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Transition Metal Complexes for Elect...

Liu, Han-Yu,

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Transition Metal Complexes for Electrocatalytic Ammonia Oxidation /

Record Type:	Electronic resources : Monograph/item
Title/Author:	Transition Metal Complexes for Electrocatalytic Ammonia Oxidation // Han-Yu Liu.
Author:	Liu, Han-Yu,
Description:	1 electronic resource (189 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 86-02, Section: B.
Contained By:	Dissertations Abstracts International86-02B.
Subject:	Physical chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30992782
ISBN:	9798383566756

Transition Metal Complexes for Electrocatalytic Ammonia Oxidation /
Liu, Han-Yu,

Transition Metal Complexes for Electrocatalytic Ammonia Oxidation /Han-Yu Liu. - 1 electronic resource (189 pages)

Source: Dissertations Abstracts International, Volume: 86-02, Section: B.

Our rapidly increasing population's growing need for food, fertilizer, and clean energy necessitates an exploration into the oxidation of ammonia (NH3) for its application as a carbon-free fuel and a precursor for nitrite and nitrate production Traditional ammonia oxidation (AO) techniques, such as the Ostwald process, demand considerable energy and result in greenhouse gas emissions. In contrast, electrochemical AO emerges as an energy-efficient solution. This thesis investigates the development and characterization of copper and iridium-based molecular and heterogeneous catalysts targeting selective electrochemical AO in aqueous environments.Chapter 2 focuses on [Cu(bipyalk)]+, a mononuclear copper electrocatalyst exhibiting selective ammonia oxidation to nitrite (NO2−) and nitrate (NO3−) in water. Notably, this catalyst showcases a 65% faradaic efficiency (FE) for nitrate production and a remarkable 94% FE for total AO, while displaying high selectivity against water oxidation (WO)-an unprecedented trait in previous molecular AO electrocatalysts, as [Cu(bipyalk)]+ is not competent for WO.Chapter 3 explores Cu(pyalk)2, an originally developed electrochemical WO catalyst, for its effectiveness in chemoselective AO in water. While Cu(pyalk)2 exhibits WO efficacy, its WO activity is considerably diminished in the presence of aqueous ammonia. Conversely, it exhibits selective AO in water and primarily yields NO2− (FE 62.3%) rather than complete oxidation to NO3−. 15N isotope labeling, modified Griess colorimetric method, electrochemical kinetics studies, and H/D kinetic isotope effects are employed to provide initial mechanistic insights for the chemoselectivity.Chapter 4 shifts to developing heterogeneous AO catalysts. Conventional AO on heterogeneous noble metal electrodes often yields undesired N2 and leads to detrimental nitride surface poisoning. We now find that our previously reported "Blue Layer" (BL), an organometallic-inorganic hybrid anode based on [IrO2]x nanoclusters (x ~ 5), is active for selective AO in aqueous solution. Through adjustment of both pH and applied potential, we identified optimal operating conditions (pH 8.0, 1.00 V) for AO, where BL achieves optimum selectivity towards NO3− (FE 90.5%), effectively minimizing competitive WO and maintaining activity against ammonia-induced degradation of the electrode.

English

ISBN: 9798383566756Subjects--Topical Terms:

1981412
Physical chemistry.
Subjects--Index Terms:

Ammonia oxidation

Transition Metal Complexes for Electrocatalytic Ammonia Oxidation /
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502 $b Ph.D. $c Yale University $d 2024.
520 $a Our rapidly increasing population's growing need for food, fertilizer, and clean energy necessitates an exploration into the oxidation of ammonia (NH3) for its application as a carbon-free fuel and a precursor for nitrite and nitrate production Traditional ammonia oxidation (AO) techniques, such as the Ostwald process, demand considerable energy and result in greenhouse gas emissions. In contrast, electrochemical AO emerges as an energy-efficient solution. This thesis investigates the development and characterization of copper and iridium-based molecular and heterogeneous catalysts targeting selective electrochemical AO in aqueous environments.Chapter 2 focuses on [Cu(bipyalk)]+, a mononuclear copper electrocatalyst exhibiting selective ammonia oxidation to nitrite (NO2−) and nitrate (NO3−) in water. Notably, this catalyst showcases a 65% faradaic efficiency (FE) for nitrate production and a remarkable 94% FE for total AO, while displaying high selectivity against water oxidation (WO)-an unprecedented trait in previous molecular AO electrocatalysts, as [Cu(bipyalk)]+ is not competent for WO.Chapter 3 explores Cu(pyalk)2, an originally developed electrochemical WO catalyst, for its effectiveness in chemoselective AO in water. While Cu(pyalk)2 exhibits WO efficacy, its WO activity is considerably diminished in the presence of aqueous ammonia. Conversely, it exhibits selective AO in water and primarily yields NO2− (FE 62.3%) rather than complete oxidation to NO3−. 15N isotope labeling, modified Griess colorimetric method, electrochemical kinetics studies, and H/D kinetic isotope effects are employed to provide initial mechanistic insights for the chemoselectivity.Chapter 4 shifts to developing heterogeneous AO catalysts. Conventional AO on heterogeneous noble metal electrodes often yields undesired N2 and leads to detrimental nitride surface poisoning. We now find that our previously reported "Blue Layer" (BL), an organometallic-inorganic hybrid anode based on [IrO2]x nanoclusters (x ~ 5), is active for selective AO in aqueous solution. Through adjustment of both pH and applied potential, we identified optimal operating conditions (pH 8.0, 1.00 V) for AO, where BL achieves optimum selectivity towards NO3− (FE 90.5%), effectively minimizing competitive WO and maintaining activity against ammonia-induced degradation of the electrode.
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650 4 $a Physical chemistry. $3 1981412
650 4 $a Chemistry. $3 516420
650 4 $a Energy. $3 876794
650 4 $a Materials science. $3 543314
650 4 $a Thermodynamics. $3 517304
653 $a Ammonia oxidation
653 $a Electrochemistry
653 $a Green chemistry
653 $a Metal complex
653 $a Sustainable fuels
653 $a Chemoselectivity
690 $a 0485
690 $a 0794
690 $a 0791
690 $a 0348
690 $a 0494
710 2 $a Yale University. $b Chemistry. $e degree granting institution. $3 3770408
720 1 $a Brudvig, Gary W. $e degree supervisor.
720 1 $a Crabtree, Robert H. $e degree supervisor.
773 0 $t Dissertations Abstracts International $g 86-02B.
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791 $a Ph.D.
792 $a 2024
856 4 0 $u https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30992782