Unraveling the active states of WO3-based catalysts in the selective conversion of cellulose to glycols

doi:10.1016/S1872-2067(22)64187-1

Abstract

Abstract:

Tungsten-based catalysts, including crystalline WO₃ and H₂WO₄, have been reported to be efficient for the selective cleavage of C−C bonds of sugar intermediates involved in the conversion of cellulose to ethylene glycol and propylene glycol in combination with hydrogenation catalysts under H₂ atmosphere. However, there is still not a consensus on the actual states of these catalysts during the reaction. Herein, we demonstrate that both WO₃ and H₂WO₄ tended to undergo reduction to hydrogen tungsten bronze (H_xWO₃) species in the cellulose reaction, consisting of H_0.23WO₃ and H_0.33WO₃, which were then re-oxidized to WO₃ upon exposure to ambient air after the reaction. Both WO₃ and H_xWO₃ were insoluble in water and acted as the heterogeneous catalysts in the cellulose reaction, as further validated by the strong dependence of the catalytic activity of WO₃ on its crystallite size and surface area. Such identification of the heterogeneous H_xWO₃ species, albeit exemplified here only from the in situ reduction of WO₃ and H₂WO₄ in the cellulose reaction, unravels the active state of the tungsten-based catalysts under reductive reaction conditions.

Key words: Cellulose, Tungsten trioxide, Hydrogen tungsten bronze, Ethylene glycol, Hydrogenation

Yue Liu, Wei Zhang, Haichao Liu. Unraveling the active states of WO₃-based catalysts in the selective conversion of cellulose to glycols[J]. Chinese Journal of Catalysis, 2023, 46: 56-63.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64187-1

https://www.cjcatal.com/EN/Y2023/V46/I3/56

Figures/Tables 11

Table 1 Cellulose conversion and product selectivity under catalysis of WO3 and Ru/C a

Entry	WO₃ loading (g)	Conversion (%)	Product selectivity (carbon%)
Entry	WO₃ loading (g)	Conversion (%)	Ethylene glycol	Triols ^b	Tetritols ^c	Pentitols ^d	Hexitols ^e
1	0	12.5	7.5	6.3	3.2	10.3	64.7
2	0.1	16.2	16.8	9.4	3.8	6.7	56.1
3	0.2	18.1	24.9	12.0	9.8	3.5	42.9
4	0.5	20.4	48.3	9.2	9.3	1.5	21.8
5	1.0	23.4	51.5	9.5	3.8	1.1	16.9

Fig. 1. XRD patterns of WO3 before and after cellulose reaction. Reaction conditions: 1.0 g WO3, 0.02 g Ru/C, 6 MPa H2, 40 mL water, 1.0 g cellulose, 478 K, 30 min.

Fig. 2. XRD patterns of WO3 before and after treatment under sugar reaction conditions in the 2θ range of 10°?60° (a) and of 22°?25° for clarity (b). Experimental conditions: 453 K, 6 MPa H2, 20 mL water, 0.02 g Ru/C, 1.0 g WO3. In order to minimize the exposure of WO3 samples to ambient air, XRD measurement was carried out immediately after their treatment by transferring them from autoclave reactor to XRD sample holder in slurry with the reaction solution.

Scheme 1. Changes of WO3 in the catalytic reaction of cellulose.

Fig. 3. (a) UV-Vis spectra of WO3 mixed with Ru/C as a function of exposure time to 1 bar H2 and 3 kPa H2O at 453 K, and (b) the evolution of reflectance at 700 nm with exposure time to H2 and water vapor at 453 K and after switching to dry air at 298 K. Experiment conditions: 1.0 g WO3, 0.01 g 3%Ru/C, 50 mL/min H2 carrying 3 kPa H2O vapor at 453 K or 50 mL/min dry air at 298 K.

Table 2 Surface W6+ fractions on fresh and used W2C, W and WO2 catalysts.a

Catalyst	W⁶⁺ fraction
Catalyst	On fresh catalyst	On used catalyst
W₂C	46%	95%
W	54%	98%
WO₂	68%	99%

Fig. 5. Comparison of WO3 and WO3(s). (a) XRD patterns of WO3 and WO3(s). (b) Conversions and product selectivities of cellulose reactions catalyzed by WO3 and WO3(s). Reaction condition: 1.0 g cellulose, 0.05 g WO3 or WO3(s), [0.5 g for WO3(s) × 10], 0.05 g Ru/C, 40 mL H2O, 6 MPa H2, 478 K, 30 min.

Fig. 4. XRD patterns of H2WO4 before and after cellulose reaction. Reaction conditions: 1.0 g H2WO4, 0.02 g Ru/C, 6 MPa H2, 40 mL water, 1.0 g cellulose, 478 K, 30 min.

Scheme 2. Changes of tungsten species during catalytic reactions of cellulose under H2 atmosphere in the presence of Ru/C.

Fig. 6. Electrical conductance of water as a function of temperature in the presence and absence of WO3 and HxWO3. For clearly discerning the data points, in the inset graph the temperature of the result from WO3 and HxWO3 were purposely shifted by ?5 K and +5 K, respectively. Experimental conditions: 10 mL water, 0.25 g WO3 or HxWO3.

Fig. 7. Comparison of cellulose reactions catalyzed by WO3 and HxWO3. (a) Cellulose conversion and yields of ethylene glycol and sorbitol as a function of reaction time. (b) Selectivity of ethylene glycol and sorbitol at different conversions of cellulose. Reaction conditions: 1.0 g cellulose, 1.0 g WO3 or HxWO3, 0.03 g Ru/C, 40 mL H2O, 6 MPa H2, 478 K.

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Unraveling the active states of WO₃-based catalysts in the selective conversion of cellulose to glycols

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