A low temperature aqueous formate fuel cell using cobalt hexacyanoferrate as a non-noble metal oxidation catalyst

Han, Lijuan; González‐Cobos, Jesús; Sánchez‐Molina, Irene; Giancola, Stefano; Folkman, Scott J.; Giménez, Sixto; Vidal‐Ferran, Anton; Galán‐Mascarós, José Ramón

doi:10.1039/d0se01398f

Cited by 8 publications

(8 citation statements)

References 56 publications

(69 reference statements)

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“…Recently, owing to their high porosity and tunable metal centers, Prussian blue analogue (PBA) electrocatalysts with good performance have been reported in various domains. − Cobalt hexacyanoferrate exhibits significantly higher oxygen evolution reaction (OER) kinetics than state-of-the-art metal oxide catalysts, which originates from the high mass transport in its open framework. , It catalyzes formate oxidation to CO 2 with near 100% Faradic efficiency (FE). , Other PBAs also achieve similar high selectivity toward the electrocatalytic conversion of various molecules including nitrite and hydrazine. , Furthermore, the facile and versatile manipulation of the metal component in PBAs provides enormous opportunities toward tailoring its electrocatalytic properties. ,− Inspiringly, the Co sites in cobalt hexacyanocobaltate (Co 3 [Co(CN) 6 ] 2 ; Co PBA) are active in the hydrogen evolution reaction (HER) and further optimized by modulating their coordination environment …”

Section: Introductionmentioning

confidence: 99%

“…22,26 It catalyzes formate oxidation to CO 2 with near 100% Faradic efficiency (FE). 28,29 Other PBAs also achieve similar high selectivity toward the electrocatalytic conversion of various molecules including nitrite and hydrazine. 30,31 Furthermore, the facile and versatile manipulation of the metal component in PBAs provides enormous opportunities toward tailoring its electrocatalytic properties.…”

Section: ■ Introductionmentioning

confidence: 99%

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On-Demand Atomic Hydrogen Provision by Exposing Electron-Rich Cobalt Sites in an Open-Framework Structure toward Superior Electrocatalytic Nitrate Conversion to Dinitrogen

Chen

Zhang

et al. 2021

Environ. Sci. Technol.

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Electrocatalytic nitrate (NO3 –) reduction to N2 via atomic hydrogen (H*) is a promising approach for advanced water treatment. However, the reduction rate and N2 selectivity are hindered by slow mass transfer and H* provision–utilization mismatch, respectively. Herein, we report an open-framework cathode bearing electron-rich Co sites with extraordinary H* provision performance, which was validated by electron spin resonance (ESR) and cyclic voltammetry (CV) tests. Benefiting from its abundant channels, NO3 – has a greater opportunity to be efficiently transferred to the vicinity of the Co active sites. Owing to the enhanced mass transfer and on-demand H* provision, the nitrate removal efficiency and N2 selectivity of the proposed cathode were 100 and 97.89%, respectively, superior to those of noble metal-based electrodes. In addition, in situ differential electrochemical mass spectrometry (DEMS) indicated that ultrafast *NO2 – to *NO reduction and highly selective *NO to *N2O or *N transformation played crucial roles during the NO3 – reduction process. Moreover, the proposed electrochemical system can achieve remarkable N2 selectivity without the additional Cl– supply, thus avoiding the formation of chlorinated byproducts, which are usually observed in conventional electrochemical nitrate reduction processes. Environmentally, energy conservation and negligible byproduct release ensure its practicability for use in nitrate remediation.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

On-Demand Atomic Hydrogen Provision by Exposing Electron-Rich Cobalt Sites in an Open-Framework Structure toward Superior Electrocatalytic Nitrate Conversion to Dinitrogen

Chen

Zhang

et al. 2021

Environ. Sci. Technol.

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“…In fact, our group also prepared a proof-of-concept formate/Ce 4+ fuel cell that, without being optimized, returned a stable maximum power output of 8.6 mW cm −2 ( Figure 11 ). This is the first reported case of a fully non-platinum group metals (PGM) direct formate fuel cell (including both anode and cathode) [ 23 ].…”

Section: Pt and Pd-free Materials For Formic Acid/formate Electrooxidationmentioning

confidence: 99%

“…It should also be noted that the expected cell voltage is also increased by employing a fuel cell configuration where the cathode and the anode operate in acid and alkaline media, respectively, as it is shown in Table 1. For instance, Li et al [21,22] and Han et al [23] employed this acid cathode/alkaline anode concept using H 2 O 2 and Ce 4+ as oxidants, respectively. i Standard potentials from Ref.…”

Section: Introductionmentioning

confidence: 99%

Benchmarking Catalysts for Formic Acid/Formate Electrooxidation

et al. 2021

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Energy production and consumption without the use of fossil fuels are amongst the biggest challenges currently facing humankind and the scientific community. Huge efforts have been invested in creating technologies that enable closed carbon or carbon neutral fuel cycles, limiting CO2 emissions into the atmosphere. Formic acid/formate (FA) has attracted intense interest as a liquid fuel over the last half century, giving rise to a plethora of studies on catalysts for its efficient electrocatalytic oxidation for usage in fuel cells. However, new catalysts and catalytic systems are often difficult to compare because of the variability in conditions and catalyst parameters examined. In this review, we discuss the extensive literature on FA electrooxidation using platinum, palladium and non-platinum group metal-based catalysts, the conditions typically employed in formate electrooxidation and the main electrochemical parameters for the comparison of anodic electrocatalysts to be applied in a FA fuel cell. We focused on the electrocatalytic performance in terms of onset potential and peak current density obtained during cyclic voltammetry measurements and on catalyst stability. Moreover, we handpicked a list of the most relevant examples that can be used for benchmarking and referencing future developments in the field.

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“…In this regard, fuel cells have gained considerable attention since they are inexpensive, easy, and environmentally friendly, which convert chemical energy directly into electrical energy. In this approach, various types of sources such as methanol, ethanol, formic acid, aqueous ammonia (NH 3 ), and hydrazine are used to generate electricity. , However, these sources have limitations including toxicity and volatilization of liquid fuel cells. To mitigate these limitations, iron (Fe) metal is currently considered as a potential alternative source of hydrogen because of its +2 and +3 oxidation states, , as it produces hydrogen with respect to the corrosion reaction that occurs on the surface of the iron metal in alkaline medium. , …”

Section: Introductionmentioning

confidence: 99%

Single-Pot Solvothermal Synthesis of Single-Crystalline Nickel–Metal Organic Framework Nanosheets for Direct Iron Fuel Cell Applications

Ravipati,

Durai,

Badhulika

2023

ACS Appl. Energy Mater.

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The usage of iron leads to the generation of large quantities of scrap iron, which is hazardous to health and causes environmental pollution. Recycling techniques are expensive and involve high energy consumption. Instead of recycling, scrap iron can be used as an alternative potential source for fuel cell applications. Here, we report the synthesis of a single-crystalline nickel-based MOF (Ni-MOF), via a single-pot solvothermal technique, as an electrocatalyst to produce hydrogen from scrap iron. Detailed characterization reveals the nanosheet morphology of the Ni-MOF obtained by FESEM; at the same time Ni-MOF formation is confirmed through the XRD spectrum. The as-synthesized Ni-MOF is deposited on nickel foam (NF) and used as an electrocatalyst (Ni-MOF/NF) which exhibits a peak current density of 8.8 A/g (scrap) and response toward hydrogen production at an onset potential of 0.5 V (vs Hg/HgO). The improved performance of the Ni-MOF/NF electrode is ascribed to the high catalytic activity of Ni-MOF owing to the multiple oxidation states of Ni (i.e., Ni2+/3+); the reversible transformation between +2 and +3 oxidation states results in the redox peaks of the catalytic reaction; and the organic ligands in the MOF structure help in improving the conductivity and pore size of the material. The Ni-MOF/NF electrode exhibits outstanding stability with ∼88.1 and ∼72.9% capacity retention after 100,000 and 50,000 s for scrap and iron metal powder, respectively. This proves that the theickel metal–organic framework coated on nickel foam (Ni-MOF/NF) electrocatalyst is an outstanding material for iron source-based fuel cell applications.

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A low temperature aqueous formate fuel cell using cobalt hexacyanoferrate as a non-noble metal oxidation catalyst

Abstract: Prussian blue is applied as the anode in the first reported metal-free fuel cell for formic acid oxidation.

Cited by 8 publications

References 56 publications

On-Demand Atomic Hydrogen Provision by Exposing Electron-Rich Cobalt Sites in an Open-Framework Structure toward Superior Electrocatalytic Nitrate Conversion to Dinitrogen

On-Demand Atomic Hydrogen Provision by Exposing Electron-Rich Cobalt Sites in an Open-Framework Structure toward Superior Electrocatalytic Nitrate Conversion to Dinitrogen

Benchmarking Catalysts for Formic Acid/Formate Electrooxidation

Single-Pot Solvothermal Synthesis of Single-Crystalline Nickel–Metal Organic Framework Nanosheets for Direct Iron Fuel Cell Applications

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