Carbon-supported Pt-free catalysts with high specificity and activity toward the oxygen reduction reaction in acidic medium

Gavidia, Luis Miguel Rivera; Garcı́a, Gonzalo; Anaya, Dalila; Querejeta, Amaia; Alcaide, Francisco; Pastor, E.

doi:10.1016/j.apcatb.2015.11.021

Cited by 55 publications

(25 citation statements)

References 49 publications

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“…The decrease in the ORR electrocatalytic activity of Pt and Pt-based electrocatalysts in the presence of methanol is caused by the adsorption of methanol molecules on the active sites for ORR. In contrast, the ORR half-wave and onset potentials of PdCu 3 and PdFeIr are not significantly affected by the presence of methanol [95,109]. These results indicate that Pd-based compounds are potential electrocatalysts for DMFCs.…”

Section: The Development Of Electrocatalysts With Simultaneously Imprmentioning

confidence: 88%

Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials

Gunji

Matsumoto

2019

Inorganics

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The structural design of nanosized electrocatalysts is extremely important for cathodic oxygen reduction reactions (ORR) and anodic oxidation reactions in small organic compounds in direct fuel cells. While Pt is still the most commonly used electrode material for ORR, the Pd electrocatalyst is a promising alternative to Pt, because it exhibits much higher electrocatalytic activity towards formic acid electrooxidation, and the electrocatalytic activity of ORR on the Pd electrode is the higher than that of all other precious metals, except for Pt. In addition, the mass activity of Pt in a core–shell structure for ORR can be improved significantly by using Pd and Pd-based materials as core materials. Herein, we review various nanoscale Pd-based bimetallic, trimetallic and core–shell electrocatalysts for formic acid oxidation and ORR of polymer electrolyte fuel cells (PEFCs). This review paper is separated into two major topics: the electrocatalytic activity towards formic acid oxidation over various Pd-based electrocatalysts, and the activity of ORR on Pd-based materials and Pd core–Pt shell structures.

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Section: The Development Of Electrocatalysts With Simultaneously Imprmentioning

confidence: 88%

Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials

Gunji

Matsumoto

2019

Inorganics

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“…2θ = 25° for all diffractograms corresponds to (002) reflection of carbon support [ 19 , 20 , 21 ]. The other displayed five peaks are characteristic of the face-centered-cubic (fcc) crystalline structure of palladium (JCPDS #46-1043) [ 13 , 19 ], ascribed to the (111), (200), (220), (311) and (222) reflections. A pronounced diffraction peak close to 35° was observed in the Pd/C commercial catalyst, which can be attributed to the main reflection of Pd oxide-hydroxide species (PdO·xH 2 O, JCPDS #09-0254) [ 22 ].…”

Section: Resultsmentioning

confidence: 99%

“…Great efforts have been made to overcome these problems, particularly to replace the platinum based catalysts with non-noble metals [ 10 ] or other cheaper noble metals to be used as methanol tolerant cathodes, such as palladium [ 11 ]. It is well known that palladium-based catalysts present a good methanol tolerance as fuel cell cathodes [ 12 ] since the methanol oxidation process is negligible on Pd in acid media [ 13 ]. In this context, there are some recent investigations explaining the methanol tolerance of Pd-based cathodes; e.g., DFT studies of methanol adsorption on a Pt and Pd single layer composed of thirteen atoms showed how platinum distorts the molecular structure of the adsorbed methanol and favors its deprotonation in the first step of methanol oxidation process [ 14 ].…”

Section: Introductionmentioning

confidence: 99%

“…It is also known that Pd alloys with several 3d transition metals present higher oxygen reduction reaction (ORR) electro-activity than pure Pd [ 15 ]. Metals like Cu, Fe [ 13 , 15 ], Ni, Cr, Co [ 16 , 17 ], have been deeply studied for improving ORR activity and methanol tolerance and, therefore, minimizing the crossover effects [ 13 , 15 , 16 , 17 ]. On the other hand, core-shell palladium nanoparticles represent a good alternative as a cathodic material [ 18 ].…”

Section: Introductionmentioning

confidence: 99%

“…This was attributed to the surface composition rich in iron and iridium oxides. Nevertheless, a PdFe/C (without iridium) exhibited a similar behavior than PdFeIr/C in the kinetic region of ORR polarization curves in RDE experiments [ 13 ]. Despite PdFeIr/C’s low Pd content, the presence of iridium results in a cost increase compared to bimetallic PdFe catalyst for equivalent Pd loadings in the electrode.…”

Section: Introductionmentioning

confidence: 99%

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Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes

et al. 2017

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Direct methanol fuel cells (DMFCs) are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM) and X-ray techniques such as photoelectron spectroscopy (XPS), diffraction (XRD) and energy dispersive spectroscopy (EDX). The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M) and temperatures (60 °C and 90 °C). The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm−2 at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation.

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Bimetallic Intersection in PdFe@FeO_x‐C Nanomaterial for Enhanced Water Splitting Electrocatalysis

Martinez

Mazarío

Olloqui‐Sariego

et al. 2022

Advanced Sustainable Systems

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zero-emission properties and high energy density, and it can be electrochemically generated from water splitting driven by renewable and intermittent power sources. [1][2][3][4][5] In fact, water splitting is one of the most critical processes for many applications associated with carbon-free energy storage and conversion, such as rechargeable metal-air batteries and regenerative fuel cells. [6][7][8][9] Up to now, there are two leading water-splitting technologies in industrial applications, one acidic water electrolyzer integrated with a polymer electrolyte membrane and the other alkaline water electrolyzer. [10,11] This process combines two half-cell reactions to produce hydrogen and oxygen gases, namely the Hydrogen Evolution Reaction (HER) at the cathode and the Oxygen Evolution Reaction (OER) at the anode.. Nevertheless, water splitting is a strenuous reaction, with a thermodynamic voltage of 1.23 V, [12,13] which is strongly influenced by the slow kinetics, large overpotential for both reactions, and long-term stability. [14][15][16] Therefore, the requirement of efficient electrocatalysts for both HER and OER is indispensable to overcome these setbacks in water splitting. The benchmark HER electrocatalysts are platinum (Pt)-based materials, but these are not good for OER, whereas iridium and ruthenium oxides are the state-of-art OER electrocatalysts. Unfortunately, they show insufficient activity toward HER. [17] Additionally, Supported Fe-doped Pd-nanoparticles (NPs) are prepared via soft transformation of a PdFe-metal oraganic framework (MOF). The thus synthesized bimetallic PdFe-NPs are supported on FeO x @C layers, which are essential for developing well-defined and distributed small NPs, 2.3 nm with 35% metal loading. They are used as bifunctional nanocatalysts for the electrocatalytic water splitting process. They display superior mass activity for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), both in alkaline and acid media, compared with those obtained for benchmarking platinum HER catalyst, and ruthenium, and iridium oxide OER catalysts. PdFe-NPs also exhibit outstanding stability against sintering that can be explained by the protecting role of graphitic carbon layers provided by the organic linker of the MOF. Additionally, the superior electrocatalytic performance of the bimetallic PdFe-NPs compared with those of monometallic Pd/C NPs and FeO x points to a synergetic effect induced by Fe-Pd interactions that facilitates the water splitting reaction. This is supported by additional characterization of the PdFe-NPs prior and post electrolysis by TEM, XRD, X-ray photoelectron spectroscopy, and Raman revealing that dispersed PdFe NPs on FeO x @C promote interactions between Pd and Fe, most likely to be Pd-O-Fe active centers.

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Carbon-supported Pt-free catalysts with high specificity and activity toward the oxygen reduction reaction in acidic medium

Cited by 55 publications

References 49 publications

Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials

Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials

Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes

Bimetallic Intersection in PdFe@FeO_x‐C Nanomaterial for Enhanced Water Splitting Electrocatalysis

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Carbon-supported Pt-free catalysts with high specificity and activity toward the oxygen reduction reaction in acidic medium

Cited by 55 publications

References 49 publications

Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials

Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials

Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes

Bimetallic Intersection in PdFe@FeOx‐C Nanomaterial for Enhanced Water Splitting Electrocatalysis

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Bimetallic Intersection in PdFe@FeO_x‐C Nanomaterial for Enhanced Water Splitting Electrocatalysis