Simultaneous control of phase, size, and morphology in nanoscale nickel phosphides is reported. Phase-pure samples of discrete nanoparticles of Ni12P5 and Ni2P in hollow and solid morphologies can be prepared in a range of sizes (10-32 nm) by tuning key interdependent synthetic levers (P:Ni precursor ratio, temperature, time, oleylamine quantity). Size and morphology are controlled by the P:Ni ratio in the synthesis of the precursor particles, with large, hollow particles formed at low P:Ni and small, solid particles formed at high P:Ni. The P:Ni ratio also impacts the phase at the crystallization temperature (300-350 °C), with metal-rich Ni12P5 generated at low P:Ni and Ni2P at high P:Ni. Moreover, the product phase formed can be decoupled from the initial precursor ratio by the addition of more "P" at the crystallization temperature. This enables formation of hollow particles (favored by low P:Ni) of Ni2P (favored by high P:Ni). Increasing temperature and time also favor formation of Ni2P, by generating more reactive P and providing sufficient time for conversion to the thermodynamic product. Finally, increasing oleylamine concentration allows Ni12P5 to be obtained under high P:Ni precursor ratios that favor solid particle formation. Oleylamine concentration also acts to "tune" the size of the voids in particles formed at low P:Ni ratios, enabling access to Ni12P5 particles with different void sizes. This approach enables an unprecedented level of control over phase and morphology of nickel phosphide nanoparticles, paving the way for systematic investigation of the impact of these parameters on hydrodesulfurization activities of nickel phosphides.
The size-dependent catalytic activity of Ni 2 P for hydrodesulfurization (HDS) remains unstudied because the traditional temperature programmed reduction (TPR) method used in catalyst preparation results in highly polydisperse Ni 2 P particles. The ability to control the Ni 2 P particle size in the range 5−20 nm by varying the quantity of oleylamine in solution-phase arrested precipitation reactions is reported. Particles were introduced to a high surface area silica support (Cab-O-Sil, M-7D grade, 200 m 2 /g) via incipient wetness, and HDS activity was probed against dibenzothiophene (DBT). All samples were less active than TPR prepared materials, and the smallest particles were the least active, contrary to expectation. This is attributed in part to particle sintering under HDS conditions. Sintering occurs independently of wt% loading of catalyst, time, incipient wetness procedure, and ionic additives, at all temperatures greater than 200 °C. Sintering is minimized by encapsulation of Ni 2 P nanoparticles in a mesoporous silica shell, achieved by sol−gel silica formation around Ni 2 P-containing surfactant liquid crystal assemblies and subsequent calcination, resulting in a doubling of HDS activity.
Surface modifications of MSN have significant effect on MTX crystallization and release behavior.
The synthesis of monodisperse 5-10 nm Pd5P2 catalytic particles by encapsulation in a mesoporous silica network, along with preliminary data on hydrodesulfurization (HDS) activity, is reported. Precursor Pd-P amorphous nanoparticles are prepared by solution-phase reaction of palladium(II) acetylacetonate with trioctylphosphine at temperatures up to 300 °C. Direct crystallization of Pd5P2 in solution by increasing the temperature to 360 °C leads to sintering, but particle size can be maintained during the transformation by encapsulation of the amorphous Pd-P particles in a mesoporous silica shell, followed by treatment of the solid at 500 °C under a reducing atmosphere, yielding Pd5P2@mSiO2. The resultant materials exhibit high BET surface areas (>1000 m(2)/g) and an average pore size of 3.7 nm. Access to the catalyst surface is demonstrated by dibenzodithiophene (DBT) HDS testing. Pd5P2@mSiO2 shows a consistent increase in HDS activity as a function of temperature, with DBT conversion approaching 60% at 402 °C. The ability to control particle size, phase, and sintering is expected to enable the fundamental catalytic attributes that underscore activity in Pd5P2 to be assessed.
Mesoporous silica nanomaterials show great potential to deliver chemotherapeutics for cancer treatment. The key challenges in the development of injectable mesoporous silica formulations are colloidal instability, hemolysis and inefficient drug loading and release. In this study, we evaluated the effect of PEGylation of mesoporous silica nanorods (MSNR) on hemolysis, colloidal stability, mitoxantrone (MTX) loading, in vitro MTX release, and cellular MTX delivery under hypoxic conditions. We found that PEGylation prevented dose-dependent hemolysis in the concentrations studied (0–10 mg/ml) and improved colloidal stability of MSNR. A negative effect of PEGylation on MTX loading was observed but PEGylated MSNR (PMSNR) demonstrated increased MTX release compared to non-PEGylated particles. Under hypoxic conditions, a decrease in the IC50 of MTX and MTX-loaded MSNR was observed when compared to normoxic conditions. These results showed that MSNR could deliver the chemotherapeutic agent, MTX to tumor cells and induce effective cell killing. However, the effect of PEGylation needs to be carefully studied due to the observed adverse effect on drug loading.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.