Cu complexes that catalyze the oxygen reduction reaction

Thorseth, Matthew A.; Tornow, Claire E.; Tse, Edmund C. M.; Gewirth, Andrew A.

doi:10.1016/j.ccr.2012.03.033

Cited by 186 publications

(202 citation statements)

References 57 publications

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“…20 After thermal activation under a N 2 atmosphere for 1 hour, the catalytic activity of the catalyst was greatly enhanced, reaching a maximum onset potential of 0.82 V at 950…”

Section: Resultsmentioning

confidence: 99%

“…[13][14][15][16]18,20,25 Figure 1 shows RDE plots for the Cu-TrPc/C catalyst before and after thermal activation, with thermal treatment temperature ranging from 600 to 950…”

Section: Resultsmentioning

confidence: 99%

“…13,[15][16][17][18][19][20][21] However, in alkaline media Cubased catalysts show higher catalytic activity, making them suitable for a wide range of applications as ORR catalysts. 3,14,[20][21][22] Gewirth's group has adsorbed Cu-based catalysts onto a carbon support and studied the catalytic activity of the non-pyrolyzed samples in acidic and alkaline media, 14,15,21 reporting rotating disk electrode (RDE) onset potentials up to 0.53 V vs. RHE at pH 1. McCrory et al 22 investigated the ORR activity, at pH 4.8, of non-pyrolyzed Cu-3-ethynyl-1-10-phenanthroline covalently attached to an azide-modified glassy carbon electrode via a "click" reaction, allowing controlled catalyst coverage on the carbon surface, finding evidence that to achieve O 2 reduction to water by an adsorbed Cu catalyst, two proximal Cu I sites are required.…”

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confidence: 99%

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Pyrolyzed Copper-Based Catalyst with High Oxygen Reduction Activity for PEM Fuel Cell Applications

Goenaga

Foister

Belapure

et al. 2014

ECS Electrochemistry Letters

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We have synthesized a copper-based catalyst for the oxygen reduction reaction in low temperature fuel cells. Catalysts were prepared by covalently attaching a phthalocyanine-type ligand to a carbon black surface, and adding Cu(OAc) 2 . The phthalocyanine-type ligand provides the nitrogen to form the presumed catalytic centers with the Cu metal. Rotating ring disk electrode experiments revealed that the catalytic activity of the as-synthesized material is greatly enhanced after one-step pyrolysis under inert atmosphere, reaching an onset potential of 0.82 V vs. RHE in acidic environment after thermal treatment at 950 • C, making this the best copper-based ORR catalyst in acid reported to date. State of the art proton exchange membrane fuel cells (PEMFCs) use Pt as the catalyst for oxygen reduction reaction (ORR) at the cathode. Due to the high cost of Pt, minimizing the Pt content of the PEMFC has become a major endeavor to make feasible the mass commercialization of PEMFC.1 While a number of efforts seek to achieve this by improving the activity and utilization of Pt-based catalysts, the most direct approach is replacing Pt with non-precious metal catalysts (NPMC). Synthesis of NPMCs is often inspired by natural systems:2 enzymes, such as laccase, are very efficient ORR catalysts. Such Cu oxidases are known to reduce oxygen at approximately 1.2 V vs. the reversible hydrogen electrode (RHE) under mild pH conditions.2-4 The ORR in these enzymes is known to occur in a three or four Cu-atom active site. 4 Since Jasinski first reported the use of Co-phthalocyanine as a catalyst for ORR, 5 a prolonged effort has been devoted to developing ORR catalyst materials based on transition metal complexes. The best NPMCs to date are based on Fe and Co, and can be unsupported 6 or supported on carbon. 7,8 In general their synthesis requires a nitrogen source (nitrogen containing molecule and/or reactive gas) and heat-treatment at high temperatures to form the presumed Me-N 2 and Me-N 4 ORR catalytic centers. After pyrolysis, the precise nature and loading of the catalytic centers are unknown. Though seemingly critical to rational development of new catalysts, the actual active structure is still the subject of speculation, uncertainty and debate.7-14 However, some significant correlative information providing insight into the most favorable nitrogen arrangement has been achieved through the systematic application of XPS methods. From this, it is suggested that the eventual formation of pyridinic nitrogen centers is associated with many successful pyrolysis attempts.Compared to Fe and Co based materials, few studies have been done on ORR using Cu-based catalysts in acidic environments. At low pH values, previous reported Cu-based catalysts exhibit overpotentials for ORR in excess of 600 mV.13,15-21 However, in alkaline media Cubased catalysts show higher catalytic activity, making them suitable for a wide range of applications as ORR catalysts.3,14,20-22 Gewirth's group has adsorbed Cu-based catalysts onto a carbon support and s...

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“…20 After thermal activation under a N 2 atmosphere for 1 hour, the catalytic activity of the catalyst was greatly enhanced, reaching a maximum onset potential of 0.82 V at 950…”

Section: Resultsmentioning

confidence: 99%

“…[13][14][15][16]18,20,25 Figure 1 shows RDE plots for the Cu-TrPc/C catalyst before and after thermal activation, with thermal treatment temperature ranging from 600 to 950…”

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Pyrolyzed Copper-Based Catalyst with High Oxygen Reduction Activity for PEM Fuel Cell Applications

Goenaga

Foister

Belapure

et al. 2014

ECS Electrochemistry Letters

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“…As a bidentate ligand, phenanthroline (phen) and its derivatives have frequently been used to construct transition metal complexes as ORR catalysts because of their high affinity for metal ions and commercial availability with low cost [26]. Recently, we immobilized the phen unit within conductive polymers via a covalent linkage, which was then composited with carbon powder to form a composite catalyst showing comparable ORR performance with respect to the Pt/C catalyst.…”

Section: Introductionmentioning

confidence: 99%

Carbon-Supported Copper-Based Nitrogen-Containing Supramolecule as an Efficient Oxygen Reduction Reaction Catalyst in Neutral Medium

Zhao

Chu

et al. 2018

Catalysts

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Abstract:In this work, a nitrogen-containing bidentate ligand named 5,5 -(9-octyl-9H-carbazole-2,7-diyl)bis(1,10-phenanthroline) (OCBP) was synthesized as a nitrogen precursor for making an oxygen reduction catalyst. The 1,10-phenanthroline unit provides a coordination site for copper ions, and the resulting Cu-N x unit may be responsible for the catalytic activities of the catalyst. Carbon black was selected as a support to improve the electroconductibility of the resulting catalyst. The metallo-supramolecule (Cu-SOCBP) was dispersed on the surface of Vulcan XC-72 carbon and was used as a catalyst (designated as Cu-SOCBP/C) for the oxygen reduction reaction (ORR). The microscope structure and surface components of the catalyst were acquired via scanning electron microscopy and X-ray photoelectron spectroscopy, as well as X-ray powder diffraction. The electrochemical property and ORR mechanism of Cu-SOCBP/C were analyzed using a variety of electroanalytical methods including cyclic voltammetry, electrochemical impedance spectroscopy, and linear sweep voltammetry. These results show that Cu-SOCBP/C was successfully synthesized and that ORR was achieved mainly via a four-electron transfer process to water. Thus, Cu-SOCBP/C was an effective catalyst and might have potential application as a cathodic catalyst in microbial fuel cells, which operate in an aqueous medium.

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“…In this context, electrocatalytic reduction of oxygen is achieved by using metalloporphyrins, metallophthalocyanines and metal oxides and other non-precious metal electrocatalysts [20][21]. Recently, various efforts have been devoted to study the electrocatalytic activities of copper complexes [22] and copper complex derived electrode surfaces [23][24][25]. Several research groups have investigated the electrocatalytic performance of copper complexes with different ligands; (a) Cu(II) complex of 4,7-diphenyll,l0-phenanthroline disulfonate adsorbed on graphite electrodes [26][27] (b) Cu(II) hexaazamacrocyclic complex on glassy carbon electrode [28] (c) copper(II)-2,4,6-tris(2-pyridyl)-1,3,5-triazine complex adsorbed on a graphite electrode [29] (d) copper(II)-tris(3-aminopropyl)amine and imidazole complex on pyrolytic graphite electrode [30], (e) substituted-1,10-phenonthroline-copper complexes on graphite [31] and edge-plane graphite electrodes [32].…”

Section: Introductionmentioning

confidence: 99%

Biomimetic Copper Complex Containing Polymer Modified Electrode for Electrocatalytic Reduction of Oxygen

Saravanakumar

Nagarale

Jirimali

et al. 2016

Journal of Electrochemical Science and Technology

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The development of non-precious metal based electrocatalysts is highly desired for the oxygen reduction reaction (ORR) as alternates to noble metal based ORR electrocatalysts. Herein, we report mononulcear copper(II) complex [CuLbpy]ClO 4 (L=4-[(2-hydroxyphenylimino)methyl]benzoic acid) containing poly(allylamine.HCl) polymer (PAlACuLbpy) as an electrocatalyst for oxygen reduction reaction (ORR). PAlACuLbpy was mixed with poly(acrylic acid) and tetraethylortho silicate to prepare a composite and then deposited on the screen printed electrode surface. The modified electrode (PAlACuLbpy/PCE) is highly stable and showed a quasi-reversible redox behavior with E 1 / 2 = -0.2 V vs. Ag/AgCl(3 M KCl) in 0.1 M phosphate buffer at pH 7 under argon atmosphere. PAlACuLbpy/PCE exhibited a remarkable ORR activity with an onset potential of -0.1 V vs Ag/AgCl in 0.1 M PB (pH 7) in the presence of oxygen. The kinetics for ORR was studied by rotating disk voltammetry in neutral aqueous medium and the results indicated that the number of electrons involving in the ORR is four and the conversion products are water and hydrogen peroxide.

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Cu complexes that catalyze the oxygen reduction reaction

Cited by 186 publications

References 57 publications

Pyrolyzed Copper-Based Catalyst with High Oxygen Reduction Activity for PEM Fuel Cell Applications

Pyrolyzed Copper-Based Catalyst with High Oxygen Reduction Activity for PEM Fuel Cell Applications

Carbon-Supported Copper-Based Nitrogen-Containing Supramolecule as an Efficient Oxygen Reduction Reaction Catalyst in Neutral Medium

Biomimetic Copper Complex Containing Polymer Modified Electrode for Electrocatalytic Reduction of Oxygen

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