Investigation of Mn-doping effects on the structural, morphological, thermal, and catalytic properties of Co ₃O ₄ spinel nanoparticle catalysts for CO oxidation

Abstract

This study reports the synthesis of three sets of high-performance manganese (Mn)-doped Co₃O₄ porous nanocrystals (PNCs) (5%Mn@Co₃O₄, 10%Mn@Co₃O₄, and 15%Mn@Co₃O₄) using a simple chemical co-precipitation method. These catalysts were then used for the catalytic oxidation of carbon monoxide (CO). This investigation focused on the effects of Co²⁺ or Co³⁺ substitution by Mn²⁺ or Mn³⁺ within the Co₃O₄ matrix on various properties of the PNCs, including their physicochemical characteristics, morphology, microstructure, reducibility, thermal stability, and their impact on the catalytic performance. Comprehensive characterization using techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) analysis, X-ray photoelectron spectroscopy (XPS), Hydrogen-Temperature Programmed Reduction and (H₂-TPR), was employed to elucidate the factors responsible for effective CO oxidation. Compared to pure Mn₃O₄ and Co₃O₄, the Mn@Co₃O₄ PNCs catalysts exhibited a more controllable microstructure and better dispersion of the active phase. The 5%Mn@Co₃O₄ catalyst demonstrated the highest activity, achieving 90% CO oxidation at 197 °C. This superior performance is attributed to its large specific surface area, excellent reduction capacity, and abundant oxygen species and vacancies. H₂-TPR and XPS analyses provided further insights into the reaction mechanism. Density functional theory calculations showed that the formation of bulk oxygen vacancies is more favorable when Mn³⁺ is substituted at the Co²⁺ sites. Overall, the chemical coprecipitation method offers a straightforward and cost-effective approach for producing Mn@Co₃O₄ catalysts suitable for CO abatement in exhaust and flue gases.

Keywords

Co-precipitation / Mn-doped Co ₃O ₄ / CO gas / Catalytic activity / Lattice thermal stability / Density functional theory

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

CRediT authorship contribution statement

Daniel Manhouli Daawe: Writing – original draft, Visualization, Methodology, Investigation, Formal analysis, Data curation. Cedric Karel Fonzeu Monguen: Visualization, Methodology, Investigation, Data curation. Stephane Kenmoe: Writing – review & editing, Writing – original draft, Visualization, Validation, Supervision, Software, Resources, Project administration, Methodology, Investigation, Conceptualization. Patrick Mountapmbeme Kouotou: Writing – review & editing, Writing – original draft, Visualization, Validation, Supervision, Software, Resources, Project administration, Methodology, Investigation, Conceptualization.

Acknowledgements

S.K. acknowledges the computing time granted by the Center for Computational Sciences and Simulation (CCSS) at Universität Duisburg-Essen and provided the supercomputer magnitude (DFG grants INST 20876/209-1 FUGG and INST 20876/243-1 FUGG) at the Zentrum fur Informations- und Mediendienste (ZIM). C.K.F.M gratefully thanks Prof. Dr. Olaf Deutschmann (Chair of the Chemical Technology at Karlsruhe Institute of Technology) for fruitful discussions.

References

[1] C. Feng, X. Liu, T. Zhu, M. Tian, Catalytic oxidation of CO on noble metal-based catalysts, Environ. Sci. Pollut. Res. 28 (2021) 24847-24871.

[2] J.P.N. Kembo, J. Wang, N. Luo, F. Gao, H. Yi, S. Zhao, Y. Zhou, X. Tang, A review of catalytic oxidation of carbon monoxide over different catalysts emphasis on hopcalite catalysts, New J. Chem. 47 (2023) 20222-20247.

[3] X. Wu, J. Lang, Z. Sun, F. Jin, Y.H. Hu, Photocatalytic conversion of carbon monoxide: From pollutant removal to fuel production, Appl. Catal. B-Environ. 295 (2021) 120312.

[4] J. Zhang, M. Shu, Y. Niu, L. Yi, H. Yi, Y. Zhou, S. Zhao, X. Tang, F. Gao, Advances in CO catalytic oxidation on typical noble metal catalysts: Mechanism, performance and optimization, Chem. Eng. J. 495 (2024) 153523.

[5] J.P.N. Kembo, J. Wang, N. Luo, F. Gao, H. Yi, S. Zhao, Y. Zhou, X. Tang, A review of catalytic oxidation of carbon monoxide over different catalysts with an emphasis on hopcalite catalysts, New J. Chem. 47 (2023) 20222-20247.

[6] K. Yuan, Y. Guo, L. Huang, L. Zhou, H.J. Yin, H. Liu, C.H. Yan, Y.W. Zhang, Tunable electronic metal-support interactions on ceria-supported noble-metal nanocatalysts in controlling the low-temperature CO oxidation activity, Inorg. Chem. 60 (2021) 4207-4217.

[7] S. Royer, D. Duprez, Catalytic oxidation of carbon monoxide over transition metal oxides, ChemCatChem 3 (2011) 24-65.

[8] O.A. Bulavchenko, T.N. Afonasenko, S.S. Sigaeva, A.V. Ivanchikova, A.A. Saraev, E. Yu. Gerasimov, V.V. Kaichev, S.V. Tsybulya, The structure of mixed Mn-Co oxide catalysts for CO oxidation, Top. Catal. 63 (2020) 75-85.

[9] P.M. Kouotou, G.F. Pan, J.J. Weng, S.B. Fan, Z.Y. Tian, Stainless steel grid mesh-supported CVD made Co₃O₄ thin films for catalytic oxidation of VOCs of olefins type at low temperature , J. Indust. Eng. Chem. 35 (2016) 253-261.

[10] V. Baldim, N. Yadav, N. Bia, A. Graillot, C. Loubat, S. Singh, A.S. Karakoti, J.F. Berret, Polymer-coated cerium oxide nanoparticles as oxidoreductase-like catalysts, ACS Appl. Mater. Interfaces 12 (2020) 42056-42066.

[11] H.T. Assaouka, D.M. Daawe, R.L. Fomekong, I.N. Nsangou, P.M. Kouotou, Z.Y. Tian, Inexpensive and easily replicable precipitation of CuO nanoparticles for low temperature carbon monoxide and toluene catalytic oxidation, Heliyon 8 (2022) e10689.

[12] C.K. Fonzeu Monguen, A. El Kasmi, M.F. Arshad, P.M. Kouotou, S. Daniel, Z.Y. Tian, Oxidative dehydrogenation of propane into propene over chromium oxides, Indust. Eng. Chem. Res. 61 (2022) 4546-4560.

[13] P.N. Ndouka, S. Kenmoe, J.R. Mache, E. Acayanka, D.H. Douma, R. Gebauer, P.M. Kouotou, Low-temperature catalytic methane deep oxidation over sol-gel derived mesoporous hausmannite (Mn₃O₄) spherical particles , ChemPhysMater 3 (2024) 329-240.

[14] P. Wang, L. Wang, Y. Zhao, D. Wang, Progress in degradation of volatile organic compounds by catalytic oxidation: A review based on the kinds of active components of catalysts, Water Air Soil Pollut 235 (2024) 7.

[15] F. Liu, H. He, Cobalt oxide-based catalysts for catalytic oxidation of volatile organic compounds, Chem. Soc. Rev. 45 (2016) 6089-6120.

[16] H. Xu, N. Yan, Z. Qu, W. Liu, J. Mei, W. Huang, S. Zhao, Gaseous heterogeneous catalytic reactions over Mn-based oxides for environmental applications: A critical review, Environ. Sci. Technol. 51 (2017) 8879-8892.

[17] Z.Y. Tian, P.M. Kouotou, N. Bahlawane, P.H.T. Ngamou, Synthesis of the catalytically active Mn₃O₄ spinel and its thermal properties , J. Phys. Chem. C 117 (2013) 6218-6224.

[18] Z.Y. Tian, P.H.T. Ngamou, V. Vannier, K. Kohse-Höinghaus, N. Bahlawane, Catalytic oxidation of VOCs over mixed Co-Mn oxides, Appl. Catal. B 117-118 (2012) 125-134.

[19] M.H. Castaño, R. Molina, S. Moreno, Cooperative effect of the Co-Mn mixed oxides for the catalytic oxidation of VOCs: Influence of the synthesis method, Appl. Catal. A 492 (2015) 48-59.

[20] H. Zhao, H. Wang, Z. Qu, Synergistic effects in Mn-Co mixed oxide supported on cordierite honeycomb for catalytic deep oxidation of VOCs, J. Environ. Sci. 112 (2022) 231-243.

[21] D. Neagu, G. Tsekouras, D.N. Miller, H. Ménard, J.T. Irvine, In situ growth of nanoparticles through control of non-stoichiometry, Nat. Chem. 5 (2013) 916-923.

[22] F. Zhang, L. Jin, H. Li, K. Xie, Coordinatively unsaturated metal-nitrogen active sites at twisted surfaces in metallic porous nitride single crystals delivering enhanced electrocatalysis activity, Chem. Eur. J. 26 (2020) 2327-2332.

[23] J.C. Groen, L.A.A. Peffer, J.P. Ramirez, Pore size determination in modified micro-and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis, Microporous Mesoporous Mater 60 (2003) 1-17.

[24] Y. Gong, Z. Xu, H. Pan, Y. Lin, Z. Yang, X. Du, Hierarchical Ni₃S₂ nanosheets coated on Co₃O₄ nanoneedle arrays on 3D nickel foam as an efficient electrocatalyst for the oxygen evolution reaction , J. Mater. Chem. A 6 (2018) 5098-5106.

[25] Z. Li, B. Tang, Mn₃O₄/nitrogen-doped porous carbon fiber hybrids involving multiple covalent interactions and open voids as flexible anodes for lithium-ion batteries , Green Chem 19 (2017) 5862-5873.

[26] S.M. Lang, T.M. Bernhardt, J.M. Bakker, R.N. Barnett, U. Landman, Cluster size dependent coordination of formate to free manganese oxide clusters, Phys. Chem. Chem. Phys. 25 (2023) 32166-32172.

[27] G.F.S. Fernandes, F.B.C. Machado, L.F.A Ferrão, Electronic structure of small isolated and supported manganese oxide clusters, J. Phys. Chem. A 127 (2023) 8773-8781.

[28] R. Medhi, M.D. Marquez, T.R. Lee, Visible-light-active doped metal oxide nanoparticles: Review of their synthesis, properties, and applications, ACS Appl. Nano Mater. 3 (2020) 6156-6185.

[29] C. Siriwong, N. Wetchakun, B. Inceesungvorn, D. Channei, T. Samerjai, S. Phanichphant, Doped-metal oxide nanoparticles for use as photocatalysts, Prog. Cryst. Growth Charact. Mater. 58 (2012) 145-163.

[30] P. Wang, J. Wang, X. An, J. Shi, W. Shangguan, X. Hao, G. Xu, B. Tang, A. Abudula, G. Guan, Generation of abundant defects in Mn-Co mixed oxides by a facile agar-gel method for highly efficient catalysis of total toluene oxidation, Appl. Catal. B 282 (2021) 119560.

[31] N. Huang, Z. Qu, C. Dong, Y. Qin, X. Duan, Superior performance of α@ β-MnO₂ for the toluene oxidation: Active interface and oxygen vacancy , Appl. Catal. A 560 (2018) 195-205.

[32] W.N.A.W. Mokhtar, W.A.W.A. Bakar, R. Ali, A. Kadir, Development of bimetallic and trimetallic oxides doped on molybdenum oxide based material on oxidative desulfurization of diesel, Arab. J. Chem. 11 (2018) 1201-1208.

[33] C. Xie, L. Li, X. Zhai, W. Chu, Improved redox synthesis of Mn-Co bimetallic oxide catalysts using citric acid and their toluene oxidation activity, RSC Adv. 13 (2023) 11069-11080.

[34] B.J. Tan, K.J. Klabunde, P.M.A. Sherwood, XPS studies of solvated metal atom dispersed (SMAD) catalysts. Evidence for layered cobalt-manganese particles on alumina and silica, J. Am. Chem. Soc. 113 (1991) 855-861.

[35] J. Li, S. Xiong, X. Li, Y. Qian, A facile route to synthesize multi-porous MnCo₂O₄ and CoMn₂O₄ spinel quasi-hollow spheres with improved lithium storage properties , Nanoscale 5 (2013) 2045-2054.

[36] S. Mo, Q: Zhang, Y. Sun, M. Zhang, J. Li, Q. Ren, M. Fu, J. Wu, L. Chen, D. Ye, Gaseous CO and toluene co-oxidation over monolithic core-shell Co₃O₄-based hetero-structured catalysts , J. Mater. Chem. A 7 (2019) 16197-16210.

[37] M. Qiu, S. Zhan, H. Yu, D. Zhu, S. Wang, Facile preparation of ordered mesoporous MnCo₂O₄ for low-temperature selective catalytic reduction of NO with NH₃ , Nanoscale 7 (2015) 2568-2577.

[38] L. Zhang, D. Zhang, J. Zhang, S. Cai, C. Fang, L. Huang, H. Li, R. Gao, L. Shi, Design of meso-TiO₂@MnO x-CeO x/CNTs with a core-shell structure as DeNO x catalysts: Promotion of activity, stability and SO₂-tolerance , Nanoscale 5 (2013) 9821-9829.

[39] Y. Wan, W. Zhao, Y. Tang, L. Li, H. Wang, Y. Cui, J. Gu, J.Shi Y.Li, Ni-Mn bi-metal oxide catalysts for the low temperature SCR removal of NO with NH₃ , Appl. Catal. B 148-149 (2014) 114-122.

[40] A.A. Zigla, T. Kox, D. Mevoa, T.H. Assaouka, N.I. Nsangou, M.D. Dawe, S. Kenmoe, P.M. Kouotou, Magnesium-modified Co₃O₄ catalyst with remarkable performance for toluene low temperature deep oxidation , Catalysts 12 (2022) 411.

[41] E.R. Stobbe, B.A. De Boer, J.W. Geus, The reduction and oxidation behavior of manganese oxides, Catal. Today 47 (1999) 161-167.

[42] S. Mo, Q. Zhang, Y. Sun, M. Zhang, J. Li, Q. Ren, M. Fu, J. Wu, L. Chen, D. Ye, Gaseous CO and toluene co-oxidation over monolithic core-shell Co₃O₄-based hetero-structured catalysts , J. Mater. Chem. A 7 (2019) 16197-16210.

[43] W. Yang, Z.A. Su, Z. Xu, W. Yang, Y. Peng, J. Li, Comparative study of α-, β-, γ-and δ-MnO₂ on toluene oxidation: Oxygen vacancies and reaction intermediates , Appl. Catal. B 260 (2020) 118150.

[44] W. Tang, X. Wu, S. Li, X. Shan, G. Liu, Y. Chen, Co-nanocasting synthesis of mesoporous Cu-Mn composite oxides and their promoted catalytic activities for gaseous benzene removal, Appl. Catal. B 162 (2015) 110-121.

[45] S. Mo, S. Li, J. Li, S. Peng, J. Chen, Y. Chen, Promotional effects of Ce on the activity of MnAl oxide catalysts derived from hydrotalcites for low temperature benzene oxidation, Catal. Commun. 87 (2016) 102-105.

[46] W. Si, Y. Wang, S. Zhao, F. Hu, J. Li, A facile method for in situ preparation of the MnO₂/LaMnO₃ catalyst for the removal of toluene , Environ. Sci. Technol. 50 (2016) 4572-4578.

[47] M. Dreyer, A. Rabe, E. Budiyanto, K.F. Ortega, S. Najafishirtari, H. Tüysüz, M. Behrens, Dynamics of reactive oxygen species on cobalt-containing spinel oxides in cyclic CO oxidation, Catalysts 11 (2021) 1312.

[48] N.J. Divins, E. López, I. Angurell, S. Neuberg, R. Zapf, G. Kolb, J. Llorca, CO total and preferential oxidation over stable Au/TiO₂ catalysts derived from preformed Au nanoparticles , Catalysts 10 (2020) 1028.

[49] S. Ponce, M.A. Peña, J.L.G. Fierro, Surface properties and catalytic performance in methane combustion of Sr-substituted lanthanum manganites, Appl. Catal. B 24 (2000) 193-205.

[50] J. Hou, Y. Li, L. Liu, L. Ren, X. Zhao, Effect of giant oxygen vacancy defects on the catalytic oxidation of OMS-2 nanorods, J. Mater. Chem. A 1 (2013) 6736-6741.

[51] O.A. Bulavchenko, E.Y. Gerasimov, T.N. Afonasenko, Reduction of double manganese-cobalt oxides: In situ XRD and TPR study, Dalton Trans. 47 (2018) 17153.

[52] N. Bahlawane, P.A. Premkumar, J. Feldmann, K. Kohse-Höinghaus, Preparation of doped spinel cobalt oxide thin films and evaluation of their thermal stability, Chem. Vap. Deposition 12 (2007) 118-122.

[53] N. Bahlawane, P.H. Tchoua Ngamou, V. Vannier, T. Kottke, J. Heberle, K.Kohse Höinghaus, Tailoring the properties and the reactivity of the spinel cobalt oxide, Phys. Chem. Chem. Phys. 11 (2009) 9224-9232.

[54] P.M. Kouotou, Z.Y. Tian, In-situ fourier transform infrared spectroscopy diagnostic for characterization and performance test of catalysts, Chin. J. Chem. Phys. 30 (2017) 513-520.

[55] Y.T. Jang, H.F. Wang, Y.M. Chiang, Room-temperature synthesis of monodisperse mixed spinel (Co_xMn_1-x)₃O₄ powder by a coprecipitation method , J. Mater. Chem. 8 (1998) 2761-2764.

[56] Q.H. Zhang, X.H. Liu, W.Q. Fan, Y. Wang, Manganese-promoted cobalt oxide as efficient and stable non-noble metal catalyst for preferential oxidation of CO in H₂ stream , Appl. Catal. B 102 (2011) 207-214.

[57] Z.Y. Tian, P.H.T. Ngamou, V. Vannier, K. Kohse-Höinghaus, N. Bahlawane, Catalytic oxidation of VOCs over mixed Co-Mn oxides, Appl. Catal. B: Environ. 117 (2012) 125-134.

[58] D.G. Klissurski, E.L. Uzunova, Cation-deficient nano-dimensional particle size cobalt-manganese spinel mixed oxides, Appl. Surf. Sci. 214 (2003) 370-374.

[59] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77 (1996) 3865-3868.

[60] P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G.L. Chiarotti, M. Cococcioni, I. Dabo, A. Dal Corso, S. de Gironcoli, S. Fabris, F. Guido, R. Gebauer, U. Gerstmann, C. Gougoussis, K. Anton, M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S. Scandolo, G. Sclauzero, A.P. Seitsonen, S. Alexander, P. Umari, R.M. Wentzcovitch, Quantum espresso: A modular and open-source software project for quantum simulations of materials, J. Phys.: Condens. Matter. 21 (2009) 395502.

[61] S. Kenmoe, D.H. Douma, A.T. Raji, B. M’Passi-Mabiala, T. Götsch, F. Girgsdies, A. Knop-Gericke, R. Schlögl, E. Spohr, X-ray absorption near-edge structure (XANES) at the O K-edge of bulk Co₃O₄: Experimental and theoretical studies , Nanomaterials 12 (2022) 921.

[62] D.H. Douma, K. Nchimi Nono, A.H. Omranpoor, A. Lamperti, A. Debernardi, S. Kenmoe, Probing the local environment of active sites during 2-propanol oxidation to acetone on the Co₃O₄(001) surface: Insights from first-principles O K-edge XANES spectroscopy , J. Phys. Chem. C 127 (2023) 5351-5357.

[63] D. Vanderbilt, Soft self-consistent pseudopotentials in a generalized eigenvalue formalism, Phys. Rev. B 41 (1990) 7892-7895.