Abstract
Structural and morphological control of crystalline nanoparticles is crucial in the field of heterogeneous catalysis and the development of “reaction specific” catalysts. To achieve this, colloidal chemistry methods are combined with ab initio calculations in order to define the reaction parameters, which drive chemical reactions to the desired crystal nucleation and growth path. Key in this procedure is the experimental verification of the predicted crystal facets and their corresponding electronic structure, which in case of nanostructured materials becomes extremely difficult. Here, by employing 31P solid-state nuclear magnetic resonance aided by advanced density functional theory calculations to obtain and assign the Knight shifts, we succeed in determining the crystal and electronic structure of the terminating surfaces of ultrafine Ni2P nanoparticles at atomic scale resolution. Our work highlights the potential of ssNMR nanocrystallography as a unique tool in the emerging field of facet-engineered nanocatalysts.
Highlights
Structural and morphological control of crystalline nanoparticles is crucial in the field of heterogeneous catalysis and the development of “reaction specific” catalysts
Shape and size engineering of functional nanocrystalline materials is an area of major scientific and technological interest[1,2,3]. This is because in many important applications which rely on surface structure and chemistry, such as heterogeneous catalysis, gas sensing, and energy conversion and storage, the properties of the materials can be tailored by controlling the size, crystal structure, and morphology of the external surfaces of the constituent particles[4,5,6]
The catalytic reactivity and selectivity changes by modifying the arrangement and coordination of the surface atoms, becoming very sensitive to the enclosing crystal facets. In this context a lot of effort has been devoted in order to understand the role of the facet morphology and crystal structure on the catalytic reactivity of Ni2P nanoparticles, a staple in the area of research of many important catalytic processes, such as the electrocatalytic hydrogen evolution reaction (HER)[7] and oxygen evolution reaction (OER)[8], the water-gas shift reaction[9], as well as the hydrodeoxygenation and the hydrodesulfurization (HDS) of hydrocarbons[10]
Summary
Structural and morphological control of crystalline nanoparticles is crucial in the field of heterogeneous catalysis and the development of “reaction specific” catalysts. Colloidal chemistry methods are combined with ab initio calculations in order to define the reaction parameters, which drive chemical reactions to the desired crystal nucleation and growth path Key in this procedure is the experimental verification of the predicted crystal facets and their corresponding electronic structure, which in case of nanostructured materials becomes extremely difficult. The catalytic reactivity and selectivity changes by modifying the arrangement and coordination of the surface atoms, becoming very sensitive to the enclosing crystal facets In this context a lot of effort has been devoted in order to understand the role of the facet morphology and crystal structure on the catalytic reactivity of Ni2P nanoparticles, a staple in the area of research of many important catalytic processes, such as the electrocatalytic hydrogen evolution reaction (HER)[7] and oxygen evolution reaction (OER)[8], the water-gas shift reaction[9], as well as the hydrodeoxygenation and the hydrodesulfurization (HDS) of hydrocarbons[10]. In this formula, Korb is the orbital part of the Knight shift, induced by the response of the orbital motions of all electrons to the applied external magnetic field, and KFC and Kdip are the Fermicontact and spin-dipolar parts of the Knight shift, respectively, due to the contact and dipolar parts of the hyperfine interaction of the nuclear spins with the net electron magnetic moment of the conduction electrons, again induced by the external magnetic field[24,25]
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