3 years ago

Catalytic activation of nitrobenzene on PVP passivated silver cluster: A DFT investigation

Catalytic activation of nitrobenzene on PVP passivated silver cluster: A DFT investigation
Indrajit Sinha, Madhulata Shukla
Poly(N-vinyl-2-pyrrolidone) (PVP) has been used extensively to stabilize the surface of noble metal nanoparticles against aggregation and also to produce anisotropic nanostructures. Naturally, it is very important to understand the effect of such surface stabilization by PVP on the catalytic activity of these nanoparticles. This communication investigates through DFT calculations the electronic properties of PVP stabilized 13-atom Ag cluster for catalytic activation of nitrobenzene (NB). These computations suggest that poly(N-vinyl-2-pyrrolidone) (PVP) interact with silver (Ag) cluster mainly through oxygen atom and acts not only as a stabilizer to prevent the aggregation of Ag clusters but also as an electron donor to activate the Ag clusters for further reaction. Natural Bonding Orbital (NBO) calculations show that catalytic activation of NB by PVP passivated Ag cluster occurs due to interaction of the oxygen of the nitro group with the Ag cluster. Weak back donation of electrons from M(dπ) orbital of Ag to antibonding σ* of one of the NO bond, facilitates the formation of the nitroso intermediate. To understand the extent and the nature of this interaction better, vibrational frequency calculation of nitrobenzene association with Ag13-2PVP cluster is carried out. Red shift in the frequencies is consequence of strong interaction with that of silver cluster present in Ag13-2PVP-NB model. Poly(N-vinyl-2-pyrrolidone) (PVP) is used extensively to stabilize the surface of noble metal nanoparticles against aggregation and to facilitate the production of anisotropic nanostructures. First-principle calculations provide insight into the nature of the interaction of PVP and silver clusters. Weak back electron donation takes place from M(dπ) orbital of Ag to antibonding σ* of one of the NO bonds facilitating the formation of the nitroso intermediate.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/qua.25490

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.