Synthesis And Characterization Of Size Controlled Transitionmetal Phosphide Nanoparticles And Their Hydrodesulfurization Catalytic Activity

<p>Transition metal phosphides are promising catalysts for hydrodesulfurization (HDS). The size-dependent catalytic activity of these metal phosphides for hydrodesulfurization (HDS) remains unstudied because the traditional temperature programmed reduction (TPR) method used in catalyst preparation results in highly polydisperse particles. </p> <p> The main goals of this dissertation research are (1) synthesize metal phosphide nanoparticles (Ni²P, Rh²P, and Pd⁵P²) with control of size and morphology using a solution based arrested precipitation method; (2) develop large scale synthesis of mesoporous silica encapsulated nanoparticles (Ni²P and Pd⁵P²) with controlled loading to prevent sintering at high temperatures; (3) establish the structure activity relationship of Ni²P nanoparticles in HDS and study the deep-HDS activity of noble metal phosphides. </p> <p> The ability to control the Ni²P particle size on the nanoscale using solution-phase arrested precipitation is reported in this dissertation. Ni²P particles were introduced to a high surface area silica support (Cab-O-Sil, M-7D grade, 200 m₂/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. </p> <p> To minimize sintering, we developed a route for in-situ mesoporous silica encapsulation of Ni²P nanoparticles. We optimized the Ni2P@mSiO2 synthesis to yield samples on large scale with controlled loading. The generality of this approach is employed to other systems such as CdSe and Au. Sintering is minimized by encapsulation of Ni²P nanoparticles in a mesoporous silica shell, resulting in a doubling of HDS activity. This enables us to study size-dependent HDS of Ni²P nanoparticles.</p> <p> 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 also reported in this dissertation. Precursor Pd-P amorphous nanoparticles are prepared by solution-phase reaction of palladium (II) acetylacetonate with trioctylphosphine at temperatures up to 300 ºC. Direct crystallization of Pd⁵P² in solution by increasing temperatures to 360 ºC 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 ºC under a reducing atmosphere, yielding Pd⁵P²@mSiO². The resultant materials exhibit high BET surface areas (> 1000 m₂/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 675 K. The ability to control particle size, phase, and sintering is expected to enable the fundamental catalytic attributes that underscore activity in Pd⁵P²to be assessed</p>

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Open Access Dissertation

Discipline thesis:degree_discipline

Chemistry

Year dc:date.available

2012

Author dc:creator

• Savithra, Galbokka Hewage Layan

Contributors dc:contributor

• Stephanie L. Brock

• catalyts
• hydrodesulfurization
• mesoporous silica
• metal phosphides
• nanoparticles
• sintering
• Inorganic Chemistry

Repository record dc:identifier

https://digitalcommons.wayne.edu/oa_dissertations/696

OAI identifier oai:identifier

oai:digitalcommons.wayne.edu:oa_dissertations-1695