Improved Surface Acidity of Niobium Doped Tungstated-Zirconia Solid Acid Catalyst over Production of 5-Hydroxymethylfurfural

Xiaojun Wang^{1, 2},
Ni Lu²,
Yuanyi Fu²,
Chang Lu²,
Meili Guan²,
Kunhua Wang^{1, 2
, ,},
Hao Yu^{1, 2
, ,}

1.
College of Energy Storage Technology, Shandong University of Science and Technology, Qingdao 266590, China
2.
College of Chemical and Biological Engineering, Shandong University of Science and Technology, Qingdao 266590, China

More Information

Corresponding author: E-mail: wangkhua@mail.ustc.edu.cn; haoyu@sdust.edu.cn

摘要

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Abstract: The 5-hydroxymethylfurfural (5-HMF) acts as an important chemical intermediate to bridge the biomass resources and industrial applications, which shows the potential for green development. However, the performance of biomass materials conversion to 5-HMF is still limited in the green solvent. Herein, an effective approach is reported to prepare the highly efficient solid acid catalysts, NbO_x /WO_y -ZrO₂, to improve fructose conversion. It is found that the introduction of Nb results in the generation of the niobium oxides, which improves acid sites and tunes the ratios of Brønsted acid and Lewis acid on the surface of the WO_y -ZrO₂ support. With the acidity improvement and increasing acid sites of the NbO_x /WO_y -ZrO₂, the highest fructose conversion is 99% in water. Meanwhile, the 5-HMF yield and the selectivity are also as high as 50.1% and 50.7% under the reaction temperature of 180 °C for a short reaction time of 30 min. The proposed NbO_x /WO_y -ZrO₂ catalyst strategy will not only open a new way for designing the solid acid catalysts to achieve high performance of the 5-HMF in the water, but also promote the green production of biomass and sustainable development in the future.
- Niobium oxide /
- Tungsten zirconia solid acid /
- Fructose /
- 5-Hydroxymethylfurfural /
- Acid site

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Figure 1. XRD patterns of pristine WO_y-ZrO₂ catalyst and NbO_x/WO_y-ZrO₂ catalysts with niobium loadings ranging from 1 wt% to 5 wt%.

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Figure 2. SEM image (a) and the corresponding elemental mapping of Zr (b), O (c), W (d), Nb, and (e) 1% NbO_x/WO_y-ZrO₂ catalyst. TEM image (f), the corresponding HRTEM characterization (g, h), and a SAED pattern (i) of 1% NbO_x/WO_y-ZrO₂ catalyst.

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Figure 3. NH₃-TPD spectra of the WO_y-ZrO₂, 1% NbO_x/WO_y-ZrO₂, and 5% NbO_x/WO_y-ZrO₂ catalyst.

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Figure 4. XPS spectra of the NbO_x /WO_y -ZrO₂ catalysts. (a) Zr 3d, (b) O 1s, (c) W 4f, and (d) Nb 3d.

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Table I. Influence of the reaction temperature on the fructose conversion under NbO_x /WO_y -ZrO₂ catalysts with different ratios of Nb loading at different temperature. Experimental condition: reaction timef Nb loading. Experimental condition: reaction time = 30 min.

Catalysts	Conversion/%			Yield/%			Selectivity/%
	160 °C	180 °C	200 °C	160 °C	180 °C	200 °C	160 °C	180 °C	200 °C
WO_y-ZrO₂	92	96	98	15.1	24.3	25.3	16.5	25.3	25.8
1%NbO_x/WO_y-ZrO₂	97	99	100	40.3	50.1	50.9	41.6	50.7	50.9
2%NbO_x/WO_y-ZrO₂	96	98	99	39.9	46.7	47.3	41.6	47.6	47.8
3%NbO_x/WO_y-ZrO₂	95	97	98	37.7	42.6	33.5	39.7	44.0	34.2
4%NbO_x/WO_y-ZrO₂	94	96	98	33.7	35.2	36.4	35.9	36.6	37.2
5%NbO_x/WO_y-ZrO₂	93	95	97	18.0	25.2	24.7	19.4	26.5	28.2

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Table II. Influence of the reaction time on the fructose conversion under NbO_x /WO_y -ZrO₂ catalysts with different ratios of Nb loading for different reaction time. Experimental conditions: temperature = 180 °C, 10 mg/mL of fructose.

Catalysts	Conversion/%
	10 min	20 min	30 min	40 min	50 min	60 min
WO_y-ZrO₂	80	90	88	85	81	78
1%NbO_x/WO_y-ZrO₂	93	96	95	94	93	90
2%NbO_x/WO_y-ZrO₂	96	99	97	97	96	95
3%NbO_x/WO_y-ZrO₂	97	99	98	98	97	96
4%NbO_x/WO_y-ZrO₂	97	99	98	99	98	97
5%NbO_x/WO_y-ZrO₂	98	99	99	99	99	97

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Table III. Influence of the reaction time on 5-HMF yield, and selectivity under NbO_x /WO_y -ZrO₂ catalysts with different ratios of Nb loading for different reaction time. Experimental conditions: temperature = 180 °C, 10 mg/mL of fructose.

Catalysts	Yield/%						Selectivity/%
Catalysts	10 min	20 min	30 min	40 min	50 min	60 min	10 min	20 min	30 min	40 min	50 min	60 min
WO_y-ZrO₂	22.1	23.3	24.3	23.0	22.2	21.3	27.7	25.1	25.3	23.7	22.8	21.7
1%NbO_x/WO_y-ZrO₂	30.7	41.3	50.1	46.3	39.6	32.9	34.1	43.0	50.7	46.8	40.0	33.2
2%NbO_x/WO_y-ZrO₂	29.9	36.0	46.7	39.3	33.3	30.1	34.0	37.9	48.1	40.1	34.0	30.4
3%NbO_x/WO_y-ZrO₂	26.5	29.9	37.6	32.3	30.8	28.7	31.2	31.8	38.8	33.0	31.1	29.0
4%NbO_x/WO_y-ZrO₂	18.7	20.4	25.2	22.1	21.9	19.7	23.1	22.0	26.2	22.8	22.3	19.9
5%NbO_x/WO_y-ZrO₂	15.0	17.2	20.9	18.4	14.1	11.5	19.3	19.1	22.0	19.1	14.5	11.8

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