A tunable library of substituted thiourea precursors to metal sulfide nanocrystals

Hendricks, Mark P.; Campos, Michael P.; Cleveland, Gregory T.; Plante, Ilan Jen‐La; Owen, Jonathan S.

doi:10.1126/science.aaa2951

Cited by 392 publications

(607 citation statements)

References 35 publications

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“…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. In the cases where it is observed, formation of the nickel-rich tetragonal Ni 12 P 5 phase precedes the formation of the hexagonal Ni 2 P phase, the latter being the final product after 30 min at 275°C in most of these cases.…”

Section: ■ Introductionmentioning

confidence: 99%

“…91−95 Organophosphites offer a distinctive system where the control of phase composition can be achieved under a single set of directly comparable (identical) reaction conditions and linked to the chemical structure, bonding, and reactivity of closely related molecular precursors. Here, we demonstrate that organophosphite precursor reactivity controllably affects the composition and phase evolution of nickel (Ni) 3 , 97%), triethyl phosphite (P(OEt) 3 , 98%), tri-n-butyl phosphite (P(OnBu) 3 , 94%), trineopentyl phosphite (P(OCH 2 Bu) 3 , 90%), tri-isopropyl phosphite (P(OiPr) 3 , 94%), triphenyl phosphite (P(OPh) 3 , 97%), and tris(2,4-di-t-butylphenyl) phosphite (P(O-2,4-tBu 2 C 6 H 4 ) 3 , 98%) were purchased from Strem; 1-octadecene (ODE, 90%) and oleylamine (80−90%) from Acros; and nickel(II) acetate (Ni(OAc) 2 , 98%) from Aldrich. All compounds were used as received and handled under an inert (dry-N 2 or Ar) atmosphere inside a glovebox or with a Schlenk line.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Aliquots were taken from the mixture after 1, 10, and 30 min reactions and the contents characterized by optical and, after precipitation, structural methods. We repeated this procedure multiple times for each of several commercially available organophosphites bearing aliphatic or aromatic substituents, including trimethyl phosphite (P(OMe) 3 ), triethyl phosphite (P(OEt) 3 ), tri-n-butyl phosphite (P(OnBu) 3 ), trineopentyl phosphite (P-(OCH 2 tBu) 3 ), triisopropyl phosphite (P(OiPr) 3 ), triphenyl phosphite (P(OPh) 3 ), and tris(2,4-ditert-butylphenyl) phosphite (P(O-2,4-tBu 2 C 6 H 4 ) 3 . Figure 1 shows representative results from our precursor screening, including powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) data for selected precursors (additional data are available from the Supporting Information).…”

Section: ■ Introductionmentioning

confidence: 99%

“…8−24 Other less explored precursors include hypophosphites (MH 2 PO 2 , M = metal or ammonium cation) 25−34 and the organophosphite P(OEt) 3 . 35 Also known as phosphite esters or simply phosphites (P(OR) 3 , R = alkyl or aryl), organophosphites are particularly appealing as synthetic precursors because they are highly reactive and potentially tunable with group (R) substitution, while also being readily commercially available and fairly inexpensive. This contrasts with other available alternatives which, while synthetically also useful, are unsupported and not tunable (P 4 ) or require relatively high reaction temperatures in excess of >320−340°C (TOP).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Phosphite Addition Solution. Inside a glovebox filled with dry N 2 , the phosphite precursor [0.40 mmol: 0.05 mL of P(OMe) 3 , 0.07 mL of P(OEt) 3 , 0.11 mL P(OnBu) 3 , 117 mg of P(OCH 2 Bu) 3 , 0.10 mL of P(OiPr) 3 , 0.11 mL of P(OPh) 3 , or 259 mg of P(O-2,4-tBu 2 C 6 H 4 ) 3 ] was thoroughly dissolved in ODE (1.00 g, 1.27 mL).…”

Section: ■ Introductionmentioning

confidence: 99%

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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%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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

et al. 2015

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Nucleation and Growth of Colloidal Semiconductor Nanoparticles

Enright

Ritchhart

Cossairt

2020

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Solution‐phase syntheses of semiconductor nanoparticles provide a versatile and scalable approach to obtain nanomaterials with desirable structure and function. The most common mechanism invoked to explain the nucleation and growth of colloidal semiconductor nanocrystals is the LaMer model, an extension of classical nucleation theory. This model is widely used to conceptualize the conversion of molecular precursors into nanoparticles, and is characterized by three stages: monomer buildup, nucleation, and particle growth. Each of these stages represents a fundamental aspect of nanoparticle synthesis, and each has been widely studied over the past several decades. One of the core successes of this model has been the prediction of the “burst nucleation” method, which has enabled the synthesis of monodisperse nanoparticles in many material systems. Increasingly, however, it has become apparent that many chemical systems do not follow classical nucleation theory, but rather grow via nonclassical cluster‐mediated or aggregative growth processes. Regardless of the nucleation mechanism, highly monodisperse semiconductor nanoparticles can be obtained through kinetic size focusing or digestive ripening. Kinetic size focusing occurs during the nanoparticle growth phase when monomer concentration is high and smaller particles grow faster than their larger counterparts, enabling the smaller particles to “catch up” in size to give a more monodisperse ensemble. Digestive ripening, on the other hand, is a postsynthetic strategy where additional ligand is provided to the system to etch larger particles and redistribute monomer to smaller particles to get a more uniform sample. Beyond the synthesis of spherical colloidal nanoparticles, procedures can be modified to achieve a range of anisotropic structures including 1D nanorods and 2D nanosheets. Seeded and templated growth strategies can lend additional synthetic flexibility to more easily access a range of complex architectures. Continued innovation in synthetic methods and mechanistic understanding will pave the way for technological translation and lasting impact across applications from biological imaging to catalysis and many other next‐generation technologies.

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