Reaction-Induced Formation of Stable Mononuclear Cu(I)Cl Species on Carbon for Low-Footprint Vinyl Chloride Production
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Date
2023-06-28
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Journal Article
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yes
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Abstract
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 CuClx 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.
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published
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Journal / series
Volume
35 (26)
Pages / Article No.
2211464
Publisher
Wiley-VCH
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Subject
acetylene hydrochlorination; copper speciation; life-cycle assessment; reaction-induced restructuring; single-atom catalysis
Organisational unit
03871 - Pérez-Ramírez, Javier / Pérez-Ramírez, Javier
03810 - Jeschke, Gunnar / Jeschke, Gunnar
09655 - Guillén Gosálbez, Gonzalo / Guillén Gosálbez, Gonzalo
Notes
Funding
180544 - NCCR Catalysis (phase I) (SNF)