Influence of the copper precursor on the catalytic transformation of oleylamine during Cu nanoparticle synthesis

Pesesse, Antoine; Carenco, Sophie

doi:10.1039/d1cy00639h

Cited by 8 publications

(5 citation statements)

References 20 publications

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“…From a previous study on copper nanoparticles, we know that water forms in variable amounts from one synthesis to another and may further react with oxophilic metals. 46 Here, small amounts of water may affect the precise nature of reactions intermediates from Co 2 (CO) 8 to metallic cobalt.…”

Section: Discussionmentioning

confidence: 99%

The delicate balance of phase speciation in bimetallic nickel cobalt nanoparticles

et al. 2022

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Section: Discussionmentioning

confidence: 99%

The delicate balance of phase speciation in bimetallic nickel cobalt nanoparticles

et al. 2022

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“…Alternatively, the imine (or aldehyde) could condense with another amine to produce the observed secondary imine product (Figure a,c, orange ). ,, Both mechanisms would also generate appreciable amounts of ammonia (Figure a, dark purple ), and this is evidenced by positive ammonia tests from a vessel containing DI water through which the reaction effluent gas was bubbled (Figure S19). Also, appreciable amounts of nitro-octane (Figure a, green ) are observed on the particle surface by FTIR (Figure S18, Table S3, N–O stretch ), , which we believe are derived from an alternative amine oxidation mechanism. , …”

Section: Resultsmentioning

confidence: 95%

“…53,54,76 Both mechanisms would also generate appreciable amounts of ammonia (Figure 4a, dark purple), and this is evidenced by positive ammonia tests from a vessel containing DI water through which the reaction effluent gas was bubbled (Figure S19). Also, appreciable amounts of nitro-octane (Figure 4a, green) are observed on the particle surface by FTIR (Figure S18, Table S3, N−O stretch), 77,78 which we believe are derived from an alternative amine oxidation mechanism. 79,80 These organic byproducts, especially the imine and amide, are difficult to purify from the resultant reaction mixture because they can precipitate upon antisolvent addition.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

General Route to Colloidally Stable, Low-Dispersity Manganese-Based Ternary Spinel Oxide Nanocrystals

et al. 2023

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While certain ternary spinel oxides have been well-explored with colloidal nanochemistry, notably the ferrite spinel family, ternary manganese (Mn)-based spinel oxides have not been tamed. A key composition is cobalt (Co)-Mn oxide (CMO) spinel, Co x Mn3–x O4, that, despite exemplary performance in multiple electrochemical applications, has few reports in the colloidal literature. Of these reports, most show aggregated and polydisperse products. Here, we describe a synthetic method for small, colloidally stable CMO spinel nanocrystals with tunable composition and low dispersity. By reacting 2+ metal-acetylacetonate (M(acac)2) precursors in an amine solvent under an oxidizing environment, we developed a pathway that avoids the highly reducing conditions of typical colloidal synthesis reactions; these reducing conditions typically push the system toward a monoxide impurity phase. Through surface chemistry studies, we identify organic byproducts and their formation mechanism, enabling us to engineer the surface and obtain colloidally stable nanocrystals with low organic loading. We report a CMO/carbon composite with low organic contents that performs the oxygen reduction reaction (ORR) with a half-wave potential (E 1/2) of 0.87 V vs RHE in 1.0 M potassium hydroxide at 1600 rpm, rivaling previous reports for the highest activity of this material in ORR electrocatalysis. We extend the general applicability of this procedure to other Mn-based spinel nanocrystals such as Zn-Mn-O, Fe-Mn-O, Ni-Mn-O, and Cu-Mn-O. Finally, we show the scalability of this method by producing inorganic nanocrystals at the gram scale.

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“…After the colloidal synthesis of CoP nano‐urchins, some organic ligands remained from the synthesis or as a result of side‐reaction during the synthesis [46,47] . These ligands were beneficial for the dispersibility and colloidal stability during catalysis although their limited amount is well below the threshold identified above.…”

Section: Resultsmentioning

confidence: 98%

“…After the colloidal synthesis of CoP nano-urchins, some organic ligands remained from the synthesis or as a result of sidereaction during the synthesis. [46,47] These ligands were beneficial for the dispersibility and colloidal stability during catalysis although their limited amount is well below the threshold identified above. Thus, we decided to extend the scope of the tested additives to molecules that were suspected to already cover the native surface in limited amount (ligands from the synthesis or degradation products).…”

Section: Activity Enhancement By Addition Of Tri-n-octylphosphine And...mentioning

confidence: 96%

Phosphine‐Enhanced Semi‐Hydrogenation of Phenylacetylene by Cobalt Phosphide Nano‐Urchins

Ropp,

André,

Carenco

2023

ChemPlusChem

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Transition metal phosphides are promising, selective, and air‐stable nanocatalysts for hydrogenation reactions. However, they often require fairly high temperatures and H2 pressures to provide quantitative conversions. This work reports the positive effect of phosphine additives on the activity of cobalt phosphide nano‐urchins for the semi‐hydrogenation of phenylacetylene. While the nanocatalyst's activity was low under mild conditions (7 bar of H2, 100 °C), the addition of a catalytic amount of phosphine remarkably increased the conversion, e. g., from 13 % to 98 % in the case of PnBu3. The heterogeneous nature of the catalyst was confirmed by negative supernatant activity tests. The catalyst integrity was carefully verified by post‐mortem analyses (TEM, XPS, and liquid 31P NMR). A stereo‐electronic map was proposed to rationalize the activity enhancement provided over a selection of nine phosphines: the strongest effect was observed for low to moderately hindered phosphines, associated with strong electron donor abilities. A threshold in phosphine stoichiometry was revealed for the enhancement of activity to occur, which was related to the ratio of phosphine to surface cobalt atoms.

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Influence of the copper precursor on the catalytic transformation of oleylamine during Cu nanoparticle synthesis

Abstract: For an optimal use of copper nanoparticles in catalysis, in-depth understanding of the reaction mechanisms and fine characterization of final products are equally relevant. Indeed, both have a direct impact...

Cited by 8 publications

References 20 publications

The delicate balance of phase speciation in bimetallic nickel cobalt nanoparticles

The delicate balance of phase speciation in bimetallic nickel cobalt nanoparticles

General Route to Colloidally Stable, Low-Dispersity Manganese-Based Ternary Spinel Oxide Nanocrystals

Phosphine‐Enhanced Semi‐Hydrogenation of Phenylacetylene by Cobalt Phosphide Nano‐Urchins

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