Defect-rich BN-supported Cu with superior dispersion for ethanol conversion to aldehyde and hydrogen

doi:10.1016/S1872-2067(21)63891-3

Abstract

Abstract:

Copper-based heterogeneous catalysts commonly exhibit uncontrolled growth of copper species under reaction conditions because of the low Hüttig temperature (surface mobility of atoms) and Tamman temperature (bulk mobility) for copper at just 134 and 405 °C, respectively. Herein, we report the use of defect-enriched hexagonal boron nitride nanosheets (BNSs) as a support to anchor the Cu species, which resulted in superior dispersion of the Cu species. The obtained Cu/BNS catalyst was highly stable for ethanol dehydrogenation, with a high selectivity of 98% for producing acetaldehyde and an exceptionally high acetaldehyde productivity of 7.33 g_AcH g_cat^‒1h^‒1under a weight hourly space velocity of 9.6 g_EtOH g_cat^‒1h^‒1. The overall performance of our designed catalyst far exceeded that of most reported heterogeneous catalysts in terms of the stability of the Cu species and the yield of acetaldehyde in this reaction. The hydroxyl groups at the defect edges of BNS were responsible for the stabilization of the copper species, and the metal-support interaction was reinforced through charge transfer, as evidenced by coupling atomic resolution images with probe molecule infrared spectroscopy and X-ray photoelectron spectroscopy. A designed in situ diffuse reflectance infrared Fourier transform spectroscopy study of ethanol/acetaldehyde adsorption further revealed that Cu/BNS favored ethanol adsorption while suppressing acetaldehyde adsorption and further side reactions. This study demonstrates a new method for designing highly dispersed Cu-based catalysts with high durability.

Key words: Ethanol dehydrogenation, Copper, Boron nitride nanosheet, Superior dispersion, In situ DRIFT

Shi-Qun Cheng, Xue-Fei Weng, Qing-Nan Wang, Bai-Chuan Zhou, Wen-Cui Li, Ming-Run Li, Lei He, Dong-Qi Wang, An-Hui Lu. Defect-rich BN-supported Cu with superior dispersion for ethanol conversion to aldehyde and hydrogen[J]. Chinese Journal of Catalysis, 2022, 43(4): 1092-1100.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63891-3

https://www.cjcatal.com/EN/Y2022/V43/I4/1092

Figures/Tables 6

Fig. 1. (a) XRD patterns of the BNS support and xCu/BNS catalysts after H2 treatment at 350 °C; Bright-field AC-STEM image (b) and the corresponding dark-field AC-STEM image (c) of 5Cu/BNS catalyst.

Fig. 2. (a) Light-off profiles of the 5Cu/BNS (red squares indicate the freshly reduced catalyst, red circles indicate the spent catalyst) and 5Cu/BN catalysts; the equilibrium conversions are presented in gray; (b) Productivity of acetaldehyde versus ethanol reaction rate for the catalysts described in this work and in the literature (the numbers in this Fig. refer to the references, Table S2); (c) Ethanol conversion as a function of time-on-stream (TOS) at 240 °C. (d) Arrhenius plots of xCu/BNS catalysts. Reaction conditions: 50 mg of catalyst, 10 vol% C2H5OH/N2, WHSV = 9.8 h-1for (a), (b), and (c); the catalyst weight was carefully varied (WHSV from 35 to 76 h-1) to keep ethanol conversion below 20%.

Fig. 3. (a) H2-TPR profiles of xCu/BNS, 5Cu/BN (8% H2/N2, 10 °C/min); (b) In situ XRD patterns of 5Cu/BNS catalyst under 8% H2/N2 at indicated temperatures; (c) FTIR spectra of CO adsorption on 1Cu/BNS and 5Cu/BNS samples at -173 °C; (d) Cu 2p XP spectra and (inset) Cu LMM XAE spectra of the in situ-reduced 5Cu/BNS; (e) NH3-TPD profiles of BNS and BN supports.

Fig. 4. Bright-field AC-STEM images (a,c) and the corresponding dark-field AC-STEM images (b,d) of the spent 5Cu/BNS catalyst for catalytic performance test.

Fig. 5. Each spectrum was collected immediately after a dose of ethanol to 5Cu/BNS, 5Cu/SiO2, and 5Cu/Al2O3 catalysts. Spectrum recorded before any ethanol dosing was used as the background. Reaction conditions: 240 °C, ~40 mg of catalyst, 5 × 10-8mol of C2H5OH in each dose, N2 as carrier gas.

Fig. 6. Each spectrum was collected immediately after a dose of acetaldehyde to the 5Cu/BNS, 5Cu/SiO2, and 5Cu/Al2O3 catalysts. Spectrum recorded before any acetaldehyde dosing was used as the background. Reaction conditions: 240 °C, ~40 mg of catalyst, 2 × 10-8mol CH3CHO in each dose, N2 as carrier gas.

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