Evaluation of transition metal phosphides supported on ordered mesoporous materials as catalysts for phenol hydrodeoxygenation

Berenguer, Antonio; Sankaranarayanan, T. M.; Gómez, Gabriel J. García; Moreno, Inés; Coronado, Juan M.; Pizarro, Patricia; Serrano, David

doi:10.1039/c5gc02188j

Cited by 122 publications

(79 citation statements)

References 53 publications

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“…By comparison, the peak temperature of Ni 2 P/SiO 2 is relatively high and that for the starting reduction is approximately 500 °C. The NiO x ‐Ni 2 P/SiO 2 precursor presents two prominent peaks that correspond to nickel oxide and nickel oxyphosphates, respectively . From the TPR results, reduction temperature in the catalyst preparation process was programmed at 550 °C to obtain NiO x that contains oxygen vacancies or Ni 2 P.…”

Section: Resultsmentioning

confidence: 99%

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: Resultsmentioning

confidence: 99%

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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“…At present, the rapidly depleting fossil fuels and escalating energy consumption coupled with rising environmental awareness among nations have led to an increased focus on alternative, viable, ecofriendly, and renewable energy sources. Biomass has considered by experts as the only truly sustainable source of energy and organic carbon for our industrial society, and it has the potential to displace petroleum for the production of chemicals and liquid transportation fuels …”

Section: Introductionmentioning

confidence: 99%

Benzoic Acid/TEMPO as a Highly Efficient Metal‐Free Catalyst System for Selective Oxidation of 5‐hydroxymethylfurfural into 2, 5‐diformylfuran

et al. 2017

Energy Tech

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The combination of benzoic acid and 2,2,6,6‐teramethylpiperidin‐1‐oxyl (TEMPO) afforded an efficient catalytic system for the aerobic oxidation of 5‐hydroxymethylfurfural (HMF) into 2,5‐diformylfuran (DFF) under certain conditions. The maximum conversion of 86.7 % for HMF was obtained with a nearly 77.8 % DFF yield at 1 mmol benzoic acid and 0.4 MPa oxygen pressure in acetonitrile. The aerobic oxidation ability of HMF into DFF depended on the electron density of the organic acid skeletal structure with the carboxyl group. Meanwhile, the catalyst system of benzoic acid/TEMPO also exhibited good performance for aerobic oxidation of other alcohols. Based on experimental results, we propose that the benzoic acid acted as the primary catalyst and TEMPO was the key co‐catalyst, oxidized into oxoammonium cation through electron transport and then regenerated by a superoxide radical during the reaction.

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“…Among numerous HDO catalysts, nickel phosphide has high catalytic activity for HDO of phenolic model compounds and even the actual pyrolysis oil and therefore attracted widespread interests . Various materials have been employed as the supports of nickel phosphides, such as metal oxide,, carbonaceous material,, and zeolites –. The neutral SiO 2 is superior to the acidic zeolite HZSM‐5 as the support of Ni 2 P in the HDO reaction in the previous report .…”

Section: Figurementioning

confidence: 97%

Nickel Phosphides Supported on HZSM-5 for Catalytic Hydrodeoxygenation of Eugenol: Effect of Phosphorus Content

Tang

Sun

et al. 2017

ChemistrySelect

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Nickel phosphides supported on HZSM‐5 zeolite with different initial P/Ni molar ratios were prepared for catalytic hydrodeoxygenation (HDO) of eugenol to produce hydrocarbons. When P/Ni<0.5, the increase of P content gave smaller and more uniform particles which was helpful for hydrogenation of aromatic ring, while the total acid sites of the catalyst decreased due to the coverage of more acid sites of HZSM‐5 by adding P which was unfavourable for the removal of oxygen. At P/Ni=0.5, the active phase supported on HZSM‐5 was mainly Ni3P with the smallest average particle size and minimum amount of acid sites which could account for the best hydrogenation activity and the lowest selectivity of hydrocarbons, respectively. Further increasing the P/Ni ratio up to 1 and 2, the active phase became Ni2P and a lot of nonuniform Ni2P nanorod crystals appeared on and out of the support HZSM‐5 which caused a sharp drop in the hydrogenation activity of the catalyst. For a combination of hydrogenation and deoxygenation considerations, The P/Ni=0.25 is the best ratio for nickel phosphides supported on HZSM‐5 zeolite to HDO of lignin‐related phenols.

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Evaluation of transition metal phosphides supported on ordered mesoporous materials as catalysts for phenol hydrodeoxygenation

Abstract: Transition metal phosphides (Ni2P, Co2P and MoP) supported over mesoporous materials: Al-SBA-15, m-Al2O3 and CMK-3 have been probed as potential catalysts in HDO of pyrolysis bio-oils using phenol as model compound.

Cited by 122 publications

References 53 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

Benzoic Acid/TEMPO as a Highly Efficient Metal‐Free Catalyst System for Selective Oxidation of 5‐hydroxymethylfurfural into 2, 5‐diformylfuran

Nickel Phosphides Supported on HZSM-5 for Catalytic Hydrodeoxygenation of Eugenol: Effect of Phosphorus Content

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