New Insights into Electrocatalysis of Nitrogen Reduction ... · NH3 s-1cm-2) Rate of of NH 3 )mol...
Transcript of New Insights into Electrocatalysis of Nitrogen Reduction ... · NH3 s-1cm-2) Rate of of NH 3 )mol...
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New Insights into Electrocatalysis of Nitrogen Reduction to Ammonia
Alex Schechter
Department of Chemical Sciences Ariel University, Israel ([email protected])
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Experimental Setup
Collected Ammonia in the Acid Trap and the Electrolyte
The electrochemical cell
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Quantification of Ammonia using Indophenol and Nessler’s method
Indophenol method Nessler’s method
Ammonia Sodiumhypochlorite
Salicylicacid
Indophenolmethod
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Voltammetry of N2 Reduction on PGM catalysts in alkaline pH
VulcanXC-72
Ru/C
Pt/C
RuPt/C
PGM-PlatinumgroupmetalRT,ambientpressure,1MKOH
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Applied Potential
)E / V vs. RHE(
Rate of ammonia
)mol s-1cm-2(
Efficiency of ammonia produced
(%)
0.123 3.0×10-10 13.20.023 6.12×10-10 4-0.077 6.37×10-10 1.15-0.177 5.95×10-10 0.75-0.277 5.45×10-10 0.35
The Effect of Applied Potential and Temperature
Electrochemical ammonia synthesis at RuPt/C at 50 °C
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NRR Catalysts Comparison Catalyst Rate of of NH3
(gNH3 s-1cm-2)Rate of of
NH3
)mol s-1cm-2(
Applied Potential (RHE)
Faradaic Efficiency (%)
Reference
Pt-electrode 1.9× 10−8 1.1× 10−9 1.6 V (Fuel cell configuration)
0.1 Sci. Rep. 3 (2013) 1145
Ru-electrode 3.57 × 10−10 2.1 × 10−11 -1.02 V (Vs. Ag/AgCl)
0.9 Chem. Commun. (2000) 1673–1674.
Fe2O3-CNT 6.11×10-10 3.57× 10−11 -2.0 (Vs. Ag/AgCl) 4.5 Angew.Chem. Int.Ed. 2017, 56,2699 –2703
Au nanorods 4.57×10-10 2.6 × 10−11 -0.2 V 4 Adv. Mater. 29 (2016) 1700001
Au nanoparticles on CeOx-RGO support
2.3×10-9 1.3 × 10−10 -0.2 V
10.1 Adv. Mater. 29 (2017) 1700001
Au subnano- clusters on TiO2
5.9×10-9 3.4 × 10−10 -0.2 V
8.1 Angew. Chemie - Int. Ed. 40 (2001) 1061–1063.
RuPt/C 7.25×10-9 4.2× 10−10 -0.077 V
3.0 Present work
RuPt/C 1.08×10−8 (50° C) 6.3×10-10 -0.077 V 3.8 Present work
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Mechanism of Electrochemical Nitrogen Reduction Reaction Nitrogen reduction reaction via a) dissociative and b) associative mechanism.
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On-Line Mass Spectrometry Analysis During N2 Electrolysis
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After CO adsorption; there was no ammonia formation
Ammonia Formation under CO Adsorption on RuPt/C
N2 Electrolysis -0.1 V
Cycle1
CyclicVoltammetry
Cycle2
LinearSweepVoltammetry
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Ammonia Formation under CO Adsorption on Pt/C and Ru/C LS-Voltammogram Ru/C N2 Electrolysis Ru/C at -0.1 V
LS-Voltammogram Pt/C N2 Electrolysis Pt/C at -0.1 V
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Proposed Cooperative Reaction Mechanism
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Acknowledgments
Sponsors
• Ministry of commerce (KAMIN prog.)
• ISF- P.M. Ministry via INREP program
• Ministry of Energy and Water
• Ministry of Defense
• Ministry of Environmental Protection
GroupMembersPostdocs• Dr.HananTeller• Dr.OlgaKrichevsky• Dr.SubramanianPalaniappan• Dr.RameshSingh• Dr.ManJunathaR.• Dr.AleksKarajichPhDStudents• Mrs.OritBen-Zazon• SrikanthKolagatla• HenFriman• RoopathyMohan• DiwakarKashyap• AntonyCyrilMscStudents• Mrs.MietalGor• Mrs.YuliaYufa• Mr.VictorMoltenan• Miss.ShaniOchanuna• Mr.YuvalMoshe• Mr.AsafCohen• Mrs.EfratTzor• Mr.ShnmuelRozenfeld• Mr.EtiPitossi• Mr.LeaOaknin• Mr.RazMasas• Mr.YakirNagar• Mr.MikeSasoon-Engineer
Collaborations • Dr. Daniel Nessim-BIU • Prof.-Yoed Tzur-Technion • Dr. David Zitoun-BIU • Dr. Amir Nathan-TAU • Dr. Rivka Cahan-AUC • Prof. Zeev Gross –Technion • Prof. Idit Avrahami-AUC • Prof. Steve Dubowsky -MIT • Prof. Edward Bormashenko –AUC • Prof. Haya Korenwitz-AUC • Prof. Aharon Gedanken-BIU • Dr. Flavio Grynszpan-AUC
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