In situ FTIR study of methanol oxidation over CuY catalyst

Chen Pengzhen 12.12.14

CH3OH(25%)

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.05 t2956

2852

0.2

0.05

1459

13601658

2956 and 2844:anti-symmetric and symmetric C-H for methanol 1459: deformation of methyl groups1360: OH deformation band for molecular methanol

CH3OH(25%)+O2

3800 3700 3600 3500 3400 3300 3200 3100

Absorbance(a.u.)

Wavenumbers(cm-1)

0.05 t

以吸附甲醇后的谱图作为背景 O2 ： 2.0mL/min 单独进样

3578

CH3OH(25%)+O2

以吸附甲醇后的谱图作为背景 O2 ： 2.0mL/min 单独进样

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.02 t

2934

2897

2830

29542850

0.1

0.3

1580

1378

2896: C-H vibration in HCHO

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.04 t

0.1

0.2

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.04 t

2960

2854

28962832

0.1

0.1

1459

1376

1589

O2:2.0 ml/minHe:30ml/min

O2:2.0 ml/min

CH3OH(25%)+O2+CH3OH

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.05t

0.1

0.05

1673

1586 1457

1370

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.04 t

0.1

0.04

CH3OH(35%)

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.05t

0.1

0.2

CH3OH(35%)+O2

O2 ： 2.0mL/min 单独进样

CH3OH(35%)+O2+CH3OH

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.04 t

0.05

0.03

CH3OH(25%)+O2

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

t

Absorbance(a.u.)

Wavenumbers(cm-1)

0.3 t

0.2

0.1

30℃ 下进行甲醇的吸附 O2 ： 2.0mL/min 单独进样

3100 3000 2900 2800 2200 2100 1800 1700 1600 1500 1400 1300

Absorbance(a.u.)

Wavenumbers(cm-1)

0.2

50

70

100

120

140

200250

0.2

0.05

Effect of temperature

16301656

2300 2200 2100 2000

Absorbance(a.u.)

Wavenumbers(cm-1)

0.2 t

2300 2200 2100 2000

Absorbance(a.u.)

Wavenumbers(cm-1)

0.1

t

2300 2200 2100 2000

Absorbance(a.u.)

Wavenumbers(cm-1)

0.1 t

CO adsorption on CuY(10)

CuY(10) 25% CuY(10) 35% CuY(10) 25%

Work plan

1 、 Adsorption of formaldehyde on CuY(10) catalyst ， followed by addition of methanol to the in situ cell 。

2 、 MS study of the oxidation of methanol over CuY(10) catalyst 。

3 、 The origin of oxygen atom in DMC ， mainly about from methanol or oxygen 。

Jakob, P. (2010). Reactions of Methanol on Ru(0001). Journal of Phsical Chemical C, 114: 2655-2663

Mingfei Zhou (2004). Matrix Isolation Infrared Spectroscopic and Density Functional Theoretical Studies of the Reactions of Scandium Atoms with Methanol. Journal of Phsical Chemical A 108: 5950-5955.

As with the other methanol isotopologues , several of the CH318OH ν8 CO-

stretching subbands show evidence of perturbations due to intermode interactions, most notably with excited torsional levels of the ground state or with the ν7 in-plane CH3-rocking mode . The perturbations can either extend over an entire substate or be strongly localized due to a sharp level-crossing resonance. An interesting aspect of this coupling is the effect of “isotopic tuning” since the CO-stretch is lowered significantly by isotopic substitution on either the C or the O atom whereas the ground state torsion and the CH3-rock are relatively unaffected. Thus, different substates come into resonance as the origin of the CO-stretch band shifts down from approximately 1034 cm-1 for the parent normal CH3OH to 1018 cm-1 for 13CH3OH and then to 1007 cm-1 for CH3

18OH.

Lees R. M. (2009). Fourier transform spectroscopy of the CO-stretching band of O-18 methanol. Journal of Molecular Spectroscopy. 256(1): 91-98.

Mingfei Zhou (2003). Matrix Isolation FTIR Spectroscopic and Density Functional Theoretical Studies of the Reactions of Magnesium Atoms with Methanol. Journal of Phsical Chemical A 107: 11380-11385.

Zhao, S. B. (1995). Fourier Transform Spectroscopy of CH318OH The In-plane CH3-Rocking Band. Journal of Molecular Spectroscopy. 172: 153-175.

Fig. 1 . IR spectrum of CH316OH(—) or CH3

18OH (····) absorbed : A) on ThO2 after a few minutes of evacuation at 200℃ ，

B) on CeO2 after a few minutes of evacuation at 100℃

J. Lamotte (1988). FTIR study of the structure and reactivity of methoxy species on ThO2 and CeO2. React. Kinet. Catal. Lett 36(1): 113-118.

1124

9851013

1088

1029

1061

1104 1068

1057

1025

1013 985

1042

1012

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