Palladium Nanoparticles Anchored on Anatase Titanium Dioxide‐Black Phosphorus Hybrids with Heterointerfaces: Highly Electroactive and Durable Catalysts for Ethanol Electrooxidation

Wu, Tong; Fan, Jinchen; Li, Qiaoxia; Shi, Penghui; Xu, Qing

doi:10.1002/aenm.201701799

Cited by 168 publications

(135 citation statements)

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CC bond cleavage, resulting in the low fuel utilization and less than theoretical 12 elections transfer. [14][15][16] At present, Pt is the most effective monometallic electrocatalyst for the EOR. [14][15][16] At present, Pt is the most effective monometallic electrocatalyst for the EOR.

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mentioning

confidence: 99%

Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation

Han

Liu

Chen

et al. 2018

Advanced Energy Materials

250

134

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CC bond cleavage, resulting in the low fuel utilization and less than theoretical 12 elections transfer. [12,13] Thus, improving the ability of electrocatalysts for splitting CC bond is critical for the development and application of DEFCs. [14][15][16] At present, Pt is the most effective monometallic electrocatalyst for the EOR. However, expensive price and weak ability of splitting CC bond seriously hamper its commercial applications. [10,17] Recently, alloying Pt with other metal is generally considered as an efficient strategy for decreasing the cost of electrocatalyst and simultaneously improving electrocatalytic activity for the EOR. [18][19][20][21] For example, the addition of Ru and Rh elements can obviously promote the CC bond cleavage, which is beneficial to the C 1 reaction pathway of the EOR. The introduction of highly oxophilic metals (such as Ni and Cu) can decrease the CO poisoning of electrocatalyst due to the bifunctional mechanism. [17,22,23] Considering that CC bond cleavage and CO poisoning, trimetallic Pt-based electrocatalysts have been designed to simultaneously improve their CC bond cleavage capability and antipoisoning capability. For example, PtPdRh [24] and PtRhNi [22] alloys nanoparticles displayed the excellent electrocatalytic activity for the EOR.Apart from chemical composition, the morphology of nanostructures also strongly affects their electrocatalytic performance. [25][26][27][28][29][30] For example, hollow nanostructures generally show enhanced activity and stability due to their unique advantages, including large surface area, abundant active sites, high atomic utilization, rich holes, fast mass transfer, stable 3D structure, and slow Ostwald ripening. [31][32][33][34][35] Given the effect of chemical composition and morphology on the EOR performance, herein, we designed and synthesized the porous trimetallic PtRhCu cubic nanoboxes (CNBs) by the galvanic reaction between K 2 PtCl 4 , RhCl 3 , and Cu 2 O nanocubes template. The shell thickness and chemical composition of PtRhCu CNBs could be easily regulated by controlling the amount and proportion of noble metal precursors. Due to geometric effect and alloy effect, the composition optimized PtRhCu CNBs exhibited a significantly enhanced C 1 pathway selectivity for the EOR, resulting in super electrocatalytic activity and stability. Additionally, the template method could also be used to synthesize other trimetallic cubic nanoboxes (such as PtIrCu and PtAuCu CNBs), showing its universality.Direct ethanol fuel cells (DEFCs) have great activity as a green energy conversion device. However, the weak activity of most anode electrocatalysts for the CC bond cleavage is an obstacle to the DEFCs development. Herein, a simple galvanic replacement reaction strategy to synthesize hollow and porous PtRhCu trimetallic nanoboxes (CNBs) with a tunable Pt/Rh atomic ratio is developed. For the ethanol oxidation reaction (EOR), PtRhCu CNBs show morphology and composition-dependent electrocatalytic activity. The composition optimized Pt...

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confidence: 99%

Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation

Han

Liu

Chen

et al. 2018

Advanced Energy Materials

250

134

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“…[1][2][3][4][5] With alkaline-type direct liquid fuel cells being given greater attention than acid-type fuel cells, [6][7] formate is an ideal fuel alternative to ethanol and methanol. In this manuscript, we demonstrate, for the first time, a class of binary PdÀ Ni alloy nanoparticles over two different carbon supports showing exceptional enhancement of the formate oxidation reaction (FOR) performance in alkaline medium, compared to Pd/C.…”

mentioning

confidence: 99%

“…[1][2][3][4][5] With alkaline-type direct liquid fuel cells being given greater attention than acid-type fuel cells, [6][7] formate is an ideal fuel alternative to ethanol and methanol. [1][2][3][4][5] With alkaline-type direct liquid fuel cells being given greater attention than acid-type fuel cells, [6][7] formate is an ideal fuel alternative to ethanol and methanol.…”

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confidence: 99%

Binary Pd−Ni Nanoalloy Particles over Carbon Support with Superior Alkaline Formate Fuel Electrooxidation Performance

et al. 2019

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Formate is the one legitimate carbon-neutral fuel that has the capability of being considered an alternative to alcohol fuels amidst the growing demand for efficient fuel-cell systems. In this manuscript, we demonstrate, for the first time, a class of binary PdÀ Ni alloy nanoparticles over two different carbon supports showing exceptional enhancement of the formate oxidation reaction (FOR) performance in alkaline medium, compared to Pd/C. The synergistic effects of Pd and oxophilic Ni along with the electronic structure alteration of Pd induced through alloying resulted in an effective change in its catalytic ability, leading to a 5-time enhancement in the overall current density along with a lower overpotential during formate oxidation compared to Pd/C. The more active Pd catalytic sites of the nanoalloy helped to yield mass activities as high as 4.5 A mg À 1 Pd and 7.8 A mg À 1 Pd during FOR. The structural and electrochemical analysis justifies the synergistic effects and alterations in the Pd lattice ensuing a superior enhancement of electrochemically active Pd sites.Direct liquid fuel cells (DLFCs) are regarded as one of the energy carriers of the future due to their plentiful advantages, including high power density, ease of handling and being part of the renewable energy series. [1][2][3][4][5] With alkaline-type direct liquid fuel cells being given greater attention than acid-type fuel cells, [6][7] formate is an ideal fuel alternative to ethanol and methanol. [8] Direct formate fuel cells (DFFCs) are also receiving immense attention due to the increased formate fuel regeneration possibilities especially those involving CO 2 . [9][10][11] Formate is further advantageous in terms of its nontoxic and environmentally friendly nature. [12][13] As such, DFFCs currently need potential efficient and stable catalysts for widespread commer-cial applications. Palladium is the catalyst that has shown the most promising prospects for enhanced liquid-fuel oxidation kinetics in alkaline media and that could effectively replace platinum. [14][15][16] However, there is an imminent need for performance improvements in Pd catalysts in terms of their efficiency and durability before they can be effectively utilized in alkaline DFFCs. Previous reports suggest that the formate oxidation reaction on the Pd surface proceeds through the decomposition of COO À into CO 3 2À in alkaline medium. [17] When considering advancements in Pd-based anode catalysts for alkaline formate oxidation, transition metal alloying has been shown to increase the alcohol and formic acid/formate fuel oxidation capabilities [5,[18][19][20][21] and to the best of our knowledge, alkaline formate oxidation using Pd-transition metal alloy catalysts has seldom been studied and is largely unexplored. Alloy catalysts of Pd with Au or Cu have been reported with marginal increases in the alkaline formate oxidation performance. [22][23] PdÀ Co alloy over Vulcan carbon obtained via solid-solution processing could yield a good FOR kinetics in our recent study. [18]...

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“…[213] They synthesized WCÀPd nanocomposites on graphene, in which small-sized Pd nanoparticles were decorated on the surfaceso fW C. Both DFT calculations and Xray photoelectrons pectroscopy( XPS) measurements confirm that there is as trong interaction betweenP da nd WC domains, which results in electron transfer from WC to Pd in the WCÀPd nanocomposites. [217][218][219][220][221][222][223][224][225][226][227][228][229][230][231][232] The enhanced EOR is derived first from surfaces rich in oxygen-containing species providedb yt he metal oxides, which are capable of removing adsorbed poisonous CO intermediates by facilitating oxidation to CO 2 .S econd, the "OH carpet" created by metal oxidesc ould precludeP t, Pd, or their alloys with other metals (e.g.,R h, Ru) from reacting with water to form compounds with ÀOH species, making them in lowcoordination states and available for ethanol oxidation. Electron transfer from WC to Pd in the nanocomposites not only modifies the electronic structure of the Pd domain,w hich is favorable for the scission of ethanol molecules on Pd sites, but also weakenst he adsorption of poisoning intermediates, such as CO, on the Pd surface by increasing the electron density around Pd atoms.…”

Section: Noble-metal-based Composite Nanocatalysts For the Eormentioning

confidence: 99%

Nanocatalysts for Electrocatalytic Oxidation of Ethanol

et al. 2019

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The use of ethanol as a fuel in direct alcohol fuel cells depends not only on its ease of production from renewable sources, but also on overcoming the challenges of storage and transportation. In an ethanol‐based fuel cell, highly active electrocatalysts are required to break the C−C bond in ethanol for its complete oxidation at lower overpotentials, with the aim of increasing the cell performance, ethanol conversion rates, and fuel efficiency. In recent decades, the development of wet‐chemistry methods has stimulated research into catalyst design, reactivity tailoring, and mechanistic investigations, and thus, created great opportunities to achieve efficient oxidation of ethanol. In this Minireview, the nanomaterials tested as electrocatalysts for the ethanol oxidation reaction in acid or alkaline environments are summarized. The focus is mainly on nanomaterials synthesized by using wet‐chemistry methods, with particular attention on the relationship between the chemical and physical characteristics of the catalysts, for example, catalyst composition, morphology, structure, degree of alloying, presence of oxides or supports, and their activity for ethanol electro‐oxidation. As potential alternatives to noble metals, non‐noble‐metal catalysts for ethanol oxidation are also briefly reviewed. Insights into further enhancing the catalytic performance through the design of efficient electrocatalysts are also provided.

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Palladium Nanoparticles Anchored on Anatase Titanium Dioxide‐Black Phosphorus Hybrids with Heterointerfaces: Highly Electroactive and Durable Catalysts for Ethanol Electrooxidation

Cited by 168 publications

References 85 publications

Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation

Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation

Binary Pd−Ni Nanoalloy Particles over Carbon Support with Superior Alkaline Formate Fuel Electrooxidation Performance

Nanocatalysts for Electrocatalytic Oxidation of Ethanol

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