Alternative synthesis of bulk and supported nickel phosphide from the thermal decomposition of hypophosphites

Guan, Qingxin; Li, Wei; Zhang, Minghui; Tao, Katsumi

doi:10.1016/j.jcat.2009.02.008

Cited by 127 publications

(60 citation statements)

References 16 publications

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“…This could be important for applications, as halides can poison the catalytic activity of nickel phosphides. 103 Evolution of Nickel Phosphides. Under the conditions studied (Scheme 1 above), the organophosphite precursors P(OMe) 3 , P(OEt) 3 , P(OnBu) 3 , P(OCH 2 tBu) 3 , P(OiPr) 3 , and P(OPh) 3 lead to nanocrystalline Ni 12 P 5 or Ni 2 P or both.…”

Section: ■ Introductionmentioning

confidence: 99%

Phase-Programmed Nanofabrication: Effect of Organophosphite Precursor Reactivity on the Evolution of Nickel and Nickel Phosphide Nanocrystals

et al. 2015

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A better understanding of the chemistry of molecular precursors is useful in achieving more predictable and reproducible nanocrystal preparations. Recently, an efficient approach was introduced that consists of finetuning the chemical reactivity of the synthetic molecular precursors used, while keeping all other reaction conditions constant. Using nickel phosphides as a research platform, we have studied how the chemical structure and reactivity of a family of commercially available organophosphite precursors (P(OR)3, R = alkyl or aryl) alter the preparation of metallic and metal phosphide nanocrystals. Organophosphites are a versatile addition to the pnictide synthetic toolbox, nicely complementing other available precursors such as elemental phosphorus or trioctylphosphine (TOP). Experimental and computational data show that different organophosphite precursors selectively yield Ni, Ni12P5, and Ni2P and that these phases evolve over time through separate mechanistic pathways. Based on our observations, we propose that nickel phosphide formation requires organophosphite coordination to a nickel precursor, followed by intramolecular rearrangement. We also propose that metallic nickel formation involves outer sphere reduction by uncoordinated organophosphite. These two independent pathways are supported by the fact that preformed Ni nanocrystals do not react with some of the most reactive phosphide-forming organophosphites, failing to evolve into nickel phosphide nanocrystals. Overall, the rate at which organophosphites react with nickel(II) chloride or acetate to form nickel phosphides increases in the order P(OMe)3 < P(OEt)3 < P(OnBu)3 < P(OCH2tBu)3 < P(OiPr)3 < P(OPh)3. Some organophosphites, such as P(OMe)3 or P(OiPr)3, transiently form zerovalent, metallic nickel, while this is the only persistent product observed with the bulky organophosphite P(O-2,4-tBu2C6H4)3. We expect that these results will alleviate the need for timeconsuming testing and random optimization of several different reaction conditions, thus enabling a faster development of these and similar pnictide nanomaterials for practical applications. Disciplines Chemistry CommentsReprinted (adapted) with permission from Chemistry of Materials 27 (2015) ABSTRACT: A better understanding of the chemistry of molecular precursors is useful in achieving more predictable and reproducible nanocrystal preparations. Recently, an efficient approach was introduced that consists of fine-tuning the chemical reactivity of the synthetic molecular precursors used, while keeping all other reaction conditions constant. Using nickel phosphides as a research platform, we have studied how the chemical structure and reactivity of a family of commercially available organophosphite precursors (P(OR) 3 , R = alkyl or aryl) alter the preparation of metallic and metal phosphide nanocrystals. Organophosphites are a versatile addition to the pnictide synthetic toolbox, nicely complementing other available precursors such as elemental phosphorus or trioctylphosphine (TO...

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Section: ■ Introductionmentioning

confidence: 99%

Phase-Programmed Nanofabrication: Effect of Organophosphite Precursor Reactivity on the Evolution of Nickel and Nickel Phosphide Nanocrystals

et al. 2015

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“…Compared with metal, metal oxide and metal sulfide materials, metal phosphide ones have seldom been control-synthesized hitherto due to the lack of appropriate methods and the high activity of phosphorus. Up to now, metal phosphides have been successfully prepared by temperature-programmed reduction [16], solvothermal method [17], and thermal decomposition [18][19][20][21], etc. In this study, the precursor of FeS and sodium hypophosphite (NaH 2 PO 2 ÁH 2 O) were thermally treated at 350°C, and bulk and supported iron phosphide (FeP/SiO 2 ) samples were successfully synthesized.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of an iron phosphide catalyst based on sulfides and hydrodesulfurization property

Song

Zhang

2015

Chemical Engineering Journal

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“…Due to the harsh preparation conditions (elevated temperatures), extremely small particles of metal phosphides are still difficult to prepare. Choice of low-valence phosphorous precursors, such as phosphites 26) , hypophosphites 27), 28) , and pyrophosphates 29) could ameliorate the preparation conditions, allowing the formation of well-dispersed metal phosphides.…”

Section: Discussionmentioning

confidence: 99%

Metal Phosphides as High-performance Hydrotreating Catalysts

Wang

Sun

et al. 2015

J. Jpn. Petrol. Inst.

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Alternative synthesis of bulk and supported nickel phosphide from the thermal decomposition of hypophosphites

Cited by 127 publications

References 16 publications

Phase-Programmed Nanofabrication: Effect of Organophosphite Precursor Reactivity on the Evolution of Nickel and Nickel Phosphide Nanocrystals

Phase-Programmed Nanofabrication: Effect of Organophosphite Precursor Reactivity on the Evolution of Nickel and Nickel Phosphide Nanocrystals

Synthesis of an iron phosphide catalyst based on sulfides and hydrodesulfurization property

Metal Phosphides as High-performance Hydrotreating Catalysts

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