# Evaluation of NO Oxidation Properties over a Mn-Ce/γ-Al2O3 Catalyst

Authors: Pan Wang; Peng Luo; Junchen Yin; Lili Lei
Journal: Journal of Nanomaterials
 (2016)

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## Abstract

With the purpose of studying the effect of diesel oxidation catalyst (DOC) on the NO oxidation activity, a series ofxMn10Ce/γ-Al2O3 (x = 4, 6, 8, and 10) catalysts were synthesized by acid-aided sol-gel method. The physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and Transmission Electron Microscope (TEM). Result showed that the crystalline size of MnOx and CeO2 ranges from 5 nm to 30 nm and manganese existed mainly in the catalysts in the form of manganese dioxide. Moreover, NO oxidation experiments were carried out to evaluate the activity of the catalysts; according to the results, 6Mn10Ce/γ-Al2O3 catalyst showed the supreme NO oxidation activity with a NO to NO2 conversion rate of 83.5% at 300°C. Compared to 500 ppm NO inlet concentration, the NO conversion was higher than that of 750 and 1000 ppm NO over 6Mn10Ce/γ-Al2O3 catalyst in the temperature range of 150–300°C.


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## Body

## 1. Introduction

Diesel engines are widely used as commercial vehicle power due to the higher thermal efficiency, durability, and fuel economy compared to gasoline engines. However, with increasingly stringent vehicle exhaust gas emission regulations and the attention to health, the NOx (NO, NO2) emission from diesel engines that caused many serious environmental problems, such as acid rain and photochemical smog, has met severe challenge [1, 2].Recently, catalysis technique adopted to oxidize NO to NO2 has been attracting enormous attention due to its role in several catalytic processes, such as NOx reduced by SCR with hydrocarbons and soot combustion in the atmosphere of NOx/O2 [3, 4]. The diesel oxidation catalyst (DOC) can not only oxidize CO, HC, and PM, but also facilitate the oxidation of NO to NO2, which is beneficial for NOx removal by the downstream SCR or NSR units [5, 6]; for urea SCR, a NO2 : NO ratio of 1 : 1 is the most effective. In the NSR process, NO needs to be oxidized to NO2 before being absorbed by storage components during the lean phase. However, according to the literature [7], the amount of NO2 in diesel engine exhaust is usually less than 10% in the total NOx. Hence, to improve the NO2/NOx ration is of great necessity for the sake of improving the posttreatment efficiency.Many metal mixed catalysts, such as CeO2/ZrO2 [8] and MnOx-TiO2 [9], can effectively oxidize NO to NO2. The MnOx-CeO2 mixed oxides have been reported to have much higher catalytic activities compared to the individual CeO2 and MnOx, for the reason that the strong interaction between MnOx and CeO2 can form solid solution [10, 11]. Li and coworkers reported that Mn-Ce oxides were active for NO to NO2 oxidation with about 80% NO conversion at 150°C over Mn-Co-Ce(20)-400 catalyst [12]. According to the literatures [13–16], CeO2 has been widely studied for its oxygen storage and redox properties, among which the most important property is that ceria can store and release oxygen via the redox shift between Ce4+ and Ce3+ under oxidizing and reducing conditions.In this work, in order to study the NO oxidation performance by DOC, Mn-Ce/γ-Al2O3 mixed oxides catalyst was synthesized by acid-aided sol-gel method. X-ray diffraction (XRD), scanning electron microscope (SEM), and Transmission Electron Microscope (TEM) were carried out to investigate the physicochemical properties of the catalyst structure, and NO oxidation experiments were carried out to evaluate the activities of the catalysts.


## 2. Experimental

### 2.1. Catalyst Preparation

A series ofxMn10Ce/γ-Al2O3 (x = 4, 6, 8, and 10, wt%) catalysts were prepared by acid-aided sol-gel method as described in the literature [17]. First, Ce(NO3)3
·6H2O, C4H6MnO4
·4H2O, and γ-Al2O3 were weighed by different Mn/Ce molar ratio and dissolved in deionized water, respectively, to obtain solution, into which citric acid was added, the amount of which was twice the sum of Ce3+ and Mn2+ total molar. Then polyethylene glycol, the quality of which is 10% of the citric acid, was introduced and magnet-stirred at 80°C until transparent gel was obtained. Then it was dried at 110°C for 24 h and calcined in air for 5 h at 500°C. Then the powder was ball-milled to obtain the required 20–40-mesh powder.


### 2.2. Catalyst Characterization

X-ray diffraction (XRD) of the as-prepared sample was measured on a Bruker D8 ADVANCE X-ray diffractometer with a Ni-filtered Cu Kα (λ = 0.154068 nm) radiation source at 40 kV and 40 mA. Powder XRD patterns were recorded at 0.02° interval in the range of 20° ≤ 2θ ≤ 80° with a scanning velocity of 7° min−1. The crystalline size was calculated by Scherrer’s formula D = Kλ/(β
cos
⁡
θ). Transmission Electron Microscope (TEM) measurement was done by using a Philips Tecnai 12 microscope, with a 120 kV accelerating voltage. Before testing, the catalyst powder was ground and dispersed ultrasonically in anhydrous ethanol and then dropped onto a carbon-coated Cu grid of 200 mesh. Scanning electron microscope (SEM) testing was performed on JSM-7001F microscope made by JEOL. Accelerating voltage was 0.5–30 kV, magnification 10–800 K, and resolution 1.2 nm (30 kV)/3.0 nm (1 kV).


### 2.3. Catalyst Evaluation

The oxidation of NO to NO2 activity was measured at the temperatures in the range of 150–450°C. The catalysts were placed in a fixed-bed quartz mircoreactor with an inside diameter of 10 mm and plugged and sandwiched between two silica wool layers to prevent the sample from being blown away. The gases used in the tests were 500 ppm NO, 10% O2, and N2 in balance with a total flow rate of 280 mL/min, giving a space velocity of 56,000 h−1. The outlet NO and NO2 concentrations were detected by Thermo Scientific Model 42i-HL NOx Analyzer. Before each NO oxidation experiment, the catalyst sample was heated to 450°C in N2 atmosphere for 30 min, in order to clean up the residual gases adsorbed in the catalyst surface, and then cooled to the required measurement temperatures.


## 2.1. Catalyst Preparation

A series ofxMn10Ce/γ-Al2O3 (x = 4, 6, 8, and 10, wt%) catalysts were prepared by acid-aided sol-gel method as described in the literature [17]. First, Ce(NO3)3
·6H2O, C4H6MnO4
·4H2O, and γ-Al2O3 were weighed by different Mn/Ce molar ratio and dissolved in deionized water, respectively, to obtain solution, into which citric acid was added, the amount of which was twice the sum of Ce3+ and Mn2+ total molar. Then polyethylene glycol, the quality of which is 10% of the citric acid, was introduced and magnet-stirred at 80°C until transparent gel was obtained. Then it was dried at 110°C for 24 h and calcined in air for 5 h at 500°C. Then the powder was ball-milled to obtain the required 20–40-mesh powder.


## 2.2. Catalyst Characterization

X-ray diffraction (XRD) of the as-prepared sample was measured on a Bruker D8 ADVANCE X-ray diffractometer with a Ni-filtered Cu Kα (λ = 0.154068 nm) radiation source at 40 kV and 40 mA. Powder XRD patterns were recorded at 0.02° interval in the range of 20° ≤ 2θ ≤ 80° with a scanning velocity of 7° min−1. The crystalline size was calculated by Scherrer’s formula D = Kλ/(β
cos
⁡
θ). Transmission Electron Microscope (TEM) measurement was done by using a Philips Tecnai 12 microscope, with a 120 kV accelerating voltage. Before testing, the catalyst powder was ground and dispersed ultrasonically in anhydrous ethanol and then dropped onto a carbon-coated Cu grid of 200 mesh. Scanning electron microscope (SEM) testing was performed on JSM-7001F microscope made by JEOL. Accelerating voltage was 0.5–30 kV, magnification 10–800 K, and resolution 1.2 nm (30 kV)/3.0 nm (1 kV).


## 2.3. Catalyst Evaluation

The oxidation of NO to NO2 activity was measured at the temperatures in the range of 150–450°C. The catalysts were placed in a fixed-bed quartz mircoreactor with an inside diameter of 10 mm and plugged and sandwiched between two silica wool layers to prevent the sample from being blown away. The gases used in the tests were 500 ppm NO, 10% O2, and N2 in balance with a total flow rate of 280 mL/min, giving a space velocity of 56,000 h−1. The outlet NO and NO2 concentrations were detected by Thermo Scientific Model 42i-HL NOx Analyzer. Before each NO oxidation experiment, the catalyst sample was heated to 450°C in N2 atmosphere for 30 min, in order to clean up the residual gases adsorbed in the catalyst surface, and then cooled to the required measurement temperatures.


## 3. Results and Discussion

### 3.1. XRD Characterization

The X-ray diffraction patterns ofxMn10Ce/γ-Al2O3 (x = 4, 6, 8, and 10) catalysts are shown in Figure 1. As can be seen in Figure 1, all the samples exhibit characteristic peaks of γ-Al2O3 at 2θ = 25.74°, 35.32°, 37.93°, 43.53°, 53.72°, 57.65°, 66.68°, and 68.36° (JCPDS: PDF 10-0173). The main diffraction peaks at 2θ = 28.880°, 33.652°, 47.918°, and 56.762° were attributed to the (111), (200), (220), and (311) planes of cubic fluorite CeO2 (JCPDS: PDF43-1002) [18, 19]. Moreover, the diffraction peaks of CeO2 shifted to lower degrees for about 0.5°, the reason of which is that a part of Ce4+ ions is replaced by Mn4+ and Mn3+ to form solid solution [20]. According to Scherrer’s formula, the crystalline size of CeO2 (111) is 26 nm. Other two diffraction peaks at 2θ = 28.823° and 56.197° (which are overlapped with the peaks of CeO2) are identified as the phase of MnO2 (JCPDS: PDF 65-7467). In addition, when x
=
4, the diffraction peaks of Mn2O3 are not detected by XRD, which is in accordance with the small amount of manganese oxides, while the intensity increased with x (when x
≥
6).Figure 1
XRD pattern ofxMn10Ce/γ-Al2O3 catalysts.


### 3.2. SEM and EDS Analysis

SEM analysis of as-prepared catalysts was used to elucidate the surface morphology and distribution of the different components present. Figure2(a) shows the micrograph of 6Mn10Ce/γ-Al2O3 catalyst. As can be seen, the catalyst presents a morphology in the form of crisscrossed nanorods, which is γ-Al2O3, on which there are some particles of 10–30 nm (red circles) deposited that are CeO2 nanoparticles; the result is in accordance with the XRD (the size of CeO2 particle is 26 nm). In addition, some agglomerate particles with different sizes (80–300 nm) also deposited on γ-Al2O3, which can be the aggregates of MnOx and CeO2 (black circles). Figure 2(b) shows the surface elements of the sample; the main elements are Al, Mn, Ce, O, and C, which are from the white box area in Figure 2(a), among which the presence of C element can be attributed to the decomposition of citric acid and C4H6MnO4
·4H2O at high temperature during calcination.Figure 2
(a) SEM micrograph of 6Mn10Ce/γ-Al2O3 catalyst. (b) EDS pattern.
(a)
(b)


### 3.3. TEM Analysis

TEM is executed to ascertain the morphology of the catalyst. Figure3 shows the morphology of 6Mn10Ce/γ-Al2O3 catalyst. Obviously, the main structure of the catalyst is strip-shaped with nanosize, which is similar to the SEM analysis results. The small near-spherical particles with the size of about 5~30 nm (marked by the red circles), homogeneously dispersed on the surface of the catalyst, could be regarded as CeO2 or MnOx nanoparticles. Besides, the darker zone on the TEM pattern indicates a certain degree of aggregation between CeO2 and MnOx.Figure 3
TEM pattern of 6Mn10Ce/γ-Al2O3 catalyst.


### 3.4. Effect of Temperature on NO Conversion

Results on NO conversion as a function of temperature overxMn10Ce/γ-Al2O3 (x
=
4, 6, 8, and 10) catalysts are given in Figure 4. It is obvious that, in the range of 150°C to 300°C, NO conversion of all the catalysts increased with temperature, but when temperature is above 300°C, NO conversion decreased with temperature except for 4Mn10Ce/γ-Al2O3 catalyst (maximum NO conversion at 350°C). The NO conversion rate decreased mainly due to the accelerated thermal decomposition of NO2 under the influence of high temperature. In the whole range of temperature, the steady-state NO conversion goes through a maximum of 83.5% at temperature of 300°C on 6Mn10Ce/γ-Al2O3 catalyst, followed by 8Mn10Ce/γ-Al2O3 (82.7% at 300°C), 10Mn10Ce/γ-Al2O3 (80.5% at 300°C), and 4Mn10Ce/γ-Al2O3 (67.2% at 350°C). Compared with other catalysts, 6Mn10Ce/γ-Al2O3 presented better NO oxidation activity. The reason was that the properties of the catalysts depend mainly on the active components, especially the Mn/Ce ratio. According to the research by Qi and Li [21], MnOx are the main contributor for NO oxidation. Hence, with the increase of MnOx, the catalysts showed better oxidation capacity, while the average chemical valence of Mn4+ decreased; the interaction between catalysts activities and Mn content is nonlinear. Therefore, in our research, the catalyst obtained the best NO oxidation activity when the Mn/Ce ratio is 6/10.Figure 4
Oxidation activity of NO to NO2 by O2 on xMn10Ce/γ-Al2O3 (x
=
4, 6, 8, and 10) catalysts at different temperatures (the conditions: 500 ppm NO, 10% O2, N2 in balance and 280 mL/min total flow rate, and space velocity 56,000 h−1).


### 3.5. Effect of NO Concentration on NO Conversion

As described above, the 6Mn10Ce/γ-Al2O3 catalyst showed the best activity on NO to NO2 conversion of 83.5% at 300°C. In order to further study the effect of inlet NO concentrations on the NO to NO2 oxidation activity, the experiment, in the atmosphere of 500, 750, and 1000 ppm NO in 10% O2 with N2 as balance, respectively, was carried out. The NO conversion rate was calculated when the outlet NO concentration stabilized for 400 s. Results on NO conversion as a function of temperature over 6Mn10Ce/γ-Al2O3 catalyst are given in Figure 5. The result indicates that, in the range of 150–300°C, when inlet NO was 500 ppm, NO conversion rate was 32.9%–83.5%. In addition, with inlet NO concentration increasing, the NO conversion deceased by around 3% (NO = 750 ppm) and 5% (NO = 1000 ppm), respectively. Moreover, the NO conversion was almost maintained the same, whatever the inlet NO concentration in the range of 350–450°C was. However, the catalysts are sensitive to other pollution gases, such as SO2, CO, and H2O, which was still needed for further research.Figure 5
Oxidation activity of NO to NO2 by O2 on 6Mn10Ce/γ-Al2O3 catalyst at different temperatures (the conditions: 500, 750, and 1000 ppm NO, 10% O2, N2 in balance and 280 mL/min total flow rate, and space velocity 56,000 h−1).


## 3.1. XRD Characterization

The X-ray diffraction patterns ofxMn10Ce/γ-Al2O3 (x = 4, 6, 8, and 10) catalysts are shown in Figure 1. As can be seen in Figure 1, all the samples exhibit characteristic peaks of γ-Al2O3 at 2θ = 25.74°, 35.32°, 37.93°, 43.53°, 53.72°, 57.65°, 66.68°, and 68.36° (JCPDS: PDF 10-0173). The main diffraction peaks at 2θ = 28.880°, 33.652°, 47.918°, and 56.762° were attributed to the (111), (200), (220), and (311) planes of cubic fluorite CeO2 (JCPDS: PDF43-1002) [18, 19]. Moreover, the diffraction peaks of CeO2 shifted to lower degrees for about 0.5°, the reason of which is that a part of Ce4+ ions is replaced by Mn4+ and Mn3+ to form solid solution [20]. According to Scherrer’s formula, the crystalline size of CeO2 (111) is 26 nm. Other two diffraction peaks at 2θ = 28.823° and 56.197° (which are overlapped with the peaks of CeO2) are identified as the phase of MnO2 (JCPDS: PDF 65-7467). In addition, when x
=
4, the diffraction peaks of Mn2O3 are not detected by XRD, which is in accordance with the small amount of manganese oxides, while the intensity increased with x (when x
≥
6).Figure 1
XRD pattern ofxMn10Ce/γ-Al2O3 catalysts.


## 3.2. SEM and EDS Analysis

SEM analysis of as-prepared catalysts was used to elucidate the surface morphology and distribution of the different components present. Figure2(a) shows the micrograph of 6Mn10Ce/γ-Al2O3 catalyst. As can be seen, the catalyst presents a morphology in the form of crisscrossed nanorods, which is γ-Al2O3, on which there are some particles of 10–30 nm (red circles) deposited that are CeO2 nanoparticles; the result is in accordance with the XRD (the size of CeO2 particle is 26 nm). In addition, some agglomerate particles with different sizes (80–300 nm) also deposited on γ-Al2O3, which can be the aggregates of MnOx and CeO2 (black circles). Figure 2(b) shows the surface elements of the sample; the main elements are Al, Mn, Ce, O, and C, which are from the white box area in Figure 2(a), among which the presence of C element can be attributed to the decomposition of citric acid and C4H6MnO4
·4H2O at high temperature during calcination.Figure 2
(a) SEM micrograph of 6Mn10Ce/γ-Al2O3 catalyst. (b) EDS pattern.
(a)
(b)


## 3.3. TEM Analysis

TEM is executed to ascertain the morphology of the catalyst. Figure3 shows the morphology of 6Mn10Ce/γ-Al2O3 catalyst. Obviously, the main structure of the catalyst is strip-shaped with nanosize, which is similar to the SEM analysis results. The small near-spherical particles with the size of about 5~30 nm (marked by the red circles), homogeneously dispersed on the surface of the catalyst, could be regarded as CeO2 or MnOx nanoparticles. Besides, the darker zone on the TEM pattern indicates a certain degree of aggregation between CeO2 and MnOx.Figure 3
TEM pattern of 6Mn10Ce/γ-Al2O3 catalyst.


## 3.4. Effect of Temperature on NO Conversion

Results on NO conversion as a function of temperature overxMn10Ce/γ-Al2O3 (x
=
4, 6, 8, and 10) catalysts are given in Figure 4. It is obvious that, in the range of 150°C to 300°C, NO conversion of all the catalysts increased with temperature, but when temperature is above 300°C, NO conversion decreased with temperature except for 4Mn10Ce/γ-Al2O3 catalyst (maximum NO conversion at 350°C). The NO conversion rate decreased mainly due to the accelerated thermal decomposition of NO2 under the influence of high temperature. In the whole range of temperature, the steady-state NO conversion goes through a maximum of 83.5% at temperature of 300°C on 6Mn10Ce/γ-Al2O3 catalyst, followed by 8Mn10Ce/γ-Al2O3 (82.7% at 300°C), 10Mn10Ce/γ-Al2O3 (80.5% at 300°C), and 4Mn10Ce/γ-Al2O3 (67.2% at 350°C). Compared with other catalysts, 6Mn10Ce/γ-Al2O3 presented better NO oxidation activity. The reason was that the properties of the catalysts depend mainly on the active components, especially the Mn/Ce ratio. According to the research by Qi and Li [21], MnOx are the main contributor for NO oxidation. Hence, with the increase of MnOx, the catalysts showed better oxidation capacity, while the average chemical valence of Mn4+ decreased; the interaction between catalysts activities and Mn content is nonlinear. Therefore, in our research, the catalyst obtained the best NO oxidation activity when the Mn/Ce ratio is 6/10.Figure 4
Oxidation activity of NO to NO2 by O2 on xMn10Ce/γ-Al2O3 (x
=
4, 6, 8, and 10) catalysts at different temperatures (the conditions: 500 ppm NO, 10% O2, N2 in balance and 280 mL/min total flow rate, and space velocity 56,000 h−1).


## 3.5. Effect of NO Concentration on NO Conversion

As described above, the 6Mn10Ce/γ-Al2O3 catalyst showed the best activity on NO to NO2 conversion of 83.5% at 300°C. In order to further study the effect of inlet NO concentrations on the NO to NO2 oxidation activity, the experiment, in the atmosphere of 500, 750, and 1000 ppm NO in 10% O2 with N2 as balance, respectively, was carried out. The NO conversion rate was calculated when the outlet NO concentration stabilized for 400 s. Results on NO conversion as a function of temperature over 6Mn10Ce/γ-Al2O3 catalyst are given in Figure 5. The result indicates that, in the range of 150–300°C, when inlet NO was 500 ppm, NO conversion rate was 32.9%–83.5%. In addition, with inlet NO concentration increasing, the NO conversion deceased by around 3% (NO = 750 ppm) and 5% (NO = 1000 ppm), respectively. Moreover, the NO conversion was almost maintained the same, whatever the inlet NO concentration in the range of 350–450°C was. However, the catalysts are sensitive to other pollution gases, such as SO2, CO, and H2O, which was still needed for further research.Figure 5
Oxidation activity of NO to NO2 by O2 on 6Mn10Ce/γ-Al2O3 catalyst at different temperatures (the conditions: 500, 750, and 1000 ppm NO, 10% O2, N2 in balance and 280 mL/min total flow rate, and space velocity 56,000 h−1).


## 4. Conclusions

In the present work, a series ofxMn10Ce/γ-Al2O3 (x
=
4, 6, 8, and 10) catalysts were prepared by acid-aided sol-gel method and found to be well crystallized and dispersed, CeO2 and MnOx with the crystalline size of 5–30 nm. Compared with other catalysts, 6Mn10Ce/γ-Al2O3 catalyst showed higher activity for NO oxidation to NO2 over the temperature range of 150–450°C, up to 83.5% at 300°C.In addition, NO oxidation to NO2 was further studied under different NO concentrations over 6Mn10Ce/γ-Al2O3 catalyst. Generally, NO conversion augmented rapidly with temperature elevating in the range of 150–300°C for all different NO conditions. On the contrary, NO conversion decreased with temperature above 300°C. NO conversion reached maximum of 83.5%, 80.9%, and 76% for 500 ppm, 750 ppm, and 1000 ppm NO concentration, respectively, at 300°C. We also found that there was almost no effect of NO concentration on NO conversion above 350°C.



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*Source: 2103647-2016-04-28.xml*