Reaction-Induced Formation of Stable Mononuclear Cu(I)Cl Species on Carbon for Low-Footprint Vinyl Chloride Production.

Autor: Faust Akl D; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland., Giannakakis G; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland., Ruiz-Ferrando A; Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, Tarragona, 43007, Spain.; Department of Physical and Inorganic Chemistry, Universitat Rovira i Virgili, Marcel·lí Domingo s/n, Tarragona, 43007, Spain., Agrachev M; Laboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland., Medrano-García JD; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland., Guillén-Gosálbez G; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland., Jeschke G; Laboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland., Clark AH; Paul Scherrer Institute, Forschungsstrasse 111, Villigen PSI, 5232, Switzerland., Safonova OV; Paul Scherrer Institute, Forschungsstrasse 111, Villigen PSI, 5232, Switzerland., Mitchell S; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland., López N; Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, Tarragona, 43007, Spain., Pérez-Ramírez J; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1-5, Zurich, 8093, Switzerland.
Jazyk: angličtina
Zdroj: Advanced materials (Deerfield Beach, Fla.) [Adv Mater] 2023 Jun; Vol. 35 (26), pp. e2211464. Date of Electronic Publication: 2023 May 12.
DOI: 10.1002/adma.202211464
Abstrakt: Copper catalysts are attractive candidates for Hg-free vinyl chloride monomer (VCM) production via acetylene hydrochlorination due to their non-toxic nature and high stability. However, the optimal architecture for Cu-based catalysts at the nanoscale is not yet fully understood. To address this gap, the metal precursor and the annealing temperature are modified to prepare copper nanoparticles or single atoms, either in chlorinated or ligand-free form, on an unmodified carbon support. Evaluation in the reaction reveals a remarkable convergence of the performance of all materials to the stable VCM productivity of the single-atom catalyst. In-depth characterization by advanced microscopy, quasi in situ and operando spectroscopy, and simulations uncover a reaction-induced formation of low-valent, single atom Cu(I)Cl site motif, regardless of the initial nanostructure. Various surface oxygen groups promote nanoparticle redispersion by stabilizing single-atom CuCl x species. The anchoring site structure does not strongly influence the acetylene adsorption energy or the crucial role they play in stabilizing key reaction intermediates. A life-cycle assessment demonstrates the potential environmental benefits of copper catalysts over state-of-the-art alternatives. This work contributes to a better understanding of optimal metal speciation and highlights the sustainability of Cu-based catalysts for VCM production.
(© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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