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Article
Revealing the Highly Catalytic Performance of Spinel CoMn2O4
for Toluene Oxidation: Involvement and Replenishment
of Oxygen Species Using in situ Designed-TP Techniques
Cui Dong, Zhenping Qu, Yuan Qin, Qiang Fu, Hongchun Sun, and Xiaoxiao Duan
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b01324 • Publication Date (Web): 17 Jun 2019
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Page 1 of 41 ACS Catalysis

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Revealing the Highly Catalytic Performance of Spinel CoMn2O4 for
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6 Toluene Oxidation: Involvement and Replenishment of Oxygen
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9 Species Using in situ Designed-TP Techniques
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Cui Donga, Zhenping Qua*, Yuan Qina, Qiang Fub, Hongchun Suna, Xiaoxiao Duana
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13 a Key
14 Laboratory of Industrial Ecology and Environmental Engineering, School of
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16 Environmental Science and Technology, Dalian University of Technology, Dalian 116024,
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18 People’s Republic of China
19 b State
20 Key Lab of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of
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22 Sciences, Dalian 116023, People’s Republic of China
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26 ABSTRACT: The catalytic oxidation of toluene to CO2 and H2O over nanoflower
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spinel CoMn2O4 synthesized by oxalic acid sol-gel method has been investigated. And
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31 it demonstrates the lower activation energy (35.5 kJ/mol) for toluene oxidation
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33 compared with the metal oxides (Co3O4, MnOx and Co3O4/MnOx), which shows nearly
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35 100% conversion of toluene at 220oC in the presence or absence of water vapor (2.0
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38 vol. %). Compared with metal oxides (Co3O4/MnOx, MnOx and Co3O4), the obtained
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40 spinel CoMn2O4 has a larger surface area, rich cationic vacancy and high mobility of
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42 oxygen species, which should be the reason for its high activity for toluene oxidation.
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The different oxygen species shows the different role in VOCs oxidation, and the in
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47 situ designed-TP techniques are conducted to investigate the involvement of surface
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49 lattice oxygen, bulk lattice oxygen and gaseous oxygen in catalytic oxidation of toluene
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over spinel CoMn2O4 and Co3O4/MnOx catalysts. For spinel CoMn2O4, the surface
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54 lattice oxygen is the reactive oxygen species, which first induces the catalytic reaction.
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56 And the gaseous oxygen moves to the bulk phase lattice and then migrates to surface to
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58 form the surface lattice oxygen, which is different from the mixed metal oxides
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3 Co3O4/MnOx that dissociates and activates gaseous oxygen only on the surface of the
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6 catalyst and requires a higher temperature. In addition, it is found that the toluene
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8 oxidation occurs via benzyl alcohol-benzoate-anhydride-acetate reaction pathway over
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10 spinel CoMn2O4, and the conversion of the surface anhydride is the rate-controlled step,
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especially at 200-210oC, which is also different from the mixed metal oxides
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15 Co3O4/MnOx. These results could provide a considerable experimental basis for
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17 understanding the mechanism by which oxygen species participate in toluene oxidation.
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Keywords: toluene oxidation, spinel CoMn2O4, oxygen species, in situ designed-TP
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22 techniques, in situ DRIFTS
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26 1. Introduction
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29 Driven by the deteriorating environmental pollution, especially the emission of
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31 volatile organic compounds (VOCs) from various sources, the abatement technologies
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33 are urged for maintaining a clean air atmosphere. The catalytic oxidation as one of the
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most effective approach and strategy attracts a great deal of attention.1-5 Transition
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38 metal oxides as promising alternative catalysts are known due to their low cost and
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40 promising activity. In addition, researchers have found that the spinel-type catalyst
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enjoys high stability compared to mixed metal oxides and perovskites in the catalytic
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45 oxidation.6, 7 Spinel (AB2O4), metals A and B are in tetrahedral and octahedral positions,
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47 and the adjacent cations (A and B) can optimize the catalytic activity via electron
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49 exchange.8-11 To obtain the excellent catalytic performance, a larger surface area and
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52 abundant defects are required in the spinel. Chen et al.12 found that spinel CoxMn3-xO4
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54 with larger surface area exhibited a considerable activity towards the oxygen
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56 reduction/evolution reactions (ORR/OER) at room temperature. Zou et al.13 constructed
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the metal defects (manganese/cobalt vacancy) by defect engineering to increase the
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3 active site for oxygen reduction reaction (ORR). Attempts have been made to apply
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6 spinel-type catalysts into the oxidation of VOCs. Finocchio et al.14 reported that the
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8 surface site Crn+ on MgCr2O4 could weaken C-H bond by hydrogen abstraction of
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10 hydrocarbons and form C-O bond (alkoxy groups). Spinel CoMn2O4 prepared by sol-
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gel method can achieved 80% toluene conversion at 320oC,15 which is lower than that
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15 of other Mn-based metal oxides (T100=210-230oC).2, 16 Also, compared with single
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17 metal oxides and mixed metal oxides, spinel is less explored in toluene oxidation and
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its reaction mechanism is still unclear.
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22 Despite the catalytic mechanism of VOCs oxidation over spinel sample is still
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24 ambiguous, the Mars-van Krevelen mechanism involving the reduction and oxidation
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26 of the catalytically active species has been proposed.17, 18 The reactant molecules
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29 (VOCs) can be oxidized by the lattice oxygen of the catalyst, which is then re-oxidized
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31 by gaseous oxygen.19 The oxygen species of the catalyst have been considered to play
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33 a key role in their activity and have been extensively studied. Chen et al.20 reported that
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the surface adsorbed species (by X-ray photoelectron spectroscopy) were reactive
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38 oxygen in the oxidation of VOCs (ethanol, toluene, acetone and acetic ether) on spinel
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40 NiCo2O4. The high concentration of surface adsorbed oxygen species on the active
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interface of Co3O4-MnCo2O4.5 shows superior catalytic activity in toluene oxidation (by
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45 hydrogen-temperature programmed reduction, O2-temperature programmed desorption
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47 and X-ray photoelectron spectroscopy).21 Jiang et al.17 had correlated the content of
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49 surface adsorbed oxygen species (by X-ray photoelectron spectroscopy) to the benzene
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52 oxidation activity of the spinel MnCo2O4. In addition, Giraudon et al.22 conducted the
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54 catalytic experiments in the absence of gaseous oxygen and found that the surface (sub-
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56 surface lattice oxygen) and lattice oxygen of spinel CuMn2O4 can participate in the
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toluene oxidation (by Gas Chromatography). Wang et al. and co-workers23 proposed
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3 that the accessibility of lattice oxygen (by thermal gravimetric analysis) should be the
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6 main determinant factor of the activity on octahedral molecular sieve (OMS-2) catalyst
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8 toward VOCs (ethanol and acetaldehyde) oxidation, instead of the content of lattice
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10 oxygen. All these researches have noticed that oxygen species in spinel can
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significantly affect the catalytic oxidation activity, but how these oxygen species
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15 participate in the reaction and the subsequent re-oxidation step of the catalyst has not
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17 been elucidated and remains unknown.
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The precipitants used to synthesize spinel are widely variety (such as NaOH, KOH,
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22 Na2CO3, NH3, H2C2O4, Na2HCO3, (NH4)2CO3 and NH4HCO3),24 and the
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24 physicochemical properties (Surface area and particle size) of the spinel will be
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26 different when we choose the different precipitant.25 In addition, oxalic acid precipitants
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29 can make the oxide form porous structure during the synthesis, which is beneficial to
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31 the distribution of manganese oxidation states and the formation of rich lattice oxygen.
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33 26 Thus in this work, the spinel CoMn2O4 catalyst with large specific surface area and
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abundant cationic defect is successful synthesized by oxalic acid sol-gel method to
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38 exclusively study the activity for toluene catalytic oxidation. In addition, we evaluate
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40 the oxidation of toluene on spinel sample from another perspective, where the pathway
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of the re-oxidation from gaseous oxygen and how the oxygen species participate in the
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45 reaction are measured by the in situ designed-TP techniques. The mixed metal oxides
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47 Co3O4/MnOx is also used for comparison to further assist in elucidating the mechanism
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49 of re-oxidation and circulation of oxygen species for toluene oxidation in spinel sample.
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52 Moreover, the surface intermediates species over spinel CoMn2O4 during toluene
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54 oxidation are also investigated via in situ DFIFTS. Spinel CoMn2O4 is more easily re-
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56 oxidized to generate a large amount of bulk phase lattice oxygen species which then
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migrate to the surface to form surface lattice oxygen. In addition, the spinel shows a
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3 high ability to destroy the aromatic ring, particularly for the breakage of benzoate to
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6 generate an anhydride species, thereby resulting in the high catalytic activity for toluene
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8 oxidation at low temperatures.
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2. Experimental Section
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15 2.1 Catalysts Preparation
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17 Synthesis of spinel CoMn2O4. Manganous acetate (0.02 mol) and cobalt acetate
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(0.01 mol) were added to 10 mL of ethanol under magnetic stirring at 80oC to form a
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22 solution. Another oxalic acid solution (0.24 mol/L) was added quickly to above solution.
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24 It was then stirred at 80oC for 0.5 hours and the resulting precipitate was centrifuged
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26 and washed 3 times with deionized water and once with alcohol. The precipitate was
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29 dried at 80oC for 12 hours and was calcined from room temperature to 400oC in air for
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31 3 hours.
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33 Synthesis of mixed metal oxides Co3O4/MnOx. The mixed metal oxide was
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prepared by impregnation of the MnOx support using solution of Co(NO3)2 with Mn/Co
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38 molar ratio of 2:1. Following impregnation, the sample was dried at room temperature
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40 for 24 hours, and then it was dried at 80oC for another 12 hours. The as-prepared sample
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was calcined from room temperature to 400oC in air for 3 hours.
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45 Synthesis of unitary MnOx and Co3O4. 0.03 mol of manganous acetate or
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47 cobalt acetate was added to 10 mL of ethanol under magnetic stirring at 80oC, then
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49 oxalic acid solution (0.24 mol/L) was added quickly to above solution. It was then
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52 stirred at 80oC for 0.5 hours and the resulting precipitate was centrifuged and washed 3
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54 times with deionized water and once with alcohol. The precipitate was dried at 80oC
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56 for 12 hours and was calcined from room temperature to 400oC in air for 3 hours.
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2.2 Catalyst Characterization
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3 The nitrogen physisorption measurements of samples were conducted on
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6 Quantachrome NOVA 4200e by Brunauer-Emmett-Teller (BET) method. X-ray
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8 diffraction (XRD) patterns were carried out on a Rigaku D/MAX-RB. X-ray
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10 diffractometer with equipment of Cu K radiation. The XRD data were scanned from
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13 10 to 90o with a rate of 8o/min. Scanning electron microscope (SEM) studies were
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15 conducted on instrument of JSM-5600LV. X-ray photoelectron spectroscopy (XPS)
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17 measurements were tested on an instrument of Thermo VG ESCALAB250, equipped
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20 with an Al K excitation source
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22 Hydrogen-temperature programmed reduction (H2-TPR) was carried out with a
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24 TCD detector on Quantachrom Automated Chemisorption. Firstly, 0.05 g catalyst was
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27 pretreated in a He stream at 200oC for 30 minutes to remove the surface weakly
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29 adsorbed materials, and cooled down to room temperature. Then the TPR experiments
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31 was programmed heated to 900oC at a rate of 10oC/min in a flow of 10 vol. % H2/He.
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2.3 Catalytic Tests
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36 Catalytic activity of toluene oxidation was evaluated in a tubular fixed-bed reactor
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38 system, and 0.2 g (40-60 mesh) catalyst was placed in fixed-bed. The component of
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reaction gas mixture contains 500 ppm toluene and 20%O2/Ar, and the total flow was
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43 75 mL/min. The equivalent of gas hourly space velocity (GHSV) was approximately
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45 22500 mL g-1 h-1. The 500 ppm toluene in the gas mixture was generate by using Ar
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bubbler through a bottle with pure toluene liquid, and chilled in an ice-water isothermal
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50 bath at 0oC. All reaction gas line was heating to 100oC by heating band in order to
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52 prevent toluene condensation on tube walls. The quantitative analysis of reactants and
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products were analyzed online at specific temperature by a gas chromatograph (GC-
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57 2014, Shimadu) equipped with flame ionization detector (FID) and thermal
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59 conductivity detector (TCD). The toluene conversion was calculated according to the
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3 following equations:
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6 [toluene]in - [toluene]out
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Xtoluene = × 100%
[toluene]in
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where [toluene]in and [toluene]out represents the toluene inlet and outlet concentrations,
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12 respectively.
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14 2.4 Kinetic Measurement
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16 The specific reaction rate was normalized on a per-catalyst weight basis, as shown
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19 below:
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21 F × X
22 R (μmol m -2 h -1) = × 10 -6
W × S
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25 where R is the specific reaction rate, F (mol s-1) is the flow of gaseous molecules, X is
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27 toluene conversion, W (g) is the weight of the catalyst and S (m2 g-1) is the specific surface
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29 area of the catalyst. To calculate the apparent activation energies (Ea) using Arrhenius
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31 𝐸𝑎
32 law (k = Aexp(𝑅𝑇)), the toluene conversion was controlled to below 15% and the gas
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hourly space velocity (GHSV) was changed from 22500 mL g-1 h-1 to 90000 mL g-1 h-1.
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37 In addition, by checking the Weistz-Prater parameter that there is no internal pore
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39 diffusion resistance.27, 28
40
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42 ′ 2
r × Rp
43 CWP =
44 Deff × Cs
45 where r’ is the reaction rate (kmol·kg-1·s-1), RP represents the catalyst particle radius (m),
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48 Deff represents the effective gas-phase diffusivity (m2·s-1), and CS represents the gas
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50 concentration at the catalyst external surface (kmol·m-3). The value of CWP was 3.7410-4
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52 < 0.3, indicating no significant mass transfer limitations in this catalytic systems.
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55 2.5 In situ Experiments
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57 In situ designed temperature programmed (TP) experiments were conducted in a
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59 tubular microreactor connected with a computer-interfaced quadruple mass
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3 spectrometer (MS) detector. The complete framework of in situ designed-TP
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6 experiments is illustrated in Scheme S1 in the Supporting Information. Here, the sample
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8 was pretreated in situ under a helium flow at 150oC for 1 hours to remove the surface
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10 weakly adsorbed H2O and CO2, and then purged to room temperature. For He-TPD
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experiment, the spinel CoMn2O4 was programmed to 900oC at a rate of 5oC/min under
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15 helium atmosphere (Step 1), and the oxygen (m/z=32) was detected.
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17 The adsorption of toluene was conducted at room temperature. After saturation,
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the system was purged with helium for 1 h to remove the physically adsorbed toluene
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22 on the surface and then began the experiment. Toluene desorption and CO2 formation
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24 were tested by raising the temperature from 25oC to 500oC at a rate of 5oC/min under
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26 helium atmosphere (t-TPD) (Step 2). After t-TPD experiment, the used catalysts were
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29 purged with He to room temperature and then heated in helium flow (t-TPD → He-
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31 TPD) (Step 2-1) to detect the residual oxygen species and CO2 in catalyst.
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33 Then an additional oxygen compensation experiment after t-TPD was performed
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on spinel CoMn2O4 with activation temperature varying at 25oC, 200oC and 250oC
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38 (Step 2-2), respectively. The experiment was performed in follows: (i): After t-TPD
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40 experiment, the catalyst was purged with helium to room temperature. (ii): The used
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catalyst was purged with 5% O2/He at different temperatures (T= 25oC, 200oC, 250oC)
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45 for 40 min, respectively, and then the reactor was purged with He to room temperature
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47 to clean the weakly physical adsorption gaseous oxygen. (iii): Then the adsorption and
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49 desorption of toluene was carried out following the above t-TPD experiment (t-
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52 TPD→O2 (T)→t-TPD) (Step 2-2-1). To more clearly compare the changes in oxygen
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54 species after oxygen supplementation, and the oxygen signal of the sample was also
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56 given in the He-TPD experiment (t-TPD→O2 (T)→He-TPD) (Step 2-2-2).
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Further, after the adsorption of toluene was saturated, the spinel CoMn2O4 system
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3 was purged with helium and then heated in a flow of 5% O2/He to investigate the
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6 temperature programmed surface reaction of toluene (t-TPSR) (Step 3). In addition,
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8 after the first t-TPD experiment, toluene was adsorbed on the used catalyst again, and
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10 then heated to 500oC under a flow of 5% O2/He to detect the formation of CO2 (t-
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TPD→t-TPSR) (Step 2-3).
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15 In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ
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17 DRIFTS) was conducted on a Thermos Nicolet iS 10 equipped with ZnSe windows.
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The powder catalyst was pretreated in N2 (25 mL/min) at 300oC for 30 minutes and
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22 then cooled to room temperature. A background spectrum was gathered at the
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24 corresponding temperature (200oC, 210oC and 220oC). The gaseous toluene (6 mL/min)
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26 was introduced into the reaction cell at 200oC for 30 minutes, then purged with helium
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29 for another 30 minutes to remove the weakly adsorbed toluene. Thereafter, a mixture
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31 reaction gas of 20 vol. % O2 + 80 vol. % N2 (25 mL/min) was introduced into the cell
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33 to react with toluene. Then, the sample was further heated to 210oC and 220oC,
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respectively. The IR spectra was collected continuously for 30 minutes at each step
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38 while the background spectra were also subtracted from each spectrum.
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3. Results and Discussion
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45 3.1. Structure and Texture of Catalysts
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47 The crystallographic structure of the samples is measured by XRD, as shown in
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49 Figure 1a. The pattern of CoMn2O4 shows well-resolved characteristic diffraction peaks
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52 which corresponds to the CoMn2O4 spinel-type structure (JCPDS Card no. 77-0471).
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54 Nevertheless, the Co3O4/MnOx sample prepared by impregnation method mainly exists
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56 in the form of Mn5O8, Mn2O3 and Co3O4 phases which are identical to pure MnOx and
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Co3O4. The morphology information on the as-prepared samples is obtained by SEM
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3 (Figure 1b). The nanoflower morphology of the spinel CoMn2O4 is basically observed.
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6 In comparison, the cotton-like and particle-like morphology of composite metal oxide
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8 Co3O4/MnOx catalyst are all observed to be identical to pure MnOx and Co3O4. Spinel
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10 CoMn2O4 shows IV isotherm with a H3 hysteresis loop lying in the range of 0.4-0.99
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(Figure S1a), indicating the formation of the uniform mesoporous structure,29 and the
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15 pore diameter is in the range of 3-5 nm (Figure S1b). Spinel CoMn2O4 sample prepared
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17 by oxalic acid sol-gel method shows the highest pore volume (0.24 m3 g-1), the largest
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specific surface area (124.4 m2 g-1) and the smallest mean pore diameter (3.7 nm)
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22 compared with those of single or mixed metal oxides (Table S1). In our work, the
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24 decomposition of oxalic acid precipitant at high temperature during the synthesis
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26 process for spinel CoMn2O4 sample can release a large amount of CO and CO2, which
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29 is beneficial to the formation of mesoporous structure and the increase of specific
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31 surface area. That is why that the specific surface area of spinel CoMn2O4 is higher than
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33 that of samples with similar spinel-like structure in the literature (45-49 m2 g-1).30 Large
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surface area of spinel can generate more oxygen vacancy and surface defects, which
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38 will introduce the formation of abundant surface active sites31 and thus the enhancement
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40 of the toluene adsorption and activation ability.32
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6 (a) CoMn2O4 Mn5O8 Mn2O3 Co3O4

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8 CoMn2O4
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11 Intensity /a.u. Co3O4/MnOx
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15 MnOx
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19 Co3O4
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21 10 20 30 40 50 60 70 80 90
22 2 /o
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43 Figure 1. XRD patterns (a) and SEM images (b) of spinel CoMn2O4, Co3O4/MnOx, MnOx and
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45 Co3O4.
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49 The surface cobalt and manganese oxidation state are probed using XPS technique.
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The XPS peaks in the Mn 2p region of all samples (Figure 2a) possess the same binding
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54 energy, indicating the identical chemical manganese composition on the surface. And
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56 the binding energy (BE) at 641.1-641.4 eV and 643.0-643.7 eV corresponds to Mn3+
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58 and Mn4+, 33-36 respectively. Note that the relative intensity of Mn4+ in comparison with
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3 Mn3+ in the Mn 2p region of spinel CoMn2O4 is 0.64 (Table S1), which should be due
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6 to the part conversion of surface Mn3+ to Mn4+. In the Co 2p spectra (Figure 2b), a
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8 satellite peak at 785.8 eV for CoMn2O4 indicates that the surface Co exists in the form
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10 of Co2+ species.37, 38 Furthermore, ΔECo2p (BE gap of Co 2p between the main peak and
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satellite peak) value of 15.46 eV also confirms that only the Co2+ exists in CoMn2O4.37
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15 For Co3O4, the peak at 781.5 eV with a low intensity shakeup satellite peak at 791.1 eV
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17 and the ΔECo2p value of 15.05 eV indicates the coexistence of the surface Co2+ and Co3+
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species, which is consistent with the results given in previous research.38 For the mixed
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22 metal oxide Co3O4/MnOx, the ΔECo2p value of 15.03 eV is very similar to that of the
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24 single metal oxides Co3O4, indicating that the element Co in the mixed metal oxides is
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26 mainly in the form of Co3O4. The higher average cation valence of 2.93 (>8/3≈2.67)
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29 for CoMn2O4 is considered to be the existence of cations with an oxidation state larger
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31 than the stoichiometric oxides, which means that cationic vacancy is formed to maintain
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33 charge balance.39 Furthermore, due to the Schottky defects in the spinel,24 oxygen
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vacancy is formed together with cationic vacancy and can be studied via O 1s, as shown
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38 in Figure 2c. The O 1s spectra are divided into three peaks of 529.8 eV, 531.0 eV and
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40 533.6 eV, which can be attributed to surface lattice oxygen (Olatt), O2- in surface oxygen
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vacancy and chemisorbed oxygen, respectively. The concentration of oxygen vacancy
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45 (OV) on spinel catalyst can be evaluated by the following equation:40
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47 𝐴 𝑂𝑉
48 𝑂𝑉 % = × 100%
49 𝐴 𝑂𝐿 + 𝐴 𝑂𝑉 + 𝐴 𝑂𝐶
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51 where 𝐴𝑂𝑉, 𝐴𝑂𝐿 and 𝐴𝑂𝐶 represents the peak area of O2- in surface oxygen
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54 vacancy, lattice oxygen and chemisorbed oxygen, respectively. And the concentration
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56 of oxygen vacancy reaches 51.6% for the spinel CoMn2O4, which can provide the
57
58 sufficient active centers or an oxygen adsorption sites for the catalysis reaction.
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1
2
3
4
5
6
(b) Co 2p
7 (a) Mn 2p (c) O 1s

8 OL
Mn 2p3/2
9 Mn3+ 15.46
OV
Mn 2p1/2
10 Mn 4+
CoMn2O4
OC
CoMn2O4
11 CoMn2O4
785.8
12
13
Intensity /a.u.

Intensity /a.u.
Co3O4/MnOx

Intensity /a.u.
15.03
14 Co3O4/MnOx

15
Co3O4/MnOx
16 15.05
17 Co3O4
MnOx
18 791.1
19 MnOx
20
21 Co3O4

22
23 635 640 645 650 655 660 770 780 790 800 810 526 528 530 532 534 536
Binding energy /eV Binding energy /eV Binding energy /eV
24
25 Figure 2. Mn 2p (a), Co 2p (b) and O 1s (c) of XPS spectra of spinel CoMn2O4, Co3O4/MnOx,
26
27 MnOx and Co3O4.
28
29
30
31
The H2-TPR profile of spinel CoMn2O4 sample (Figure 3) shows three reduction
32
33
34 peaks. The weak peak viewed at 302oC can be attributed to the reduction of Mn4+ to
35
36 Mn3+. The second peak, at 405oC, is ascribed to the reduction of Mn3+ to Mn2+. The
37
38 high temperature peak at 556oC corresponds to the reduction of spinel-like environment
39
40
41 Co2+ to metallic Co0 .15 Compared with other single metal oxides MnOx or mixed metal
42
43 oxides Co3O4/MnOx, the reduction of Mn4+ in spinel CoMn2O4 turns significantly to
44
45 the lower temperature. It has been known that the metal-oxygen bond in Schottky defect
46
47
48 will be shorten,39 which results in the asymmetric metal-oxygen distortion or
49
50 lengthening in neighborhood of periodic crystal framework, and thus the high mobility
51
52 of oxygen species in spinel catalyst .
53
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56
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3
4
5
6
7 405 556
8 CoMn2O4 302
9 H2 Consumption /a.u.
10
11 340 382 457 535
12 Co3O4/MnOx
13
369 492
14
15
16 MnOx
17
18 437
19
20
377
21 Co3O4
22
23
24 100 200 300 400 500 600 700 800
25 Temperature /oC
26
27 Figure 3. H2-TPR profiles of spinel CoMn2O4, Co3O4/MnOx, MnOx and Co3O4.
28
29
30
31 3.2 Catalytic Performance and Kinetic Studies of Catalysts
32
33 The toluene oxidation measurement was conducted to assess the catalytic
34
35
36
performance of samples. Figure 4a exhibits the temperature dependence of toluene
37
38 conversion of samples, and the toluene conversion rises with an increase in temperature.
39
40 The spinel CoMn2O4 sample, which reaches 50% conversion at 202oC and 90%
41
42
conversion at 210oC, shows the higher catalytic activity than those of single metal
43
44
45 oxides (Co3O4 and MnOx) and mixed metal oxides (Co3O4/MnOx). And no other gas-
46
47 phase by-products were detected and only CO2 and H2O were observed by gas
48
49 chromatography and mass spectrometry (Figure S2), which demonstrates that toluene
50
51
52 can be completely converted to the final products CO2 and H2O. The reaction rate per
53
54 unit weight and unit surface area is measured at 210oC, and the spinel reaction rate is
55
56 3.3 μmol m-2 h-1, which is 1.73 times higher than the mixed metal oxides Co3O4/MnOx
57
58
59 (1.91 μmol m-2 h-1).
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1
2
3
4
5 100 (a)
6
7 80

Toluene conversion /%
8
9 60
10
11 40
12
13 20
CoMn2O4
Co3O4/MnOx
14 MnOx
15 Co3O4
0
16
17 150 160 170 180 190 200 210 220 230 240 250 260
Temperature /oC
18
19 100 (c)
-16.8 (b)
20
75 2 vol% H2O
21 o
T=220 C
22 50
Toluene conversion /%
-17.2
Ea=35.5 KJ/mol
23
ln r /mol s-1 g-1

25
24
-17.6
25 Ea=51.8 KJ/mol 100
26 o
T=220 C
75
27 -18.0
CoMn2O4 Ea=53.1 KJ/mol
28 Co3O4/MnOx
50
o
T=200 C
29 Co3O4 Ea=63.7 KJ/mol
25
-18.4
30 MnOx
0
31 0 100 200 300 400 500 600 700
2.20 2.25 2.30 2.35 2.40
32 1000/Temperature /K-1 Time /min
33
34 Figure 4. (a) Toluene conversion of spinel CoMn2O4, Co3O4/MnOx, MnOx and Co3O4 catalysts. (b)
35
36 Arrhenius plots of toluene reaction rates of spinel CoMn2O4, Co3O4/MnOx, MnOx and Co3O4
37
38 catalysts. (c) On-stream toluene oxidation (200oC and 220oC) and effect of water vapor on catalytic
39
40 oxidation at 220oC over spinel CoMn2O4 at GHSV=22500 mL g-1 h-1.
41
42
43
44
45 To further better evaluate the catalytic performance, Table S2 shows the catalytic
46
47 activity of different catalysts for toluene oxidation, including CoMn2O4 in this work,
48
49 other Mn-based catalysts, perovskite, spinel and noble metal catalysts reported in the
50
51
references. Under the similar conditions, the catalytic activity (T90=210oC) over spinel
52
53
54 CoMn2O4 catalyst is much higher than those over rod-like MnO2 (T90=225oC),
55
56 perovskite La0.8Ce0.2MnO3/CeO2 (T90=240oC), perovskite LaNiO3 (T90=250oC),
57
58 MnAl/Na-L(II) (T90=246oC), spinel CoMn2O4 (T80=320oC), noble metal 1.67Mn3O4-
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3 2Au/3DOM LSCO (T90=230oC) and noble metal Pd/Co3AlO (T90=230oC), but lower
4
5
6 than that 1.99AuPd/3DOM Co3O4 catalyst (T90=168oC). The apparent activation energy
7
8 is evaluated and shown in Figure 4b. Compared with the single metal oxides Co3O4
9
10 (Ea=63.7 kJ/mol), MnOx (Ea=51.8 kJ/mol) and mixed metal oxides Co3O4/MnOx
11
12
13
(Ea=53.1 kJ/mol), the spinel CoMn2O4 shows an apparent decrease of activation energy
14
15 (Ea=35.5 kJ/mol). Inspired by the literature,41 the stability of catalysts in a continuous
16
17 reaction is checked at 200oC (39% of toluene conversion) and 220oC (100% of toluene
18
19
conversion), and as shown in Figure 4c. During the stability test in 700 min, the spinel
20
21
22 shows a change in toluene conversion from 39% to 26% at 200oC, and can maintain
23
24 above 98% of toluene conversion at 220oC in the presence or absence of water vapor
25
26 (2.0 vol.%). Further increase GHSV from 22500 to 45000 mL g-1 h-1, the toluene
27
28
29 conversion still reaches 90% at 227oC on spinel CoMn2O4.
30
31 3.3 Exploration of Reaction and Recovery Mechanism of Oxygen Species
32
33 From the relationship between structure and activity, it has been found that spinel
34
35
36
CoMn2O4 with high mobility of oxygen species exhibits the high activity and excellent
37
38 stability for toluene oxidation, which indicates that oxygen species in catalyst should
39
40 play an important role in the reaction. Oxygen species in catalyst involved in the
41
42
oxidation of VOCs are excited by Mars and van Krevelen mechanism (MVK), where
43
44
45 the reactant is oxidized by lattice oxygen species of catalyst, and then it is re-oxidized
46
47 by gaseous oxygen.19, 42-44 It is necessary to study how oxygen species (including
48
49 surface lattice oxygen and bulk lattice oxygen) participate in the reaction and the
50
51
52 pathway of oxygen species consumed by gaseous oxygen supplementation.
53
54 3.3.1 Determination of Lattice Oxygen and its Reaction with Toluene
55
56 The on-stream reaction at 220oC on spinel CoMn2O4 sample is performed, as
57
58
59
shown in Figure 5a. When the gaseous oxygen is turned off, the toluene conversion of
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3 spinel CoMn2O4 decreases with time, but still remains above 80% for 14 minutes, and
4
5
6 reaches 16% while continuing the reaction for another 33 minutes. Differently, for
7
8 mixed metal oxides Co3O4/MnOx sample, the toluene conversion immediately
9
10 decreases to 16% in 14 minutes at 240oC when gaseous oxygen is cut off. After the
11
12
13
gaseous oxygen is again introduced into the feed gas, the toluene conversion nearly
14
15 achieves 100% and recoveries for both samples. Toluene oxidation still occurs
16
17 gradually with time in the absence of gaseous oxygen for both samples, which means
18
19
that the oxygen species in the catalyst can react with toluene. However, the decrease in
20
21
22 toluene conversion rate for the two samples is dramatically different. Thus, the
23
24 composition and content of the oxygen species are further studied by temperature-
25
26 programmed desorption (He-TPD) experiments, as shown in Figure 5b. Based on the
27
28
29 literatures,45-47 in general, the low-temperature peak (300-500oC) represents the surface
30
31 lattice oxygen species, and the high-temperature peak (T >500oC) is deemed to the
32
33 releasing of the bulk lattice oxygen species of crystal structure.47, 48 For spinel CoMn2O4
34
35
36
sample, the lower desorption temperature of the surface lattice oxygen species means
37
38 the higher activity of oxygen species.48
39
40 A toluene-adsorbed spinel CoMn2O4 is measured for temperature-programmed
41
42
desorption (t-TPD) in helium gas flow (Figure 5c). The amount of toluene desorbed
43
44
45 from spinel CoMn2O4 is obviously higher than that of mixed metal oxides Co3O4/MnOx,
46
47 and the adsorption capacity of spinel CoMn2O4 is higher. In addition to the observation
48
49 of toluene desorption from spinel CoMn2O4, the oxidation of adsorbed toluene by the
50
51
52 active oxygen species in the catalyst is also observed during the t-TPD experiment, and
53
54 CO2 product (m/z=44) is generated (Figure 5d). Compared with Co3O4/MnOx catalyst,
55
56 larger amount of CO2 formation suggests that more toluene can be activated and more
57
58
59
reactive oxygen species in CoMn2O4 can participate in the toluene oxidation. The broad
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3 CO2 generation peak in the range of 46-460oC for the CoMn2O4 spinel catalyst also
4
5
6 indicates that the active oxygen species gradually participate in the oxidation reaction,
7
8 and the oxygen species are diverse and own the good activity at low temperatures. At
9
10 the same time, it is found that the reactive oxygen species in the spinel CoMn2O4 can
11
12
13
fully participate in the t-TPD reaction (Figure S3), and no desorption of reactive oxygen
14
15 species is observed during our experiment range after the spinel CoMn2O4 catalyst
16
17 undergoes t-TPD. Importantly, the spinel CoMn2O4 still keeps the good spinel structure
18
19
after t-TPD experiment (Figure S4). Differently, for mixed metal oxides Co3O4/MnOx,
20
21
22 an oxygen desorption peak at 638oC is still retained after t-TPD experiment (Figure S3),
23
24 indicating that the oxygen species in the catalyst cannot all participate in the reaction.
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
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48
49
50
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52
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1
2
3
4
5 (a) OFF ON ON (b) m/z=32
6 100
7 300-500
Toluene Conversion / %

1E-12
8 80 >500
CoMn2O4
9

Mass Signal /a.u.

10 60
o
T=240 C T=220 C o

11
12
40
13
14 Co3O4/MnOx
20 CoMn2O4
15 14 min 33 min Co3O4/MnOx
16
17 0
18 0 50 100 150 200 100 200 300 400 500 600 700 800 900
Time /min Temperature /oC
19
20
(c) (d) m/z=44
21 m/z=92
22 2E-14
5E-13
23
24
Mass Signal /a.u.
Mass Signal /a.u.

25
CoMn2O4
26
CoMn2O4
27 46 460
28
29
30 Co3O4/MnOx Co3O4/MnOx
31 150 384
32
33 50 100 150 200 250 300 350 400 450 500 50 100 150 200 250 300 350 400 450 500
34 Temperature /oC Temperature /oC
35
Figure 5. (a) Toluene conversion in O2-free as a function of time of spinel CoMn2O4 and Co3O4/MnOx.
36
37
(b) He-TPD profiles of spinel CoMn2O4 and Co3O4/MnOx. (c) Toluene desorption and (d) CO2
38
39
production profiles in t-TPD of spinel CoMn2O4 and Co3O4/MnOx.
40
41
42
43
44 3.3.2 Determination of Oxygen Replenishment Mechanism by in situ Designed-TP
45
46 Techniques
47
48
49
It has been known that most of the reactive oxygen species in the CoMn2O4
50
51 catalyst can be consumed during the toluene temperature-programmed reaction (t-
52
53 TPD→He-TPD, Figure S3). Then it is essential to well understand whether the gaseous
54
55 oxygen can be directly dissociated and activated on the surface or move into the lattice
56
57
58 of the catalyst to form the oxygen cycle during the real reaction process. The oxygen
59
60 replenishment experiments for spinel CoMn2O4 sample at different temperatures
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1
2
3 (T=25oC, 200oC and 250oC) are executed, as shown in Figure 6a. When the gaseous
4
5
6 oxygen is added into the used catalyst (after t-TPD) at 25oC, and then the temperature-
7
8 programmed desorption experiment (t-TPD→O2 (25oC)→He-TPD) is performed, a small
9
10 amount of bulk lattice oxygen species is desorbed at high temperature (T=664oC).
11
12
13
Interestingly, when the temperature for gaseous oxygen supplying increases to 200oC,
14
15 the intensity of oxygen desorption peaks at high temperature (T=664oC) is significantly
16
17 enhanced, and more bulk lattice oxygen species are formed. And meanwhile a new
18
19
oxygen desorption peaks is also detected at 486oC. This phenomenon becomes more
20
21
22 apparent as the oxygen supplemental temperature continues to increase (200-250oC),
23
24 and the oxygen desorption peak shifts to the lower temperature and meanwhile its
25
26 amount increases. The desorption temperature of oxygen species drops slightly to
27
28
29 659oC and 471oC, and a new oxygen desorption peak also appears at 420oC. Based on
30
31 the above results, thus it is reasonable to suggest that the addition of gaseous oxygen at
32
33 25oC mainly supplements the bulk lattice oxygen of the spinel catalysts. Moreover, with
34
35
36
the increase of temperature, the amount of bulk lattice oxygen at high temperature is
37
38 significantly enhanced and is larger than that of the surface lattice oxygen. The gaseous
39
40 oxygen is more easily moved to the bulk phase lattice for the spinel catalyst, and the
41
42
active surface lattice oxygen species desorbed at low-temperature is primarily caused
43
44
45 by the migration of bulk lattice oxygen to the surface. The higher oxygen supplemental
46
47 temperature (200-250oC) favors the oxygen migration process. That means the higher
48
49 reaction temperature contributes to the toluene oxidation in the practical flow reaction,
50
51
52 which is well consistent with toluene oxidation results (Figure 4, T90=210oC). To
53
54 further realize the reaction properties of the supplement oxygen species with toluene,
55
56 the toluene adsorption-desorption experiment on the re-oxidation sample (t-TPD→O2
57
58
59 (T)→t-TPD) was also performed (Figure 6b). The CO2 signal is detected to demonstrate
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2
3 the reaction between the oxygen species and toluene. To clearly compare the toluene
4
5
6 reaction performance of the re-oxidation catalyst, the results of the toluene reaction
7
8 with oxygen species in fresh catalyst are also given. When the used catalyst (after t-
9
10 TPD) was supplemented with gaseous oxygen at 25oC, two CO2 peaks are observed at
11
12
13
301oC and 388oC (t-TPD →O2 (25oC)→t-TPD), respectively. This further suggest that the
14
15 oxygen species in the catalyst can be replenished by the gaseous oxygen at 25oC and is
16
17 also an active oxygen species for toluene oxidation. As the temperature for oxygen
18
19
supplemental rises to 200oC, the amount of CO2 production is increased, particularly at
20
21
22 low temperature, and the CO2 peaks move significantly toward low temperature (279oC
23
24 and 361oC). More importantly, it is found that when the temperature is increased to
25
26 250oC, three CO2 peaks can be obtained, which is similar to the profile of CO2
27
28
29 production during the t-TPD. Therefore, the oxygen species consumed in spinel catalyst
30
31 are fully supplemented by gaseous oxygen during the reaction. At relatively higher
32
33 temperature (200-250oC), gaseous oxygen is more easily replenished into the catalyst,
34
35
36
while gaseous oxygen accelerates the rate of oxygen migration from bulk to surface,
37
38 thereby improving the surface oxidation reaction with toluene. Therefore, surface
39
40 lattice oxygen can react with the toluene at low temperature (< 200oC), but migration
41
42
of the supplemental oxygen species to form surface lattice oxygen at low temperature
43
44
45 limits the reaction, and as the temperature increases (200-250oC), the migration and
46
47 catalytic reaction can be accelerated. The spinel CoMn2O4 sample is mainly composed
48
49 of Co and Mn elements, to clearly explain the uniqueness of oxygen species in the
50
51
52 spinel structure for toluene oxidation, oxygen supplementation experiment (t-TPD→O2
53
54 (T)→He-TPD) at different temperature and toluene reaction experiment (t-TPD→O2
55
56
(T)→t-TPD) are also performed for Co3O4/MnOx sample (Figure S5 and Figure S6). For
57
58
59
Co3O4/MnOx, only one O2 desorption peak (T=638oC) was observed after the first t-
60
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1
2
3 TPD experiment (Figure S3). No O2 desorption peaks at low temperatures (surface
4
5
6 lattice oxygen species) is observed compared with the fresh Co3O4/MnOx, even if the
7
8 oxygen supplemental temperature is increased (Figure S5). Moreover, no low-
9
10 temperature CO2 production peak is observed on Co3O4/MnOx after oxygen
11
12
13
supplementation (Figure S6), which suggests that the bulk lattice oxygen formed at high
14
15 temperature hardly migrates to the surface for Co3O4/MnOx catalyst. This also reflects
16
17 the difference in the oxygen migration properties between the Co3O4/MnOx and spinel
18
19
CoMn2O4 sample. The mixed metal oxides Co3O4/MnOx sample is not easy to undergo
20
21
22 oxygen migration at low temperature or high temperature. Besides, it is known from
23
24 the actual reaction (Figure 4) that toluene can be completely oxidized over the mixed
25
26 metal oxides Co3O4/MnOx at 230oC, and gaseous oxygen can accelerate the production
27
28
29 of CO2 (Figure S7). Combining with the above results, it is thought that gaseous oxygen
30
31 can be dissociated and activated at a certain temperature to carry out the reaction on
32
33 mixed metal oxides Co3O4/MnOx, but the temperature required for the toluene
34
35
36
oxidation is high. For spinel CoMn2O4, the bulk oxygen species supplemented at 200-
37
38 250oC can migrate to the surface of the catalyst synchronously, which results in the
39
40 high catalytic performance for toluene oxidation at low temperature (3.30 mol m-2 h-1
41
42
43 at 210oC) compared to the mixed metal oxides Co3O4/MnOx (1.91 mol m-2 h-1 at
44
45 210oC). The surface lattice oxygen species in spinel CoMn2O4 catalyst should be the
46
47 main active oxygen species in actual VOCs oxidation reaction, and oxygen migration
48
49
50 of bulk lattice oxygen promotes the formation and reaction of surface lattice oxygen
51
52 species.
53
54
55
56
57
58
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2
3
4 (a) m/z=32
5 300-500
1E-12
6 >500
368
7 fresh 472 582

Mass Signal /a.u.

8
659
9
O2 (250oC) 420 471
10
11
12 O2 (200oC) 486 664
13
14
15 O2 (25oC) 664
16
17
18 200 300 400 500 600 700 800 900
Temperature /oC
19
20
21 (b) m/z=44 (c) m/z=44
22
5E-13 376
23 216
302
24
Mass Signal /a.u.

25 t-TPD
Mass Signal /a.u.

26 311 144
27 O2 (250oC) 200
386
t-TPSR
28
29 361
30 O2 (200oC) 279
31 388
32 O2 (25oC) 301
33 t-TPD t-TPSR
34
35 55 110 165 220 275 330 385 440 495 50 100 150 200 250 300 350 400
Temperature /oC Temperature /oC
36
37 Figure 6. (a) Profiles of O2 generation during the t-TPD→O2 (T)→He-TPD experiments, (b) CO2 generation
38
39 during the t-TPD→O2 (T)→t-TPD experiments and (c) CO2 formation during t-TPSR and t-TPD→t-TPSR
40
41 experiment on spinel CoMn2O4.
42
43
44
45
46 The results for toluene surface oxidation with 5% O2/He (t-TPSR) over spinel
47
48 CoMn2O4 is shown in Figure 6c. The spinel catalyst is very active, and CO2 peak (224oC)
49
50
51
with a shoulder (144oC) is observed. Compared with the t-TPD and t-TPD→O2 (T)→t-
52
53 TPD results (Figure 5d and Figure 6b), the peak of CO2 formation (Figure 6c) is larger
54
55 and shifts to a lower temperature, and the content of desorbed toluene is reduced (Figure
56
57
S8). Thus it is thought the gaseous oxygen accelerates the reaction rate of toluene
58
59
60 oxidation. When the catalyst after t-TPD experiment is further executed the t-TPSR
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2
3 experiment (t-TPD→t-TPSR), the CO2 peak becomes narrow compared to that of the
4
5
6 direct t-TPSR experiment and moreover the peak at low temperature (T=144oC)
7
8 disappears. Therefore, it can be concluded that the CO2 peak formed at 144oC is
9
10 attributed to the reaction between toluene and surface lattice oxygen species in catalyst,
11
12
13
which in turn induces the reaction. When a large amount of oxygen species is first
14
15 removed from the catalyst, the gaseous oxygen replenishment process is accelerated
16
17 and CO2 generation peak becomes narrow, which further confirms the gaseous oxygen
18
19
replenishment pathway.
20
21
22 It has been known in our experiments that the nanoflower spinel CoMn2O4 with
23
24 large specific surface area and abundant cationic vacancy is successfully synthesized
25
26 by oxalic acid sol-gel method according to N2 adsorption-desorption and XPS
27
28
29 techniques. In order to maintain the electrical neutrality, the cationic vacancy in the
30
31 spinel is paired with oxygen vacancy (Schottky defect), which promotes the subsequent
32
33 re-oxidation cycle of the spinel catalyst. Herein the properties of the oxygen species
34
35
36
and the pathway of re-oxidation on the spinel CoMn2O4 catalyst during the toluene
37
38 oxidation can be well defined, and the proposed mechanism is illustrated in Figure 7.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55 Figure 7. Proposed replenishment mechanism of oxygen species on spinel CoMn2O4 during
56
57 toluene oxidation.
58
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2
3 Gaseous oxygen is easily replenished to the bulk lattice at low temperatures, which
4
5
6 means that the gaseous oxygen is first moved to the bulk phase lattice via oxygen
7
8 vacancy of the catalyst, and the supplement process becomes easier at high temperature.
9
10 When the temperature rises (200-250oC), a large amount of supplemental oxygen
11
12
13
species can migrate to the surface of the spinel catalyst. We believe that these two steps
14
15 occur simultaneously, and this migration is irreversible. More importantly, it is found
16
17 that the toluene oxidation starts with the reaction between surface lattice oxygen in
18
19
fresh CoMn2O4 catalyst and the adsorbed toluene (Figure 6c), and an oxygen vacancy
20
21
22 would occur. The surface lattice oxygen induces the toluene oxidation reaction and
23
24 gaseous oxygen species accelerate the replenishment and migration of reactive oxygen
25
26 species through oxygen vacancy. In contrast, the mixed metal oxides Co3O4/MnO4
27
28
29 shows different character that needs the direct dissociation of gaseous oxygen on the
30
31 surface of the catalyst for toluene oxidation. In addition to this, further characterization
32
33 (H2-TPR) indicates that oxygen species of the spinel CoMn2O4 catalyst can be reduced
34
35
36
at lower temperature. The structure difference between spinel CoMn2O4 and metal
37
38 oxides Co3O4/MnOx results in the difference in oxygen species properties, which seems
39
40 to be a key factor that plays a decisive role in catalytic activity.
41
42
3.4 Determination of Adsorption Intermediates for Toluene Oxidation by in situ
43
44
45 DRIFTS
46
47 In situ DRIFTS spectra of toluene adsorption over spinel CoMn2O4 at 200oC are
48
49 shown in Figure 8a. The strong bands located at 1600 cm-1, 1520 cm-1 and 1492 cm-1
50
51
52 are attributed to aromatic ring out-plane and in-plane vibrations.49 Notably, the bands
53
54 at 1177 cm-1 and 1020 cm-1 are characteristic of alkoxide species (C-O stretching
55
56 vibration).50 This means that the adsorbed toluene can interact with the catalyst by
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58
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breaking the C-H bond of the methyl (-CH3) to produce benzyl alcohol. The bands at
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3 1558 cm-1, 1542 cm-1 and 1423 cm-1 are assigned to the carboxylate group (1558 cm-1,
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6 asymmetric –COO- stretching vibration; 1423 cm-1, symmetric –COO- stretching
7
8 vibration),51 indicating the formation of benzoate species. The peak located at 1305 cm-
9
10 1 can be assigned to anhydride species,50, 52, 53 and the band at 1361 cm-1 is characteristic
11
12
13
of the acetate species.54 The intensity of these bands becomes stronger on the spinel
14
15 CoMn2O4 with the time, indicating that these intermediates is gradually accumulated
16
17 on the spinel catalyst. Aldehydes (1654 cm-1 and 1467 cm-1, C=O stretching vibration)55
18
19
is detected on Co3O4 sample (Figure S9), but no such bands are observed on CoMn2O4,
20
21
22 Co3O4/MnOx and MnOx, indicating that manganese element promotes the rapid
23
24 conversion of aldehydes. Furthermore, when N2 is introduced into the system at 200oC
25
26 for 30 minutes, no changes are observed in the spectra (Figure 8b), demonstrating the
27
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29 fine stability of these intermediates.
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6 (a) 1305

7 1558 1542 1423

8 1600 1520 1492 1177 1020

9 0.001
10
Absorbance /a.u.
11
12 1361

13
14
15
16 30 min
17
18
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20
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22 1 min

23 2000 1800 1600 1400 1200 1000

24 Wavenumbers /cm-1
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28 (b)
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0.001
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Absorbance /a.u.

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34
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42 30 min
43
44 0 min

45 2000 1800 1600 1400 1200 1000

46 -1
47 Wavenumbers /cm
48 Figure 8. In situ DRIFTS study of (a) toluene adsorption (toluene flow rate, 6 mL min-1;
49
50 temperature, 200oC) and (b) N2 purging (N2, 25 mL min-1; temperature, 200oC) on CoMn2O4.
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5 1305
6 (a) 1557 1540 1425

7 1604 1520 1492 1178 1025

8
9 0.002 1363

10 Absorbance /a.u.
11 30 min
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13
14
15
16
17
18
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20 0 min
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22 2000 1800 1600 1400 1200 1000
23 Wavenumbers /cm-1
24
25
26 (b) Alkoxide
Kubelka-Munk peak area /a.u.

Kubelka-Munk peak area /a.u.

27 Anhydride
0.01
28 0.001 Benzoate
29 Acetate
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32
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34
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41
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
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43 Time /min
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45 Figure 9. (a) In situ DRIFTS spectra after reaction of gaseous oxygen with pre-adsorbed toluene
46
47
and (b) characteristic IR peak area of surface alkoxide, benzoate, anhydride and acetate species
48
49
50 versus time during reaction over spinel CoMn2O4 at 200oC.
51
52
53 The oxidation process corresponding to the intermediate species shows the change
54
55 in intensity with time after introduction of O2 in the spinel sample at 200oC (Figure 9a),
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58 the characteristic IR peak of the intermediates (1177 cm-1, alkoxide; 1423 cm-1,
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4 benzoate; 1305 cm-1, anhydride; 1358 cm-1, acetate) is calculated by integral area, as
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6
7 shown in Figure 9b. For the spinel CoMn2O4 sample, the alkoxide species initially grow
8
9 (<4 minutes) and then follow a decrease, indicating that the alkoxide can be quickly
10
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12 formed by introduction O2 to cell and then begins to be oxidized rapidly after 4 minutes.
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14
The surface anhydride species are populated rapidly with time while the surface benzyl
15
16
17 alcohol and benzoate species decrease significantly, which can be explained by the
18
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20 further conversion of benzyl alcohol and benzoate to anhydride. In addition, the
21
22 intensity of acetate species continues to decrease. This suggests that the reaction occurs
23
24
25 via benzyl alcohol-benzoate-anhydride-acetate pathway. However, introducing O2 at
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27
200oC does not increase the formation of anhydride, and slight reduces the benzoate in
28
29
30 mixed metal oxides Co3O4/MnOx (Figure S10), suggesting that the aromatic ring is
31
32
33 difficult to break.
34
35
Toluene oxidation over spinel CoMn2O4 catalyst is further carried out under O2
36
37 atmosphere at high temperatures (210oC and 220oC). The decreasing trend for these
38
39 intermediates is shown in Figure 10a. To clearly distinguish the conversion of the
40
41
intermediate, the integrated area of the four intermediates (1177 cm-1, alkoxide; 1423
42
43
44 cm-1, benzoate; 1305 cm-1, anhydride; 1358 cm-1, acetate) at various temperatures is
45
46 calculated ， as shown in Figure 10b. As the temperature increases, the Kubelka-
47
48
49 Munk peak area of anhydride first increases (T ≤ 210oC) ， while alkoxide and
50
51 benzoate species decreases, suggesting that a fast breakage of aromatic ring results in
52
53
54
an increase in the type of anhydride on the surface. And the acetate species quickly
55
56 decrease at 210oC. In addition, it is found that the surface anhydride accumulates and
57
58 reaches a maximum at 210oC, that is, the rate of formation of the anhydride is higher
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3 than its oxidation rate, which should be a rate-controlled step for toluene oxidation
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6 over spinel CoMn2O4, especially at 200-210oC. The catalytic cycle of toluene
7
8 oxidation over spinel CoMn2O4 is summarized in Figure 10c. Adsorbed toluene is first
9
10 oxidized by surface lattice oxygen into alkoxide, benzoate, anhydride, acetate and CO2,
11
12
13
and the oxidation of anhydride species is a rate determining step (200-210oC) in
14
15 toluene oxidation. Nevertheless, for mixed metal oxides Co3O4/MnOx (Figure S11),
16
17 the characteristic band of the anhydride does not significant increase before 220oC,
18
19
indicating that the catalytic oxidation is stopped on the benzoate intermediate, which
20
21
22 cannot be rapidly transformed to an anhydride over Co3O4/MnOx (T ≤ 210oC).
23
24
25 (a)
1305
26 1558 1542 1423

27 0.001 1600 15201492 1177 1020

28
Absorbance /a.u.

29
30 1358

31
32
200oC-N2
33
34 200oC-O2
35 210oC-O2
36 220oC-O2
37
38 2000 1800 1600 1400 1200 1000
Wavenumbers /cm-1
39
40 (b) CoMn2O4
(c)
Alkoxide Anhydride Acetate
41
Kubelka-Munk peak area /a.u.
Kubelka-Munk peak area /a.u.

Benzoate
42 200oC+N2
43
44
45 0.02
0.006 200oC+O2
46
47 210oC+O2
48 220oC+O2
49
50
51
52
53
54 Figure 10. (a) In situ DRIFTS spectra after reaction of O2 with pre-adsorbed toluene at various
55
56 temperature, (b) characteristic IR peak area of surface alkoxide, benzoate, anhydride and acetate species
57
58 versus temperature during reaction over spinel CoMn2O4 and (c) proposed mechanism of toluene
59
60 degradation pathway on spinel CoMn2O4.
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3 4. Conclusions
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6 In summary, spinel CoMn2O4 with defined phase-pure structure and large surface
7
8 area is synthesized by a facile approach and the catalytic performance for toluene
9
10 oxidation is investigated. The spinel CoMn2O4 shows the highest catalytic performance,
11
12
13
and the T50 and T90 values are 202oC and 210oC, respectively, which is significantly
14
15 higher than that of metal oxides (Co3O4, MnOx and Co3O4/MnOx). And it can also keep
16
17 above 98% of toluene conversion at 220oC after the 700 min stability test in the
18
19
presence or absence of water vapor (2.0 vol.%). In situ designed TP experiments have
20
21
22 been concluded that the surface lattice oxygen induces the catalytic reaction, and
23
24 gaseous oxygen is moved to the bulk phase lattice and then bulk oxygen species is
25
26 easily migrated to surface to form more surface lattice oxygen species at 200-250oC.
27
28
29 Oxygen vacancy in the spinel can accelerate the entire cycle of oxygen specie. The in
30
31 situ DRIFTS results suggest that the toluene oxidation over spinel CoMn2O4 occurs
32
33 through the benzyl alcohol-benzoate-anhydride-acetate pathway, and the conversion of
34
35
36
the surface anhydride is the rate-controlled step for toluene oxidation. It is completely
37
38 different from the mixed metal oxides Co3O4/MnOx, in which the bulk lattice oxygen
39
40 hardly migrates to the surface and the direct dissociation of gaseous oxygen on the
41
42
surface is important, and the breakage of the benzoate is difficult. The structure
43
44
45 difference between spinel CoMn2O4 and mixed metal oxides Co3O4/MnOx causes the
46
47 different mobility and content of active oxygen species in the sample, which plays a
48
49 decisive role in the catalytic activity.
50
51
52
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54
55 ASSOCIATED CONTENT
56
57
58 Supporting Information
59
60 The supporting information is available free of charge via the Internet at
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1
2
3
4 [Link]
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7 Framework for in situ designed-TP experiments, N2 adsorption-desorption results,
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9 XRD patterns, figures showing the on-stream reaction of gaseous oxygen with pre-
10
11
12 adsorbed toluene on spinel CoMn2O4 at 200oC and 220oC, figures showing the in situ
13
14
TP results for spinel CoMn2O4 or mixed metal oxides Co3O4/MnOx, in situ DRIFTS
15
16
17 spectra for metal oxides Co3O4, MnOx or Co3O4/MnOx, and the table containing the
18
19
20 surface area, pore diameter, pore volume, surface element compositions and catalytic
21
22 activity for toluene oxidation over different catalysts.
23
24
25 AUTHOR INFORMATION
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27
Corresponding Author
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29
30 * E-mail: quzhenping@[Link]
31
32
33 Notes
34
35 The authors declare no competing financial interest.
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37
38
39
ACKNOWLEDGMENTS
40
41
42 This work was financially supported by the National Nature Science Foundation
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44 of China (21876019, 21806017), Programme of Introducing Talents of Discipline to
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46 Universities (B13012) and the fund of the State Key Laboratory of Catalysis in DICP
47
48
49 (Y401010502.
50
51
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