In this work, a methodology is demonstrated to engineer gas diffusion electrodes for nonprecious metal catalysts. Highly active transition metal phosphides are prepared on carbon‐based gas diffusion electrodes with low catalyst loadings by modifying the O/C ratio at the surface of the electrode. These nonprecious metal catalysts yield extraordinary performance as measured by low overpotentials (51 mV at −10 mA cm−2), unprecedented mass activities (>800 A g−1at 100 mV overpotential), high turnover frequencies (6.96 H2s−1at 100 mV overpotential), and high durability for a precious metal‐free catalyst in acidic media. It is found that a high O/C ratio induces a more hydrophilic surface directly impacting the morphology of the CoP catalyst. The improved hydrophilicity, stemming from introduced oxyl groups on the carbon electrode, creates an electrode surface that yields a well‐distributed growth of cobalt electrodeposits and thus a well‐dispersed catalyst layer with high surface area upon phosphidation. This report demonstrates the high‐performance achievable by CoP at low loadings which facilitates further cost reduction, an important part of enabling the large‐scale commercialization of non‐platinum group metal catalysts. The fabrication strategies described herein offer a pathway to lower catalyst loading while achieving high efficiency and promising stability on a 3D electrode.
Unravelling the potential of disposable and modifiable pencils as catalyst supports for hydrogen evolution reaction
Increasing fossil fuel demands and growing concerns of global climate change have stimulated interest in the development of electrocatalysts to produce H 2 as an alternative zero-emission fuel from the electrolysis of water via hydrogen evolution reaction (HER). Precious or non-precious catalysts are typically loaded on high surface area carbon materials, and these supports play a critical role in both thermodynamics and kinetics of the HER. In this paper, we evaluate the electrocatalytic activity of a molecular hydrogen evolving catalyst, diacetyl-bis(4-methyl)-3-thiosemicarbazone Ni( ii ) (Ni-ATSM), on three different carbon surfaces: glassy carbon, carbon paste and pencil graphite. The overpotential for each modified electrode was benchmarked at a current density of −10 mA cm −2 . Carbon paste electrodes showed highest overpotentials (495 mV) compared to the other electrode surfaces. Polished pencil and glassy carbon modified electrodes performed similarly ( η = 395 mV for GCE and η = 400 mV for pencil). Pencil electrodes etched in acetone overnight prior to Ni-ATSM deposition produced lowest overpotentials ( η = 354 mV). Etching results in an increase in electroactive surface area and substantial decrease in the charge transfer resistance of the graphitic interface from 275 Ω to 50 Ω, verified using electrochemical impedance spectroscopy (EIS). Our studies demonstrate pencil graphite may serve as versatile, disposable, cost effective, and reproducible electrode surface for the evaluation of heterogeneous HER catalysts. Moreover, pencils can be easily cut with table saw to generate new surface for easy characterization of the surface such as electrochemistry, imaging and spectroscopy.
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- Award ID(s):
- 1955268
- NSF-PAR ID:
- 10422603
- Date Published:
- Journal Name:
- New Journal of Chemistry
- Volume:
- 46
- Issue:
- 39
- ISSN:
- 1144-0546
- Page Range / eLocation ID:
- 18832 to 18838
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
null (Ed.)The alkaline hydrogen evolution reaction (A-HER) holds great promise for clean hydrogen fuel generation but its practical utilization is severely hindered by the sluggish kinetics for water dissociation in alkaline solutions. Traditional ways to improve the electrochemical kinetics for A-HER catalysts have been focusing on surface modification, which still can not meet the demanding requirements for practical water electrolysis because of catalyst surface deactivation. Herein, we report an interior modification strategy to significantly boost the A-HER performance. Specifically, a trace amount of Pt was doped in the interior Co 2 P (Pt–Co 2 P) to introduce a stronger dopant–host interaction than that of the surface-modified catalyst. Consequently, the local chemical state and electronic structure of the catalysts were adjusted to improve the electron mobility and reduce the energy barriers for hydrogen adsorption and H–H bond formation. As a proof-of-concept, the interior-modified Pt–Co 2 P shows a reduced onset potential at near-zero volts for the A-HER, low overpotentials of 2 mV and 58 mV to achieve 10 and 100 mA cm −2 , and excellent durability for long-term utilization. The interior-modified Pt–Co 2 P delivers superior A-HER performance to Pt/C and other state-of-the-art electrocatalysts. This work will open a new avenue for A-HER catalyst design.more » « less
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The efficient production of green hydrogen via electrochemical water splitting is important for improving the sustainability and enabling the electrification of the chemical industry. One of the major goals of water electrolysis is to utilize non-precious metal catalysts, which can be accomplished with alkaline electrolyzer technologies. However, there is a continuing need for designing catalysts that can operate in alkaline environments with high efficiencies under high current densities. Here we describe a simple, aqueous-based synthesis method to incorporate sulfur into NiFe-based electrocatalysts for the oxygen evolution reaction (OER). Sulfur incorporation was able to reduce the overpotential for the OER from ca. 350 mV on a NiFe catalyst to ca. 290 mV on the NiFeS catalyst at 100 mA cm −2 on a flat supporting electrode. Electrochemical impedance spectroscopy data showed a small decrease in the charge transfer resistance of the NiFeS catalysts, showing that sulfur incorporation may improve the electronic conductivity. Surface-interrogation scanning electrochemical microscopy (SI-SECM) studies combined with Tafel slope analysis suggested that the NiFeS catalyst was able to have vacant surface sites available under OER conditions and was able to maintain a Tafel slope of 39 mV dec −1 . This is in contrast to the NiFe catalyst, for which the SI-SECM studies showed a saturated surface under OER conditions with the Tafel slope transitioning from 39 mV dec −1 to 118 mV dec −1 . The low Tafel slope enabled the NiFeS catalyst to maintain low overpotentials under high current densities, which we attribute to the ability of the NiFeS catalyst to maintain vacant sites during the OER.more » « less
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In the face of rising atmospheric carbon dioxide (CO 2 ) emissions from fossil fuel combustion, the hydrogen evolution reaction (HER) continues to attract attention as a method for generating a carbon-neutral energy source for use in fuel cells. Since some of the best-known catalysts use precious metals like platinum, which have low natural abundance and high cost, developing efficient Earth abundant transition metal catalysts for HER is an important objective. Building off previous work with transition metal catalysts bearing 2,2′-bipyridine-based ligand frameworks, this work reports the electrochemical analysis of a molecular nickel( ii ) complex, which can act as an electrocatalyst for the HER with a faradaic efficiency for H 2 of 94 ± 8% and turnover frequencies of 103 ± 6 s −1 when pentafluorophenol is used as a proton donor. Computational studies of the Ni catalyst suggest that non-covalent interactions between the proton donor and ligand heteroatoms are relevant to the mechanism for electrocatalytic HER.more » « less
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Abstract Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt‐free and Fe‐free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high‐performance nitrogen‐coordinated single Co atom catalyst is derived from Co‐doped metal‐organic frameworks (MOFs) through a one‐step thermal activation. Aberration‐corrected electron microscopy combined with X‐ray absorption spectroscopy virtually verifies the CoN4coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half‐wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe‐based catalysts and 60 mV lower than Pt/C ‐60 μg Pt cm−2). Fuel cell tests confirm that catalyst activity and stability can translate to high‐performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well‐dispersed CoN4active sites embedded in 3D porous MOF‐derived carbon particles, omitting any inactive Co aggregates.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2NJ03359C
