Small palladium islands embedded in palladium–tungsten bimetallic nanoparticles form catalytic hotspots for oxygen reduction

Hu, Guangzhi; Nitze, Florian; Gracia‐Espino, Eduardo; Ma, Jingyuan; Barzegar, Hamid Reza; Sharifi, Tiva; Jia, Xueen; Shchukarev, Andrey; Lu, Lu; Ma, Chuansheng; Yang, Guang; Wågberg, Thomas

doi:10.1038/ncomms6253

Cited by 79 publications

(65 citation statements)

References 51 publications

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“…deposited silver–palladium core–shell alloy nanoparticles (diameter: 7.5 nm) onto multiwall carbon nanotubes and observed an onset potential of oxygen reduction around +0.9 V versus RHE and an n value of about 3. In another study, Hu et al . decorated ordered mesoporous carbons with palladium–tungsten alloy nanoparticles that featured segregated nanoislands of palladium (ca.…”

Section: Resultsmentioning

confidence: 99%

Alkyne‐Protected AuPd Alloy Nanoparticles for Electrocatalytic Reduction of Oxygen

Deming

Zhao²,

Yang

et al. 2015

ChemElectroChem

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Dodecyne‐capped AuPd alloy nanoparticles of varying compositions were prepared through the co‐reduction of metal‐salt precursors with NaBH4. TEM measurements showed that the particles were largely in the range of 2–6 nm in diameter. XPS studies showed that the atomic Pd concentration varied from 65 to 100 %. Infrared spectroscopic measurements confirmed the bonding attachment of the dodecyne ligands on the nanoparticle surfaces, which rendered the nanoparticles readily dispersible in common organic media. Electrochemically, the resulting nanoparticles exhibited apparent catalytic activity in oxygen reduction with a volcano‐shaped variation with the metal composition. The best performance was identified with the sample composed of 91.2 at % Pd that exhibited a mass activity over eight times better than that of commercial palladium black, and almost twice as good in terms of specific activity. This remarkable performance was accounted for by both alloying with gold and surface functionalization with alkyne ligands that manipulated the electronic interactions between palladium and oxygen species.

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Section: Resultsmentioning

confidence: 99%

Alkyne‐Protected AuPd Alloy Nanoparticles for Electrocatalytic Reduction of Oxygen

Deming

Zhao²,

Yang

et al. 2015

ChemElectroChem

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“…So far, the synthesis of NPs composed of two elements (bi-NPs) has stimulated research efforts [8][9][10][11][12][13] due to their remarkably enhanced catalytic, microbicidal, optical, electronic, and mechanical properties, which goes beyond the mere sum of the effects of the constituent materials. Ag/Fe a Author to whom correspondence should be addressed.…”

confidence: 99%

“…9 Small quantities of Pd inside Pd-W NPs metal are sufficient to enhance the cluster stability and catalytic properties due to the formation of ultra-active Pd hot-spots. 10 Moreover, Ag can broaden the bactericidal activity of TiO 2 -based photocatalyst composite materials and can also act against silver-resistant microorganisms due to their photooxidative mechanism, 14 and various wet synthesis methods have been used resulting in Ag decoration of TiO 2 nanostructures. [15][16][17][18] However, very little is known about the formation and properties of bi-NPs-based coatings.…”

confidence: 99%

Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

et al. 2017

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Ultrathin coatings based on bi-elemental nanoparticles (NPs) are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. This work is expected to significantly spread the range of applications of NPs coatings, not only as an effective tool in the prevention of healthcare-associated infections but also in other technologically relevant fields like sensors or nano-/micro joining

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“…From DFT calculations it is commonly modeled that the active site for the oxygen reduction in both acidic and alkaline medium is the central metal atom. In alkaline medium the ORR process is represented by the scheme

\begin{matrix} left \\ I) * + {normalO}_{2 (g)} + {normalH}_{2} {normalO}_{(l)} + {normale}^{-} \to * OOH + {normalOH}^{-} \\ II) * OOH + {normale}^{-} \to * O + {normalOH}^{-} \\ III) * O + {normalH}_{2} {normalO}_{(l)} + {normale}^{-} \to * OH + {normalOH}^{-} \\ IV) * OH + {normale}^{-} \to {normalOH}^{-} + * \end{matrix}

where the * represents the active site (cobalt). It was shown that the rate limiting steps in the scheme above were the formation of *OOH and OH − (steps I and IV).…”

Section: Cobalt‐based Electrocatalystsmentioning

confidence: 99%

Oxygen Reduction Reactions on Single‐ or Few‐Atom Discrete Active Sites for Heterogeneous Catalysis

Sharifi

Gracia‐Espino

Chen

et al. 2019

Advanced Energy Materials

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The oxygen reduction reaction (ORR) is of great importance in energy‐converting processes such as fuel cells and in metal–air batteries and is vital to facilitate the transition toward a nonfossil dependent society. The ORR has been associated with expensive noble metal catalysts that facilitate the O2 adsorption, dissociation, and subsequent electron transfer. Single‐ or few‐atom motifs based on earth‐abundant transition metals, such as Fe, Co, and Mo, combined with nonmetallic elements, such as P, S, and N, embedded in a carbon‐based matrix represent one of the most promising alternatives. Often these are referred to as single atom catalysts; however, the coordination number of the metal atom as well as the type and nearest neighbor configuration has a strong influence on the function of the active sites, and a more adequate term to describe them is metal‐coordinated motifs. Despite intense research, their function and catalytic mechanism still puzzle researchers. They are not molecular systems with discrete energy states; neither can they fully be described by theories that are adapted for heterogeneous bulk catalysts. Here, recent results on single‐ and few‐atom electrocatalyst motifs are reviewed with an emphasis on reports discussing the function and the mechanism of the active sites.

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Small palladium islands embedded in palladium–tungsten bimetallic nanoparticles form catalytic hotspots for oxygen reduction

Cited by 79 publications

References 51 publications

Alkyne‐Protected AuPd Alloy Nanoparticles for Electrocatalytic Reduction of Oxygen

Alkyne‐Protected AuPd Alloy Nanoparticles for Electrocatalytic Reduction of Oxygen

Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

Oxygen Reduction Reactions on Single‐ or Few‐Atom Discrete Active Sites for Heterogeneous Catalysis

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