Ammonia (NH3) is a promising carbon-free fuel when prepared from sustainable resources. First-row transition metal electrocatalysts for ammonia oxidation are an enabling technology for sustainable energy production. We describe electrocatalytic ammonia oxidation using robust molecular complexes based on Earth-abundant iron. Electrochemical studies of ferrocenes with covalently attached pyridine arms reveal facile ammonia oxidation in DMSO (2.4 M NH3) with modest overpotentials (eta = 770-820 mV) and turnover frequencies (125-560 h-1). Experimental and computational studies indicate that the pendant pyridyl base serves as an H-bond acceptor with an N-H bond of ammonia that transfers a proton to the pyridine following oxidation by the attached ferrocenium moiety in a proton-coupled electron transfer (PCET) step. This generates an amidyl (center dot NH2) radical stabilized via H-bonding to a pendant pyridinium moiety that rapidly dimerizes to hydrazine (H2N-NH2), which is easily oxidized to nitrogen (N2) at the glassy carbon working electrode. This report identifies a general strategy to oxidize ammonia via H-bonding to a base (B:), thereby activating [B<middle dot><middle dot><middle dot>H-NH2] toward PCET by a proximal oxidant to form [BH<middle dot><middle dot><middle dot>NH2]+/center dot radical cations, which are susceptible to dimerization to form easily oxidized hydrazine.
机构:
Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USAUniv Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
Adli, Nadia Mohd
;
Zhang, Hao
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Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USAUniv Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
Zhang, Hao
;
Mukherjee, Shreya
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Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USAUniv Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
Mukherjee, Shreya
;
Wu, Gang
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Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USAUniv Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
机构:
Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Ahmed, Md Estak
;
Boroujeni, Mahdi Raghibi
论文数: 0引用数: 0
h-index: 0
机构:
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Boroujeni, Mahdi Raghibi
;
Ghosh, Pokhraj
论文数: 0引用数: 0
h-index: 0
机构:
Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Ghosh, Pokhraj
;
Greene, Christine
论文数: 0引用数: 0
h-index: 0
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Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Greene, Christine
;
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Kundu, Subrata
;
Bertke, Jeffery A.
论文数: 0引用数: 0
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Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Bertke, Jeffery A.
;
Warren, Timothy H.
论文数: 0引用数: 0
h-index: 0
机构:
Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
机构:
King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Saudi Aramco, Dhahran 31311, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Alamoudi, Omar M.
;
Khan, Wasim Ullah
论文数: 0引用数: 0
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King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
King Fahd Univ Petr & Minerals, Interdisciplinary Res Ctr Refining & Adv Chem, Dhahran 31261, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Khan, Wasim Ullah
;
Hantoko, Dwi
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King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
King Fahd Univ Petr & Minerals, Interdisciplinary Res Ctr Refining & Adv Chem, Dhahran 31261, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Hantoko, Dwi
;
Ali, Syed A.
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King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Ali, Syed A.
;
Hossain, Mohammad M.
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King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
King Fahd Univ Petr & Minerals, Interdisciplinary Res Ctr Refining & Adv Chem, Dhahran 31261, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
机构:
Univ Mohammed VI Polytech, Lab Inorgan Mat Sustainable Energy Technol LIMSET, Benguerir 43150, MoroccoUniv Mohammed VI Polytech, Lab Inorgan Mat Sustainable Energy Technol LIMSET, Benguerir 43150, Morocco
Bora, Debajeet K.
;
Faik, Abdessamad
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Univ Mohammed VI Polytech, Lab Inorgan Mat Sustainable Energy Technol LIMSET, Benguerir 43150, MoroccoUniv Mohammed VI Polytech, Lab Inorgan Mat Sustainable Energy Technol LIMSET, Benguerir 43150, Morocco
机构:
Indira Gandhi Natl Open Univ, Dept Environm Studies, New Delhi 110068, IndiaTezpur Univ, Dept Energy, Tezpur 784028, Assam, India
Venkatramanan, Veluswamy
;
Prasad, Shiv
论文数: 0引用数: 0
h-index: 0
机构:
ICAR Indian Agr Res Inst, Div Environm Sci, New Delhi 110012, IndiaTezpur Univ, Dept Energy, Tezpur 784028, Assam, India
Prasad, Shiv
;
Singh, Anoop
论文数: 0引用数: 0
h-index: 0
机构:
Minist Sci & Technol, Dept Scient & Ind Res DSIR, Govt India, New Mehrauli Rd, New Delhi 110016, IndiaTezpur Univ, Dept Energy, Tezpur 784028, Assam, India
机构:
Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USAUniv Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
Adli, Nadia Mohd
;
Zhang, Hao
论文数: 0引用数: 0
h-index: 0
机构:
Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USAUniv Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
Zhang, Hao
;
Mukherjee, Shreya
论文数: 0引用数: 0
h-index: 0
机构:
Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USAUniv Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
Mukherjee, Shreya
;
Wu, Gang
论文数: 0引用数: 0
h-index: 0
机构:
Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USAUniv Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
机构:
Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Ahmed, Md Estak
;
Boroujeni, Mahdi Raghibi
论文数: 0引用数: 0
h-index: 0
机构:
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Boroujeni, Mahdi Raghibi
;
Ghosh, Pokhraj
论文数: 0引用数: 0
h-index: 0
机构:
Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Ghosh, Pokhraj
;
Greene, Christine
论文数: 0引用数: 0
h-index: 0
机构:
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Greene, Christine
;
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机构:
Kundu, Subrata
;
Bertke, Jeffery A.
论文数: 0引用数: 0
h-index: 0
机构:
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Bertke, Jeffery A.
;
Warren, Timothy H.
论文数: 0引用数: 0
h-index: 0
机构:
Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA
Georgetown Univ, Dept Chem, Washington, DC 20057 USAMichigan State Univ, Dept Chem, E Lansing, MI 48824 USA
机构:
King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Saudi Aramco, Dhahran 31311, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Alamoudi, Omar M.
;
Khan, Wasim Ullah
论文数: 0引用数: 0
h-index: 0
机构:
King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
King Fahd Univ Petr & Minerals, Interdisciplinary Res Ctr Refining & Adv Chem, Dhahran 31261, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Khan, Wasim Ullah
;
Hantoko, Dwi
论文数: 0引用数: 0
h-index: 0
机构:
King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
King Fahd Univ Petr & Minerals, Interdisciplinary Res Ctr Refining & Adv Chem, Dhahran 31261, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Hantoko, Dwi
;
Ali, Syed A.
论文数: 0引用数: 0
h-index: 0
机构:
King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
Ali, Syed A.
;
Hossain, Mohammad M.
论文数: 0引用数: 0
h-index: 0
机构:
King Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
King Fahd Univ Petr & Minerals, Interdisciplinary Res Ctr Refining & Adv Chem, Dhahran 31261, Saudi ArabiaKing Fahd Univ Petr & Minerals, Dept Chem Engn, Dhahran 31261, Saudi Arabia
机构:
Univ Mohammed VI Polytech, Lab Inorgan Mat Sustainable Energy Technol LIMSET, Benguerir 43150, MoroccoUniv Mohammed VI Polytech, Lab Inorgan Mat Sustainable Energy Technol LIMSET, Benguerir 43150, Morocco
Bora, Debajeet K.
;
Faik, Abdessamad
论文数: 0引用数: 0
h-index: 0
机构:
Univ Mohammed VI Polytech, Lab Inorgan Mat Sustainable Energy Technol LIMSET, Benguerir 43150, MoroccoUniv Mohammed VI Polytech, Lab Inorgan Mat Sustainable Energy Technol LIMSET, Benguerir 43150, Morocco
机构:
Indira Gandhi Natl Open Univ, Dept Environm Studies, New Delhi 110068, IndiaTezpur Univ, Dept Energy, Tezpur 784028, Assam, India
Venkatramanan, Veluswamy
;
Prasad, Shiv
论文数: 0引用数: 0
h-index: 0
机构:
ICAR Indian Agr Res Inst, Div Environm Sci, New Delhi 110012, IndiaTezpur Univ, Dept Energy, Tezpur 784028, Assam, India
Prasad, Shiv
;
Singh, Anoop
论文数: 0引用数: 0
h-index: 0
机构:
Minist Sci & Technol, Dept Scient & Ind Res DSIR, Govt India, New Mehrauli Rd, New Delhi 110016, IndiaTezpur Univ, Dept Energy, Tezpur 784028, Assam, India