Mechanistic control of a galvanic replacement reaction on cuprous oxide

Lowe, James M.; Coridan, Robert H.

doi:10.1039/c8na00396c

Cited by 9 publications

(7 citation statements)

References 34 publications

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“…It is driven by the difference in reduction potentials between the surface metal atoms and the cations in solution, resulting in oxidation of the surface atom via reduction of the cation to its neutral state. As such, the process is sensitive to the chemistry of the metallic species at the surface and the cation in solution . Galvanic replacement demonstrates a flexible design approach in which the morphology and electronic composition of the active sites of the TMNP can be finely and independently tuned. − Equation summarizes the overall reaction occurring at the surface sites: The process effectively replaces n surface atoms of metal M2 with m atoms of metal M3, resulting in an M1M2@M1M3 pseudo-core@shell structure.…”

Section: Preparation Of Trimetallic Catalystsmentioning

confidence: 99%

Heterogeneous Trimetallic Nanoparticles as Catalysts

et al. 2022

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The development and application of trimetallic nanoparticles continues to accelerate rapidly as a result of advances in materials design, synthetic control, and reaction characterization. Following the technological successes of multicomponent materials in automotive exhausts and photovoltaics, synergistic effects are now accessible through the careful preparation of multielement particles, presenting exciting opportunities in the field of catalysis. In this review, we explore the methods currently used in the design, synthesis, analysis, and application of trimetallic nanoparticles across both the experimental and computational realms and provide a critical perspective on the emergent field of trimetallic nanocatalysts. Trimetallic nanoparticles are typically supported on high-surface-area metal oxides for catalytic applications, synthesized via preparative conditions that are comparable to those applied for mono- and bimetallic nanoparticles. However, controlled elemental segregation and subsequent characterization remain challenging because of the heterogeneous nature of the systems. The multielement composition exhibits beneficial synergy for important oxidation, dehydrogenation, and hydrogenation reactions; in some cases, this is realized through higher selectivity, while activity improvements are also observed. However, challenges related to identifying and harnessing influential characteristics for maximum productivity remain. Computation provides support for the experimental endeavors, for example in electrocatalysis, and a clear need is identified for the marriage of simulation, with respect to both combinatorial element screening and optimal reaction design, to experiment in order to maximize productivity from this nascent field. Clear challenges remain with respect to identifying, making, and applying trimetallic catalysts efficiently, but the foundations are now visible, and the outlook is strong for this exciting chemical field.

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Section: Preparation Of Trimetallic Catalystsmentioning

confidence: 99%

Heterogeneous Trimetallic Nanoparticles as Catalysts

et al. 2022

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“…The experimental results revealed that the GRR mechanism in the metal oxide is based on redox couple reactions between multivalent metallic ions, replacing the ions with a higher oxidation state in the templates with metal ions of a lower oxidation state from the solution. This strategy has been further developed to synthesize oxide/metal heteronanostructures 85 . The experimental and theoretical studies revealed that the cost‐effective transition metal oxides (CuO x , FeO x , and MnO 2 ) could react with Pt due to their higher galvanic potential than Pt 4+ and Rh 3+ 86–88 .…”

Section: Grr In the Unconventional Nanoparticle Systemsmentioning

confidence: 99%

Galvanic replacement reaction to prepare catalytic materials

Hong

Venkateshalu

Jeong

et al. 2022

Bulletin Korean Chem Soc

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Galvanic replacement reaction (GRR) has gained considerable interest as a facile and versatile synthetic method for modulating compositions, morphologies, and corresponding physicochemical properties of metallic nanoparticles. Thus far, extensive knowledge of GRR on monometallic templates has been accumulated, backed with ample experimental data and computational modeling and validation. The GRR templates have recently been extended to other materials such as alloys, oxides, sulfides, and liquid metals. These new materials have demonstrated potential applications in electrochemical energy conversion systems, which have been relatively unexplored for GRR-originated materials. In this review, the recent findings in GRR on these new template materials are introduced, pointing to the incredible versatility of the GRR methodology in diversifying the catalytic materials classes. We further discuss the remaining critical issues and future research directions of GRRs to fully exploit the potential of GRR in spearheading future advances in electrocatalytic energy conversion and other important applications.

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“…22 Aqueous solutions of lactate-stabilized Cu 2+ at high pH (9)(10)(11)(12) are used for the electrodeposition of Cu2O in the narrow range of electrode potentials noted by the Pourbaix diagram. [23][24][25][26] The Pourbaix diagram also suggests that metallic copper can be deposited at more negative potentials in the same alkaline conditions. Therefore, the electrodeposition of copper in dendritic morphologies is possible at sufficiently negative potentials while mitigating the morphological consequences of DHBT.…”

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confidence: 92%

Electrochemical control of the morphology and functional properties of hierarchically structured, dendritic Cu surfaces

Mehrabi

Conlin

Hollis

et al. 2022

Preprint

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Electrodeposited dendritic copper foams have been extensively studied as an electrocatalyst for CO2 reduction reaction (CO2RR). Many parameters, such as dendrite size, porosity, pore size, and crystal faceting, define the hierarchical properties of these structures and their subsequent bubble evolution and CO2RR capabilities. Here we studied the effects the electrodeposition conditions (potential, pH) have on the resulting crystallinity, microstructure, and macroporosity of the copper foam. We characterized these morphological differences and the corresponding effects on electrocatalytic activity. We showed that the composition of the electrodeposition bath can have significant effects on the mechanics of bubble formation and detachment at the surface during hydrogen evolution reaction (HER) in acidic solutions. Similarly, the electrodeposition conditions for the synthesis of the foam affected the product selectivity during CO2RR electrocatalysis. Foams deposited in alkaline electrodeposition solutions showed high faradaic efficiency and specificity towards C2H6, an uncommon product of CO2RR, at modest applied potentials (-0.8 V vs. RHE).

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Mechanistic control of a galvanic replacement reaction on cuprous oxide

Abstract: The galvanic replacement (GR) reaction of Au on Cu2O is mediated by the disproportionation of the substrate. As a result, the morphology of the deposited film can be controlled by the chemical conditions.

Cited by 9 publications

References 34 publications

Heterogeneous Trimetallic Nanoparticles as Catalysts

Heterogeneous Trimetallic Nanoparticles as Catalysts

Galvanic replacement reaction to prepare catalytic materials

Electrochemical control of the morphology and functional properties of hierarchically structured, dendritic Cu surfaces

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