Abstract
A series of xCe-MnO2 (x = 0–1) catalysts were synthesized using ammonium oxalate as a precipitator via the redox precipitation method and hydrothermal synthesis method. The results indicate that 0.25Ce-MnO2 exhibited the highest catalytic activity for toluene oxidation, with the T99 of 240 °C. Characterization results from XRD, Raman, SEM, TEM, EDS-mapping, BET, and other techniques reveal that the 0.25Ce-MnO2 catalyst exhibited a three-dimensional multistage ultrathin nanosheet structure by adjusting the introduction amount of Ce, with abundant active sites, and effectively formed Ce-Mn homogeneous dispersion. The larger pore size and volume of 0.25Ce-MnO2 catalyst lead to it excellent toluene transfer ability. Furthermore, compared with MnO2, the crystal pattern of 0.25Ce-MnO2 shifted to the tetragonal cryptomelane type α-MnO2 phase and exposed more crystal planes which are beneficial to catalyze toluene. H2-TPR, O2-TPD, and XPS characterization further confirmed the strong interaction between Ce and Mn oxides, which exhibited better low-temperature reducibility and oxygen migration, along with abundant Ce3+ and Mn3+ species, where lattice oxygen played a major role. Moreover, in situ DRIFTS revealed that the 0.25Ce-MnO2 catalyst showed higher adsorption and desorption capacity for toluene than the MnO2 catalyst, and benzoate species were the key intermediates for catalytic oxidation. Additionally, benzoate and surface phenolic species were the key intermediates for catalytic oxidation of MnO2. Because 0.25Ce-MnO2 possesses better ability of converting toluene to benzoate species, it exhibits better activity.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
The data and materials are available from the corresponding author on reasonable request.
References
Brummer V, Teng SY, Jecha D, Skryja P, Vavrcikova V, Stehlik P (2022) Contribution to cleaner production from the point of view of VOC emissions abatement: a review. J Clean Prod 361:132112. https://doi.org/10.1016/j.jclepro.2022.132112
Chen Y, Zheng H, Guo Z, Zhou C, Wang C, Borgna A, Yang Y (2011) Pd catalysts supported on MnCeOx mixed oxides and their catalytic application in solvent-free aerobic oxidation of benzyl alcohol: support composition and structure sensitivity. J Catal 283(1):34–44. https://doi.org/10.1016/j.jcat.2011.06.021
Chen X, Chen X, Yu E, Cai S, Jia H, Chen J, Liang P (2018) In situ pyrolysis of Ce-MOF to prepare CeO2 catalyst with obviously improved catalytic performance for toluene combustion. Chem Eng J 344:469–479. https://doi.org/10.1016/j.cej.2018.03.091
Chen L, Tsumori N, Xu Q (2020) Quasi-MOF-immobilized metal nanoparticles for synergistic catalysis. Sci Chin Chem 63(11):1601–1607. https://doi.org/10.1007/s11426-020-9781-7
Du J, Qu Z, Dong C, Song L, Qin Y, Huang N (2018) Low-temperature abatement of toluene over Mn-Ce oxides catalysts synthesized by a modified hydrothermal approach. Appl Surf Sci 433:1025–1035. https://doi.org/10.1016/j.apsusc.2017.10.116
Durán FG, Barbero BP, Cadús LE, Rojas C, Centeno MA, Odriozola JA (2009) Manganese and iron oxides as combustion catalysts of volatile organic compounds. Appl Catal B 92(1):194–201. https://doi.org/10.1016/j.apcatb.2009.07.010
Fan J, Ren Q, Mo S, Sun Y, Fu M, Wu J, Ye D (2020) Transient in-situ DRIFTS Investigation of Catalytic Oxidation of Toluene over α-, γ- and β-MnO. Journal of Hazardous Materials 12(4):1046–1054. https://doi.org/10.1002/cctc.201901839
Filatov IE, Uvarin VV, Kuznetsov DL (2016) Cleaning air from multicomponent impurities of volatile organic compounds by pulsed corona discharge. Tech Phys Lett 42(9):927–931. https://doi.org/10.1134/S1063785016090169
Gong P, He F, Xie J, Fang D (2023) Catalytic removal of toluene using MnO2-based catalysts: a review. Chemosphere 318:137938. https://doi.org/10.1016/j.chemosphere.2023.137938
González-Prior J, López-Fonseca R, Gutiérrez-Ortiz JI, de Rivas B (2018) Catalytic removal of chlorinated compounds over ordered mesoporous cobalt oxides synthesised by hard-templating. Appl Catal B 222:9–17. https://doi.org/10.1016/j.apcatb.2017.09.050
He C, Yu Y, Shi J, Shen Q, Chen J, Liu H (2015) Mesostructured Cu-Mn-Ce-O composites with homogeneous bulk composition for chlorobenzene removal: catalytic performance and microactivation course. Mater Chem Phys 157:87–100. https://doi.org/10.1016/j.matchemphys.2015.03.020
He H, Lin X, Li S, Wu Z, Gao J, Wu J, Fu M (2018) The key surface species and oxygen vacancies in MnOx(0.4)-CeO2 toward repeated soot oxidation. Appl Catal B 223:134–142. https://doi.org/10.1016/j.apcatb.2017.08.084
He C, Cheng J, Zhang X, Douthwaite M, Pattisson S, Hao Z (2019) Recent advances in the catalytic oxidation of volatile organic compounds: a review based on pollutant sorts and sources. Chem Rev 119(7):4471–4568. https://doi.org/10.1021/acs.chemrev.8b00408
Huang L, Zheng M, Yu D, Yaseen M, Duan L, Jiang W, Shi L (2018) In-situ fabrication and catalytic performance of Co-Mn@CuO core-shell nanowires on copper meshes/foams. Mater Des 147:182–190. https://doi.org/10.1016/j.matdes.2018.03.046
Kang SB, Kalamaras C, Balakotaiah V, Epling W (2017) Hydrocarbon trapping over Ag-Beta zeolite for cold-start emission control. Catal Lett 147(6):1355–1362. https://doi.org/10.1007/s10562-017-2044-2
Larachi F, Pierre J, Adnot A, Bernis A (2002) Ce 3d XPS study of composite CexMn1−xO2−y wet oxidation catalysts. Appl Surf Sci 195(1):236–250. https://doi.org/10.1016/S0169-4332(02)00559-7
Li L, Jing F, Yan J, Jing J, Chu W (2017) Highly effective self-propagating synthesis of CeO2-doped MnO2 catalysts for toluene catalytic combustion. Catal Today 297:167–172. https://doi.org/10.1016/j.cattod.2017.04.053
Li G, Zhang C, Wang Z, Huang H, Peng H, Li X (2018) Fabrication of mesoporous Co3O4 oxides by acid treatment and their catalytic performances for toluene oxidation. Appl Catal A 550:67–76. https://doi.org/10.1016/j.apcata.2017.11.003
Li JJ, Yu EQ, Cai SC, Chen X, Chen J, Jia HP, Xu YJ (2019) Noble metal free CeO2/LaMnO3 hybrid achieving efficient photo-thermal catalytic decomposition of volatile organic compounds under IR light. Appl Catal B 240:141–152. https://doi.org/10.1016/j.apcatb.2018.08.069
Li S, Lin Y, Wang D, Zhang C, Wang Z, Li X (2021) Polyhedral cobalt oxide supported Pt nanoparticles with enhanced performance for toluene catalytic oxidation. Chemosphere 263:127870. https://doi.org/10.1016/j.chemosphere.2020.127870
Lin LY, Bai H (2016) Salt-induced formation of hollow and mesoporous CoOx/SiO2 spheres and their catalytic behavior in toluene oxidation. RSC Adv 6(29):24304–24313. https://doi.org/10.1039/C5RA27488E
Lin X, Li S, He H, Wu Z, Wu J, Chen L, Fu M (2018) Evolution of oxygen vacancies in MnOx-CeO2 mixed oxides for soot oxidation. Appl Catal B 223:91–102. https://doi.org/10.1016/j.apcatb.2017.06.071
Luo Y, Wang K, Zuo J, Qian Q, Xu Y, Liu X, Chen Q (2017) Selective corrosion of LaCoO3 by NaOH: structural evolution and enhanced activity for benzene oxidation. Catal Sci Technol 7(2):496–501. https://doi.org/10.1039/C6CY02489K
Luo Y, Lin D, Zheng Y, Feng X, Chen Q, Zhang K, Jiang L (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 504:144481. https://doi.org/10.1016/j.apsusc.2019.144481
Ma L, Seo CY, Nahata M, Chen X, Li J, Schwank JW (2018) Shape dependence and sulfate promotion of CeO2 for selective catalytic reduction of NOx with NH3. Appl Catal B: Environ 232:246–259. https://doi.org/10.1016/j.apcatb.2018.03.065
Mi R, Li D, Hu Z, Yang RT (2021) Morphology effects of CeO2 nanomaterials on the catalytic combustion of toluene: a combined kinetics and diffuse reflectance infrared Fourier transform spectroscopy study. ACS Catal 11(13):7876–7889. https://doi.org/10.1021/acscatal.1c01981
Murugan B, Ramaswamy AV, Srinivas D, Gopinath CS, Ramaswamy V (2005) Nature of manganese species in Ce1-xMnxO2-δ solid solutions synthesized by the solution combustion route. Chem Mater 17(15):3983–3993. https://doi.org/10.1021/cm050401j
Nischk M, Mazierski P, Gazda M, Zaleska A (2014) Ordered TiO2 nanotubes: the effect of preparation parameters on the photocatalytic activity in air purification process. Appl Catal B 144:674–685. https://doi.org/10.1016/j.apcatb.2013.07.041
Piumetti M, Fino D, Russo N (2015) Mesoporous manganese oxides prepared by solution combustion synthesis as catalysts for the total oxidation of VOCs. Appl Catal B 163:277–287. https://doi.org/10.1016/j.apcatb.2014.08.012
Rafeeq H, Afsheen N, Rafique S, Arshad A, Intisar M, Hussain A, Bilal M, Iqbal HMN (2023) Genetically engineered microorganisms for environmental remediation. Chemosphere 310:136751. https://doi.org/10.1016/j.chemosphere.2022.136751
Ren Q, Mo S, Peng R, Feng Z, Zhang M, Chen L, Ye D (2018) Controllable synthesis of 3D hierarchical Co3O4 nanocatalysts with various morphologies for the catalytic oxidation of toluene. J Mater Chem A 6(2):498–509. https://doi.org/10.1039/C7TA09149D
Ren S, Liang W, Li Q, Zhu Y (2020) Effect of Pd/Ce loading on the performance of Pd-Ce/γ-Al2O3 catalysts for toluene abatement. Chemosphere 251:126382. https://doi.org/10.1016/j.chemosphere.2020.126382
Ruan Y, Guo H, Li J, Liu Z, Jiang N, Wu Y (2020) Enhanced removal of toluene by pulse discharge plasma coupled with MgO cathode and graphene Mn-Ce bimetallic oxide. Chemosphere 258:127334. https://doi.org/10.1016/j.chemosphere.2020.127334
Si W, Wang Y, Peng Y, Li X, Li K, Li J (2015) A high-efficiency γ-MnO2-like catalyst in toluene combustion. Chem Commun 51(81):14977–14980. https://doi.org/10.1039/C5CC04528B
Sihaib Z, Puleo F, Garcia-Vargas JM, Retailleau L, Descorme C, Liotta LF, Giroir-Fendler A (2017) Manganese oxide-based catalysts for toluene oxidation. Appl Catal B 209:689–700. https://doi.org/10.1016/j.apcatb.2017.03.042
Suárez-Vázquez SI, Moreno-Román EJ, Zanella R, Cruz-López A, García-Goméz C, Nieto-Márquez A, Gil S (2022) Insight into the surface reaction mechanism of toluene oxidation over a composite CeOx/La1-xCexMnO3 catalyst using DRIFTS. Chem Eng Sci 259:117831. https://doi.org/10.1016/j.ces.2022.117831
Sun H, Yu X, Ma X, Yang X, Lin M, Ge M (2020) MnOx-CeO2 catalyst derived from metal-organic frameworks for toluene oxidation. Catal Today 355:580–586. https://doi.org/10.1016/j.cattod.2019.05.062
Tsumori N, Chen L, Wang Q, Zhu QL, Kitta M, Xu Q (2018) Quasi-MOF: exposing inorganic nodes to guest metal nanoparticles for drastically enhanced catalytic activity. Chem 4(4):845–856. https://doi.org/10.1016/j.chempr.2018.03.009
Wang Z, Shen G, Li J, Liu H, Wang Q, Chen Y (2013) Catalytic removal of benzene over CeO2-MnOx composite oxides prepared by hydrothermal method. Appl Catal B 138–139:253–259. https://doi.org/10.1016/j.apcatb.2013.02.030
Wang L, Wu Y, Feng N, Meng J, Wan H, Guan G (2016) Accelerated synthesis of MnO2 nanocomposites by acid-free hydrothermal route for catalytic soot combustion. RSC Adv 6(55):50288–50296. https://doi.org/10.1039/C6RA02045C
Wang X, Liu Y, Zhang T, Luo Y, Lan Z, Zhang K, Wang R (2017) Geometrical-site-dependent catalytic activity of ordered mesoporous co-based spinel for benzene oxidation: in situ DRIFTS study coupled with Raman and XAFS spectroscopy. ACS Catal 7(3):1626–1636. https://doi.org/10.1021/acscatal.6b03547
Wang C, Zou X, Liu H, Chen T, Suib SL, Chen D, Sun F (2019) A highly efficient catalyst of palygorskite-supported manganese oxide for formaldehyde oxidation at ambient and low temperature: performance mechanism and reaction kinetics. Appl Surf Sci 486:420–430. https://doi.org/10.1016/j.apsusc.2019.04.257
Wei X, Li K, Zhang X, Tong Q, Ji J, Cai Y, Dong L (2022) CeO2 nanosheets with anion-induced oxygen vacancies for promoting photocatalytic toluene mineralization: toluene adsorption and reactive oxygen species. Appl Catal B: Environ 317:121694. https://doi.org/10.1016/j.apcatb.2022.121694
Xiong S, Huang N, Peng Y, Chen J, Li J (2021) Balance of activation and ring-breaking for toluene oxidation over CuO-MnOx bimetallic oxides. J Hazard Mater 415:125637. https://doi.org/10.1016/j.jhazmat.2021.125637
Xu R, Wang X, Wang D, Zhou K, Li Y (2006) Surface structure effects in nanocrystal MnO2 and Ag/MnO2 catalytic oxidation of CO. J Catal 237(2):426–430. https://doi.org/10.1016/j.jcat.2005.10.026
Xu W, Wang N, Chen Y, Chen J, Xu X, Yu L, Ye D (2016) In situ FT-IR study and evaluation of toluene abatement in different plasma catalytic systems over metal oxides loaded γ-Al2O3. Catal Commun 84:61–66. https://doi.org/10.1016/j.catcom.2016.06.004
Yang Y, Huang J, Wang S, Deng S, Wang B, Yu G (2013) Catalytic removal of gaseous unintentional POPs on manganese oxide octahedral molecular sieves. Appl Catal B 142–143:568–578. https://doi.org/10.1016/j.apcatb.2013.05.048
Yang P, Fan S, Chen Z, Bao G, Zuo S, Qi C (2018) Synthesis of Nb2O5 based solid superacid materials for catalytic combustion of chlorinated VOCs. Appl Catal B 239:114–124. https://doi.org/10.1016/j.apcatb.2018.07.061
Ye Z, Giraudon JM, Nuns N, Simon P, De Geyter N, Morent RL, Amonier JF (2018) Influence of the preparation method on the activity of copper-manganese oxides for toluene total oxidation. Appl Catal B 223:154–166. https://doi.org/10.1016/j.apcatb.2017.06.072
You X, Sheng Z, Yu D, Yang L, Xiao X, Wang S (2017) Influence of Mn/Ce ratio on the physicochemical properties and catalytic performance of graphene supported MnOx-CeO2 oxides for NH3-SCR at low temperature. Appl Surf Sci 423:845–854. https://doi.org/10.1016/j.apsusc.2017.06.226
Zhang Z, Chen L, Li Z, Li P, Yuan F, Niu X, Zhu Y (2016) Activity and SO2 resistance of amorphous CeaTiOx catalysts for the selective catalytic reduction of NO with NH3: in situ DRIFT studies. Catal Sci Technol 6(19):7151–7162. https://doi.org/10.1039/C6CY00475J
Zhang X, Li H, Hou F, Yang Y, Dong H, Liu N, Cui L (2017) Synthesis of highly efficient Mn2O3 catalysts for CO oxidation derived from Mn-MIL-100. Appl Surf Sci 411:27–33. https://doi.org/10.1016/j.apsusc.2017.03.179
Zhang S, Guo Y, Li X, Li Z (2018) Effects of cerium doping position on physicochemical properties and catalytic performance in methanol total oxidation. J Rare Earths 36(8):811–818. https://doi.org/10.1016/j.jre.2018.01.012
Zhang X, Zhao J, Song Z, Liu W, Zhao H, Zhao M, Du H (2020) The catalytic oxidation performance of toluene over the Ce-Mn-Ox catalysts: effect of synthetic routes. J Colloid Interface Sci 562:170–181. https://doi.org/10.1016/j.jcis.2019.12.029
Zhang X, Bi F, Zhu Z, Yang Y, Zhao S, Chen J, Liu N (2021) The promoting effect of H2O on rod-like MnCeOx derived from MOFs for toluene oxidation: a combined experimental and theoretical investigation. Appl Catal B: Environ 297:120393. https://doi.org/10.1016/j.apcatb.2021.120393
Zhao L, Zhang Z, Li Y, Leng X, Zhang T, Yuan F, Zhu Y (2019) Synthesis of CeaMnOx hollow microsphere with hierarchical structure and its excellent catalytic performance for toluene combustion. Appl Catal B 245:502–512. https://doi.org/10.1016/j.apcatb.2019.01.005
Zheng Y, Wang W, Jiang D, Zhang L (2016) Amorphous MnOx modified Co3O4 for formaldehyde oxidation: improved low-temperature catalytic and photothermocatalytic activity. Chem Eng J 284:21–27. https://doi.org/10.1016/j.cej.2015.08.137
Funding
This work was supported by the National Natural Science Foundation of China (518708079) the National Key Research and Development Plan (2018YFB0605200) and China Postdoctoral Science Foundation (2020M682715).
Author information
Authors and Affiliations
Contributions
Zhi Li: conceptualization, methodology, validation, investigation, For-malanalysis, writing—original draft, writing—review and editing. Chunjing Su: methodology, validation, formal analysis. Yan Ying: data curation, resources. Mingli Fu: resources, writing—review and editing, visualization, supervision, project administration, funding acquisition.
Corresponding author
Ethics declarations
Ethical approval
This paper does not address ethical issues.
Consent to participate
All authors agree to participate as in this article.
Consent for publication
This paper’s publication has been approved by all authors.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: George Z. Kyzas
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Li, Z., Su, C., Yan, Y. et al. Synthesis of xCe–MnO2 with three-dimensional ultra-thin nanosheet structure and its excellent low-temperature reducibility for toluene catalysis. Environ Sci Pollut Res 30, 92238–92254 (2023). https://doi.org/10.1007/s11356-023-28715-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-023-28715-2