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Title: Nanostructured Ternary Nickel‐Based Mixed Anionic (Telluro)‐Selenide as a Superior Catalyst for Oxygen Evolution Reaction
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Award ID(s):
2155175
NSF-PAR ID:
10419101
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Energy Technology
Volume:
11
Issue:
7
ISSN:
2194-4288
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    Transition metal sulfides with a multi‐elemental nature represent a class of promising catalysts for oxygen evolution reaction (OER) owing to their good catalytic activity. However, their synthesis remains a challenge due to the thermodynamic immiscibility of the constituent multimetallic elements in a sulfide structure. Herein, for the first time the synthesis of high‐entropy metal sulfide (HEMS, i.e., (CrMnFeCoNi)Sx) solid solution nanoparticles is reported. Computational and X‐ray photoelectron spectroscopy analysis suggest that the (CrMnFeCoNi)Sxexhibits a synergistic effect among metal atoms that leads to desired electronic states to enhance OER activity. The (CrMnFeCoNi)Sxnanoparticles show one of the best activities (low overpotential 295 mV at 100 mA cm−2in 1mKOH solution) and good durability (only slight polarization after 10 h by chronopotentiometry) compared with their unary, binary, ternary, and quaternary sulfide counterparts. This work opens up a new synthesis paradigm for high‐entropy compound nanoparticles for highly efficient electrocatalysis applications.

     
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  2. Water splitting has been widely considered to be an efficient way to generate sustainable and renewable energy resources in fuel cells, metal–air batteries and other energy conversion devices. Exploring efficient electrocatalysts to expedite the anodic oxygen evolution reaction (OER) is a crucial task that needs to be addressed in order to boost the practical application of water splitting. Intensive efforts have been devoted to develop mixed transition metal based chalcogenides as effective OER electrocatalysts. Herein, we have reported synthesis of a series of mixed metal selenides containing Co, Ni and Cu employing combinatorial electrodeposition, and systematically investigated how the transition metal doping affects the OER catalytic activity in alkaline medium. Energy dispersive spectroscopy (EDS) was performed to detect the elemental compositions and confirm the feasibility of compositional control of 66 metal selenide thin films. It was observed that the OER catalytic activity is sensitive to the concentration of Cu in the catalysts, and the catalyst activity tended to increase with increasing Cu concentration. However, increasing the Cu concentration beyond a certain limit led to decrease in catalytic efficiency, and copper selenide by itself, although catalytically active, showed higher onset potential and overpotential for OER compared to the ternary and quaternary mixed metal selenides. Interestingly, the best quaternary composition (Co 0.21 Ni 0.25 Cu 0.54 ) 3 Se 2 showed similar crystal structure as its parent compound of Cu 3 Se 2 with slight decrease in lattice spacings of (101) and (210) lattice planes (0.0222 Å and 0.0148 Å, respectively) evident from the powder X-ray diffraction pattern. (Co 0.21 Ni 0.25 Cu 0.54 ) 3 Se 2 thin film exhibited excellent OER catalytic activity and required an overpotential of 272 mV to reach a current density of 10 mA cm −2 , which is 54 mV lower than Cu 3 Se 2 , indicating a synergistic effect of transition metal doping in enhancing catalytic activity. 
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  3. Earth-abundant oxygen evolution catalysts (OECs) with extended stability in acid can be constructed by embedding active sites within an acid-stable metal-oxide framework. Here, we report stable NiPbOxfilms that are able to perform oxygen evolution reaction (OER) catalysis for extended periods of operation (>20 h) in acidic solutions of pH 2.5; conversely, native NiOxcatalyst films dissolve immediately. In situ X-ray absorption spectroscopy and ex situ X-ray photoelectron spectroscopy reveal that PbO2is unperturbed after addition of Ni and/or Fe into the lattice, which serves as an acid-stable, conductive framework for embedded OER active centers. The ability to perform OER in acid allows the mechanism of Fe doping on Ni catalysts to be further probed. Catalyst activity with Fe doping of oxidic Ni OEC under acid conditions, as compared to neutral or basic conditions, supports the contention that role of Fe3+in enhancing catalytic activity in Ni oxide catalysts arises from its Lewis acid properties.

     
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  4. 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.

     
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  5. Abstract

    The application of Co2‐xRhxP nanoparticles as electrocatalysts for the hydrogen evolution reaction (HER) and overall water splitting in basic media is reported. The experimental design seeks to dilute rhodium with earth‐abundant cobalt as a means to lower the cost of the material and achieve catalytic synergism, as reported for related bimetallic phosphides. The HER activity of Co2‐xRhxP is found to be composition‐dependent, with the rhodium‐rich compositions being more active as compared to their cobalt‐rich counterparts, with overpotentials (η) at 10 mA/cm2geometricof 58.1–63.9 mV vs. 82.1–188.1 mV, respectively. In contrast, Co‐rich Co2‐xRhxP nanoparticles are active for the oxygen evolution reaction (OER) process in basic media, with η= 290 mV for x=0.25. A full water electrolysis cell was created using the most active compositions for OER and HER as the anode and cathode, respectively, generating an overall η= 390 mV. Notably, the cell became more active over a 50 h stability test, increasing by 2 mV/cm2geometricat a constant applied voltage of 1.62 V vs NHE. This enhanced activity correlates with nanoscale phase segregation of Rh in the anode. Thus, the lower overpotential achieved for Co1.75Rh0.25P relative to Co2P, and the augmented activity over time in the former, may be a consequence of restructuring of the anode driven by Rh phase‐segregation. The augmentation in activity at the anode more than compensates for small losses at the cathode.

     
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