Supporting Information 

Transformylating Amine with DMF to Formamide over CeO2 

Catalyst 

Yehong Wang, Feng Wang,* Chaofeng Zhang, Mingrun Li, Jian Zhang, and Jie Xu* 

 

State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian 

Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China) 

E‐mail: wangfeng@dicp.ac.cn; xujie@dicp.ac.cn 

Website: www.fwang.dicp.ac.cn 

 

Contents 

1. Chemicals and Reagents 

2. Catalyst Preparation 

3. Catalyst Characterization 

4. Catalytic Tests 

5. GC and MS spectra of the isotopic labelling experiments, reactions 3a‐3s.   

   

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1. Chemicals and Reagents 

All chemicals were of analytical grade and used as purchased without further 

purification. Most of chemicals were purchased from J&K Chemicals. 

(NH4)2[Ce(NO3)6], Ce(NO3)3∙6H2O, benzylamine and other various amines were 

purchased from Aladdin Chemicals.   

2. Catalyst Preparation   

The CeO2 samples were prepared by a precipitation method. Generally, 5.0 g of 

Ce(NO3)3∙6H2O was dissolved in 100 mL of Millipore purified water (18 mΩ∙cm‐1), and 

the solution was adjusted to pH=11.0 by NH4OH (3.4 M) under stirring at room 

temperature. The resulting gel mixture was then washed with water, dried in an oven 

at 115 ° C for 12 h, then calcined at 500 °C in air for 4 h. Some other catalysts were 

also obtained for comparison. The MoO3 sample was prepared according to the 

reference. [1] Nb2O5 was prepared by the calcination of NH4[Nb(C2O4)2(H2O)]∙6(H2O)n 

(provided by CBMM, Brazil) at 500 oC for 3 h. The oxides (TiO2, WO3, V2O5, ZrO2, Y2O3, 

Eu2O3, MnO2, Al2O3, MgO), zeolites (ZSM‐22, H‐ZSM‐5, Y, HY, H‐Beta, H‐MOR, 

SAPO‐11), and homogeneous acids [Sc(CF3SO3)3, Yb(CF3SO3)3], H3PO40W12∙xH2O and 

H4[Si(W3O10)4] were all commercially available (Aladdin and J&K).   

3. Catalyst Characterization 

The DMF/n‐butylamine‐adsorption IR method was conducted on a Tensor 27 

(Bruker) IR spectrometer. The sample was pressed into a self‐supporting disk (13 mm 

diameter, 25− 27.7 mg) and placed in a homemade IR cell a ached to a closed 

glass‐circulation system. Prior to adsorption, the sample disk was pretreated by 

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heating at 200 ° C for 1 h in vacuum (pressure <5.4×10−1Pa) and then cooled to 30 °C. 

After a spectrum was collected, the sample disk was exposed to DMF or 

n‐butylamine vapor. IR spectra of the chemisorbed DMF or n‐butylamine were 

recorded after evacuation at 100 °C, 150 °C, 200 °C for 0.5 h to eliminate physically 

adsorbed DMF or n‐butylamine. Spectra were collected after cooling to 30 °C. The 

surface area and of the samples were measured at ‐196 oC by using nitrogen 

adsorption according to the Brunauer–Emmett–Teller method (BET) by using a 

Quantachrome QUADRASORB‐SI apparatus. The acidity or alkali of the samples was 

characterized by performing temperature‐programmed desorption of ammonia or 

carbon dioxide (NH3‐TPD, CO2‐TPD) with an automated catalyst characterization 

system (Autochem 2920, Micromeritics) with a TCD detector. We used a calibration 

curve to calculate the ammonia or carbon dioxide amount by converting the peak 

area to concentration.   

4. Catalytic Tests   

The catalytic reactions were conducted in a glass batch reactor. Typically, 

benzylamine (1.5 mmol), N, N‐dimethylformamide (DMF, 2 mL), catalyst (100 mg) 

and a stirring bar were placed in a glass pressure reactor (heavy wall, max: 0.6 MPa, 

Synthware Glass) with a Teflon bushing. The reactor was then immersed in an oil 

bath preheated at the desired reaction temperature. After the reaction was 

completed in 0.5 h‐12 h, the catalyst was filtered out, washed with acetone for three 

times, dried at 115 oC and then calcined at 500 oC for 4 h prior to further use in 

recycling experiment. Products were confirmed by a GC‐MS (Agilent 7890A‐5975C). 

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The conversion and selectivity were determined by normalizing Gas Chromatography 

(GC, Agilent 7890A) integration area. Product yields were calculated by multiplying 

conversion by selectivity.   

 

 

   

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Table S1. Catalyst screening in the formylation of benzyl amine to benzyl amide.[a] 

No.  Catalyst  A–B[b]  SBET (m2 g–1) Conv (%) Select (%) 

1  –  –  –  0  0 

Zeolites 

2  NaY  MA  17  6  17 

3  H‐MOR  SA  80  15  80 

4  HZSM‐5  SA  79  19  79 

5  HY  SA  59  22  59 

6  ZSM‐22  SA  77  22  77 

7  SAPO‐11  SA  65  23  65 

8  H‐β  SA  91  43  91 

Metal oxides 

9  Eu2O3  WB  23  5  40 

10  MgO  SB  32  8  25 

11  WO3  MA  8  8  50 

12  Y2O3  WB  8  9  33 

13  Nb2O5  MA  21  14  93 

14  V2O5  MA  13  82  32 

15  α‐MnO2  MA  49  95  5 

16  ZrO2  MA+MB 9  23  52 

17  α‐Al2O3  SA+WB  74  23  65 

18  TiO2[c]  MA+MB 73  25  96 

19  CeO2  MA+SB  67  80  >99 

20  CeO2[d]  MA+SB  67  95  >99 

21  CeO2[e]  MA+SB  67  67  98 

[a] Reaction conditions: catalyst 100 mg, BAn 1.5 mmol, DMF 2 mL, 100 oC, 4 h. 

[b] Classification of metal oxides was from literature.[2] Symbols: Weak (W), Medium 

(M) and Strong (S); Acid (A) and Base (B). [c] Anatase. [d] 180 oC, 8h. [e] 100 oC, 4 h, 

1.9 mL DMF, 0.1 mL H2O.   

   

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0 20 40 60 80 100

0

20

40

60

80

100

Yiel

d of

BAd

/ %

Specific surface area / m2 g-1

CeO2

Figure S3 The relationship of the specific surface of zeolites and metal oxides against 

the yield of BAd. No clear dependence of surface area was observed. The data were 

from Table S1. 

   

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0 1 2 3 4 5 6

0

20

40

60

80

100 P

erce

ntag

e (%

)

Conversion of benzyl amine Selectivity for benzyl amide Conversion fo benzyl amine in hot filtration test Selectivity for benzyl amide in hot filtration test

Time (h)

Figure S4 Catalyst hot filtration test. Reaction condition: catalyst 100 mg, benzyl 

amine 1.5 mmol, DMF 2 mL. The catalyst was filtered out in 30 min and the filtrate 

was further reacted under the same reaction condition at 100 oC. 

   

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0

20

40

60

80

100

Catalyst reusability test

4th

Perc

enta

ge (%

)

Conversion Selectivity

fresh 1st 2nd 3rd

 

Figure S5 Reusability of ceria in the transformylation of benzyl amine to benzyl amide. 

Reaction conditions: Catalyst 100 mg, benzy amine 1.5 mmol, DMF 2mL, 160 oC, 5h.   

   

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Figure S6 TEM of (a) nano‐rod, (b) nano‐octahedral, and (c) nano‐cube and HETEM of 

(e) nano‐rod, (f) nano‐octahedral, and (g) nano‐cube.   

   

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100 200 300 400 500

Inte

nsity

(a.u

.)

Temperature (oC)

after TEA treatment CeO

2

(a)163 246

315 394

 

100 200 300 400 500

Inte

nsity

(a.u

.)

Temperature (oC)

after HCl treatment CeO

2

(b)

103

 

Figure S7 (a) NH3‐TPD of ceria and ceria after TEA treatment (b) CO2‐TPD of ceria and 

ceria after HCl treatment   

   

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Figure S8. Tentative reaction mechanism. 

 

   

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3500 3400 3300 3200 3100

B

(c)

(b)

Abso

rban

ce (a

.u.)

Wavenumber (cm-1)

33403268

33503415

0.1

(a)

(c)

(b)

(a)

A

1700 1650 1600 1550

Wavenumber (cm-1)

1560

1623

0.2

 

Figure S9 In situ FT‐IR of n‐butylamine absorbed on CeO2 and desorption at (a) 100 oC 

and (b) 150 oC (c) FT‐IR of liquid n‐butylamine   

   

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1740 1720 1700 1680 1660 1640 1620 1600

Wavenumber (cm-1)

Abso

rban

ce (a

.u.)

100 oC

150 oC

200 oC

1646

0.2

 

Figure S10 In situ absorbing FT‐IR of DMF absorbed on CeO2 pretreated at 500 oC. 

   

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Reference   

[1]  F. Wang, W. Ueda, Chemical Communications 2008, 3196‐3198. 

[2]  G. Busca, Phys. Chem. Chem. Phys. 1999, 1, 723‐736. 

 

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TIC: 130709-12-B.D\data.ms

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79.1

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225.2

51.028.0 39.0165.1118.0 152.1 194.1178.1140.9127.1 206.798.914.9 58.4

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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130.085.0 97.918.0 45.1 71.1 207.1157.5

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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18.0 98.085.0 113.7 206.8143.4127.7 160.9

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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134.1

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57.0 85.014.9 97.8 127.9 163.0 175.2113.6 142.7 206.8

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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65.038.950.928.0 210.2165.0

178.817.0 191.0139.9 147.2

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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77.0125.0

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51.028.0 63.0 113.099.039.0 168.0152.057.015.9 69.8 119.1 206.9185.982.6

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111.050.038.9 199.0190.082.128.0 206.9131.6 176.9118.0 214.0158.815.1

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165.1121.1

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132.065.051.0 106.938.9 167.0 196.0180.0 210.1139.014.9 224.2154.127.9 83.5 98.2

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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度71.0

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46.015.0 61.9 134.1 207.074.7 117.0 140.9 149.0

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.81.0

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28.0 71.118.0 94.0 108.0

36.9 65.047.5 188.2141.0 154.1 162.8

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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.141.0

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53.018.070.0

63.0 78.0122.9105.9 207.090.9 170.0 194.0153.8128.7 134.9 180.9161.1

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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110.028.0 63.0 83.0 178.938.0 134.989.0 103.4 146.977.0 162.0 172.0140.9117.0 153.9 191.8 219.9

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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丰121.1

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59.9 87.0 104.0 135.015.9 44.7 207.1192.8

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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91.1 106.1

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57.0 73.0 85.016.0 149.098.9 157.1 207.145.1

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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57.0 73.0 84.816.0 148.899.7 207.0

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: 91.1

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28.0 165.0152.1 179.0134.0 140.917.8 71.3 126.1 207.2

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013

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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013