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Title: Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

Abstract

Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarcity. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides are their low electronic conductivity and durability. The carbon encapsulating transition metal nanoparticles are expected to address these challenges. However, the relationship between precursor compositions and catalyst properties, and the intrinsic functions of each component has been rarely studied. In this paper, we report a highly durable (no degradation after 20,000 cycles) and highly active (360 mV overpotential at 10 mA cm –2 GEO) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron–donation/deviation from Fe and tuned lattice and electronic structures of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. Finally, we further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by themore » chemical state of precursors.« less

Authors:
 [1];  [2];  [3];  [4];  [2];  [5];  [6];  [6];  [7];  [4];  [8];  [2]
  1. Harbin Inst. of Technology (China). School of Chemistry and Chemical Engineering; Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States). The Gene and Linda Voiland School of Chemical Engineering and Bioengineering
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Oregon State Univ., Corvallis, OR (United States). School of Chemical, Biological and Environmental Engineering
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab.
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  6. Washington State Univ., Pullman, WA (United States). The Gene and Linda Voiland School of Chemical Engineering and Bioengineering
  7. Harbin Inst. of Technology (China). School of Chemistry and Chemical Engineering
  8. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States). The Gene and Linda Voiland School of Chemical Engineering and Bioengineering
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Harbin Inst. of Technology (China)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Natural Science Foundation of China (NNSFC); China Scholarship Council
Contributing Org.:
Washington State Univ., Pullman, WA (United States); Oregon State Univ., Corvallis, OR (United States)
OSTI Identifier:
1368554
Grant/Contract Number:
AC05-76RL01830; AC02-06CH11357; 21433003
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 39; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; Electrocatalysis; Oxygen evolution reaction; Metal–organic frameworks; Graphitized carbon shell; Encapsulated nanoparticles

Citation Formats

Du, Lei, Luo, Langli, Feng, Zhenxing, Engelhard, Mark, Xie, Xiaohong, Han, Binghong, Sun, Junming, Zhang, Jianghao, Yin, Geping, Wang, Chongmin, Wang, Yong, and Shao, Yuyan. Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst. United States: N. p., 2017. Web. doi:10.1016/j.nanoen.2017.07.006.
Du, Lei, Luo, Langli, Feng, Zhenxing, Engelhard, Mark, Xie, Xiaohong, Han, Binghong, Sun, Junming, Zhang, Jianghao, Yin, Geping, Wang, Chongmin, Wang, Yong, & Shao, Yuyan. Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst. United States. doi:10.1016/j.nanoen.2017.07.006.
Du, Lei, Luo, Langli, Feng, Zhenxing, Engelhard, Mark, Xie, Xiaohong, Han, Binghong, Sun, Junming, Zhang, Jianghao, Yin, Geping, Wang, Chongmin, Wang, Yong, and Shao, Yuyan. Wed . "Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst". United States. doi:10.1016/j.nanoen.2017.07.006.
@article{osti_1368554,
title = {Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst},
author = {Du, Lei and Luo, Langli and Feng, Zhenxing and Engelhard, Mark and Xie, Xiaohong and Han, Binghong and Sun, Junming and Zhang, Jianghao and Yin, Geping and Wang, Chongmin and Wang, Yong and Shao, Yuyan},
abstractNote = {Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarcity. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides are their low electronic conductivity and durability. The carbon encapsulating transition metal nanoparticles are expected to address these challenges. However, the relationship between precursor compositions and catalyst properties, and the intrinsic functions of each component has been rarely studied. In this paper, we report a highly durable (no degradation after 20,000 cycles) and highly active (360 mV overpotential at 10 mA cm–2GEO) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron–donation/deviation from Fe and tuned lattice and electronic structures of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. Finally, we further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by the chemical state of precursors.},
doi = {10.1016/j.nanoen.2017.07.006},
journal = {Nano Energy},
number = ,
volume = 39,
place = {United States},
year = {Wed Jul 05 00:00:00 EDT 2017},
month = {Wed Jul 05 00:00:00 EDT 2017}
}

Journal Article:
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  • Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhanced reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and poor durability. Here, we report OER catalysts of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells derived from bimetallic metal–organic frameworks (MOFs) precursors. The optimal OER catalyst shows excellent activity (360 mV overpotential atmore » 10 mA cm–2GEO) and durability (no obvious degradation after 20 000 cycles). The electron-donation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by chemical state of precursors. Severe metal particle growth probably caused by oxidation of carbon shells and encapsulated nanoparticles is believed to the main mechanism for activity degradation in these catalysts.« less
  • Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and durability. Herein, we report a highly active (360 mV overpotential at 10 mA cm–2GEO) and durable (no degradation after 20000 cycles) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists ofmore » NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron-donation/deviation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by the chemical state of precursors.« less
  • Pt-based nanomaterials are regarded as the most efficient electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, widespread adoption of PEMFCs requires solutions to major challenges encountered with ORR catalysts, namely high cost, sluggish kinetics, and low durability. In this paper, a new efficient method utilizing Co-based metal-organic frameworks is developed to produce PtCo bimetallic nanoparticles embedded in unique nitrogen-doped hollow porous carbon capsules. The obtained catalyst demonstrates an outstanding ORR performance, with a mass activity that is 5.5 and 13.5 times greater than that of commercial Pt/C and Pt black, respectively. Most importantly,more » the product exhibits dramatically improved durability in terms of both electrochemically active surface area (ECAS) and mass activity compared to commercial Pt/C and Pt black catalysts. Finally, the remarkable ORR performance demonstrated here can be attributed to the structural features of the catalyst (its alloy structure, high dispersion and fine particle size) and the carbon support (its nitrogen dopant, large surface area and hollow porous structure).« less
  • A novel method for the synthesis of high-performance Pt electrocatalysts on graphitized carbon nanotubes (GCNTs) is reported. GCNTs are first noncovalently functionalized with a polyelectrolyte, poly(diallyldimethylammonium chloride) (PDDA). Pt precursors are uniformly distributed on the surface of PDDA-functionalized GCNTs via the electrostatic self-assembly between negatively charged PtCl62- and positively charged functional groups of PDDA and then Pt nanoparticles are in-situ prepared with the ethylene glycol reduction method. X-ray photoelectron spectroscopy measurement confirms the successful functionalization of PDDA on GCNTs. X-ray diffraction and transmission electron microscope images reveal that Pt nanoparticles with an average size of ~ 2.7 nm are uniformlymore » dispersed on the PDDA-functionalzied GCNTs. Pt/GCNTs electrocatalyst exhibits two times higher activity towards oxygen reduction reaction than Pt/CNTs because of the higher Pt electrochemical surface area and the higher electrical conductivity of GCNTs. Also, Pt/GCNTs exhibit a higher stability than Pt/CNTs. This enhanced durability can be attributed to the structural integrity and higher graphitization degree of GCNTs.« less
  • We report a unique synthesis of core/shell Pd/FePt nanoparticles (NPs) and their catalysis of the oxygen reduction reaction (ORR). The uniform FePt shell is formed by controlled nucleation of Fe(CO){sub 5} in the presence of a Pt salt and Pd NPs at designated reaction temperatures. The Pd/FePt NPs show FePt shell-dependent catalytic properties, and those having a 1 nm FePt shell exhibit a drastic increase in durability and activity (15 times more active with a 140 mV gain in onset potential in comparison with those having a 3 nm coating). These Pd/FePt NPs are promising new catalysts for practical fuelmore » cell applications.« less