4.8 Article

Shape-Controlled Pathways in the Hydrogen Production from Ethanol Steam Reforming over Ceria Nanoparticles

Journal

ACS CATALYSIS
Volume 12, Issue 16, Pages 10482-10498

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c02117

Keywords

ceria nanostructures; green hydrogen; ethanol decomposition; ethylenedioxy species; facet-dependent activity

Funding

  1. ANPCyT [2015-3651, 2017-4063, 2017-3846]
  2. UNL of Argentina [CAID-PI 50420150100066LI]
  3. MICINN-Spain [RTI2018-101604-B-I00]
  4. European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie Grant [832121]
  5. Marie Curie Actions (MSCA) [832121] Funding Source: Marie Curie Actions (MSCA)

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The ethanol surface reaction over CeO2 nanooctahedra and nanocubes was studied using infrared spectroscopy, mass spectrometry, and density functional theory calculations. The results show that the production of H2 is 2.4 times higher on CeO2-NC than on CeO2-NO, which can be explained by the different types of adsorbed ethoxy species on the different surfaces. The study also reveals the different pathways for H2 formation on the two surfaces of CeO2 nanoshapes.
The ethanol surface reaction over CeO2 nanooctahedra (NO) and nanocubes (NC), which mainly expose (111) and (100) surfaces, respectively, was studied by means of infrared spectroscopy (TPSR-IR), mass spectrometry (TPSR-MS), and density functional theory (DFT) calculations. TPSR-MS results show that the production of H-2 is 2.4 times higher on CeO2-NC than on CeO2-NO, which is rationalized starting from the different types of adsorbed ethoxy species controlled by the shape of the ceria particles. Over the CeO2(111) surface, monodentate type I and II ethoxy species with the alkyl chain perpendicular or parallel to the surface, respectively, were identified. Meanwhile, on the CeO2(100) surface, bidentate and monodentate type III ethoxy species on the checkerboard O-terminated surface and on a pyramid of the reconstructed (100) surface, respectively, are found. The more labile surface ethoxy species on each ceria nanoshape, which are the monodentate type I or III ethoxy on CeO2-NO and CeO2-NC, respectively, react on the surface to give acetate species that decompose to CO2 and CH4, while H2 is formed via the recombination of hydroxyl species. In addition, the more stable monodentate type II and bidentate ethoxy species on CeO2-NO and CeO2-NC, respectively, give an ethylenedioxy intermediate, the binding of which is facet-dependent. On the (111) facet, the less strongly bound ethylenedioxy desorbs as ethylene, whereas on the (100) facet, the more strongly bound intermediate also produces CO2 and H-2 via formate species. Thus, on the (100) facet, an additional pathway toward H-2 formation is found. ESR activity measurements show an enhanced H2 production on the nanocubes.

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