Two-dimensional manganese oxide on ceria for the catalytic partial oxidation of hydrocarbons

Abstract

Although the rational synthesis of catalysts with strong oxide-support interactions to modulate the geometric and electronic structures and achieve unusual catalytic performance is challenging in heterogeneous catalysis, it is in significant demand for the efficient and sustainable transformation of chemicals. Here, we report the synthesis and performance of a ceria-supported two-dimensional manganese oxide catalyst with strong metal oxide-support interactions, which help to produce well-dispersed and amorphous MnO_x layers on the CeO₂ matrix (MnO_x/CeO₂). This catalyst readily reacts with molecular oxygen to give a high capacity of active oxygen species, owing to the interfacial effect. The C-H bonds are adsorbed and activated by these active interfacial oxygen species, leading to high activities and selectivities in the industrially important C-H bond activation reactions, such as the oxidation of hydrocarbons to alcohols and ketones with molecular oxygen under solvent- and initiator-free conditions at mild temperature. The performance of the MnO_x/CeO₂ catalyst is greater than that of noble metal and highly efficient Mn-Ce solid-solution catalysts. More importantly, the catalyst is stable and exhibits constant reactivity in continuous recycling tests. These results are important for the design of highly efficient catalysts for the selective oxidation of hydrocarbons.

Keywords

Strong oxide-support interactions / C-H oxidation / MnO_x/CeO₂ catalyst / heterogeneous catalysis

References

[1] White MC.Chemistry. Adding aliphatic C-H bond oxidations to synthesis.Science2012;335:807-9

[2] ten Brink GJ,Sheldon RA.Green, catalytic oxidation of alcohols in water.Science2000;287:1636-9

[3] Marimuthu A,Linic S.Tuning selectivity in propylene epoxidation by plasmon mediated photo-switching of Cu oxidation state.Science2013;339:1590-3

[4] Liu W,Liu X.Discriminating catalytically active FeN_x species of atomically dispersed Fe-N-C catalyst for selective oxidation of the C-H bond.J Am Chem Soc2017;139:10790-8

[5] Kulangiappar K,Raju T.Conversion of benzylic bromides to benzaldehydes using sodium nitrate as an oxidant.Ind Eng Chem Res2010;49:6670-3

[6] Frei H.Chemistry. Selective hydrocarbon oxidation in zeolites.Science2006;313:309-10

[7] Hughes MD,Jenkins P.Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions.Nature2005;437:1132-5

[8] Pradhan S,Bethell D.Non-lattice surface oxygen species implicated in the catalytic partial oxidation of decane to oxygenated aromatics.Nat Chem2012;4:134-9

[9] Yuan C,Hernandez T,Houk KN.Metal-free oxidation of aromatic carbon-hydrogen bonds through a reverse-rebound mechanism.Nature2013;499:192-6

[10] Zope BN,Neurock M.Reactivity of the gold/water interface during selective oxidation catalysis.Science2010;330:74-8

[11] Fu Q,Yao Y.Interface-confined ferrous centers for catalytic oxidation.Science2010;328:1141-4

[12] Wang L,Wang JQ.Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds.Nat Commun2015;6:6957 PMCID:PMC4421807

[13] Liu Y,Akita T,Tsukuda T.Aerobic oxidation of cyclohexane catalyzed by size-controlled Au clusters on hydroxyapatite: size effect in the sub-2 nm regime.ACS Catal2011;1:2-6

[14] Turner M,Vaughan OP.Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters.Nature2008;454:981-3

[15] Neufeldt SR.Controlling site selectivity in palladium-catalyzed C-H bond functionalization.Acc Chem Res2012;45:936-46 PMCID:PMC3378812

[16] Muzart J.Ionic liquids as solvents for catalyzed oxidations of organic compounds.Adv Synth Catal2006;348:275-95

[17] Qi G,Chang R.MnO_x-CeO₂ mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH₃ at low temperatures.Appl Catal B2004;51:93-106

[18] Zhang P,Zhou Y.Mesoporous MnCeO_x solid solutions for low temperature and selective oxidation of hydrocarbons.Nat Commun2015;6:8446 PMCID:PMC4633985

[19] Venkataswamy P,Jampaiah D.Nanostructured manganese doped ceria solid solutions for CO oxidation at lower temperatures.Appl Catal B2015;162:122-32

[20] Zou Z,Zha Y.Surfactant-assisted synthesis, characterizations, and catalytic oxidation mechanisms of the mesoporous MnO_x-CeO₂ and Pd/MnO_x-CeO₂ catalysts used for CO and C₃H₈ oxidation.J Phys Chem C2010;114:468-77

[21] Elias JS,Giordano L,Shao-Horn Y.Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO₂ nanoparticles.J Am Chem Soc2014;136:17193-200

[22] Wang C,Lauterbach J.Superior oxygen transfer ability of Pd/MnO_x-CeO₂ for enhanced low temperature CO oxidation activity.Appl Catal B2017;206:1-8

[23] Zhang X,Tian P,Xu J.Dynamic active sites over binary oxide catalysts: In situ/operando spectroscopic study of low-temperature CO oxidation over MnO_x-CeO₂ catalysts.Appl Catal B2016;191:179-91

[24] Delimaris D.VOC oxidation over MnO_x-CeO₂ catalysts prepared by a combustion method.Appl Catal B2008;84:303-12

[25] Cen W,Wu Z,Weng X.A theoretic insight into the catalytic activity promotion of CeO₂ surfaces by Mn doping.Phys Chem Chem Phys2012;14:5769-77

[26] Wang Z,Li J,Wang Q.Catalytic removal of benzene over CeO₂-MnO_x composite oxides prepared by hydrothermal method.Appl Catal B2013;138-139:253-9

[27] Tang X,Huang X,Shen W.Pt/MnO_x-CeO₂ catalysts for the complete oxidation of formaldehyde at ambient temperature.Appl Catal B2008;81:115-21

[28] Quiroz J,Gervasini A.Total oxidation of formaldehyde over MnO_x-CeO₂ catalysts: the effect of acid treatment.ACS Catal2015;5:2260-9

[29] Li X,Pfeifer V.Selective alkane oxidation by manganese oxide: site isolation of MnO_x chains at the surface of MnWO₄ nanorods.Angew Chem Int Ed Engl2016;55:4092-6

[30] Lin X,He H.Evolution of oxygen vacancies in MnO_x-CeO₂ mixed oxides for soot oxidation.Appl Catal B2018;223:91-102

[31] Xu J,Song X,Yu J.Operando raman spectroscopy for determining the active phase in one-dimensional Mn_1-xCe_xO_2±y nanorod catalysts during methane combustion.J Phys Chem Lett2010;1:1648-54

[32] Figaj M.An electron paramagnetic resonance study of impurities in ceria, CeO₂.Solid State Ionics2001;141-142:507-12

[33] Yang X,Qin H,Xu Z.Temperature- and Mn²⁺ concentration-dependent emission properties of Mn²⁺-doped ZnSe nanocrystals.J Am Chem Soc2019;141:2288-98

[34] Kurz T,Brieler FJ.Minimal number of atoms to constitute a magnet: Suppression of magnetic order in spherical MnS nanoparticles.Phys Rev B2008;78:132408

[35] Goede O,Heimbrodt W.EPR study of the antiferromagnetic phase transition in (Cd, Mn)S.phys stat sol (b)1989;151:311-8

[36] Sato T.Selective oxidation of alcohols with molecular oxygen catalyzed by Ru/MnO/CeO₂ under mild conditions.Catalysis Communications2009;10:1095-8

[37] Xie X,Liu ZQ,Shen W.Low-temperature oxidation of CO catalysed by Co(3)O(4) nanorods.Nature2009;458:746-9

[38] Chen G,Fu G.Interfacial effects in iron-nickel hydroxide-platinum nanoparticles enhance catalytic oxidation.Science2014;344:495-9

[39] Gu D,Weidenthaler C.Gold on different manganese oxides: ultra-low-temperature CO oxidation over colloidal gold supported on bulk-MnO₂ nanomaterials.J Am Chem Soc2016;138:9572-80

[40] Yu WZ,Li SQ.Construction of active site in a sintered copper-ceria nanorod catalyst.J Am Chem Soc2019;141:17548-57