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Title: High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells

Abstract

Low-temperature direct ammonia fuel cells (DAFCs) use carbon-neutral ammonia as a fuel, which has attracted increasing attention recently due to ammonia's low source-to-tank energy cost, easy transport and storage, and wide availability. However, current DAFC technologies are greatly limited by the kinetically sluggish ammonia oxidation reaction (AOR) at the anode. Herein, we report an AOR catalyst, in which ternary PtIrZn nanoparticles with an average size of 2.3 ± 0.2 nm were highly dispersed on a binary composite support comprising cerium oxide (CeO2) and zeolitic imidazolate framework-8 (ZIF-8)-derived carbon (PtIrZn/CeO2-ZIF-8) through a sonochemical-assisted synthesis method. Additionally, the PtIrZn alloy, with the aid of abundant OHad provided by CeO2 and uniform particle dispersibility contributed by porous ZIF-8 carbon (surface area: ~600 m2 g-1), has shown highly efficient catalytic activity for the AOR in alkaline media, superior to that of commercial PtIr/C. The rotating disk electrode (RDE) results indicate a lower onset potential (0.35 vs. 0.43 V), relative to the reversible hydrogen electrode at room temperature, and a decreased activation energy (~36.7 vs. 50.8 kJ mol-1) relative to the PtIr/C catalyst. Notably, the PtIrZn/CeO2-ZIF-8 catalyst was assembled with a high-performance hydroxide anion-exchange membrane to fabricate an alkaline DAFC, reaching a peak power densitymore » of 91 mW cm-2. Unlike in aqueous electrolytes, supports play a critical role in improving uniform ionomer distribution and mass transport in the anode. PtIrZn nanoparticles on silicon dioxide (SiO2) integrated with carboxyl-functionalized carbon nanotubes (CNT–COOH) were further studied as the anode in a DAFC. A significantly enhanced peak power density of 314 mW cm-2 was achieved. Density functional theory calculations elucidated that Zn atoms in the PtIr alloy can reduce the theoretical limiting potential of *NH2 dehydrogenation to *NH by ~0.1 V, which can be attributed to a Zn-modulated upshift of the Pt–Ir d-band that facilitates the N–H bond breakage.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3];  [5]; ORCiD logo [2]; ORCiD logo [6];  [5]; ORCiD logo [7];  [8]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [5]
+ Show Author Affiliations
  1. State Univ. of New York (SUNY), Buffalo, NY (United States); Jiangsu Univ., Zhenjiang (China)
  2. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  3. Univ. of Delaware, Newark, DE (United States). Center for Catalytic Science and Technology
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  5. State Univ. of New York (SUNY), Buffalo, NY (United States)
  6. Univ. of South Carolina, Columbia, SC (United States)
  7. Jiangsu Univ., Zhenjiang (China)
  8. Center for Functional Nanomaterials;Brookhaven National Laboratory;Upton;USA
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); China Scholarship Council
OSTI Identifier:
1773118
Alternate Identifier(s):
OSTI ID: 1765914
Report Number(s):
BNL-221222-2021-JAAM
Journal ID: ISSN 1754-5692
Grant/Contract Number:  
SC0012704; 51972150; 201808320253
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 14; Journal Issue: 3; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Li, Yi, Pillai, Hemanth Somarajan, Wang, Teng, Hwang, Sooyeon, Zhao, Yun, Qiao, Zhi, Mu, Qingmin, Karakalos, Stavros, Chen, Mengjie, Yang, Juan, Su, Dong, Xin, Hongliang, Yan, Yushan, and Wu, Gang. High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells. United States: N. p., 2021. Web. doi:10.1039/d0ee03351k.
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Li, Yi, Pillai, Hemanth Somarajan, Wang, Teng, Hwang, Sooyeon, Zhao, Yun, Qiao, Zhi, Mu, Qingmin, Karakalos, Stavros, Chen, Mengjie, Yang, Juan, Su, Dong, Xin, Hongliang, Yan, Yushan, & Wu, Gang. High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells. United States. https://doi.org/10.1039/d0ee03351k
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Li, Yi, Pillai, Hemanth Somarajan, Wang, Teng, Hwang, Sooyeon, Zhao, Yun, Qiao, Zhi, Mu, Qingmin, Karakalos, Stavros, Chen, Mengjie, Yang, Juan, Su, Dong, Xin, Hongliang, Yan, Yushan, and Wu, Gang. Thu . "High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells". United States. https://doi.org/10.1039/d0ee03351k. https://www.osti.gov/servlets/purl/1773118.
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@article{osti_1773118,
title = {High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells},
author = {Li, Yi and Pillai, Hemanth Somarajan and Wang, Teng and Hwang, Sooyeon and Zhao, Yun and Qiao, Zhi and Mu, Qingmin and Karakalos, Stavros and Chen, Mengjie and Yang, Juan and Su, Dong and Xin, Hongliang and Yan, Yushan and Wu, Gang},
abstractNote = {Low-temperature direct ammonia fuel cells (DAFCs) use carbon-neutral ammonia as a fuel, which has attracted increasing attention recently due to ammonia's low source-to-tank energy cost, easy transport and storage, and wide availability. However, current DAFC technologies are greatly limited by the kinetically sluggish ammonia oxidation reaction (AOR) at the anode. Herein, we report an AOR catalyst, in which ternary PtIrZn nanoparticles with an average size of 2.3 ± 0.2 nm were highly dispersed on a binary composite support comprising cerium oxide (CeO2) and zeolitic imidazolate framework-8 (ZIF-8)-derived carbon (PtIrZn/CeO2-ZIF-8) through a sonochemical-assisted synthesis method. Additionally, the PtIrZn alloy, with the aid of abundant OHad provided by CeO2 and uniform particle dispersibility contributed by porous ZIF-8 carbon (surface area: ~600 m2 g-1), has shown highly efficient catalytic activity for the AOR in alkaline media, superior to that of commercial PtIr/C. The rotating disk electrode (RDE) results indicate a lower onset potential (0.35 vs. 0.43 V), relative to the reversible hydrogen electrode at room temperature, and a decreased activation energy (~36.7 vs. 50.8 kJ mol-1) relative to the PtIr/C catalyst. Notably, the PtIrZn/CeO2-ZIF-8 catalyst was assembled with a high-performance hydroxide anion-exchange membrane to fabricate an alkaline DAFC, reaching a peak power density of 91 mW cm-2. Unlike in aqueous electrolytes, supports play a critical role in improving uniform ionomer distribution and mass transport in the anode. PtIrZn nanoparticles on silicon dioxide (SiO2) integrated with carboxyl-functionalized carbon nanotubes (CNT–COOH) were further studied as the anode in a DAFC. A significantly enhanced peak power density of 314 mW cm-2 was achieved. Density functional theory calculations elucidated that Zn atoms in the PtIr alloy can reduce the theoretical limiting potential of *NH2 dehydrogenation to *NH by ~0.1 V, which can be attributed to a Zn-modulated upshift of the Pt–Ir d-band that facilitates the N–H bond breakage.},
doi = {10.1039/d0ee03351k},
journal = {Energy & Environmental Science},
number = 3,
volume = 14,
place = {United States},
year = {Thu Jan 14 00:00:00 EST 2021},
month = {Thu Jan 14 00:00:00 EST 2021}
}
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https://doi.org/10.1039/d0ee03351k
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Works referenced in this record:

Fabrication of gold nanoparticles/graphene oxide films with surface-enhanced Raman scattering activity by a simple electrostatic self-assembly method
journal, January 2017

A Roadmap to the Ammonia Economy
journal, June 2020

Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation
journal, January 2015

  • Zhu, Jing; Zheng, Xin; Wang, Jie
  • Journal of Materials Chemistry A, Vol. 3, Issue 44
  • DOI: 10.1039/C5TA05699C

Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study
journal, February 2015

  • Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos
  • The Journal of Physical Chemistry C, Vol. 119, Issue 26
  • DOI: 10.1021/jp512981f

Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction
journal, November 2019

  • Li, Jiazhan; Zhang, Hanguang; Samarakoon, Widitha
  • Angewandte Chemie International Edition, Vol. 58, Issue 52
  • DOI: 10.1002/anie.201909312

Surface engineering in improving activity of Pt nanocubes for ammonia electrooxidation reaction
journal, July 2020

High-Efficiency Direct Ammonia Fuel Cells Based on BaZr 0.1 Ce 0.7 Y 0.2 O 3− δ /Pd Oxide-Metal Junctions
journal, December 2017

  • Aoki, Yoshitaka; Yamaguchi, Tomoyuki; Kobayashi, Shohei
  • Global Challenges, Vol. 2, Issue 1
  • DOI: 10.1002/gch2.201700088

Electrochemical Oxidation of Ammonia over Rare Earth Oxide Modified Platinum Catalysts
journal, April 2015

  • Katayama, Yu; Okanishi, Takeou; Muroyama, Hiroki
  • The Journal of Physical Chemistry C, Vol. 119, Issue 17
  • DOI: 10.1021/acs.jpcc.5b01710

A Covalent Triazine Framework, Functionalized with Ir/N-Heterocyclic Carbene Sites, for the Efficient Hydrogenation of CO 2 to Formate
journal, August 2017

  • Gunasekar, Gunniya Hariyanandam; Park, Kwangho; Ganesan, Vinothkumar
  • Chemistry of Materials, Vol. 29, Issue 16
  • DOI: 10.1021/acs.chemmater.7b01539

A Roadmap to Low‐Cost Hydrogen with Hydroxide Exchange Membrane Electrolyzers
journal, December 2018

  • Abbasi, Reza; Setzler, Brian P.; Lin, Saisai
  • Advanced Materials, Vol. 31, Issue 31
  • DOI: 10.1002/adma.201805876

Anodically electrodeposited Co+Ni mixed oxide electrode: preparation and electrocatalytic activity for oxygen evolution in alkaline media
journal, October 2004

  • Wu, Gang; Li, Ning; Zhou, De-Rui
  • Journal of Solid State Chemistry, Vol. 177, Issue 10, p. 3682-3692
  • DOI: 10.1016/j.jssc.2004.06.027

Low-temperature ammonia decomposition catalysts for hydrogen generation
journal, June 2018

Investigation of cubic Pt alloys for ammonia oxidation reaction
journal, February 2020

Advanced Electrocatalysis for Energy and Environmental Sustainability via Water and Nitrogen Reactions
journal, July 2020

Catalytically Active Bimetallic Nanoparticles Supported on Porous Carbon Capsules Derived From Metal–Organic Framework Composites
journal, August 2016

  • Yang, Hui; Bradley, Siobhan J.; Chan, Andrew
  • Journal of the American Chemical Society, Vol. 138, Issue 36
  • DOI: 10.1021/jacs.6b06736

Synthesis, Characterization of Mixed Cu(II) Pyridyl Tetrazoles and 1,10-Phenanthroline Complexes - DFT and Biological Activity
journal, January 2019

Hydrogen generation from ammonia electrolysis on bifunctional platinum nanocubes electrocatalysts
journal, August 2020

Hard-Magnet L10-CoPt Nanoparticles Advance Fuel Cell Catalysis
journal, January 2019

Ordered Pt 3 Co Intermetallic Nanoparticles Derived from Metal–Organic Frameworks for Oxygen Reduction
journal, June 2018

A general synthesis approach for supported bimetallic nanoparticles via surface inorganometallic chemistry
journal, November 2018

Activation of surface lattice oxygen in single-atom Pt/CeO 2 for low-temperature CO oxidation
journal, December 2017

Dynamic traction of lattice-confined platinum atoms into mesoporous carbon matrix for hydrogen evolution reaction
journal, January 2018

An Efficient Direct Ammonia Fuel Cell for Affordable Carbon-Neutral Transportation
journal, October 2019

New Insights into Electrochemical Ammonia Oxidation on Pt(100) from First Principles
journal, June 2019

  • Pillai, Hemanth Somarajan; Xin, Hongliang
  • Industrial & Engineering Chemistry Research, Vol. 58, Issue 25
  • DOI: 10.1021/acs.iecr.9b01471

High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites
journal, January 2019

  • Zhang, Hanguang; Chung, Hoon T.; Cullen, David A.
  • Energy & Environmental Science, Vol. 12, Issue 8
  • DOI: 10.1039/C9EE00877B

High performance PtxEu alloys as effective electrocatalysts for ammonia electro-oxidation
journal, July 2017

Enhanced Supply of Hydroxyl Species in CeO 2 -Modified Platinum Catalyst Studied by in Situ ATR-FTIR Spectroscopy
journal, February 2016

Shape-controlled synthesis of Pt-Ir nanocubes with preferential (100) orientation and their unusual enhanced electrocatalytic activities
journal, December 2014

Ammonia oxidation kinetics on bimetallic clusters of platinum and iridium: A theoretical approach
journal, February 2018

Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation
journal, July 2019

Revisiting the electrochemical oxidation of ammonia on carbon-supported metal nanoparticle catalysts
journal, February 2017

Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells
journal, April 2019

Review—Ammonia Oxidation Electrocatalysis for Hydrogen Generation and Fuel Cells
journal, January 2018

  • Adli, Nadia Mohd; Zhang, Hao; Mukherjee, Shreya
  • Journal of The Electrochemical Society, Vol. 165, Issue 15
  • DOI: 10.1149/2.0191815jes

Ternary PtIrNi Catalysts for Efficient Electrochemical Ammonia Oxidation
journal, March 2020

Pt/CeO 2 @MOF Core@Shell Nanoreactor for Selective Hydrogenation of Furfural via the Channel Screening Effect
journal, August 2018

Atomically dispersed metal–nitrogen–carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement
journal, January 2020

  • He, Yanghua; Liu, Shengwen; Priest, Cameron
  • Chemical Society Reviews, Vol. 49, Issue 11
  • DOI: 10.1039/C9CS00903E

Highly active atomically dispersed CoN 4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy
journal, January 2019

  • He, Yanghua; Hwang, Sooyeon; Cullen, David A.
  • Energy & Environmental Science, Vol. 12, Issue 1
  • DOI: 10.1039/C8EE02694G

Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells
journal, January 2020

  • Shi, Qiurong; He, Yanghua; Bai, Xiaowan
  • Energy & Environmental Science, Vol. 13, Issue 10
  • DOI: 10.1039/D0EE01968B

Evidence for Decoupled Electron and Proton Transfer in the Electrochemical Oxidation of Ammonia on Pt(100)
journal, January 2016

  • Katsounaros, Ioannis; Chen, Ting; Gewirth, Andrew A.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
  • DOI: 10.1021/acs.jpclett.5b02556

DFT calculations of ammonia oxidation reactions on bimetallic clusters of platinum and iridium
journal, September 2016

Local Platinum Environments in a Solid Analogue of the Molecular Periana Catalyst
journal, March 2016

Dynamic charge and oxidation state of Pt/CeO2 single-atom catalysts
journal, August 2019

  • Daelman, Nathan; Capdevila-Cortada, Marçal; López, Núria
  • Nature Materials, Vol. 18, Issue 11
  • DOI: 10.1038/s41563-019-0444-y

Temperature-Dependent Kinetics and Reaction Mechanism of Ammonia Oxidation on Pt, Ir, and PtIr Alloy Catalysts
journal, January 2018

  • Song, Liang; Liang, Zhixiu; Ma, Zhong
  • Journal of The Electrochemical Society, Vol. 165, Issue 15
  • DOI: 10.1149/2.0181815jes

Newly Designed Graphene Cellular Monolith Functionalized with Hollow Pt-M (M = Ni, Co) Nanoparticles as the Electrocatalyst for Oxygen Reduction Reaction
journal, September 2016

  • Zhou, Yazhou; Yang, Juan; Zhu, Chengzhou
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 39
  • DOI: 10.1021/acsami.6b04963

Mechanism of electrochemical oxidation of ammonia
journal, October 2011

Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion
journal, November 2019

  • Zhu, Yuanzhi; Sokolowski, Joshua; Song, Xiancheng
  • Advanced Energy Materials, Vol. 10, Issue 11
  • DOI: 10.1002/aenm.201902844

Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells
journal, January 2018

  • Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin
  • Advanced Materials, Vol. 30, Issue 11
  • DOI: 10.1002/adma.201706758

Alkaline Anion-Exchange Membrane Fuel Cells: Challenges in Electrocatalysis and Interfacial Charge Transfer
journal, November 2019

High Power Density Platinum Group Metal-free Cathodes for Polymer Electrolyte Fuel Cells
journal, December 2019

  • Uddin, Aman; Dunsmore, Lisa; Zhang, Hanguang
  • ACS Applied Materials & Interfaces, Vol. 12, Issue 2
  • DOI: 10.1021/acsami.9b13945

Porous graphene doped with Fe/N/S and incorporating Fe 3 O 4 nanoparticles for efficient oxygen reduction
journal, January 2018

  • Li, Yi; Zhou, Yazhou; Zhu, Chengzhou
  • Catalysis Science & Technology, Vol. 8, Issue 20
  • DOI: 10.1039/C8CY01328D

Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N 2 and H 2 O
journal, February 2020

CuPt and CuPtRu Nanostructures for Ammonia Oxidation Reaction
journal, March 2018

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