Co3O4 Synthesized with the Assistance of Plasma for Photocatalytic Purification of Toluene

doi:10.12422/j.issn.1006-396X.2023.02.006

Abstract

Abstract:

Plasma modification is an effective way to improve the catalytic activities of materials.Firstly,Co₂(OH)₂CO₃ precursor was synthesized by a hydrothermal method.Then,the precursor was subjected to the oxygen atmosphere low?temperature plasma, and the surface modified Co₃O₄ catalyst (Co₃O₄?P) was obtained,which was further characterized the XRD,SEM,H₂?TPR,O₂?TPD,TEM,XPS,FTIR,Raman spectrum and UV?visible spectrum.The results demonstrate that plasma treatment could reduce the average valence state of Co elements in Co₃O₄ to form more defective sites on the catalyst surface,and lower the Co-O bond energy of Co₃O₄ to improve its low temperature reduction performance.Under the irradiation of full solar spectrum light with intensity of 776 mW/cm²,reaction space velocity of 30 000 mL/（g·h）and toluene concentration of 500 μg/g，the toluene degradation performance of the Co₃O₄?P catalyst could reach 100.0%，which was approximately twice that of the Co₃O₄ catalyst (Co₃O₄?T) prepared by thermal calcination.

Key words: Plasma technology, Co₃O₄, Toluene, Photo?thermal catalysis

摘要：

等离子体改性是提高催化材料性能的有效途径。利用水热法合成了Co₂(OH)₂CO₃前驱体，通过氧气低温等离子体技术，制备了表面改性的Co₃O₄催化剂(Co₃O₄?P)，并对其进行了XRD、O₂?TPD、H₂?TPR、SEM、TEM、XPS、FTIR、Raman和UV?Vis等表征。结果表明，等离子体处理可以降低Co₃O₄中Co元素的平均价态，在其表面形成更多的缺陷点位，降低Co₃O₄的Co-O键能，增强其低温还原性能；在全太阳光谱的光强为776 mW/cm²、反应空速为30 000 mL/（g·h）、甲苯质量分数为500 μg/g的测试条件下，Co₃O₄?P的甲苯降解率为100.0%,其值约为通过焙烧法制备的Co₃O₄催化剂（Co₃O₄?T）的2倍。

关键词: 等离子体技术, Co₃O₄, 甲苯, 光热催化

CLC Number:

TQ110.9

Min Qi, Dongliang Gao, Shuai Zhao, Xu Qiao, Mifen Cui, Zhaoyang Fei. Co₃O₄ Synthesized with the Assistance of Plasma for Photocatalytic Purification of Toluene[J]. Journal of Petrochemical Universities, 2023, 36(2): 42-50.

齐敏, 高栋梁, 赵帅, 乔旭, 崔咪芬, 费兆阳. 等离子体辅助制备的Co₃O₄光催化甲苯净化性能研究[J]. 石油化工高等学校学报, 2023, 36(2): 42-50.

Figures/Tables 12

Fig.1 Photocatalytic activity testing device

Fig.2 XRD patterns of Co2(OH)2CO3 precursor and Co3O4 series catalysts

Table 1 Physical?chemical properties of Co3O4 series catalysts

催化剂	比表面积/(m²·g^-1)	脱氧量/(mmol·g^-1)			耗氢量/(mmol·g^-1)		n（Co³⁺）/n（Co²⁺）		n（O_sur）/n（/O_lat）
催化剂	比表面积/(m²·g^-1)	区域 I	区域 II	区域 Ⅲ	区域 I	区域 II	反应前	反应后	反应前	反应后
Co₃O₄⁃T	35.0	0.01	0.10	2.32	3.82	20.38	0.50	1.00	0.40	0.28
Co₃O₄⁃P	135.0	0.04	1.55	2.14	4.23	23.97	0.42	1.21	0.76	0.40

Fig.3 O2?TPD and H2?TPR profiles of Co3O4 series catalysts

Fig.4 SEM and TEM images of Co3O4 series catalysts

Fig.5 Co 2p,O 1s spectra of Co3O4 series catalysts

Fig.6 FT?IR and Raman spectra of Co3O4 series catalysts

Fig.7 UV?Vis absorption spectrum of Co3O4 series catalysts

Fig.8 Catalytic activity of Co3O4 series catalysts and stability test of Co3O4?P catalyst for toluene oxidation under light irradiation

Fig.9 Catalytic activity curve for toluene by Co3O4?P under the light of different wavelengths

Fig.10 Co 2p and O 1s spectra of Co3O4 series catalysts after the reaction test

Fig.11 In situ infrared spectra of the oxidation process for toluene over Co3O4?P catalyst at different temperature and with or without light irradiation

References 34

1	李长英，陈明功，盛楠，等.挥发性有机物处理技术的特点与发展［J］.化工进展，2016，35（3）：917⁃925.
	Li C Y，Chen M G，Sheng N，et al.The characteristics and development of volatile organic compounds treatment technology［J］.Chemical Industry and Engineering Progress，2016，35（3）：917⁃925.
2	Rastegarpanah A，Meshkani F，Liu Y X，et al.Toluene oxidation over the M⁃Al（M=Ce，La，Co，Ce⁃La，and Ce⁃Co） catalysts derived from the modified “one⁃pot” evaporation⁃induced self⁃assembly method：Effects of microwave or ultrasound irradiation and noble⁃metal loading on catalytic activity and stability［J］.Industrial & Engineering Chemistry Research，2020，59（13）：5624⁃5635.
3	王雪，建伟伟，陆毅，等.Cu和Sn改性多壁碳纳米管对VOCs气体的吸附［J］.辽宁石油化工大学学报，2021，41（5）：44⁃49.
	Wang X，Jian W W，Lu Y，et al.Adsorption of VOCs using MWCNTs modified with Cu and Sn［J］.Journal of Liaoning Petrochemical University，2021，41（5）：44⁃49.
4	李昱慧，张静，张昱屾，等.石墨相氮化碳光催化剂改性的研究进展［J］.石油化工高等学校学报，2019，32（2）：1⁃7.
	Li Y H，Zhang J，Zhang Y S，et al.The research progress of modified g⁃C₃N₄ composite photocatalyst［J］.Journal of Petrochemical Universities，2019，32（2）：1⁃7.
5	秦宏宇，柯义虎，李景云，等.光热协同效应在催化反应中的应用研究进展［J］.分子催化，2021，35（4）：375⁃389.
	Qin H Y，Ke Y H，Li J Y，et al.Application of photo⁃thermal synergistic effect in catalytic reactions［J］.Journal of Molecular Catalysis，2021，35（4）：375⁃389.
6	Du S H，Bian X A，Zhao Y X，et al.Progress and prospect of photothermal catalysis［J］.Chemical Research in Chinese Universities，2022，38（3）：723⁃734.
7	Wei L F，Yu C L，Yang K，et al.Recent advances in VOCs and CO removal via photothermal synergistic catalysis［J］.Chinese Journal of Catalysis，2021，42（7）：1078⁃1095.
8	吝美霞，李法云，王艳杰，等.改性石墨相氮化碳光催化降解有机污染物［J］.辽宁石油化工大学学报，2019，32（2）：1⁃9.
	Lin M X，Li F Y，Wang Y J，et al.Photocatalytic degradation of organic pollutants by modified graphite phase carbonitride［J］.Journal of Liaoning Petrochemical University，2019，32（2）：1⁃9.
9	李娟娟，张梦，蔡松财，等.光热催化氧化VOCs的研究进展［J］.环境工程，2020，38（1）：13⁃20.
	Li J J，Zhang M，Cai S C，et al.Light⁃driven thermocatalysis/photo⁃thermocatalysis of VOCs：Recent advances and future perspectives［J］.Environment Engineering，2020，38（1）：13⁃20.
10	Liotta L F.Catalytic oxidation of volatile organic compounds on supported noble metals［J］.Applied Catalysis B：Environmental，2010，100（3⁃4）：403⁃412.
11	芮泽宝，杨晓庆，陈俊妃，等.光热协同催化净化挥发性有机物的研究进展及展望［J］.化工学报，2018，69（12）：4947⁃4958.
	Rui Z B，Yang X Q，Chen J F，et al.Photo⁃thermal synergistic catalysis for VOCs purification：Current status and future perspectives［J］.CIESC Journal，2018，69（12）：4947⁃4958.
12	Dai W L，Zou M L，Zhao C，et al.Monoatomic oxygen fueled by oxygen vacancies governs the photothermocatalytic deep oxidation of toluene on Na⁃doped Co₃O₄［J］.Applied Catalysis B：Environmental，2022，317：121769.
13	Zheng Y L，Weng W Z，Jiang D，et al.Ultrathin mesoporous Co₃O₄ nanosheets with excellent photo⁃/thermo⁃catalytic activity［J］.Journal of Materials Chemistry A，2016，4（1）：105⁃112.
14	Li L，Wei M J，Chen F，et al.Pt⁃embedded⁃Co₃O₄ hollow structure as a highly efficient catalyst for toluene combustion［J］.Catalysis Science & Technology，2021，11（16）：5491⁃5497.
15	Zeng Y K，Zhong J P，Wang H B，et al.Synergistic effect of tunable oxygen⁃vacancy defects and graphene on accelerating the photothermal degradation of methanol over Co₃O₄/rGO nanocomposites［J］.Chemical Engineering Journal，2021，425：131658.
16	Lan L，Zheng S，Qian Z，et al.Defects lead to a massive enhancement in the UV⁃Vis⁃IR driven thermo⁃catalytic activity of Co₃O₄ mesoporous nanorod［J］.Journal of Materials Chemistry A，2018，6（16）：7194⁃7205.
17	刘星慧.等离子体表面处理对光催化材料性能的影响［D］.大连：大连理工大学，2021.
18	苏风梅，张达，梁风，等.低温等离子体制备与改性纳米催化材料的研究进展［J］.应用化学，2019，36（8）：882⁃891.
	Su F M，Zhang D，Liang F，et al.Progress in preparation and modification of nano⁃catalytic materials by low⁃temperature plasma［J］.Chinese Journal of Applied Chemistry，2019，36（8）：882⁃891.
19	Tian Q Q，Wang Z C，Yuan M H，et al.Plasma⁃induced construction of defect⁃enriched perovskite oxides for catalytic methane combustion［J］.Environmental Science：Nano，2021，8（8）：2386⁃2395.
20	Han H S，Jin S，Park S M，et al.Plasma⁃induced oxygen vacancies in amorphous MnOx boost catalytic performance for electrochemical CO₂ reduction［J］.Nano Energy，2021，79：105492.
21	谢莉婧，金小青，付国瑞，等.碱式碳酸钴的水热合成及其结构表征［J］.化学研究与应用，2010，22（8）：985⁃988.
	Xie L J，Jin X Q，Fu G R，et al.Shape⁃controlled synthesis and structural characterization of cobalt basic carbonate by hydrothermal method［J］.Chemical Research and Application，2010，22（8）：985⁃988.
22	Liu B C，Liu Y，Li C Y，et al.Three⁃dimensionally ordered macroporous Au/CeO₂⁃Co₃O₄ catalysts with nanoporous walls for enhanced catalytic oxidation of formaldehyde［J］.Applied Catalysis B：Environmental，2012，127（9）：47⁃58.
23	Cai T，Huang H，Deng W，et al.Catalytic combustion of 1，2⁃dichlorobenzene at low temperature over Mn⁃modified Co₃O₄ catalysts［J］.Applied Catalysis B：Environmental，2015，166⁃167：393⁃405.
24	Lan L，Shi Z K，Zhang Q，et al.Defects lead to a massive enhancement in the UV⁃Vis⁃IR driven thermocatalytic activity of Co₃O₄ mesoporous nanorods［J］.Journal of Materials Chemistry，2018，6（16）：7194⁃7205.
25	曹茂启，吴大旺，向丁玎，等.氧空位Co₃O₄纳米线阵列的制备及其高效电催化合成氨［J］.微纳电子技术，2021，58（12）：1114⁃1120.
	Cao M Q，Wu D W，Xiang D D，et al.Preparation of Co₃O₄ nanowire array with oxygen vacancy and its efficient electrocatalytic synthesis of ammonia［J］.Micronanoelectronic Technology，2021，58（12）：1114⁃1120.
26	Wang F，Dai H X，Deng J G，et al.Nanoplate⁃aggregate Co₃O₄ microspheres for toluene combustion［J］.Chinese Journal of Catalysis，2014，35（9）：1475⁃1481.
27	Feng Y J，Li L，Niu S F，et al.Controlled synthesis of highly active mesoporous Co₃O₄ polycrystals for low temperature CO oxidation［J］.Applied Catalysis B：Environmental，2012，111⁃112（9）：461⁃466.
28	Xie X W，Li Y，Liu Z Q，et al.Low⁃temperature oxidation of CO catalysed by Co₃O₄ nanorods［J］.Nature，2009，458：746⁃749.
29	刘先红，李德炳，范文青，等.纳米Co₃O₄的制备及其在富氢气氛下CO选择氧化反应中的催化性能［J］.厦门大学学报，2009，48（6）：773⁃779.
	Liu X H，Li D R，Fan W Q，et al.The synthesis of Co₃O₄ nanoparticles and catalytic performance of carbon monoxide preferential oxidation in H₂⁃rich gas［J］.Journal of Xiamen University （Natural Science），2009，48（6）：773⁃779.
30	Li W，Feng X L，Zhang Z，et al.A controllable surface etching strategy for well⁃defined spiny yolk@shell CuO@CeO₂ cubes and their catalytic performance boost［J］.Advanced Functional Materials，2018，28（49）：1802559.
31	Zhang Q，Mo S P，Chen B X，et al.Hierarchical Co₃O₄ nanostructures in⁃situ grown on 3D nickel foam towards toluene oxidation［J］.Moleccular Catalysis，2018，454：12⁃20.
32	Zeng M，Li Y Z，Liu F，et al.Cu doped OL⁃1 nanoflower：A UV⁃vis⁃infrared light⁃driven catalyst for gas⁃phase environmental purification with very high efficiency［J］.Applied Catalysis B：Environmental，2017，200：521⁃529.
33	Yu E Q，Li J J，Chen J，et al.Enhanced photothermal catalytic degradation of toluene by loading Pt nanoparticles on manganese oxide：Photoactivation of lattice oxygen［J］.Journal of Hazardous Materials，2020，388：121800.
34	Brault P.Review of low pressure plasma processing of proton exchange membrane fuel cell electrocatalysts［J］.Plasma Processes and Polymers，2016，13（1）：10⁃18.

[1]	. Research and Application of Selective Oxidation of p⁃Methylsulfonyl Toluene [J]. Journal of Petrochemical Universities, 2020, 33(1): 12-16.
[2]	HOU Tao,GAO Xiao-xin. The Simulation and Optimization of Toluene-Ethanol Azeotrope With Extractive Distillation [J]. Journal of Petrochemical Universities, 2012, 25(4): 21-23.
[3]	XIONG Jie-ming, ZHANG Li-ping, GONG Liang-fa, REN Xiao-guang. Isobaric Vapor-Liquid Equilibrium for the Toluene and N-Formylmorpholine System  [J]. Journal of Petrochemical Universities, 2008, 21(4): 11-14.
[4]	HAI-Feng1,2, JIA Mei-lin, BAO Zhaorigetu, Mengntuya, LI Da， LI Yan-feng. Preparation of Au/Co₃O₄ and It’s Catalytic Performance for CO Oxidation  [J]. Journal of Petrochemical Universities, 2008, 21(2): 20-24.
[5]	CHANG Xiao-ping,QIN Jian-hua, Yigong LOU. Application of Particle Swarm Algorithms to Optimization of Chemical Production Process [J]. Journal of Petrochemical Universities, 2007, 20(1): 90-93.

Co₃O₄ Synthesized with the Assistance of Plasma for Photocatalytic Purification of Toluene

等离子体辅助制备的Co₃O₄光催化甲苯净化性能研究

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Figures/Tables 12

References 34

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