Anion replacement in silver chlorobromide nanocubes: two distinct hollowing mechanisms

Abeyweera, Sasitha C.; Stewart, Shea; Sun, Yugang

doi:10.1039/c9qm00544g

Cited by 6 publications

(7 citation statements)

References 41 publications

(45 reference statements)

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“…In the case of an AER in silver chlorobromide nanocubes reported by Sun and colleagues, S 2À could easily facilitate the AER from cubic AgCl 0.5 Br 0.5 to monoclinic Ag 2 S owing to the comparable sizes of S 2À and halide ions, whereas benzenethiolate anions (BT À ) could hardly achieve a similar AER owing to the larger size of BT À ions. 72 Similarly, differences in the crystal structure of reactants facilitating the diffusive abilities of different ions were also reported by Manna and colleagues in the case of a CER between Cu 2 Se NCs and Pb 2+ . 73 As for perovskite NCs, Yang and colleagues reported that intrinsic anion diffusivity in lead halide perovskites was facilitated by a soft lattice.…”

Section: Effects Of Solvent and Ligandssupporting

confidence: 53%

Cation/Anion Exchange Reactions toward the Syntheses of Upgraded Nanostructures: Principles and Applications

et al. 2020

Matter

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The last 5 years have witnessed rapid progress in the field of hybrid nanostructures toward enhanced optical and electronic properties. On this topic, we focus on the relevant progress that has been achieved on the basis of cation/anion exchange reactions (CERs/AERs). Different from those direct synthesis strategies, CERs/AERs can offer more freedom in tuning the chemical composition, crystal phases, doping, interfaces, and morphologies, which are key parameters to determine the optical and electronic properties of the target products. We present several examples, e.g., doped quantum dots (QDs), engineered core-shell QDs, metal-semiconductor hybrid nanostructures, hollow structures, and inorganic perovskite nanocrystals. These upgraded structures afforded by CERs/ AERs generally exhibit improved properties, such as increased quantum yields, prolonged lifetimes, and well-engineered band gaps for charge transportation and recombination, thus providing more opportunities for further advanced applications.

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Section: Effects Of Solvent and Ligandssupporting

confidence: 53%

Cation/Anion Exchange Reactions toward the Syntheses of Upgraded Nanostructures: Principles and Applications

et al. 2020

Matter

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“…The synthesis relies on the direct electrochemical reduction of nanoboxes of silver benzenethiolate (AgBT) that are synthesized through the hollowing transformation of AgCl 0.5 Br 0.5 nanocubes in the presence of thiophenol (Figures S1–S3). , The resulting hierarchical three-dimensional (3D) porous structures exhibit nanosized pores on the scale of 10 nm and submicron hollow interiors on the scale of 160 nm, which are more like nanocages in morphology. The presence of the submicron hollow interiors promotes the diffusion of reactive species in the course of the eCO 2 RR, further increasing the current density of electrochemical reduction up to ∼500 A/g in an aqueous solution.…”

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confidence: 99%

Hierarchically 3D Porous Ag Nanostructures Derived from Silver Benzenethiolate Nanoboxes: Enabling CO₂ Reduction with a Near-Unity Selectivity and Mass-Specific Current Density over 500 A/g

Abeyweera

Perdew

et al. 2020

Nano Lett.

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Silver nanostructures with hierarchical porosities of multiple length scales have been synthesized through electrochemical reduction of silver benzenethiolate nanoboxes. The porous Ag nanostructures exhibit superior catalytic performance toward electrochemical reduction of CO 2 . The Faradaic efficiency of reducing CO 2 to CO can be close to 100% at high cathodic potentials, benefiting from the readsorbed benzenethiolate ions on the Ag surface that can suppress the hydrogen evolution reaction (HER). Density functional theory calculations using the SCAN functional reveal that the disfavored H binding on the benzenethiolate-modified Ag surface is responsible for inhibiting the HER. The mass-specific activity of CO 2 reduction can be over 500 A/g because the multiple-scale porosities maximize the diffusion of reactive species to and away from the Ag surface. The unique multiscale porosities and surface modification of the as-synthesized Ag nanostructures make them a class of promising catalysts for electrochemical reduction of CO 2 in protic electrolytes to achieve maximum activity and selectivity.

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“…AgABT nucleates on the surfaces of the AgCl 0.5 Br 0.5 nanocubes during the anion replacement reaction because heterogeneous nucleation is preferable to homogeneous nucleation in the presence of solid nanoparticles in the synthesis solution. The following continuous growth of AgABT against the nanocube surfaces forms nanoplates with smooth surfaces (FigureS2A) until the complete consumption of AgCl 0.5 Br 0.5 40,41. The resulting AgABT nanoplates are crystallized in a layered structure confirmed by the XRD pattern shown in FigureS2B.…”

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confidence: 88%

Interfaced Ag/Cu nanostructures derived from metal thiolate nanoplates: A highly selective catalyst for electrochemical reduction of CO₂ to ethanol

et al. 2022

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Selective reduction of CO2 into liquid products such as ethanol through electrochemical catalysis is promising in storing renewable energy in more deliverable chemicals and balancing the carbon footprint in the environment. However, the lack of efficient catalysts for electrochemical CO2 reduction reaction (eCO2RR) makes the promise challenging because the formation of C2+ alcohols requires coupling reactions between the shallow reduction intermediates and deep reduction intermediates that are usually difficult to form on uniform catalyst surfaces simultaneously with appropriate transient kinetics. Herein, we report a new strategy for synthesizing bimetallic nanostructures with high densities of interfaced Ag/Cu boundaries, which facilitate the coupling reaction of the high‐oxidation‐number intermediates (CO) formed on the Ag surface and the low‐oxidation‐number intermediates (CHx) formed on the Cu surface. The synthesis relies on the electrochemical reduction of bilayered nanoplates made of silver thiolate and copper thiolate, resulting in Ag/Cu nanostructures exposing Ag surface, Cu surface, and the Ag/Cu interfaced boundaries. Balancing the accessible surface areas of the Ag surface, Cu surface, and Ag/Cu boundaries is beneficial for maximizing the activity and selectivity of eCO2RR towards ethanol production. Faradaic efficiency of forming ethanol has been observed as high as about 50% using the Ag/Cu nanostructure catalyst with molar ratio nAg:nCu of 1:1. Moreover, the promoted coupling reaction at the Ag/Cu boundaries and surface modification with thiolate anions significantly suppress the undesirable hydrogen evolution reaction, particularly at high cathodic potentials, maintaining high energy efficiency for eCO2RR.

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Anion replacement in silver chlorobromide nanocubes: two distinct hollowing mechanisms

Abstract: Mechanistic studies on the controlled conversion of silver chlorobromide nanocubes into silver-based hollow nanostructures through chemical transformations.

Cited by 6 publications

References 41 publications

Cation/Anion Exchange Reactions toward the Syntheses of Upgraded Nanostructures: Principles and Applications

Cation/Anion Exchange Reactions toward the Syntheses of Upgraded Nanostructures: Principles and Applications

Hierarchically 3D Porous Ag Nanostructures Derived from Silver Benzenethiolate Nanoboxes: Enabling CO₂ Reduction with a Near-Unity Selectivity and Mass-Specific Current Density over 500 A/g

Interfaced Ag/Cu nanostructures derived from metal thiolate nanoplates: A highly selective catalyst for electrochemical reduction of CO₂ to ethanol

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Anion replacement in silver chlorobromide nanocubes: two distinct hollowing mechanisms

Abstract: Mechanistic studies on the controlled conversion of silver chlorobromide nanocubes into silver-based hollow nanostructures through chemical transformations.

Cited by 6 publications

References 41 publications

Cation/Anion Exchange Reactions toward the Syntheses of Upgraded Nanostructures: Principles and Applications

Cation/Anion Exchange Reactions toward the Syntheses of Upgraded Nanostructures: Principles and Applications

Hierarchically 3D Porous Ag Nanostructures Derived from Silver Benzenethiolate Nanoboxes: Enabling CO2 Reduction with a Near-Unity Selectivity and Mass-Specific Current Density over 500 A/g

Interfaced Ag/Cu nanostructures derived from metal thiolate nanoplates: A highly selective catalyst for electrochemical reduction of CO2 to ethanol

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Product

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Hierarchically 3D Porous Ag Nanostructures Derived from Silver Benzenethiolate Nanoboxes: Enabling CO₂ Reduction with a Near-Unity Selectivity and Mass-Specific Current Density over 500 A/g

Interfaced Ag/Cu nanostructures derived from metal thiolate nanoplates: A highly selective catalyst for electrochemical reduction of CO₂ to ethanol