Controlling the radical-induced redox chemistry inside a liquid-cell TEM

Ambrožič, Bojan; Prašnikar, Anže; Hodnik, Nejc; Kostevšek, Nina; Likozar, Blaž; Rožman, Kristina Žužek; Šturm, Sašo

doi:10.1039/c9sc02227a

Cited by 41 publications

(51 citation statements)

References 39 publications

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“…[11,12] Vavra et al [11] revealed dissolution/redeposition as the main degradation mechanism in the initial stages of ERC. Nevertheless, the insitu liquid TEM with all its limitations (e. g., beam-induced radiolysis effects) [23,24] provides only low-resolution morphological changes of the of Cu-based catalyst. Even though the exsitu characterization cannot probe the nature of catalytic sites, [14] it is still common and very useful to observe and follow morphological changes.…”

Section: Introductionmentioning

confidence: 99%

Reconstruction of Copper Nanoparticles at Electrochemical CO₂ Reduction Reaction Conditions Occurs via Two‐step Dissolution/Redeposition Mechanism

2021

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Copper is still the monometallic electrocatalyst of choice for electrochemical reduction of CO 2 (ERC) when added-value products, such as hydrocarbons and alcohols, are desired. However, severe morphological and structural changes are observed upon exposure to the ERC operation conditions. One of the pending questions in the community is what the mechanism behind this reconstruction is. In the present study, pulse-electrodeposited copper nanoparticles were exposed to different ERC relevant reductive potentials and tracked with identical location scanning electron microscopy (IL-SEM). This approach provides information on the morphological and structural history and subsequent change of Cu nanoparticles and with that a deep insight into the reconstruction events. With this evidence, we could interpret the observed structural changes as two separate electrochemical processes occurring one after another, namely copper dissolution from pre-oxidized native nanoparticles and subsequent (electro-) redeposition of the dissolved copper species in a form of new smaller Cu fragments.

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Section: Introductionmentioning

confidence: 99%

Reconstruction of Copper Nanoparticles at Electrochemical CO₂ Reduction Reaction Conditions Occurs via Two‐step Dissolution/Redeposition Mechanism

2021

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“…[ 5 ] Interestingly, the dynamics of colloidal assemblies composed of several hundred nano‐objects can be monitored to extract statistical information on the nucleation and growth processes [ 6 ] and the chemical reactions can also be observed at the single NP level to provide in situ insights into the atomic‐scale mechanisms driving NP size and shape. [ 7 ] However, as the use of LCTEM with temperature control is very recent, [ 8 ] the direct observations of thermal effects on the formation processes of nanomaterials are still in their infancy.…”

Section: Introductionmentioning

confidence: 99%

Quantitative In Situ Visualization of Thermal Effects on the Formation of Gold Nanocrystals in Solution

et al. 2021

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Understanding temperature effects in nanochemistry requires real‐time in situ measurements because this key parameter of wet‐chemical synthesis simultaneously influences the kinetics of chemical reactions and the thermodynamic equilibrium of nanomaterials in solution. Here, temperature‐controlled liquid cell transmission electron microscopy is exploited to directly image the radiolysis‐driven formation of gold nanoparticles between 25 °C and 85 °C and provide a deeper understanding of the atomic‐scale processes determining the size and shape of gold colloids. By quantitatively comparing the nucleation and growth rates of colloidal assemblies with classical models for nanocrystal formation, it is shown that the increase of the molecular diffusion and the solubility of gold governs the drastic changes in the formation dynamics of nanostructures in solution with temperature. In contraction with the common view of coarsening processes in solution, it is also demonstrated that the dissolution of nanoparticles and thus the Ostwald ripening is not only driven by size effects. Furthermore, visualizing thermal effects on faceting processes at the single nanoparticle level reveals how the competition between the growth speed and the surface diffusion dictates the final shape of nanocrystals.

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“…can be produced in water by high energy electron beam irradiation and the etching mechanisms in LCTEM are very complicated. [ 14–17 ] ZnO is an amphoteric oxide which can be etched in deionized water (pH ≈ 6.7–6.9), ambient environment, H 2 O 2 , acid, and alkali solution. [ 18–22 ] Hence, most radicals (H 2 O 2 , H 3 O + , OH•, HO 2 •,etc.)…”

Section: Figurementioning

confidence: 99%

Controlling the Facet of ZnO during Wet Chemical Etching Its (0001¯) O‐Terminated Surface

Sun

Hong

et al. 2020

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Special surface plays a crucial role in nature as well as in industry. Here, the surface morphology evolution of ZnO during wet etching is studied by in situ liquid cell transmission electron microscopy and ex situ wet chemical etching. Many hillocks are observed on the (000 1) O-terminated surface of ZnO nano/micro belts during in situ etching. Nanoparticles on the apex of the hillocks are observed to be essential for the formation of the hillocks, providing direct experimental evidence of the micromasking mechanism. The surfaces of the hillocks are identified to be {0113} crystal facets, which is different from the known fact that {01 1 1} crystal facets appear on the (000 1) O-terminated surface of ZnO after wet chemical etching. O 2 plasma treatment is found to be the key factor for the appearance of {0113} instead of {011 1} crystal facets after etching for both ZnO nano/micro belts and bulk materials. The synergistic effect of acidic etching and O-rich surface caused by O 2 plasma treatment is proposed to be the cause of the appearance of {0113} crystal facets. This method can be extended to control the surface morphology of other materials during wet chemical etching.

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Controlling the radical-induced redox chemistry inside a liquid-cell TEM

Abstract: A holistically described radical-induced redox chemistry modelling allows for a direct assessment of the in situ experiments inside a liquid-cell TEM.

Cited by 41 publications

References 39 publications

Reconstruction of Copper Nanoparticles at Electrochemical CO₂ Reduction Reaction Conditions Occurs via Two‐step Dissolution/Redeposition Mechanism

Reconstruction of Copper Nanoparticles at Electrochemical CO₂ Reduction Reaction Conditions Occurs via Two‐step Dissolution/Redeposition Mechanism

Quantitative In Situ Visualization of Thermal Effects on the Formation of Gold Nanocrystals in Solution

Controlling the Facet of ZnO during Wet Chemical Etching Its (0001¯) O‐Terminated Surface

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Controlling the radical-induced redox chemistry inside a liquid-cell TEM

Abstract: A holistically described radical-induced redox chemistry modelling allows for a direct assessment of the in situ experiments inside a liquid-cell TEM.

Cited by 41 publications

References 39 publications

Reconstruction of Copper Nanoparticles at Electrochemical CO2 Reduction Reaction Conditions Occurs via Two‐step Dissolution/Redeposition Mechanism

Reconstruction of Copper Nanoparticles at Electrochemical CO2 Reduction Reaction Conditions Occurs via Two‐step Dissolution/Redeposition Mechanism

Quantitative In Situ Visualization of Thermal Effects on the Formation of Gold Nanocrystals in Solution

Controlling the Facet of ZnO during Wet Chemical Etching Its (0001¯) O‐Terminated Surface

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Reconstruction of Copper Nanoparticles at Electrochemical CO₂ Reduction Reaction Conditions Occurs via Two‐step Dissolution/Redeposition Mechanism

Reconstruction of Copper Nanoparticles at Electrochemical CO₂ Reduction Reaction Conditions Occurs via Two‐step Dissolution/Redeposition Mechanism