Preparation of MIL-88B(Fex,Co1‒x) catalysts and their application in one-step liquid-phase methanol oxidation to methyl formate using H2O2

doi:10.1016/S1872-2067(20)63749-4

Abstract

Abstract:

The selective oxidation of methanol to methyl formate is one of the most attractive processes to obtain value-added methanol-downstream products. The development of highly efficient and stable catalysts is critical for this transformation. In this study, a series of MIL-88B(Fe_x,Co_1-_x) bimetallic catalysts with different Fe/Co molar ratios were prepared through a one-pot hydrothermal method. X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, energy dispersive spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, N₂ adsorption-desorption, and inductively coupled plasma-mass spectrometry characterization were performed to elucidate the structure of the catalysts. The activity of the catalysts were assessed in the one-step oxidation of methanol to methyl formate with H₂O₂ in a liquid-phase batch reactor. The results show that the MIL-88B(Fe_x,Co_1-_x) catalysts exhibit uniform needle-like morphologies with an average length and width of 400-600 nm and 100-150 nm, respectively. Co²⁺ is incorporated into the framework by partially replacing Fe³⁺ in MIL-88B. Moreover, the catalyst efficiently promoted the conversion of methanol to methyl formate. When MIL-88B(Fe_0.7,Co_0.3) catalyst was used with a molar ratio of H₂O₂ to methanol of 0.5 at 80 °C for 60 min, 34.8% methanol conversion was achieved, and the selectivity toward methyl formate was 67.6%. The catalysts also showed great stability with a steady conversion and selectivity even after four cycles. The preliminary oxidation mechanism was also studied. It was determined that H₂O₂ is first adsorbed on the Fe³⁺ sites and subsequently activates these sites. Methanol is adsorbed by the O atoms of the framework through hydrogen bonding and is gradually oxidized to formic acid. Subsequently, formic acid reacts with the residual methanol at the Fe³⁺ and Co²⁺ Lewis acid sites to form methyl formate.

Key words: Bimetal-organic frameworks, Methanol oxidation, Liquid phase, One-step transformation, Methyl formate

Jianfang Liu, Zhenzhen Ran, Qiyan Cao, Shengfu Ji. Preparation of MIL-88B(Fe_x,Co_1‒_x) catalysts and their application in one-step liquid-phase methanol oxidation to methyl formate using H₂O₂[J]. Chinese Journal of Catalysis, 2021, 42(12): 2254-2264.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63749-4

https://www.cjcatal.com/EN/Y2021/V42/I12/2254

Figures/Tables 17

Fig. 1. Powder XRD patterns of MIL-88B(Fe), MIL-88B(Fe0.8,Co0.2), MIL-88B(Fe0.7,Co0.3), MIL-88B(Fe0.4,Co0.6), MOF-Co, and the simulated MIL-88B.

Fig. 2. SEM images of MIL-88B(Fe) (a), MIL-88B(Fe0.8,Co0.2) (b), MIL-88B(Fe0.7,Co0.3) (c), MIL-88B(Fe0.4,Co0.6) (d), MOF-Co (e,f); (g) SEM-EDS images of MIL-88B(Fe0.7,Co0.3).

Fig. 3. HAADF-STEM image and STEM-EDS mapping images of MIL-88B(Fe0.7,Co0.3).

Fig. 4. FTIR spectra of MIL-88B(Fe) (a), MIL-88B(Fe0.8,Co0.2) (b), MIL-88B(Fe0.7,Co0.3) (c), MIL-88B(Fe0.4,Co0.6) (d), and MOF-Co (e) samples.

Table 1 XPS data of the MIL-88B(Fe0.7,Co0.3) catalysts.

Element	Binding energy (eV)	FWHM (eV)	Atomic (%)
C 1s	284.8	3.11	74.49
O 1s	532.4	3.04	24.41
Fe 2p	711.2	3.97	0.85
Co 2p	778.0	0.18	0.24

Fig. 5. High-resolution XPS spectra of Fe 2p (a) and Co 2p (b) for MIL-88B(Fe), MIL-88B(Fe0.7,Co0.3), and MOF-Co.

Fig. 6. N2 adsorption-desorption isotherms of MIL-88B(Fe), MIL-88B(Fe0.7,Co0.3), and MOF-Co.

Table 2 Surface area, pore volume, and diameter parameters of the samples.

Sample	A_BET (m² g^‒1)	V (cm³ g^‒1)	D (nm)
MIL-88B(Fe)	179	0.15	1.2
MIL-88B(Fe_0.7,Co_0.3)	46	0.09	11.3
MOF-Co	18	0.07	22.8

Fig. 7. Effect of the reaction temperature on the catalytic performance of MIL-88B(Fe0.7,Co0.3). Reaction conditions: V(MeOH) = 5 mL, m(catalyst) = 30 mg, n(H2O2/MeOH) = 0.5, t = 60 min.

Fig. 8. Effect of catalyst dosage on the catalytic performance of MIL-88B(Fe0.7,Co0.3). Reaction conditions: V(MeOH) = 5 mL, n(H2O2/MeOH) = 0.5, T = 80 °C, and t = 60 min.

Fig. 9. Effect of H2O2 dosage on the catalytic performance of MIL-88B(Fe0.7,Co0.3). Reaction conditions: V(MeOH) = 5 mL, m(catalyst) = 30 mg, T = 80 °C, and t = 60 min.

Fig. 10. Effect of the reaction time on the catalytic performance of MIL-88B(Fe0.7,Co0.3). Reaction conditions: V(MeOH) = 5 mL, m(catalyst) = 30 mg, n(H2O2/MeOH) = 0.5, and T = 80 °C.

Fig. 11. Catalytic performance of MIL-88B(Fex,Co1-x) containing different Co-doping contents. Reaction conditions: V(MeOH) = 5 mL, m(catalyst) = 30 mg, n(H2O2/MeOH) = 0.5, T = 80 °C, and t = 60 min.

Table 3 Catalytic performances of the different catalysts.

Entry	Catalyst	Conversion (%)	MF selectivity (%)	Yield of MF (%)
1	MIL-88B(Fe)	41.8	50.7	21.2
2	MIL-88B(Fe_0.7,Co_0.3)	34.8	67.6	23.5
3	MIL-88B(Fe_0.7,Ni_0.3)	34.8	56.1	19.5
4	MIL-88B(Fe_0.7,Zn_0.3)	17.8	45.9	8.2
5	MIL-88B(Fe_0.7,Cu_0.3)	28.5	50.9	14.5
6	MIL-88B(Fe_0.7,Cr_0.3)	25.0	48.8	12.2

Fig. 12. Reusability of the MIL-88B(Fe0.7,Co0.3) catalyst. Reaction conditions: V(MeOH) = 5 mL, m(catalyst) = 30 mg, n(H2O2/MeOH) = 0.5, T = 80 °C, and t = 60 min.

Fig. 13. XRD patterns (a) and FTIR spectra (b) of fresh and used MIL-88B(Fe0.7,Co0.3) catalyst.

Fig. 14. Possible reaction mechanism for the methanol oxidation conversion.

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Preparation of MIL-88B(Fe_x,Co_1‒_x) catalysts and their application in one-step liquid-phase methanol oxidation to methyl formate using H₂O₂

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