Activity-Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal-Nitrogen-Carbon Catalysts

Yanyan Sun; Luca Silvioli; Nastaran Ranjbar Sahraie; Wen Ju; Jingkun Li; Andrea Zitolo; Shuang Li; Alexander Bagger; Logi Arnarson; Xingli Wang; Tim Moeller; Denis Bernsmeier; Jan Rossmeisl; Frederic Jaouen; Peter Strasser

doi:10.1021/jacs.9b05576

Activity-Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal-Nitrogen-Carbon Catalysts

Yanyan Sun, Luca Silvioli, Nastaran Ranjbar Sahraie, Wen Ju, Jingkun Li, Andrea Zitolo, Shuang Li, Alexander Bagger, Logi Arnarson, Xingli Wang, Tim Moeller, Denis Bernsmeier, Jan Rossmeisl, Frederic Jaouen, Peter Strasser

Department of Chemistry

91 Citations (Scopus)

Abstract

Nitrogen-doped carbon materials featuring atomically dispersed metal cations (M-N-C) are an emerging family of materials with potential applications for electrocatalysis. The electrocatalytic activity of M-N-C materials toward four-electron oxygen reduction reaction (ORR) to H₂O is a mainstream line of research for replacing platinum-group-metal-based catalysts at the cathode of fuel cells. However, fundamental and practical aspects of their electrocatalytic activity toward two-electron ORR to H₂O₂, a future green "dream" process for chemical industry, remain poorly understood. Here we combined computational and experimental efforts to uncover the trends in electrochemical H₂O₂ production over a series of M-N-C materials (M = Mn, Fe, Co, Ni, and Cu) exclusively comprising atomically dispersed M-N_x sites from molecular first-principles to bench-scale electrolyzers operating at industrial current density. We investigated the effect of the nature of a 3d metal within a series of M-N-C catalysts on the electrocatalytic activity/selectivity for ORR (H₂O₂ and H₂O products) and H₂O₂ reduction reaction (H₂O₂RR). Co-N-C catalyst was uncovered with outstanding H₂O₂ productivity considering its high ORR activity, highest H₂O₂ selectivity, and lowest H₂O₂RR activity. The activity-selectivity trend over M-N-C materials was further analyzed by density functional theory, providing molecular-scale understandings of experimental volcano trends for four- and two-electron ORR. The predicted binding energy of HO∗ intermediate over Co-N-C catalyst is located near the top of the volcano accounting for favorable two-electron ORR. The industrial H₂O₂ productivity over Co-N-C catalyst was demonstrated in a microflow cell, exhibiting an unprecedented production rate of more than 4 mol peroxide g_catalyst ^-1 h^-1 at a current density of 50 mA cm^-2.

Original language	English
Journal	Journal of the American Chemical Society
Volume	141
Issue number	31
Pages (from-to)	12372-12381
ISSN	0002-7863
DOIs	https://doi.org/10.1021/jacs.9b05576
Publication status	Published - 7 Aug 2019

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Sun, Y., Silvioli, L., Sahraie, N. R., Ju, W., Li, J., Zitolo, A., Li, S., Bagger, A., Arnarson, L., Wang, X., Moeller, T., Bernsmeier, D., Rossmeisl, J., Jaouen, F., & Strasser, P. (2019). Activity-Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal-Nitrogen-Carbon Catalysts. Journal of the American Chemical Society, 141(31), 12372-12381. https://doi.org/10.1021/jacs.9b05576

Activity-Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal-Nitrogen-Carbon Catalysts. / Sun, Yanyan; Silvioli, Luca; Sahraie, Nastaran Ranjbar et al.
In: Journal of the American Chemical Society, Vol. 141, No. 31, 07.08.2019, p. 12372-12381.

Research output: Contribution to journal › Journal article › Research › peer-review

Sun, Y, Silvioli, L, Sahraie, NR, Ju, W, Li, J, Zitolo, A, Li, S, Bagger, A, Arnarson, L, Wang, X, Moeller, T, Bernsmeier, D, Rossmeisl, J, Jaouen, F & Strasser, P 2019, 'Activity-Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal-Nitrogen-Carbon Catalysts', Journal of the American Chemical Society, vol. 141, no. 31, pp. 12372-12381. https://doi.org/10.1021/jacs.9b05576

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title = "Activity-Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal-Nitrogen-Carbon Catalysts",

abstract = "Nitrogen-doped carbon materials featuring atomically dispersed metal cations (M-N-C) are an emerging family of materials with potential applications for electrocatalysis. The electrocatalytic activity of M-N-C materials toward four-electron oxygen reduction reaction (ORR) to H2O is a mainstream line of research for replacing platinum-group-metal-based catalysts at the cathode of fuel cells. However, fundamental and practical aspects of their electrocatalytic activity toward two-electron ORR to H2O2, a future green {"}dream{"} process for chemical industry, remain poorly understood. Here we combined computational and experimental efforts to uncover the trends in electrochemical H2O2 production over a series of M-N-C materials (M = Mn, Fe, Co, Ni, and Cu) exclusively comprising atomically dispersed M-Nx sites from molecular first-principles to bench-scale electrolyzers operating at industrial current density. We investigated the effect of the nature of a 3d metal within a series of M-N-C catalysts on the electrocatalytic activity/selectivity for ORR (H2O2 and H2O products) and H2O2 reduction reaction (H2O2RR). Co-N-C catalyst was uncovered with outstanding H2O2 productivity considering its high ORR activity, highest H2O2 selectivity, and lowest H2O2RR activity. The activity-selectivity trend over M-N-C materials was further analyzed by density functional theory, providing molecular-scale understandings of experimental volcano trends for four- and two-electron ORR. The predicted binding energy of HO∗ intermediate over Co-N-C catalyst is located near the top of the volcano accounting for favorable two-electron ORR. The industrial H2O2 productivity over Co-N-C catalyst was demonstrated in a microflow cell, exhibiting an unprecedented production rate of more than 4 mol peroxide gcatalyst -1 h-1 at a current density of 50 mA cm-2.",

author = "Yanyan Sun and Luca Silvioli and Sahraie, {Nastaran Ranjbar} and Wen Ju and Jingkun Li and Andrea Zitolo and Shuang Li and Alexander Bagger and Logi Arnarson and Xingli Wang and Tim Moeller and Denis Bernsmeier and Jan Rossmeisl and Frederic Jaouen and Peter Strasser",

year = "2019",

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day = "7",

doi = "10.1021/jacs.9b05576",

language = "English",

volume = "141",

pages = "12372--12381",

journal = "Journal of the American Chemical Society",

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T1 - Activity-Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal-Nitrogen-Carbon Catalysts

AU - Sun, Yanyan

AU - Silvioli, Luca

AU - Sahraie, Nastaran Ranjbar

AU - Ju, Wen

AU - Li, Jingkun

AU - Zitolo, Andrea

AU - Li, Shuang

AU - Bagger, Alexander

AU - Arnarson, Logi

AU - Wang, Xingli

AU - Moeller, Tim

AU - Bernsmeier, Denis

AU - Rossmeisl, Jan

AU - Jaouen, Frederic

AU - Strasser, Peter

PY - 2019/8/7

Y1 - 2019/8/7

N2 - Nitrogen-doped carbon materials featuring atomically dispersed metal cations (M-N-C) are an emerging family of materials with potential applications for electrocatalysis. The electrocatalytic activity of M-N-C materials toward four-electron oxygen reduction reaction (ORR) to H2O is a mainstream line of research for replacing platinum-group-metal-based catalysts at the cathode of fuel cells. However, fundamental and practical aspects of their electrocatalytic activity toward two-electron ORR to H2O2, a future green "dream" process for chemical industry, remain poorly understood. Here we combined computational and experimental efforts to uncover the trends in electrochemical H2O2 production over a series of M-N-C materials (M = Mn, Fe, Co, Ni, and Cu) exclusively comprising atomically dispersed M-Nx sites from molecular first-principles to bench-scale electrolyzers operating at industrial current density. We investigated the effect of the nature of a 3d metal within a series of M-N-C catalysts on the electrocatalytic activity/selectivity for ORR (H2O2 and H2O products) and H2O2 reduction reaction (H2O2RR). Co-N-C catalyst was uncovered with outstanding H2O2 productivity considering its high ORR activity, highest H2O2 selectivity, and lowest H2O2RR activity. The activity-selectivity trend over M-N-C materials was further analyzed by density functional theory, providing molecular-scale understandings of experimental volcano trends for four- and two-electron ORR. The predicted binding energy of HO∗ intermediate over Co-N-C catalyst is located near the top of the volcano accounting for favorable two-electron ORR. The industrial H2O2 productivity over Co-N-C catalyst was demonstrated in a microflow cell, exhibiting an unprecedented production rate of more than 4 mol peroxide gcatalyst -1 h-1 at a current density of 50 mA cm-2.

AB - Nitrogen-doped carbon materials featuring atomically dispersed metal cations (M-N-C) are an emerging family of materials with potential applications for electrocatalysis. The electrocatalytic activity of M-N-C materials toward four-electron oxygen reduction reaction (ORR) to H2O is a mainstream line of research for replacing platinum-group-metal-based catalysts at the cathode of fuel cells. However, fundamental and practical aspects of their electrocatalytic activity toward two-electron ORR to H2O2, a future green "dream" process for chemical industry, remain poorly understood. Here we combined computational and experimental efforts to uncover the trends in electrochemical H2O2 production over a series of M-N-C materials (M = Mn, Fe, Co, Ni, and Cu) exclusively comprising atomically dispersed M-Nx sites from molecular first-principles to bench-scale electrolyzers operating at industrial current density. We investigated the effect of the nature of a 3d metal within a series of M-N-C catalysts on the electrocatalytic activity/selectivity for ORR (H2O2 and H2O products) and H2O2 reduction reaction (H2O2RR). Co-N-C catalyst was uncovered with outstanding H2O2 productivity considering its high ORR activity, highest H2O2 selectivity, and lowest H2O2RR activity. The activity-selectivity trend over M-N-C materials was further analyzed by density functional theory, providing molecular-scale understandings of experimental volcano trends for four- and two-electron ORR. The predicted binding energy of HO∗ intermediate over Co-N-C catalyst is located near the top of the volcano accounting for favorable two-electron ORR. The industrial H2O2 productivity over Co-N-C catalyst was demonstrated in a microflow cell, exhibiting an unprecedented production rate of more than 4 mol peroxide gcatalyst -1 h-1 at a current density of 50 mA cm-2.

U2 - 10.1021/jacs.9b05576

DO - 10.1021/jacs.9b05576

M3 - Journal article

C2 - 31306016

SN - 0002-7863

VL - 141

SP - 12372

EP - 12381

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 31

ER -

Activity-Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal-Nitrogen-Carbon Catalysts

Abstract

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