Supported metallic nanoparticles prepared by an organometallic route to boost the electrocatalytic conversion of CO2

• Published in: Journal of CO2 utilization 2021-08, Vol.50, p.101613, Article 101613
• Main Authors: Marepally, B.C., Ampelli, C., Genovese, C., Sayah, R., Veyre, L., Dalverny, C., Thieuleux, C., Quadrelli, E.A., Perathoner, S., Centi, G.
• Format: Article
• Language: English
• Subjects: Carbon dioxide; Catalysis; Chemical Sciences; CO2 electroreduction; Metal nanoparticles; Organometallic preparation; Ru nanoparticles
• ISSN: 2212-9820
• DOI: 10.1016/j.jcou.2021.101613

[Display omitted] •Synthesis of very fine nanoparticles of metals (Ru, Pt, Fe) using organometallic routes.•Effects of metal nanoparticle size on the catalytic activity on the CO2 reduction reaction.•Comparison of productivity and selectivity for organometallic vs inorganic routes.•Ruthenium nanoparticles on CNTs, generated two-order higher Turn-over-frequency values in the two compared synthesis routes.•Ru nanoparticles showed higher methanol selectivity, whereas Pt and Fe selectivity bent towards formic acid. Electrocatalysts based on metal nanoparticles (metal = Ru, Fe and Pt), prepared by an organometallic (OM) route, and supported on carbon nanotubes (CNTs), have been studied in the electro-catalytic reduction of CO2 in comparison with those prepared using inorganic salts to deposit the metal nanoparticles (NPs) over CNTs (INORG route). The OM route allows to obtain electrocatalysts with superior performances in terms of productivity and especially turnover frequency, with an enhanced formation of C1 products (methanol and formic acid) with respect to C2+ products (acetic acid, acetone, isopropanol and ethanol). Particularly for Ru samples, there is an increase up to nearly two order of magnitude in the cumulative TOF with respect to a sample with an equivalent metal loading and mean particle size but prepared by the INORG route. Carbon selectivity to methanol reaches the interesting value of 65 %. The analysis of this intrinsic boosting of both activity and selectivity in the electrocatalytic reduction of CO2 suggests a role in this enhanced performance of small oxide patches on the metal nanoparticles formed as residues of the process of removal of the ligands present in the OM route.