Oxygen Reduction Activity of a Copper Complex of 3,5‐Diamino‐1,2,4‐triazole Supported on Carbon Black

Thorum, Matthew S.; Yadav, Jessica; Gewirth, Andrew A.

doi:10.1002/anie.200803554

Cited by 167 publications

(165 citation statements)

References 16 publications

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“…Ideally, one could do away with Pt altogether, and use catalysts made from more abundant elements. However, the acidic and oxidising environment of a PEMFC places severe constraints upon the choice of materials that can be deployed: even Pt corrodes at $1 V. 11,12 Apart from Pt, only Au and Ir are thermodynamically stable in the bulk metallic form at potentials greater than 0.9 V. 13 There are notable examples whereby non-precious metals have been stabilised in non-metallic forms, such as metalorganic complexes, 14,15 enzymes, 16,17 oxides 18,19 or N-functionalised graphene-based materials. [20][21][22] Although they can exhibit activity close to or even better than that of Pt, they often suffer from poor stability (especially in acidic solutions), or a low density of active sites.…”

Section: Introductionmentioning

confidence: 99%

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Stephens

Bondarenko

Grønbjerg

et al. 2012

Energy Environ. Sci.

1,088

1,024

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The high cost of low temperature fuel cells is to a large part dictated by the high loading of Pt required to catalyse the oxygen reduction reaction (ORR). Arguably the most viable route to decrease the Pt loading, and to hence commercialise these devices, is to improve the ORR activity of Pt by alloying it with other metals. In this perspective paper we provide an overview of the fundamentals underlying the reduction of oxygen on platinum and its alloys. We also report the ORR activity of Pt 5 La for the first time, which shows a 3.5-to 4.5-fold improvement in activity over Pt in the range 0.9 to 0.87 V, respectively. We employ angle resolved X-ray photoelectron spectroscopy and density functional theory calculations to understand the activity of Pt 5 La.

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Section: Introductionmentioning

confidence: 99%

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Stephens

Bondarenko

Grønbjerg

et al. 2012

Energy Environ. Sci.

1,088

1,024

View full text Add to dashboard Cite

show abstract

“…Previous work showed that laccase in vitro is more desirable as the quasichampion potential (onset at 1.2 V versus reversible hydrogen electrode (RHE), pH ¼ 4) is observed on its modified electrode 21 , suggesting that Cu 2 þ ion is supposed to be an ideal catalytic site as long as the energy level of the d-electrons is tuned to a reasonable state. However, directly mimicking the Cu 2 þ complexes as in enzyme might not be a reasonable strategy, by which the achieved activity is clearly not as good as the natural state 22,23 . Low overpotential and high reaction rate are hard to be simultaneously achieved 22 .…”

mentioning

confidence: 99%

Bioinspired copper catalyst effective for both reduction and evolution of oxygen

et al. 2014

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In many green electrochemical energy devices, the conversion between oxygen and water suffers from high potential loss due to the difficulty in decreasing activation energy. Overcoming this issue requires full understanding of global reactions and development of strategies in efficient catalyst design. Here we report an active copper nanocomposite, inspired by natural coordination environments of catalytic sites in an enzyme, which catalyzes oxygen reduction/evolution at potentials closely approaching standard potential. Such performances are related to the imperfect coordination configuration of the copper(II) active site whose electron density is tuned by neighbouring copper(0) and nitrogen ligands incorporated in graphene. The electron transfer number of oxygen reduction is estimated by monitoring the redox of hydrogen peroxide, which is determined by the overpotential and electrolyte pH. An in situ fluorescence spectroelectrochemistry reveals that hydroxyl radical is the common intermediate for the electrochemical conversion between oxygen and water.

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“…We used a dinuclear copper complex with a nitrogen-rich ligand of 3,5-diamino-1,2,4-triazole (Cu-Hdatrz) 12 as the copper source and chloro(protoporphyrinato)iron(III) (hemin) as the iron source (Scheme 1). Cu-Hdatrz is known to show high ORR activity in copper-based ORR electrocatalysts, particularly in alkaline solution, 1214 and pyrolysis of Cu-Hdatrz and graphene oxide provides a Cu-doped carbon electrocatalyst with higher ORR activity than the pristine Cu-Hdatrz.…”

mentioning

confidence: 99%

Bioinspired Iron- and Copper-incorporated Carbon Electrocatalysts for Oxygen Reduction Reaction

Kato¹,

Murotani²,

Yagi³

2016

Chem. Lett.

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We report an Fe/Cu/N-doped carbon electrocatalyst for the oxygen reduction reaction to water. Pyrolysis of metal precursors supported on oxidized carbon black provides the electrocatalyst with high catalytic activity and selectivity. Detailed physicalchemical studies have revealed that the copresence of iron and copper catalytic sites in carbon in a 1:1 mole ratio, which is the same as that of an enzyme of cytochrome c oxidase, might be the key to synthesize highly active and selective electrocatalysts. Keywords: Oxygen reduction reaction (ORR) |Polymer electrolyte fuel cell | Non-platinum group metal (non-PGM) electrocatalystThe oxygen reduction reaction (ORR) to water is a key reaction in respiration and electricity generation devices of polymer electrolyte fuel cells (PEFCs) and metal-air batteries. In nature, metalloenzymes such as cytochrome c oxidases (CcOs) efficiently catalyze the ORR with almost no overpotential. 1,2Such an enzymatic ORR is efficiently catalyzed at non-preciousmetal-based reaction centers including a dinuclear heme/Cuhistidine complex in CcOs.2 In the energy devices, on the other hand, platinum group metal (PGM) alloys are widely used as the cathodic material for the ORR. 35 The scarcity and high cost of PGM alloys limit the widespread application of PEFCs, and ideally we should develop non-precious-metal-based electrocatalysts for the ORR like the natural enzymes.Intensive efforts have been devoted to developing non-PGM electrocatalysts for the ORR over the past several decades. 69 The most promising approach to highly efficient and durable non-PGM ORR electrocatalysts is pyrolysis. 8Pyrolysis of metal, nitrogen, and carbon sources has provided metal-and nitrogen-doped carbon electrocatalysts, and some of them show high activity and durability comparable with that of PGM alloys. 10,11 Although the pyrolytic approach has been successful, the choice of precursors is unclear, and finding the best precursors is still based on trial-and-error experiments. Thus, guidance on the choice of precursors will open up possibilities to develop non-PGM ORR electrocatalysts for practical applications.Herein we report Fe/Cu/N-incorporated carbon electrocatalysts, inspired by the active site of CcO, and synergistic effects of the dopants on the ORR catalytic activity. We used a dinuclear copper complex with a nitrogen-rich ligand of 3,5-diamino-1,2,4-triazole (Cu-Hdatrz) 12 as the copper source and chloro(protoporphyrinato)iron(III) (hemin) as the iron source (Scheme 1). Cu-Hdatrz is known to show high ORR activity in copper-based ORR electrocatalysts, particularly in alkaline solution, 1214 and pyrolysis of Cu-Hdatrz and graphene oxide provides a Cu-doped carbon electrocatalyst with higher ORR activity than the pristine Cu-Hdatrz. 15 Hemin is also known to catalyze the ORR, and the pyrolysis of hemin gives Fe-doped carbon electrocatalysts for the ORR. 16 Furthermore, hemin and Cu-Hdatrz have similar ligand structures to heme a 3 and the Cuhistidine complex found at the catalytic active site of CcO...

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Oxygen Reduction Activity of a Copper Complex of 3,5‐Diamino‐1,2,4‐triazole Supported on Carbon Black

Cited by 167 publications

References 16 publications

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Bioinspired copper catalyst effective for both reduction and evolution of oxygen

Bioinspired Iron- and Copper-incorporated Carbon Electrocatalysts for Oxygen Reduction Reaction

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