Abstract
Co3O4 nanorods with diameters of ~0.15 μm and lengths of ~1 μm were prepared using a hydrothermal method via the assembly of microcrystals and tested in the catalytic oxidation of toluene. The catalytic performance of Co3O4 nanorods was improved by the addition of Ag at various concentrations, and the 7% Ag/Co3O4 catalyst achieves a toluene conversion of 90% at 256 °C with a space velocity of 78,000 mL g−1 h−1, which is much lower than that of the pristine Co3O4 (269 °C). The addition of Ag promoted the activation of the surface oxygen species and the formation of more oxygen vacancies, improving the relative low-temperature reducibility of Co3O4, which is favorable for toluene oxidation. Moreover, the 7% Ag/Co3O4 catalyst showed an excellent stability for toluene oxidation at 250 and 260 °C for 50 h under the same conditions.
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The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.
References
Aguero FN, Barbero BP, Gambaro L, Cadús LE (2009) Catalytic combustion of volatile organic compounds in binary mixtures over MnOx/Al2O3 catalyst. Appl Catal B Environ 91:108–112. https://doi.org/10.1016/j.apcatb.2009.05.012
Bai B, Li J (2014) Positive effects of K+ ions on three-dimensional mesoporous Ag/Co3O4 catalyst for HCHO oxidation. ACS Catal 4:2753–2762. https://doi.org/10.1021/cs5006663
Bai G, Dai H, Deng J, Liu Y, Wang F, Zhao Z, Qiu W, Au CT (2013) Porous Co3O4 nanowires and nanorods: highly active catalysts for the combustion of toluene. Appl Catal A Gen 450:42–49. https://doi.org/10.1016/j.apcata.2012.09.054
Carabineiro SAC, Chen X, Konsolakis M, Psarras AC, Tavares PB, Órfão JJM, Pereira MFR, Figueiredo JL (2015) Catalytic oxidation of toluene on Ce-Co and La-Co mixed oxides synthesized by exotemplating and evaporation methods. Catal Today 244:161–171. https://doi.org/10.1016/j.cattod.2014.06.018
Castaño MH, Molina R, Moreno S (2015) Cooperative effect of the Co-Mn mixed oxides for the catalytic oxidation of VOCs: influence of the synthesis method. Appl Catal A Gen 492:48–59. https://doi.org/10.1016/j.apcata.2014.12.009
Chu J, Dong Y, Han X et al (2020) Short-term prediction of urban PM2.5 based on a hybrid modified variational mode decomposition and support vector regression model. Environ Sci Pollut Res. https://doi.org/10.1007/s11356-020-11065-8
Dégé P, Pinard L, Magnoux P, Guisnet M (2000) Catalytic oxidation of volatile organic compounds. II. Influence of the physicochemical characteristics of Pd/HFAU catalysts on the oxidation of o-xylene. Appl Catal B Environ 27:17–26. https://doi.org/10.1016/S0926-3373(00)00135-1
Fei Z, He S, Li L, Ji W, Au CT (2012) Morphology-directed synthesis of Co3O4 nanotubes based on modified Kirkendall effect and its application in CH4 combustion. Chem Commun 48:853–855. https://doi.org/10.1039/c1cc15976c
Feng Z, Bao W, Xu X, Ma X, Zhan J, Yin Y (2016) Heteroepitaxial growth of well-dispersed Co3O4 nanocatalysts on porous ZnO nanoplates via successive hydrothermal deposition. ChemNanoMat 2:946–951. https://doi.org/10.1002/cnma.201600204
Fiorenza R, Crisafulli C, Condorelli GG, Lupo F, Scirè S (2015) Au-Ag/CeO2 and Au-Cu/CeO2 catalysts for volatile organic compounds oxidation and CO preferential oxidation. Catal Letters 145:1691–1702. https://doi.org/10.1007/s10562-015-1585-5
Fu J, Dong N, Ye Q, Cheng S, Kang T, Dai H (2018) Enhanced performance of the OMS-2 catalyst by Ag loading for the oxidation of benzene, toluene, and formaldehyde. New J Chem 42:18117–18127. https://doi.org/10.1039/c8nj04030c
Gac W, Giecko G, Pasieczna-Patkowska S, Borowiecki T, Kępiński L (2008) The influence of silver on the properties of cryptomelane type manganese oxides in N2O decomposition reaction. Catal Today 137:397–402. https://doi.org/10.1016/j.cattod.2007.11.008
Gao QX, Wang XF, Di JL et al (2011) Enhanced catalytic activity of α-Fe2O3 nanorods enclosed with {110} and {001} planes for methane combustion and CO oxidation. Catal Sci Technol 1:574–577. https://doi.org/10.1039/c1cy00080b
Garcia T, Agouram S, Sánchez-Royo JF, Murillo R, Mastral AM, Aranda A, Vázquez I, Dejoz A, Solsona B (2010) Deep oxidation of volatile organic compounds using ordered cobalt oxides prepared by a nanocasting route. Appl Catal A Gen 386:16–27. https://doi.org/10.1016/j.apcata.2010.07.018
Hu L, Peng Q, Li Y (2008) Selective synthesis of Co3O4 nanocrystal with different shape and crystal plane effect on catalytic property for methane combustion. J Am Chem Soc 130:16136–16137. https://doi.org/10.1021/ja806400e
Huang XS, Sun H, Wang LC, Liu YM, Fan KN, Cao Y (2009) Morphology effects of nanoscale ceria on the activity of Au/CeO2 catalysts for low-temperature CO oxidation. Appl Catal B Environ 90:224–232. https://doi.org/10.1016/j.apcatb.2009.03.015
Ji K, Dai H, Deng J, Li X, Wang Y, Gao B, Bai G, Au CT (2012) A comparative study of bulk and 3DOM-structured Co3O4, Eu0.6Sr0.4FeO3, and Co3O4/Eu0.6Sr0.4FeO3: preparation, characterization, and catalytic activities for toluene combustion. Appl Catal A Gen 447-448:41–48. https://doi.org/10.1016/j.apcata.2012.09.004
Kang Y, Sun M, Li A (2012) Studies of the catalytic oxidation of CO over Ag/CeO2 catalyst. Catal Letters 142:1498–1504. https://doi.org/10.1007/s10562-012-0893-2
Li P, Chen X, Ma L, Bhat A, Li Y, Schwank JW (2019) Effect of Ce and La dopants in Co3O4 nanorods on the catalytic activity of CO and C3H6 oxidation. Catal Sci Technol 9:1165–1177. https://doi.org/10.1039/c8cy02460j
Li P, He C, Cheng J, Ma CY, Dou BJ, Hao ZP (2011) Catalytic oxidation of toluene over Pd/Co3AlO catalysts derived from hydrotalcite-like compounds: effects of preparation methods. Appl Catal B Environ 101:570–579. https://doi.org/10.1016/j.apcatb.2010.10.030
Liotta LF, Wu H, Pantaleo G, Venezia AM (2013) Co3O4 nanocrystals and Co3O4-MOx binary oxides for CO, CH4 and VOC oxidation at low temperatures: a review. Catal Sci Technol 3:3085–3102. https://doi.org/10.1039/c3cy00193h
Luo D, Liu S, Liu J, Zhao J, Miao C, Ren J (2018) Catalytic combustion of toluene over cobalt oxides supported on graphitic carbon nitride (CoOx/g-C3N4) catalyst. Ind Eng Chem Res 57:11920–11928. https://doi.org/10.1021/acs.iecr.8b02625
Luo Y, Lin D, Zheng Y et al (2020) MnO2 nanoparticles encapsuled in spheres of Ce-Mn solid solution: efficient catalyst and good water tolerance for low-temperature toluene oxidation. Appl Surf Sci 504. https://doi.org/10.1016/j.apsusc.2019.144481
Ma CY, Mu Z, Li JJ, ** YG, Cheng J, Lu GQ, Hao ZP, Qiao SZ (2010) Mesoporous Co3O4 and Au/Co3O4 catalysts for low-temperature oxidation of trace ethylene. J Am Chem Soc 132:5–7. https://doi.org/10.1021/ja906274t
Ma L, Geng Y, Chen X, Yan N, Li J, Schwank JW (2020a) Reaction mechanism of propane oxidation over Co3O4 nanorods as rivals of platinum catalysts. Chem Eng J 402:125911. https://doi.org/10.1016/j.cej.2020.125911
Ma L, Seo CY, Chen X, Sun K, Schwank JW (2018) Indium-doped Co3O4 nanorods for catalytic oxidation of CO and C3H6 towards diesel exhaust. Appl Catal B Environ 222:44–58. https://doi.org/10.1016/j.apcatb.2017.10.001
Ma L, Wang D, Li J, Bai B, Fu L, Li Y (2014) Ag/CeO2 nanospheres: efficient catalysts for formaldehyde oxidation. Appl Catal B Environ 148-149:36–43. https://doi.org/10.1016/j.apcatb.2013.10.039
Ma L, Zhang W, Wang YG, Chen X, Yu W, Sun K, Sun H, Li J, Schwank JW (2020b) Catalytic performance and reaction mechanism of NO oxidation over Co3O4 catalysts. Appl Catal B Environ 267:118371. https://doi.org/10.1016/j.apcatb.2019.118371
Mo S, Li S, Li W, Li J, Chen J, Chen Y (2016) Excellent low temperature performance for total benzene oxidation over mesoporous CoMnAl composited oxides from hydrotalcites. J Mater Chem A 4:8113–8122. https://doi.org/10.1039/c6ta02593e
Özacar M, Poyraz AS, Genuino HC, Kuo CH, Meng Y, Suib SL (2013) Influence of silver on the catalytic properties of the cryptomelane and Ag-hollandite types manganese oxides OMS-2 in the low-temperature CO oxidation. Appl Catal A Gen 462-463:64–74. https://doi.org/10.1016/j.apcata.2013.04.027
Peng R, Li S, Sun X, Ren Q, Chen L, Fu M, Wu J, Ye D (2018) Size effect of Pt nanoparticles on the catalytic oxidation of toluene over Pt/CeO2 catalysts. Appl Catal B Environ 220:462–470. https://doi.org/10.1016/j.apcatb.2017.07.048
Qu Z, Bu Y, Qin Y, Wang Y, Fu Q (2013) The improved reactivity of manganese catalysts by Ag in catalytic oxidation of toluene. Appl Catal B Environ 132-133:353–362. https://doi.org/10.1016/j.apcatb.2012.12.008
Qu Z, Shen S, Chen D, Wang Y (2012) Highly active Ag/SBA-15 catalyst using post-grafting method for formaldehyde oxidation. J Mol Catal A Chem 356:171–177. https://doi.org/10.1016/j.molcata.2012.01.013
Ren Q, Mo S, Peng R, Feng Z, Zhang M, Chen L, Fu M, Wu J, Ye D (2018) Controllable synthesis of 3D hierarchical Co3O4 nanocatalysts with various morphologies for the catalytic oxidation of toluene. J Mater Chem A 6:498–509. https://doi.org/10.1039/c7ta09149d
Song W, Poyraz AS, Meng Y, Ren Z, Chen SY, Suib SL (2014) Mesoporous Co3O4 with controlled porosity: inverse micelle synthesis and high-performance catalytic Co oxidation at -60 °C. Chem Mater 26:4629–4639. https://doi.org/10.1021/cm502106v
Sun J, Shen Z, Zhang Y, Zhang Z, Zhang Q, Zhang T, Niu X, Huang Y, Cui L, Xu H, Liu H, Cao J, Li X (2019) Urban VOC profiles, possible sources, and its role in ozone formation for a summer campaign over **’an, China. Environ Sci Pollut Res 26:27769–27782. https://doi.org/10.1007/s11356-019-05950-0
Szegedi Á, Popova M, Lázár K, Klébert S, Drotár E (2013) Impact of silica structure of copper and iron-containing SBA-15 and SBA-16 materials on toluene oxidation. Microporous Mesoporous Mater 177:97–104. https://doi.org/10.1016/j.micromeso.2013.04.024
Tang W, Li W, Li D, Liu G, Wu X, Chen Y (2014) Synergistic effects in porous Mn-Co mixed oxide nanorods enhance catalytic deep oxidation of benzene. Catal Letters 144:1900–1910. https://doi.org/10.1007/s10562-014-1340-3
Topka P, Dvořáková M, Kšírová P, Perekrestov R, Čada M, Balabánová J, Koštejn M, Jirátová K, Kovanda F (2020) Structured cobalt oxide catalysts for VOC abatement: the effect of preparation method. Environ Sci Pollut Res 27:7608–7617. https://doi.org/10.1007/s11356-019-06974-2
Wang H, Luo S, Zhang M, Liu W, Wu X, Liu S (2018) Roles of oxygen vacancy and Ox− in oxidation reactions over CeO2 and Ag/CeO2 nanorod model catalysts. J Catal 368:365–378. https://doi.org/10.1016/j.jcat.2018.10.018
Wang K, Cao Y, Hu J, Li Y, **e J, Jia D (2017) Solvent-free chemical approach to synthesize various morphological Co3O4 for CO oxidation. ACS Appl Mater Interfaces 9:16128–16137. https://doi.org/10.1021/acsami.7b01142
Wang Y, Xue Y, Zhao C, Zhao D, Liu F, Wang K, Dionysiou DD (2016) Catalytic combustion of toluene with La0.8Ce0.2MnO3 supported on CeO2 with different morphologies. Chem Eng J 300:300–305. https://doi.org/10.1016/j.cej.2016.04.007
**ong H, Zhang Y, Liew K, Li J (2008) Fischer-Tropsch synthesis: the role of pore size for Co/SBA-15 catalysts. J Mol Catal A Chem 295:68–76. https://doi.org/10.1016/j.molcata.2008.08.017
Yan Z, Xu Z, Cheng B, Jiang C (2017) Co3O4 nanorod-supported Pt with enhanced performance for catalytic HCHO oxidation at room temperature. Appl Surf Sci 404:426–434. https://doi.org/10.1016/j.apsusc.2017.02.010
Yu H, Wang X, Wu X, Chen Y (2018a) Promotion of Ag for Co3O4 catalyzing N2O decomposition under simulated real reaction conditions. Chem Eng J 334:800–806. https://doi.org/10.1016/j.cej.2017.10.079
Yu L, Peng R, Chen L, Fu M, Wu J, Ye D (2018b) Ag supported on CeO2 with different morphologies for the catalytic oxidation of HCHO. Chem Eng J 334:2480–2487. https://doi.org/10.1016/j.cej.2017.11.121
Yuan B, Hu WW, Shao M, Wang M, Chen WT, Lu SH, Zeng LM, Hu M (2013) VOC emissions, evolutions and contributions to SOA formation at a receptor site in eastern China. Atmos Chem Phys 13:8815–8832. https://doi.org/10.5194/acp-13-8815-2013
Zhang YH, Su H, Zhong LJ, Cheng YF, Zeng LM, Wang XS, **ang YR, Wang JL, Gao DF, Shao M (2008) Regional ozone pollution and observation-based approach for analyzing ozone-precursor relationship during the PRIDE-PRD2004 campaign. Atmos Environ 42:6203–6218. https://doi.org/10.1016/j.atmosenv.2008.05.002
Zhang X, Yang Y, Song L, Wang Y, He C, Wang Z, Cui L (2018) High and stable catalytic activity of Ag/Fe2O3 catalysts derived from MOFs for CO oxidation. Mol Catal 447:80–89. https://doi.org/10.1016/j.mcat.2018.01.007
Zhao S, Hu F, Li J (2016) Hierarchical core-shell Al2O3@Pd-CoAlO microspheres for low-temperature toluene combustion. ACS Catal 6:3433–3441. https://doi.org/10.1021/acscatal.6b00144
Zhong J, Zeng Y, Zhang M, Feng W, **ao D, Wu J, Chen P, Fu M, Ye D (2020) Toluene oxidation process and proper mechanism over Co3O4 nanotubes: investigation through in-situ DRIFTS combined with PTR-TOF-MS and quasi in-situ XPS. Chem Eng J 397:125375. https://doi.org/10.1016/j.cej.2020.125375
Zhu Z, Lu G, Zhang Z, Guo Y, Guo Y, Wang Y (2013) Highly active and stable Co3O4/ZSM-5 catalyst for propane oxidation: effect of the preparation method. ACS Catal 3:1154–1164. https://doi.org/10.1021/cs400068v
Acknowledgements
This work described above was supported by the National Natural Science Foundation of China (Grant No. 21776194 and 21606159). We thank International Science Editing (http://www.internationalscienceediting.com) for editing this manuscript.
Funding
This work described above was supported by the National Natural Science Foundation of China (Grant No. 21776194 and 21606159).
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All authors contributed to the study conception and design. Tao Li, Dongmou Luo, and Chao Miao conceived the study, established the design, and performed the experimental work. Tao Li, Dongmou Luo, and Chao Miao participated in data acquisition and analysis. Tao Li and Dongmou Luo participated in the drafting of the manuscript. Jun Ren, **xian Zhao, and Yanhong Quan worked on aspects of the revision of the manuscript. All authors read and approved the final manuscript.
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Li, T., Zhao, J., Quan, Y. et al. The improved activity of Co3O4 nanorods using silver in the catalytic oxidation of toluene. Environ Sci Pollut Res 28, 37592–37602 (2021). https://doi.org/10.1007/s11356-021-13351-5
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DOI: https://doi.org/10.1007/s11356-021-13351-5