One-Pot Aqueous Synthesis of Porous Hollow PdCu Alloy Nanoparticles for Enhanced Ethanol Electrooxidation

Zhu, Luyu; Song, Kai; Yi, Changfeng

doi:10.1021/acs.inorgchem.2c00486

Cited by 16 publications

(10 citation statements)

References 31 publications

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“…The PdM did not reveal any peaks for pure metals (i.e., Pd, Au, Mn, and Cu) or their oxides, which implies the formation of pure Pd alloys with highly ordered nanostructures in line with reports elsewhere. 45,46 This is further proved by the small-angle XRD of the PdM nanostructures with an intense diffraction at 2θ (∼0.11°), assigned to the {111} facet of Pd crystals (Figure S3a). These peaks also are resolved for the commercial Pd/C catalyst, but with a slight shift toward lower 2θ values for the PdM nanocrystals.…”

Section: Physical Characterizationmentioning

confidence: 64%

Interfacial Engineering of Porous Pd/M (M = Au, Cu, Mn) Sponge-like Nanocrystals with a Clean Surface for Enhanced Alkaline Electrochemical Oxidation of Ethanol

Ipadeola,

Abdelgawad,

Salah

et al. 2023

Langmuir

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The interfacial engineering of Pd-based alloys (i.e., PdM with distinct morphologies, compositions, and strain defects) is an efficient way for enhanced catalytic activity; however, it remains a grand challenge to fabricate such alloys in aqueous solutions without heating, organic solvents, and multiple reaction steps. Herein, we present a simple, aqueous-phase, one-step, and ultrafast approach for the interfacial engineering of surfactant-free porous PdM (M = Cu, Au, and Mn) nanocrystals with well-controlled spongy-like morphology and compositions. The electronic interaction in PdM nanocrystals and their effect on the alkaline electrochemical ethanol oxidation reaction (EOR) are investigated using XRD, XPS, and electrochemical tests. Notably, integrating M metals into Pd atoms results in upshifting the d-band center of Pd and subsequently modulating the EOR activity and stability substantially. The EOR mass activity (10.78 A/mg Pd (6.93 A/ mg PdCu )) of PdCu was 1.83, 3.09, 4.51, and 53.90 times higher than those of AuPd (5.90 A/mg Pd (3.27 A/mg AuPd )), PdMn (3.48 A/mg Pd (3.19 A/mg PdMn )), Pd (2.39 A/mg Pd ), and Pd/C (0.20 A/mg Pd ), respectively, besides substantial durability after 1000 cycles. This is due to the porous two-dimensional morphology, a low synergetic effect, higher interfacial interaction, and greater active surface area of PdCu, besides a high Cu content with more oxophilicity that facilitates activation/dissociation of H 2 O to generate − OH species needed for quick EOR electrocatalysis. The electrochemical impedance spectroscopy (EIS) reveals better electrolyte/electrode interfacial interaction and lower charge transfer resistance on PdCu. The EOR activity of PdCu porous sponge-like nanocrystals was superior to all previously reported Pd-based alloys for electrochemical EOR. This study indicates that binary Pd-based catalysts with less synergetic effect are preferred for boosting the EOR activity, which could help in manipulating the surface properties of Pd-based alloys to optimize EOR performance.

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Section: Physical Characterizationmentioning

confidence: 64%

Interfacial Engineering of Porous Pd/M (M = Au, Cu, Mn) Sponge-like Nanocrystals with a Clean Surface for Enhanced Alkaline Electrochemical Oxidation of Ethanol

Ipadeola,

Abdelgawad,

Salah

et al. 2023

Langmuir

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“…For the coupled system of cost-effective and widespread application, anodic EOR catalysts with high efficiency, stability, and selectivity are required. To date, noble metals such as Pt and Pd are still the state-of-the-art candidates for EOR, but they suffer from high cost, reaction intermediate poisoning, and sluggish kinetics in EOR. − An effective strategy to overcome these challenges is to alloy the noble metals with certain metals such as Cu, Ag, Au, and Pb. − Our recent work revealed that Sb as an adatom in the branched PdSb alloy not only modifies the electronic nature of Pd active sites but also participates the electrocatalysis reaction itself, thus enhancing the EOR activity . Previous works also demonstrated that the introduction of the Bi atom into Pd can facilitate the removal of carbonaceous intermediates in the EOR process and thus improve the stability for electrocatalytic reactions. − Despite that tremendous studies have been made to produce multimetallic alloys to maximize the EOR performance, the Pd-based catalysts with both Sb and Bi incorporation have rarely been paid to simultaneously increase the EOR activity and stability. − …”

Section: Introductionmentioning

confidence: 99%

Boosting Hydrogen Production by Selective Anodic Electrooxidation of Ethanol over Trimetallic PdSbBi Nanoparticles: Composition Matters

Wang

Yan

et al. 2022

Inorg. Chem.

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The conventional hydrogen evolution from water electrolysis is severely impeded by the sluggish kinetics of oxygen evolution reaction (OER). In this work, an integrated electrolysis system of replacing the anodic OER with a thermodynamically favorable ethanol oxidation reaction (EOR) has been developed by using PdSbBi/C as an electrocatalyst. To maximize the EOR performance, the composition of PdSbBi nanoparticles is tuned by varying the ratio of Sb and Bi precursors. Ternary PdSbBi-based electrocatalysts exhibit enhanced activity and stability toward EOR compared to commercial Pd/C and binary catalysts. In particular, the Pd 76 Sb 17 Bi 7 /C catalyst delivers a very high specific activity up to 52.4 mA cm −2 and mass activity of 2.66 A mg −1 Pd . Besides, this EOR process is demonstrated to have high selectivity with acetic acid as the oxidation product in the electrolyte. When coupled with a cathodic platinum mash, the two-electrode electrolyzer cell requires a voltage input of merely 0.61 V to afford a current density of 10 mA cm −2 . Density functional theory calculations reveal that the presence of Sb and Bi can promote the adsorption of hydroxide ions and facilitate the removal of reaction intermediates in the EOR pathway. This work provides a novel catalyst for the energy-efficient coproduction of acetic acid and hydrogen fuel.

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“…Direct ethanol fuel cells (DEFCs) involve reactions between ethanol oxidation at the anode and oxygen reduction at the cathode. − Both of the reactions need high-efficiency electrocatalysts that can enhance electrocatalytic performance for practical application of DEFCs. Especially, the anode reaction that electrochemically oxidizes ethanol is of big significance owing to high energy and power density (see eqs 1–5 in Figure S1 for EOR pathways). − So far, palladium (Pd) is still the most used electrocatalyst for the electrocatalytic ethanol oxidation reaction (EOR). − A possible route to enhance EOR performance is the fabrication of Pd-based alloys with 3d metals (such as Au, Ag, Cu, Ni, etc. ). − Alloying 3d metals can optimize the electronic structure of Pd, thus weakening the adsorption of poisoning intermediates.…”

Section: Introductionmentioning

confidence: 99%

“…Especially, the anode reaction that electrochemically oxidizes ethanol is of big significance owing to high energy and power density (see eqs 1–5 in Figure S1 for EOR pathways). − So far, palladium (Pd) is still the most used electrocatalyst for the electrocatalytic ethanol oxidation reaction (EOR). − A possible route to enhance EOR performance is the fabrication of Pd-based alloys with 3d metals (such as Au, Ag, Cu, Ni, etc. ). − Alloying 3d metals can optimize the electronic structure of Pd, thus weakening the adsorption of poisoning intermediates. Very recently, nonmetals, for example, P and S, have also been alloyed into Pd-based nanocrystals. − In addition to the optimized electronic structure, nonmetals also facilitate the adsorption of OH species (OH ads ) of Pd catalysts and consequently accelerate the oxidation removal of poisonous species during EOR electrocatalysis.…”

Section: Introductionmentioning

confidence: 99%

Quaternary PdCuNiP Porous Nanosheets with Enhanced Electrochemical Performance in the Ethanol Oxidation Reaction

Chen

Huang

2022

Inorg. Chem.

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The ability to manipulate metal electrocatalysts with satisfactory performance for the ethanol oxidation reaction (EOR) is promising but still unsatisfactory for practical application in direct ethanol fuel cells. Beyond traditional metal–metal alloys, we herein report a novel metal–nonmetal alloy electrocatalyst that takes advantage of quaternary PdCuNiP alloy composition and the ultrathin/porous nanosheet (NS) structure. The optimized PdCuNiP porous NSs feature more undercoordinated active sites and modified electron/function structures, enabling better antipoisoning ability. Under alkaline conditions, this electrocatalyst shows excellent electrochemical EOR performance with a high EOR activity of 4.05 A mgPd –1 and a low activation energy of 21.2 kJ mol–1, comparable to the state-of-the-art electrocatalysts reported in the literature. Meanwhile, PdCuNiP porous NSs are electrocatalytically active for electrochemical oxidation of other fuels (methanol, glycerol, and glucose), highlighting their great potential for various direct alcohol fuel cells. The findings reported here may put forward some insights into designing new functional electrocatalysts for various fuel cell electrocatalysis and beyond.

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One-Pot Aqueous Synthesis of Porous Hollow PdCu Alloy Nanoparticles for Enhanced Ethanol Electrooxidation

Cited by 16 publications

References 31 publications

Interfacial Engineering of Porous Pd/M (M = Au, Cu, Mn) Sponge-like Nanocrystals with a Clean Surface for Enhanced Alkaline Electrochemical Oxidation of Ethanol

Interfacial Engineering of Porous Pd/M (M = Au, Cu, Mn) Sponge-like Nanocrystals with a Clean Surface for Enhanced Alkaline Electrochemical Oxidation of Ethanol

Boosting Hydrogen Production by Selective Anodic Electrooxidation of Ethanol over Trimetallic PdSbBi Nanoparticles: Composition Matters

Quaternary PdCuNiP Porous Nanosheets with Enhanced Electrochemical Performance in the Ethanol Oxidation Reaction

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