Ultrasmall Palladium Nanoclusters Encapsulated in Porous Carbon Nanosheets for Oxygen Electroreduction in Alkaline Media

Yan, Wei; Tang, Zhenghua; Li, Ligui; Wang, Likai; Yang, Hongyu; Wang, Qiannan; Wu, Wen Chung; Chen, Shaowei

doi:10.1002/celc.201600885

Cited by 31 publications

(15 citation statements)

References 51 publications

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“…The marriage of two metals can endorse both a geometric effect and an electronic effect. The geometric effect refers to the generation of a new catalytic active site due to the Encouraged by these findings, our group prepared Pd clusters in situ encapsulated in porous carbon nanosheets (CNS) for ORR in alkaline media [70]. Electrochemical tests showed that Pd/CNS-20% (Pd mass loading is 20%) displayed superior activity than Pd black, with mass activity five-times greater than Pd black [70].…”

Section: Alloyed Noble Metal Clusters For Orrmentioning

confidence: 99%

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Tang

Wang

2018

Catalysts

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Highly-efficient catalysts for the oxygen reduction reaction (ORR) have been extensively investigated for the development of proton exchange membrane fuel cells (PEMFCs). The state-ofthe-art Pt/C catalysts suffer from high price, limited accessibility of Pt, sluggish reaction kinetics, as well as undesirable long-term durability. Engineering ultra-small noble metal clusters with high surface-to-volume ratios and robust stabilities for ORR represents a new avenue. After a simple introduction regarding the significance of ORR and the recent development of noble metal clusters, the general ORR mechanism in both acidic and basic media is firstly discussed. Subsequently, we will summarize the recent efforts employing Pt, Au, Ag, Pd and Ru clusters, as well as the alloyed bi-metallic clusters for acquiring highly efficient catalysts to enhance both the activity and stability of ORR. Molecular noble metal clusters with definitive composition to reveal the relevant ORR mechanism will be particularly highlighted. Finally, the current challenges, the future outlook, as well as the perspectives in this booming field will be proposed, featuring the great opportunities and potentials to engineering noble metal clusters as highly-efficient and durable cathodic catalysts for fuel cell applications.

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Section: Alloyed Noble Metal Clusters For Orrmentioning

confidence: 99%

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Tang

Wang

2018

Catalysts

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“…For CS/CP, there are only two broad diffractions at 20-30°and 40-50°, which correspond to characteristic peaks of graphite. [26,27] In the typical Raman spectra of CS/CP and Mn 3 O 4 @CS/CP as shown in Figure 1b, there are two remarkable peaks at about 1036.2 and 1601.9 cm À 1 , which represent disordered carbon (D band) and graphitized carbon (G band), [28] respectively. The graphitization degree was judged through the I D /I G value.…”

Section: Materials Structure Characterizationmentioning

confidence: 99%

Mn₃O₄@C Nanoparticles Supported on Porous Carbon as Bifunctional Oxygen Electrodes and their Electrocatalytic Mechanism

Cao

et al. 2018

ChemElectroChem

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Mn3O4 nanoparticles encapsulated inside carbon nanospheres supported on a carbon plate (Mn3O4@CS/CP) were designed, their bifunctional electrocatalytic performance for both, the oxygen evolution reaction (OER) at the anode and the oxygen reduction reaction (ORR) at the cathode were studied in alkaline solution. The prepared Mn3O4@CS/CP catalyst exhibits excellent electrocatalytic performance towards ORR, with less negative onset potential and long durability. Combining the results of in‐situ Fourier transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations, it is revealed that Mn3O4 acts as active site for ORR to promote the transformation of OH* into OH−. In addition, Mn3O4@CS/CP possesses an excellent electrochemical OER performances with the lower overpotential along with prosper Tafel slope and robust durability. DFT calculations show the transformation from O* to OOH* is the rate determining step for OER, and Mn3O4@CS/CP shows the minimum barrier, indicating that graphene sheet on the outer of Mn3O4 improves the transformation from O* to OOH*. The oxygen electrode activity parameter (potential difference between OER at current density of 10 mA/cm2 and ORR at current density of −2 mA/cm2) on Mn3O4@CS/CP is 0.72 V, which is superior to those of most bifunctional electrocatalysts reported to date, predicting a promising application in metal‐air batteries and fuel cells.

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“…On the basis of our previous work of preparing porous carbon nanosheets (CNs) from metal-organic frameworks [36,37], herein, to the best of our knowledge, the Pd-Ru alloyed nanoparticles encapsulated in porous carbon nanosheets derived from MOFs were first fabricated and employed as a bifunctional electrocatalyst for both ORR and HER. By changing the variation of the Pd-to-Ru ratio, the composition and structure of the as-formed catalysts were fine-tuned.…”

Section: Introductionmentioning

confidence: 99%

Oxygen Reduction Reaction and Hydrogen Evolution Reaction Catalyzed by Pd–Ru Nanoparticles Encapsulated in Porous Carbon Nanosheets

Tian

Tang

et al. 2018

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Developing bi-functional electrocatalysts for both oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is crucial for enhancing the energy transfer efficiency of metal-air batteries and fuel cells, as well as producing hydrogen with a high purity. Herein, a series of Pd-Ru alloyed nanoparticles encapsulated in porous carbon nanosheets (CNs) were synthesized and employed as a bifunctional electrocatalyst for both ORR and HER. The TEM measurements showed that Pd-Ru nanoparticles, with a size of approximately 1-5 nm, were uniformly dispersed on the carbon nanosheets. The crystal and electronic structures of the Pd x Ru 100−x /CNs series were revealed by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The as-prepared samples exhibited effective ORR activity in alkaline media and excellent HER activity in both alkaline and acid solutions. The Pd 50 Ru 50 /CNs sample displayed the best activity and stability among the series, which is comparable and superior to that of commercial 10% Pd/C. For ORR, the Pd 50 Ru 50 /CNs catalyst exhibited an onset potential of 0.903 V vs. RHE (Reversible Hydrogen Electrode) and 11.4% decrease of the current density after 30,000 s of continuous operation in stability test. For HER, the Pd 50 Ru 50 /CNs catalyst displayed an overpotential of 37.3 mV and 45.1 mV at 10 mA cm −2 in 0.1 M KOH and 0.5 M H 2 SO 4 , respectively. The strategy for encapsulating bimetallic alloys within porous carbon materials is promising for fabricating sustainable energy toward electrocatalysts with multiple electrocatalytic activities for energy related applications.

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Ultrasmall Palladium Nanoclusters Encapsulated in Porous Carbon Nanosheets for Oxygen Electroreduction in Alkaline Media

Cited by 31 publications

References 51 publications

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Mn₃O₄@C Nanoparticles Supported on Porous Carbon as Bifunctional Oxygen Electrodes and their Electrocatalytic Mechanism

Oxygen Reduction Reaction and Hydrogen Evolution Reaction Catalyzed by Pd–Ru Nanoparticles Encapsulated in Porous Carbon Nanosheets

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Ultrasmall Palladium Nanoclusters Encapsulated in Porous Carbon Nanosheets for Oxygen Electroreduction in Alkaline Media

Cited by 31 publications

References 51 publications

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Mn3O4@C Nanoparticles Supported on Porous Carbon as Bifunctional Oxygen Electrodes and their Electrocatalytic Mechanism

Oxygen Reduction Reaction and Hydrogen Evolution Reaction Catalyzed by Pd–Ru Nanoparticles Encapsulated in Porous Carbon Nanosheets

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Mn₃O₄@C Nanoparticles Supported on Porous Carbon as Bifunctional Oxygen Electrodes and their Electrocatalytic Mechanism