Energy conversion catalysis using semiconducting transition metal cluster compounds

Vante, N. Alonso; Tributsch, H.

doi:10.1038/323431a0

Cited by 284 publications

(95 citation statements)

References 7 publications

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“…While many types of non-platinum electrocatalyst have been reported, such as metal-oxides, metal macrocyclic complex, metal chalcogenides, and nitrogen-containing carbon, none of them has been applied to practice due to poor performance or durability. [1][2][3][4][5][6][7][8][9][10][11][12] We have been focusing on lead-ruthenium oxide (Pb 2 Ru 2 O 7-δ ) as a candidate of non-platinum electrocatalyst for ORR. [13][14][15][16] Pb 2 Ru 2 O 7-δ has a pyrochlore-type structure with some oxygen vacancies, and shows high electronic conductivity.…”

mentioning

confidence: 99%

Effects of Oxygen Vacancies and Reaction Conditions on Oxygen Reduction Reaction on Pyrochlore-Type Lead-Ruthenium Oxide

Fujii

Satô

Takase

2014

J. Electrochem. Soc.

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A series of pyrochlore-type lead-ruthenium oxide (Pb 2 Ru 2 O 7-δ ) containing various amounts of oxygen vacancies was prepared by varying the heat-treatment temperature, and the oxygen reduction reaction (ORR) activity as well as the electrochemical redox property in acid and alkaline solution was evaluated using rotating disk electrode. The specific ORR activity was increased with increasing the amount of oxygen vacancies, and linearly correlated to the charge amount of electrochemical redox of Pb 2 Ru 2 O 7-δ both in acid and alkaline solution. We concluded that the surface oxygen vacancy participates in the electrochemical redox of Pb 2 Ru 2 O 7-δ , and at the same time, behaves as the active site for ORR. The ORR activity in alkaline solution was much higher than that in acid solution, possibly because of the difference of the facility of electrochemical desorption of adsorbed oxygen species in the ORR process. Additionally, the effect of humidity on the ORR activity was investigated by single cell test. Proton exchange membrane fuel cells (PEMFCs) are promising alternative power sources for home co-generation system and transportation applications due to advantages such as low emission and high efficiency. There are, however, still many problems remaining for widespread commercialization of PEMFCs. In the current PEMFCs, platinum based catalyst is used as the cathode electrocatalyst for oxygen reduction reaction (ORR). From the view of cost and availability, alternative electrocatalyst to platinum is strongly required. While many types of non-platinum electrocatalyst have been reported, such as metal-oxides, metal macrocyclic complex, metal chalcogenides, and nitrogen-containing carbon, none of them has been applied to practice due to poor performance or durability. 1-12We have been focusing on lead-ruthenium oxide (Pb 2 Ru 2 O 7-δ ) as a candidate of non-platinum electrocatalyst for ORR. [13][14][15][16] Pb 2 Ru 2 O 7-δ has a pyrochlore-type structure with some oxygen vacancies, and shows high electronic conductivity. [17][18][19][20][21][22][23][24][25][26] Horowitz et al. 20 have firstly reported that Pb 2 Ru 2 O 7-δ which is prepared by co-precipitation method in aqueous solution and post heat-treatment at 300-750• C shows high ORR activity in alkaline solution. Afterwards, several researches aimed at application of Pb 2 Ru 2 O 7-δ to electrochemical devices such as fuel cell, metal-air battery and oxygen sensor have been conducted. 20,21,[27][28][29][30][31][32][33][34] For example, Goodenough et al. 31,35 have reported that Pb 2 Ru 2 O 7-δ shows ORR activity and high stability not only in alkaline solution but also in acid solution and proton exchange membrane such as Nafion. Also, we have found that partial substitution of other cations such as Bi, In, or Sb with Pb site in Pb 2 Ru 2 O 7-δ have a positive effect on the ORR activity.13 Nevertheless, the ORR activity of Pb 2 Ru 2 O 7-δ is needed to be drastically enhanced for practical use as the cathode electrocatalyst of PEMFC. For this purpose, it ...

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mentioning

confidence: 99%

Effects of Oxygen Vacancies and Reaction Conditions on Oxygen Reduction Reaction on Pyrochlore-Type Lead-Ruthenium Oxide

Fujii

Satô

Takase

2014

J. Electrochem. Soc.

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“…Particularly, cobalt sulfides (Co x S y ) with different phases have been previously investigated as ORR and OER electrode catalysts and exhibited attractive electrocatalytic performance among different nonprecious and late transition metal chalcogenides. [18][19][20][21][22][23] For instance, CoS 2 is a good electrocatalyst for ORR and OER; 24 Co 3 S 4 has excellent performance for ORR 25,26 and OER; 26 while…”

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confidence: 99%

Cobalt sulfide/N,S codoped porous carbon core–shell nanocomposites as superior bifunctional electrocatalysts for oxygen reduction and evolution reactions

et al. 2015

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Exploring highly-efficient and low-cost bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) in the renewable energy area has gained its momentum but still remains a significant challenge. Here we represent a simple but efficient way that utilizes ZIF-67 as the precursor and template for the one-step generation of homogeneous dispersed cobalt sulfide/N,S-codoped porous carbon nanocomposites as high-performance electrocatalysts. Due to the favourable molecular-like structural features and uniform dispersed active sites in the precursor, the resulting nanocomposites featured with unique core-shell structure, high porosity, homogeneous dispersion active components together with N and S-doping effect, not only show excellent electrocatalytic activity towards ORR with the high onset potential (around -0.04 V vs -0.02 V for benchmark Pt/C catalyst) and four-electron pathway, and OER with a small overpotential of 0.47 V for 10 mA cm −2 current density, but also exhibit superior stability (92%) to commercial Pt/C catalyst (74%) in ORR and promising OER stability (80%) with good methanol tolerance. Our findings suggest that the transition metal sulfide-porous carbon nanocomposites derived from the one-step simultaneously sulfurization and carbonization of zeolitic imidazolate frameworks are excellent alternative bifuncitonal electrocatalysts towards ORR and OER in the next generation of energy storage and conversion technologies.With the depletion of hydrocarbon-based energy resources and the increasing global energy demands, it is imperative to develop green and sustainable energy storage and conversion technologies as alternatives to currently widely used fossil fuels. 1-3 Electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play key roles in several important next-generation energy storage and conversion technologies, such as fuel cells, metal-air batteries and water splitting. [4][5][6][7][8][9][10][11][12][13] Hitherto, most efficient electrocatalysts for ORR/OER contain precious metals including Pt or Ir; however, due to the prohibitive cost, poor stability of precious metals, the sluggish kinetics for ORR and the large polarisation, it is highly desirable to discover highly efficient and low-cost earthabundant non-precious electroactive materials that can rival the performances of precious metal-based catalysts. 14-17Many efforts have, therefore, been devoted to transition metal oxides/sulfides based materials, as many transition metals like cobalt, manganese have been widely considered to be electrochemical active for ORR and OER. Particularly, cobalt sulfides (Co x S y ) with different phases have been previously investigated as ORR and OER electrode catalysts and exhibited attractive electrocatalytic performance among different nonprecious and late transition metal chalcogenides.18 Co 9 S 8 is a good catalyst for ORR. 21 However, the complicated preparation procedures coupled with the low electrical conductivities of cobalt s...

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“…The use of such transition metal chalcogenides (Mo 4.2 Ru 1.8 Se 8 ) as electrocatalysts for the oxygen reduction in acid medium was reported in 1986 [68]. The authors reported the first test of such materials to perform the ORR with an appreciable cost advantage with respect to platinum [68].…”

Section: Transition Metal Chalcogenidesmentioning

confidence: 99%

“…The authors reported the first test of such materials to perform the ORR with an appreciable cost advantage with respect to platinum [68]. It was further assessed that the Mo 4.2 Ru 1.8 Se 8 cluster, in powder form fixed on supports with the help of of Nafion ® ionomer thin film, onto glassy carbon, Figure 7a, and on p-type gallium phosphide (p-GaP) semiconductor, Figure 7b, favored the ORR, and hydrogen evolution reaction (HER) under Visible illumination [69].…”

Section: Transition Metal Chalcogenidesmentioning

confidence: 99%

What Can We Learn in Electrocatalysis, from Nanoparticulated Precious and/or Non-Precious Catalytic Centers Interacting with Their Support?

2016

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This review is devoted to discussing the state of the art in the relevant aspects of the synthesis of novel precious and non-precious electrocatalysts. It covers the production of Pt-and Pd-based electrocatalysts synthesized by the carbonyl chemical route, the synthesis description for the preparation of the most catalytically active transition metal chalcogenides, then the employment of free-surfactants synthesis routes to produce non-precious electrocatalysts. A compilation of the best precious electrocatalysts to perform the hydrogen oxidation reaction (HOR) is described; a section is devoted to the synthesis and electrocatalytic evaluation of non-precious materials which can be used to perform the HOR in alkaline medium. Apropos the oxygen reduction reaction (ORR), the synthesis and modification of the supports is also discussed as well, aiming at describing the state of the art to improve kinetics of low temperature fuel cell reactions via the hybridization process of the catalytic center with a variety of carbon-based, and ceramic-carbon supports. Last, but not least, the review covers the experimental half-cells results in a micro-fuel cell platform obtained in our laboratory, and by other workers, analyzing the history of the first micro-fuel cell systems and their tailoring throughout the time bestowing to the design and operating conditions.

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Energy conversion catalysis using semiconducting transition metal cluster compounds

Cited by 284 publications

References 7 publications

Effects of Oxygen Vacancies and Reaction Conditions on Oxygen Reduction Reaction on Pyrochlore-Type Lead-Ruthenium Oxide

Effects of Oxygen Vacancies and Reaction Conditions on Oxygen Reduction Reaction on Pyrochlore-Type Lead-Ruthenium Oxide

Cobalt sulfide/N,S codoped porous carbon core–shell nanocomposites as superior bifunctional electrocatalysts for oxygen reduction and evolution reactions

What Can We Learn in Electrocatalysis, from Nanoparticulated Precious and/or Non-Precious Catalytic Centers Interacting with Their Support?

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