skip to main content

Attention:

The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 11:00 PM ET on Friday, September 29 until 11:59 PM ET on Saturday, September 30 due to maintenance. We apologize for the inconvenience.


Title: Highly Active Trimetallic NiFeCr Layered Double Hydroxide Electrocatalysts for Oxygen Evolution Reaction
Abstract

The development of efficient and robust earth‐abundant electrocatalysts for the oxygen evolution reaction (OER) is an ongoing challenge. Here, a novel and stable trimetallic NiFeCr layered double hydroxide (LDH) electrocatalyst for improving OER kinetics is rationally designed and synthesized. Electrochemical testing of a series of trimetallic NiFeCr LDH materials at similar catalyst loading and electrochemical surface area shows that the molar ratio Ni:Fe:Cr = 6:2:1 exhibits the best intrinsic OER catalytic activity compared to other NiFeCr LDH compositions. Furthermore, these nanostructures are directly grown on conductive carbon paper for a high surface area 3D electrode that can achieve a catalytic current density of 25 mA cm−2at an overpotential as low as 225 mV and a small Tafel slope of 69 mV dec−1in alkaline electrolyte. The optimized NiFeCr catalyst is stable under OER conditions and X‐ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and elemental analysis confirm the stability of trimetallic NiFeCr LDH after electrochemical testing. Due to the synergistic interactions among the metal centers, trimetallic NiFeCr LDH is significantly more active than NiFe LDH and among the most active OER catalysts to date. This work also presents general strategies to design more efficient metal oxide/hydroxide OER electrocatalysts.

 
more » « less
NSF-PAR ID:
10050914
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Energy Materials
Volume:
8
Issue:
15
ISSN:
1614-6832
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Transition metal selenides have attracted intensive interest as cost-effective electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) because of the continuous thrust in sustainable energy conversion. In this article a Mn-based bifunctional electrocatalyst, MnSe, has been identified which shows efficient OER and ORR activity in alkaline medium. The catalytic activity could be further enhanced by using multiwalled carbon nanotubes (MWCNTs) which increases the charge transfer and electronic conductivity of the catalyst composite. This MnSe@MWCNT catalyst composite exhibits a very low overpotential of 290 mV at 10 mA cm −2 , which outperforms state-of-the-art RuO 2 as well as other oxide based electrocatalysts. Furthermore, the composite's facile OER kinetics was evidenced by its small Tafel slope of 54.76 mV dec −1 and low charge transfer resistance, indicating quick transport of the reactant species at the electrode interface. The MnSe@MWCNT also exhibited efficient electrocatalytic activity for ORR with an E onset of 0.94 V, which is among the best reported to date for chalcogenide based ORR electrocatalysts. More importantly, this MnSe-based ORR electrocatalyst exhibits high degree of methanol tolerance, showing no degradation of catalyst performance in the presence of copious quantities of methanol, thereby out-performing the state-of-the-art Pt electrocatalyst. The catalyst composite also exhibited exceptional functional and compositional stability for OER and ORR after a prolonged period of continuous operation in alkaline medium. The surface Raman analysis after OER revealed the retention of manganese selenide surface with evidence of oxo coordination, confirming the formation of an (oxy)selenide as the active surface for OER. Such efficient bifunctional OER and ORR activity makes this MnSe based catalyst attractive for overall electrolysis in regenerative as well as direct methanol fuel cells. 
    more » « less
  2. Designing efficient electrocatalysts has been one of the primary goals for water electrolysis, which is one of the most promising routes towards sustainable energy generation from renewable sources. In this article, we have tried to expand the family of transition metal chalcogenide based highly efficient OER electrocatalysts by investigating nickel telluride, Ni 3 Te 2 as a catalyst for the first time. Interestingly Ni 3 Te 2 electrodeposited on a GC electrode showed very low onset potential and overpotential at 10 mA cm −2 (180 mV), which is the lowest in the series of chalcogenides with similar stoichiometry, Ni 3 E 2 (E = S, Se, Te) as well as Ni-oxides. This observation falls in line with the hypothesis that increasing the covalency around the transition metal center enhances catalytic activity. Such a hypothesis has been previously validated in oxide-based electrocatalysts by creating anion vacancies. However, this is the first instance where this hypothesis has been convincingly validated in the chalcogenide series. The operational stability of the Ni 3 Te 2 electrocatalyst surface during the OER for an extended period of time in alkaline medium was confirmed through surface-sensitive analytical techniques such as XPS, as well as electrochemical methods which showed that the telluride surface did not undergo any corrosion, degradation, or compositional change. More importantly we have compared the catalyst activation step (Ni 2+ → Ni 3+ oxidation) in the chalcogenide series, through electrochemical cyclic voltammetry studies, and have shown that catalyst activation occurs at lower applied potential as the electronegativity of the anion decreases. From DFT calculations we have also shown that the hydroxyl attachment energy is more favorable on the Ni 3 Te 2 surface compared to the Ni-oxide, confirming the enhanced catalytic activity of the telluride. Ni 3 Te 2 also exhibited efficient HER catalytic activity in alkaline medium making it a very effective bifunctional catalyst for full water splitting with a cell voltage of 1.66 V at 10 mA cm −2 . It should be noted here that this is the first report of OER and HER activity in the family of Ni-tellurides. 
    more » « less
  3. Developing simple, affordable, and environmentally friendly water oxidation electrocatalysts with high intrinsic activity and low overpotential continues to be an area of intense research. In this article, a trichromium diselenide carbonyl cluster complex (Et4N)2[Se2Cr3(CO)10], with a unique bonding structure comprising bridging Se groups, has been identified as a promising electrocatalyst for oxygen evolution reaction (OER). This carbonyl cluster exhibits a promising overpotential of 310 mV and a low Tafel slope of 82.0 mV dec−1 at 10 mAcm−2, with superior durability in an alkaline medium, for a prolonged period of continuous oxygen evolution. The mass activity and turnover frequency of 62.2 Ag−1 and 0.0174 s−1 was achieved, respectively at 0.390 V vs. RHE. The Cr-complex reported here shows distinctly different catalytic activity based on subtle changes in the ligand chemistry around the catalytically active Cr site. Such dependence further corroborates the critical influence of ligand coordination on the electron density distribution which further affects the electrochemical activation and catalytic efficiency of the active site. Specifically, even partial substitution with more electronegative substituents leads to the weakening of the catalytic efficiency. This report further demonstrates that metal carbonyl chalcogenides cluster-type materials which exhibit partially occupied sites and high valence in their metal sites can serve as catalytically active centers to catalyze OER exhibiting high intrinsic activity. The insight generated from this report can be directly extrapolated to 3-dimensional solids containing similar structural motifs, thereby aiding in optimal catalyst design. 
    more » « less
  4. Abstract

    The large‐scale hydrogen production and application through electrocatalytic water splitting depends crucially on the development of highly efficient, cost‐effective electrocatalysts for oxygen evolution reaction (OER), which, however, remains challenging. Here, a new electrocatalyst of trimetallic Fe–Co–Ni hydroxide (denoted as FeCoNiOxHy) with a nanotubular structure is developed through an enhanced Kirkendall process under applied potential. The FeCoNiOxHyfeatures synergistic electronic interaction between Fe, Co, and Ni, which not only notably increases the intrinsic OER activity of FeCoNiOxHyby facilitating the formation of *OOH intermediate, but also substantially improves the intrinsic conductivity of FeCoNiOxHyto facilitate charge transfer and activate catalytic sites through electrocatalyst by promoting the formation of abundant Co3+. Therefore, FeCoNiOxHydelivers remarkably accelerated OER kinetics and superior apparent activity, indicated by an ultra‐low overpotential potential of 257 mV at a high current density of 200 mA cm−2. This work is of fundamental and practical significance for synergistic catalysis related to advanced energy conversion materials and technologies.

     
    more » « less
  5. 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