanghai Jiao Tong University Scientific and Technological Innovation Funds (2019QYB06), China Shipbuilding Industry Corporation (CSIC) and Zhejiang XinAn Chemical Industry Corporation.

Abstract: A mechanochemical redox reaction between KMnO₄ and CoCl₂ was developed to obtain a Co_xMn_1-xO_y catalyst with a specific surface area of 479 m² g^-1, which was higher than that obtained using a co-precipitation (CP) method (34 m² g^-1), sol-gel (SG) method (72 m² g^-1), or solution redox process (131 m² g^-1). During catalytic combustion, this Co_xMn_1-xO_y catalyst exhibited better activity (T₁₀₀ for propylene= ~200 ℃) than the control catalysts obtained using the SG (325 ℃) or CP (450 ℃) methods. The mechanical action, mainly in the form of kinetic energy and frictional heating, may generate a high degree of interstitial porosity, while the redox reaction could contribute to good dispersion of cobalt and manganese species. Moreover, the as-prepared Co_xMn_1-xO_y catalyst worked well in the presence of water vapor (H₂O 4.2%, >60 h) or SO₂ (100 ppm) and at high temperature (400 ℃, >60 h). The structure MnO₂·(CoOOH)_2.93 was suggested for the current Co_xMn_1-xO_y catalyst. This catalyst could be extended to the total oxidation of other typical hydrocarbons (T₉₀=150 ℃ for ethanol, T₉₀ =225 ℃ for acetone, T₉₀=250 ℃ for toluene, T₉₀ =120 ℃ for CO, and T₉₀=540 ℃ for CH₄). Scale-up of the synthesis of Co_xMn_1-xO_y catalyst (1 kg) can be achieved via ball milling, which may provide a potential strategy for real world catalysis.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

基于机械化学的高比表面积Co_xMn_1-xO_y催化剂合成及其VOCs燃烧研究

English

Mechanochemical redox-based synthesis of highly porous Co_xMn_1-xO_y catalysts for total oxidation

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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中国化学会秘书处

基于机械化学的高比表面积CoxMn1-xOy催化剂合成及其VOCs燃烧研究

English

Mechanochemical redox-based synthesis of highly porous CoxMn1-xOy catalysts for total oxidation

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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基于机械化学的高比表面积Co_xMn_1-xO_y催化剂合成及其VOCs燃烧研究

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