Author Correction: Dynamic transformations of cubic copper catalysts during CO2 electroreduction and its impact on catalytic selectivity.
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ABSTRACT:
SUBMITTER: Grosse P
PROVIDER: S-EPMC8671503 | biostudies-literature | 2021 Dec
REPOSITORIES: biostudies-literature
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Author Correction: Dynamic transformations of cubic copper catalysts during CO<sub>2</sub> electroreduction and its impact on catalytic selectivity.
Grosse Philipp P Yoon Aram A Rettenmaier Clara C Herzog Antonia A Chee See Wee SW Roldan Cuenya Beatriz B
Nature communications 20211214 1
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Project description:To rationally design effective and stable catalysts for energy conversion applications, we need to understand how they transform under reaction conditions and reveal their underlying structure-property relationships. This is especially important for catalysts used in the electroreduction of carbon dioxide where product selectivity is sensitive to catalyst structure. Here, we present real-time electrochemical liquid cell transmission electron microscopy studies showing the restructuring of copper(I) oxide cubes during reaction. Fragmentation of the solid cubes, re-deposition of new nanoparticles, catalyst detachment and catalyst aggregation are observed as a function of the applied potential and time. Using cubes with different initial sizes and loading, we further correlate this dynamic morphology with the catalytic selectivity through time-resolved scanning electron microscopy measurements and product analysis. These comparative studies reveal the impact of nanoparticle re-deposition and detachment on the catalyst reactivity, and how the increased surface metal loading created by re-deposited nanoparticles can lead to enhanced C2+ selectivity and stability.
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Project description:Electrochemical conversion of CO2 is an attractive alternative to releasing it to the atmosphere. Catalysts derived from electroreduction of metal oxides are often more active than when starting with metallic phase catalyst. The origin of this effect is not yet clear. Using ZnO nanorods, we show that the initial structure of the oxide as well as the electrolyte medium have a profound impact on the structure of the catalytic active Zn phase, and thereby the selectivity of the catalysts. ZnO nanorods with various aspect ratios were electrochemically reduced in different electrolytes leading to metallic Zn with different structures; a sponge-like structure, nanorods and nanoplates. The sponge-like Zn produced syngas with H2 : CO=2, and some formate, the nanorods produced only syngas with H2 : CO=1, while Zn nanoplates exhibited 85 % selectivity towards CO. These results open a pathway to design new electrocatalysts with optimized properties by modifying the structure of the starting material and the electroreduction medium.
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Project description:A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO2 reduction reaction over a competitive H2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential UL = -0.41 V) and Pt@dv-Gr (-0.27 V) for CH3OH production, and Os@dv-Gr (-0.52 V) and Ru@dv-Gr (-0.52 V) for CH4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH3OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals.
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Project description:The electrochemical carbon dioxide reduction reaction to syngas with controlled CO/H2 ratios has been studied on Pd-based bimetallic hydrides using a combination of in situ characterization and density functional theory calculations. When compared with pure Pd hydride, the bimetallic Pd hydride formation occurs at more negative potentials for Pd-Ag, Pd-Cu, and Pd-Ni. Theoretical calculations show that the choice of the second metal has a more significant effect on the adsorption strength of *H than *HOCO, with the free energies between these two key intermediates (i.e., ΔG(*H)-ΔG(*HOCO)) correlating well with the carbon dioxide reduction reaction activity and selectivity observed in the experiments, and thus can be used as a descriptor to search for other bimetallic catalysts. The results also demonstrate the possibility of alloying Pd with non-precious transition metals to promote the electrochemical conversion of CO2 to syngas.
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Project description:A key challenge in electrocatalysis remains controlling a catalyst's structural, chemical, and electrical properties under reaction conditions. While organic coatings showed promise for enhancing the selectivity and stability of catalysts for CO2 electroreduction (CO2RR), their impact on the chemical state of underlying metal electrodes has remained unclear. In this study, we show that organic thin films on polycrystalline copper (Cu) enable retaining Cu+ species at reducing potentials down to -1.0 V vs RHE, as evidenced by operando Raman and quasi in situ X-ray photoelectron spectroscopy. In situ electrochemical atomic force microscopy revealed the integrity of the porous organic film and nearly unaltered Cu electrode morphology. While the pristine thin film enhances the CO2-to-ethylene conversion, the addition of organic modifiers into electrolytes gives rise to improved CO2RR performance stability. Our findings showcase hybrid metal-organic systems as a versatile approach to control, beyond morphology and local environment, the oxidation states of catalysts and energy conversion materials.
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Project description:Among metals used for CO2 electroreduction in water, Cu appears to be unique in its ability to produce C2+ products like ethylene. Bimetallic combinations of Cu with other metals have been investigated with the goal of steering selectivity via creating a tandem pathway through the CO intermediate or by changing the surface electronic structure. Here, we demonstrate a facile cation exchange method to synthesize Ag/Cu electrocatalysts for CO2 reduction using Cu sulfides as a growth template. Beginning with Cu2-x S nanosheets (C-nano-0, 100 nm lateral dimension, 14 nm thick), varying the Ag+ concentration in the exchange solution produces a gradual change in crystal structure from Cu7S4 to Ag2S, as the Ag/Cu mass ratio varies from 0.3 to 25 (CA-nano-x, x indicating increasing Ag fraction). After cation exchange, the nanosheet morphology remains but with increased shape distortion as the Ag fraction is increased. Interestingly, the control (C-nano-0) and cation exchanged nanosheets have very high faradaic efficiency for producing formate at low overpotential (-0.2 V vs. RHE). The primary effect of Ag incorporation is increased production of C2+ products at -1.0 V vs. RHE compared with C-nano-0, which primarily produces formate. Cation exchange can also be used to modify the surface of Cu foils. A two-step electro-oxidation/sulfurization process was used to form Cu sulfides on Cu foil (C-foil-x) to a depth of a few 10 s of microns. With lower Ag+ concentrations, cation exchange produces uniformly dispersed Ag; however, at higher concentrations, Ag particles nucleate on the surface. During CO2 electroreduction testing, the product distribution for Ag/Cu sulfides on Cu foil (CA-foil-x-y) changes in time with an initial increase in ethylene and methane production followed by a decrease as more H2 is produced. The catalysts undergo a morphology evolution towards a nest-like structure which could be responsible for the change in selectivity. For cation-exchanged nanosheets (CA-nano-x), pre-reduction at negative potentials increases the CO2 reduction selectivity compared to tests of as-synthesized material, although this led to the aggregation of nanosheets into filaments. Both types of bimetallic catalysts are capable of selective reduction of CO2 to multi-carbon products, although the optimal configurations appear to be metastable.
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Project description:Electrochemical AFM is a powerful tool for the real-space characterization of catalysts under realistic electrochemical CO2 reduction (CO2 RR) conditions. The evolution of structural features ranging from the micrometer to the atomic scale could be resolved during CO2 RR. Using Cu(100) as model surface, distinct nanoscale surface morphologies and their potential-dependent transformations from granular to smoothly curved mound-pit surfaces or structures with rectangular terraces are revealed during CO2 RR in 0.1 m KHCO3 . The density of undercoordinated copper sites during CO2 RR is shown to increase with decreasing potential. In situ atomic-scale imaging reveals specific adsorption occurring at distinct cathodic potentials impacting the observed catalyst structure. These results show the complex interrelation of the morphology, structure, defect density, applied potential, and electrolyte in copper CO2 RR catalysts.
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Project description:Atomically precise nanoclusters (NCs) provide opportunities for correlating the structure and electrocatalytic properties at atomic level. Herein, we report the single-atom doping effect and ligand effect on CO2 electroreduction (eCO2RR) by comparing monogold-doped Au1Cu24 and homocopper Cu25 NCs protected by triphenylphosphine or/and tris(4-fluorophenyl)phosphine. Catalytic results revealed that the electronic distribution of Cu25 NCs is enormously contracted by doping Au atoms, entitling it to exhibit the unique inhibition of hydrogen evolution reaction. And the inductive effect of ligand strongly favors the formation of formate in eCO2RR. Overall, this work will provide guidance for the rational design of the copper-based catalysts in the eCO2RR.
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