PO43- coordinated Co2+ species on yttrium phosphate boosting the valorization of ethanol to butadiene

doi:10.1016/S1872-2067(23)64567-X

Abstract

Abstract:

Upgrading of sustainable ethanol into C₄ olefins by C-C coupling contributes to alleviating the dependency towards petroleum. The reaction network consists several key steps, whereas dehydration often competes with dehydrogenation over acidic catalyst. Herein, we report a designed bifunctional Co-YPO₄ catalyst with balanced active sites for dehydrogenation and condensation that can directly catalyze ethanol to butadiene. The YPO₄ can stabilize Co²⁺ species to form highly dispersed [Co-O-P] sites, which catalyze ethanol dehydrogenation to acetaldehyde. Additionally, the YPO₄ surface exposed Y³⁺ site, as Lewis acid center, which can effectively catalyze C-C coupling reaction. The addition of cobalt enhances the ethanol dehydrogenation process while reducing the surface acidity, thus inhibiting the formation of dehydration products and promoting the formation of butadiene. Kinetic measurements suggest that the rate-limiting step is the dehydrogenation of ethanol to acetaldehyde. The synthesized Co-YPO₄ shows a 68.5% selectivity of butadiene under a conversion of 78.2% at 350 °C and a weight hourly space velocity of 1.0 g_C2H5OH•g_Cat.^-1•h^-1.

Key words: Ethanol, Butadiene, Dehydrogenation, C-C coupling, Phosphate

Bai-Chuan Zhou, Wen-Cui Li, Jia Wang, Dan-Hui Sun, Shi-Yu Xiang, Xin-Qian Gao, An-Hui Lu. PO₄^3- coordinated Co²⁺ species on yttrium phosphate boosting the valorization of ethanol to butadiene[J]. Chinese Journal of Catalysis, 2024, 56: 166-175.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64567-X

https://www.cjcatal.com/EN/Y2024/V56/I1/166

Figures/Tables 9

Fig. 1. Temperature-dependence of ethanol conversion and products distribution over Co-YPO4 (1.0 wt%) (a), and YPO4 (b). Reaction conditions: 100 mg Co-YPO4 or YPO4, C2H5OH/N2 = 5.7/94.3, WHSV = 2.0 gC2H5OH?gcat-1?h-1. (c) Effect of Co loadings on ethanol conversion and products distribution. (d) Ethanol conversion and the selectivity of butadiene over different catalysts. Reaction conditions: 350 °C, 100 mg catalyst, C2H5OH/N2 = 5.7/94.3, WHSV = 2.0 gC2H5OH?gCat.-1?h-1, Vtotal = 30 mL?min-1.

Fig. 2. Characterization of Co-YPO4. Dark-field STEM image (a) and bright-field STEM image (b) of reduced Co-YPO4 (1.0 wt%) sample, and corresponding elemental maps for O, P, Co, Y (c-f).

Fig. 3. Characterization of Co-YPO4 and YPO4. In situ UV-vis DRS (a) and ex situ XPS (b) of Co-YPO4 (1.0 wt%) catalyst pretreatment at different atmosphere (air, H2, and ethanol). (c) In situ FTIR spectra of CO adsorption on YPO4 and Co-YPO4 (1.0 wt%) catalysts, recorded at -173 °C. (d) 31P MAS NMR spectra of YPO4 and Co-YPO4 (1.0 wt%) catalysts.

Fig. 4. Acid and base characterization of xCo-YPO4 and YPO4. (a) NH3- and (b) CO2-TPD-MS profiles.

Fig. 5. FTIR spectra of pyridine adsorbed on YPO4 and Co-YPO4 (1.0 wt%) catalysts.

Fig. 6. Dependence of product selectivity on the ethanol conversion over Co-YPO4 (a) and YPO4 (b) catalysts. Reaction conditions: 350 °C, C2H5OH/N2 = 5.7/94.3, WHSV = 1-50 gC2H5OH?gCat.-1?h-1, Vtotal = 30 mL?min-1.

Fig. 7. MS signal profiles of ethanol temperature-programmed surface reaction (TPSR) profiles over Co-YPO4 (a) and YPO4 (b) catalysts.

Scheme 1. Proposed reaction pathway for butadiene formation.

Fig. 8. (a) Ethanol conversion and products selectivity as a function of time-on-stream over Co-YPO4. Reaction conditions: 200 mg catalyst mass, T = 350 °C, PC2H5OH = 5.7 kPa, PN2 = 94.3 kPa, Vtotal = 30 mL·min-1. (b,c) Thermogravimetry (TG)-MS profiles of spent Co-YPO4 catalyst under a TPO environment.

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PO₄^3- coordinated Co²⁺ species on yttrium phosphate boosting the valorization of ethanol to butadiene

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