Group 10 Metal Allyl Amidinates: A Family of Readily Accessible and Stable Molecular Precursors to Generate Supported Nanoparticles

Abstract

The synthesis of well-defined materials as model systems for catalysis and related fields is an important pillar in the understanding of catalytic processes at a molecular level. Various approaches employing organometallic precursors have been developed and established to make monodispersed supported nanoparticles, nanocrystals, and films. Using rational design principles, a new family of precursors based on group 10 metals suitable for the generation of small and monodispersed nanoparticles on metal oxides has been developed. Particle formation on SiO2 and Al2O3 supports is demonstrated, as well as the potential in the synthesis of bimetallic catalyst materials exemplified with a PdGa/SiO2 system capable in the hydrogenation of CO2 to methanol. In addition to surface organometallic chemistry (SOMC), it is envisioned that these precursors could also be employed in related applications such as atomic layer deposition, due to their inherent volatility and relative thermal stability.

Implications of Ga Promotion and Metal-Oxide Interfaces in Tailored Propane Dehydrogenation Catalysts Supported on Carbon

“…Two different classes of organometallic precursorsamidinate/alkyl vs. siloxidewere used as a strategy to prepare a set of Pt and PtGa based catalysts with a tailored interface on carbon. On the one hand, molecular precursors such as [Ga(Mes3)] 16 and platinum allyl-(N-N'-diisopropyl)acetamidinate ([PtAMD]) 17 are used for the preparation of carbon-supported Pt and PtGa nanoparticles, while thermolytic molecular siloxide precursors 10 [Ga(OSi(O t Bu3)3)3(THF)] 18 and [Pt(OSi(O t Bu3)3)2(COD)] 19 are used to prepare the corresponding supported Pt and PtGa nanoparticles with an oxide interface (Figure 1B). This approach based on (thermolytic) molecular precursors containing or not a source of Si thus enables the study of the implications of Ga promotion and metal-oxide interfaces on PtGa PDH catalysts.…”

“…). [Mg(Bn)2(THF)2]26 , [Pt(COD)(OSi(O t Bu3)3)2]19 , [Ga(OSi(O t Bu3)3)3(THF)]18 , [Ga(Mes)3]16 , platinum allyl-(N-N'-diisopropyl)acetamidinate ([PtAMD])17 and were prepared according to literature procedures. Experimental details, the purification of chemicals and instrument specifications are summarized in the supporting information in more details.…”

Implications of Ga Promotion and Metal-Oxide Interfaces in Tailored Propane Dehydrogenation Catalysts Supported on Carbon

“…). [Mg(Bn)2(THF)2] 26 , [Pt(COD)(OSi(O t Bu3)3)2] 19 , [Ga(OSi(O t Bu3)3)3(THF)] 18 , [Ga(Mes)3] 16 , platinum allyl-(N-N'-diisopropyl)acetamidinate ([PtAMD])17 and were prepared according to literature procedures. Experimental details, the purification of chemicals and instrument specifications are summarized in the supporting information in more details.…”