Hydrodeoxygenation of phenol as a bio-oil model compound over intimate contact noble metal–Ni<sub>2</sub>P/SiO<sub>2</sub> catalysts

Li, Yunhua; Yang, Xin; Zhu, Linhui; Zhang, Hua; Chen, Binghui

doi:10.1039/c5ra11203f

Cited by 32 publications

(16 citation statements)

References 25 publications

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“…For the 3.1 % NiO x ‐6.9 % Ni 2 P/SiO 2 catalysts, the conversion of phenol was 97.3 % and the selectivity of cyclohexane was 73.7 %. The yield of cyclohexane (71.7 %) over 3.1 % NiO x ‐6.9 % Ni 2 P/SiO 2 was much higher than that of the other three catalysts and those reported previously, which confirmed that there are distinct synergistic effects of oxygen vacancies in NiO x for hydrogenation and Lewis acid sites in Ni 2 P for deoxygenation (Figure ).…”

Section: Resultssupporting

confidence: 78%

Synergetic Catalysis of Nickel Oxides with Oxygen Vacancies and Nickel Phosphide for the Highly Efficient Hydrodeoxygenation of Phenolic Compounds

Zhao

Chen

et al. 2018

ChemCatChem

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The highly efficient hydrodeoxygenation of oxygenated chemicals at a low temperature is a critical issue for biomass crude oil upgrading to reduce equipment and operation expense. The unique electronic features of oxygen vacancies have been found to facilitate deoxygenation above 250 °C. In this work, a series of NiOx/SiO2 catalysts that contain oxygen vacancies was prepared by a sol–gel and controllable temperature‐programmed reduction method. Results show that NiOx/SiO2 has a superior phenol hydrogenation activity in deoxygenation even at 180 °C to Ni2P/SiO2. The high hydrogenation activity derives from the flat adsorption of phenolics over low‐valence Ni cations induced by connected oxygen vacancies. After the introduction of NiOx into Ni2P catalysts, composite NiOx‐Ni2P/SiO2 (0.43≤x<1) bifunctional catalysts demonstrate better phenol hydrodeoxygenation performances under mild reaction conditions in comparison with individual Ni2P and NiOx catalysts and most catalysts presented previously because the coexistence of oxygen vacancies from NiOx and the acidity induced by Ni2P results in the synergistic effect of the adsorption configuration and hydrodeoxygenation ability. Besides, this composite catalyst also has a high activity for the hydrodeoxygenation of different bio‐derived cresol isomers. The reuse test results confirm that oxygen vacancies are relatively stable in comparison with the phosphide.

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Section: Resultssupporting

confidence: 78%

Synergetic Catalysis of Nickel Oxides with Oxygen Vacancies and Nickel Phosphide for the Highly Efficient Hydrodeoxygenation of Phenolic Compounds

Zhao

Chen

et al. 2018

ChemCatChem

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“…It is well known that P sites in the phosphides have “ligand” (or electronic) and “ensemble” (or geometrical) effects on metal sites, and the metal phosphides have both metallic and acidic properties. Hence, several researchers have been applied them for the hydrodeoxygenation of biofuel model compounds, such as phenol, 4‐methylphenol, guaiacol, anisole, palmitic acid, methyl palmitate, methyl oleate, and so on. However, to the best of our knowledge, the bulk metal phosphide catalysts have not been reported in liquid phase HDO of FAL to 2‐MF …”

Section: Introductionmentioning

confidence: 99%

Metal Phosphide:A Highly Efficient Catalyst for the Selective Hydrodeoxygenation of Furfural to 2‐Methylfuran

et al. 2018

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A series of metal phosphides were prepared by temperature programmed reduction and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), 31 P magic angle spinning nuclear magnetic resonance ( 31 P MAS NMR), ammonia temperature programmed desorption (NH 3 -TPD) and pyridine infrared spectroscopy (Py-IR), their catalytic performance were investigated in the hydrodeoxygenation of furfural to form 2methylfuran. The effects of metal phosphide and the initial P/Ni molar ratios on the hydrodeoxygenation of furfural were studied, and the reaction conditions were optimized. Furfural was thoroughly converted when the reaction was carried out under 240 8C and 2.0 MPa for 4 h over MoP or Ni 2 P, and the selectivity of 2-methylfuran was achieved 83.1% when the Ni 2 P_0.5 was employed as a catalyst. Under the optimal reaction conditions, the Ni 2 P_0.5 catalyst could be used for six times with slightly decrease in catalytic performance.

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“…35 In the previous study, we systematically studied phenol HDO over Ni 2 P and Ni 2 P@Pd supported catalysts using autoclave reactors. 36,37 However, the main products are cyclohexane and cyclohexanol over these catalysts. Herein, the inuence of the HDO reaction conditions on the reaction products is investigated over the base metal phosphide in a xed bed.…”

Section: -34mentioning

confidence: 99%

“…36. In a typical preparation, 2.62 g Ni (NO 3 ) 2 $6H 2 O and 60 g urea were dissolved in 225 mL deionized water and stirred for 30 min.…”

Section: Catalyst Synthesismentioning

confidence: 99%

Highly selective hydrodeoxygenation of anisole, phenol and guaiacol to benzene over nickel phosphide

Juan

Chen

2017

RSC Adv.

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Ni 2 P supported catalysts have extensively been studied for various hydrodeoxygenation (HDO) reactions.However, the main products are cyclohexane or cyclohexanol for lignin-derived compounds HDO over these catalysts. In this study, we investigate the catalytic conversion of anisole, phenol and guaiacol to benzene over Ni 2 P/SiO 2 by probing the reaction conditions. The results show that a lower reaction temperature and higher H 2 pressure favour the hydrogenation of these model chemicals to cyclohexane, whereas a higher reaction temperature and lower H 2 pressure aid the generation of benzene. The cyclohexane and benzene yields are 89.8% and 96.0% at 1.5 MPa and 573 K and 0.5 MPa and 673 K, respectively. By eliminating the influence of internal and external diffusion, the low intrinsic activation energy of 58.2 kJ mol À1 is obtained, which explains the high catalytic activity. In addition, although guaiacol HDO has a low conversion due to the space steric effect of its substituents, it presents a similar reaction pathway to obtain anisole and phenol, which is dependent on reaction conditions. The long-run evaluation experiment shows that the activity and selectivity of anisole HDO to benzene changes slightly for 36 h.

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Hydrodeoxygenation of phenol as a bio-oil model compound over intimate contact noble metal–Ni₂P/SiO₂ catalysts

Abstract: 1% Pd–10% Ni2P/SiO2, from a Ni2P reducing noble metal precursor, presents a high activity and cyclohexanol or cyclohexane selectivity due to more active sites and electrons transferring from Ni2P to the noble metal.

Cited by 32 publications

References 25 publications

Synergetic Catalysis of Nickel Oxides with Oxygen Vacancies and Nickel Phosphide for the Highly Efficient Hydrodeoxygenation of Phenolic Compounds

Synergetic Catalysis of Nickel Oxides with Oxygen Vacancies and Nickel Phosphide for the Highly Efficient Hydrodeoxygenation of Phenolic Compounds

Metal Phosphide:A Highly Efficient Catalyst for the Selective Hydrodeoxygenation of Furfural to 2‐Methylfuran

Highly selective hydrodeoxygenation of anisole, phenol and guaiacol to benzene over nickel phosphide

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Hydrodeoxygenation of phenol as a bio-oil model compound over intimate contact noble metal–Ni2P/SiO2 catalysts

Abstract: 1% Pd–10% Ni2P/SiO2, from a Ni2P reducing noble metal precursor, presents a high activity and cyclohexanol or cyclohexane selectivity due to more active sites and electrons transferring from Ni2P to the noble metal.

Cited by 32 publications

References 25 publications

Synergetic Catalysis of Nickel Oxides with Oxygen Vacancies and Nickel Phosphide for the Highly Efficient Hydrodeoxygenation of Phenolic Compounds

Synergetic Catalysis of Nickel Oxides with Oxygen Vacancies and Nickel Phosphide for the Highly Efficient Hydrodeoxygenation of Phenolic Compounds

Metal Phosphide:A Highly Efficient Catalyst for the Selective Hydrodeoxygenation of Furfural to 2‐Methylfuran

Highly selective hydrodeoxygenation of anisole, phenol and guaiacol to benzene over nickel phosphide

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Hydrodeoxygenation of phenol as a bio-oil model compound over intimate contact noble metal–Ni₂P/SiO₂ catalysts