Lignin-derived bimetallic platinum group metal-free oxygen reduction reaction electrocatalysts for acid and alkaline fuel cells

Mohsin Muhyuddin; Ariel Friedman; Federico Poli; Elisabetta Petri; Hilah Honig; Francesco Basile; Andrea Fasolini; Roberto Lorenzi; Enrico Berretti; Marco Bellini; Alessandro Lavacchi; Lior Elbaz; Carlo Santoro; Francesca Soavi

doi:10.1016/j.jpowsour.2022.232416

Lignin-derived bimetallic platinum group metal-free oxygen reduction reaction electrocatalysts for acid and alkaline fuel cells

Mohsin Muhyuddin
, Ariel Friedman
, Federico Poli
, Elisabetta Petri
, Hilah Honig
, Francesco Basile
, Andrea Fasolini
, Roberto Lorenzi
, Enrico Berretti
, Marco Bellini
, Alessandro Lavacchi
, Lior Elbaz
, Carlo Santoro
, Francesca Soavi

Department of Chemistry

University of Milan - Bicocca
University of Bologna
National Research Council of Italy

Research output: Contribution to journal › Article › peer-review

50 Scopus citations

Abstract

Metal-nitrogen-carbons (M-N-Cs) as a reliable substitution for platinum-group-metals (PGMs) for oxygen reduction reaction (ORR) are emerging candidates to rationalize the technology of fuel cells. The development of M-N-Cs can further be economized by consuming waste biomass as an inexpensive carbon source for the electrocatalyst support. Herein, we report the simple fabrication and in-depth characterization of electrocatalysts using lignin-derived activated char. The activated char (LAC) was functionalized with metal phthalocyanine (FePc and MnPc) via atmosphere-controlled pyrolysis to produce monometallic M-N-Cs (L_Mn and L_Fe) and bimetallic M1-M2-N-Cs (L_FeMn) electrocatalysts. Raman spectroscopy and transmission electron microscopy (TEM) revealed a defect-rich architecture. XPS confirmed the coexistence of various nitrogen-containing active moieties. L_Fe and L_FeMn demonstrated appreciable ORR in both acidic and alkaline conditions whereas L_FeMn helped in restricting the peroxide yield, particularly in alkaline media. L_Fe and L_FeMn demonstrated remarkable onset potential (E_onset) of ∼0.942 V (vs RHE) with an E_1/2 of 0.874 V (vs RHE) in 0.1 M KOH. In acid, L_FeMn had an E_onset of 0.817 V (vs RHE) and an E_1/2 of ∼0.76 V (vs RHE). Finally, the L_FeMn as a cathode electrocatalyst was integrated and tested in PEMFC and AEMFC. AEMFC demonstrated optimistic performance with a peak power density of 261 mW cm⁻² at the current density of ∼577 mA cm⁻².

Original language	English
Article number	232416
Journal	Journal of Power Sources
Volume	556
DOIs	https://doi.org/10.1016/j.jpowsour.2022.232416
State	Published - 1 Feb 2023

Bibliographical note

Publisher Copyright:
© 2022 Elsevier B.V.

Funding

C.S. would like to thank the support from the Italian Ministry of University and Research (Ministero dell'Università e della Ricerca – MUR) through the “Rita Levi Montalcini 2018” fellowship (Grant number PGR18MAZLI). The authors also thank the Italian ministry MIUR for funding through the FISR 2019 project AMPERE (FISR2019_01294). University of Bologna authors acknowledge MUR and UE support under the project “ECOSYSTEM FOR SUSTAINABLE TRANSITION IN EMILIA-ROMAGNA” of the National Recovery and Resilience Plan (NRRP-PNRR). C.S. would like to thank the support from the Italian Ministry of University and Research (Ministero dell’Università e della Ricerca – MUR) through the “Rita Levi Montalcini 2018” fellowship (Grant number PGR18MAZLI ). The authors also thank the Italian ministry MIUR for funding through the FISR 2019 project AMPERE ( FISR2019_01294 ). University of Bologna authors acknowledge MUR and UE support under the project “ECOSYSTEM FOR SUSTAINABLE TRANSITION IN EMILIA-ROMAGNA” of the National Recovery and Resilience Plan (NRRP-PNRR).

Funders	Funder number
Italian ministry MIUR	FISR2019_01294
NRRP-PNRR
National Recovery and Resilience Plan
Ministero dell’Istruzione, dell’Università e della Ricerca	PGR18MAZLI
Università di Bologna

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

Anion exchange membrane fuel cell
Lignin-derived char
Oxygen reduction reaction
Platinum group metal-free
Proton exchange membrane fuel cell

Access to Document

10.1016/j.jpowsour.2022.232416

Cite this

Muhyuddin, M., Friedman, A., Poli, F., Petri, E., Honig, H., Basile, F., Fasolini, A., Lorenzi, R., Berretti, E., Bellini, M., Lavacchi, A., Elbaz, L., Santoro, C., & Soavi, F. (2023). Lignin-derived bimetallic platinum group metal-free oxygen reduction reaction electrocatalysts for acid and alkaline fuel cells. Journal of Power Sources, 556, Article 232416. https://doi.org/10.1016/j.jpowsour.2022.232416

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title = "Lignin-derived bimetallic platinum group metal-free oxygen reduction reaction electrocatalysts for acid and alkaline fuel cells",

abstract = "Metal-nitrogen-carbons (M-N-Cs) as a reliable substitution for platinum-group-metals (PGMs) for oxygen reduction reaction (ORR) are emerging candidates to rationalize the technology of fuel cells. The development of M-N-Cs can further be economized by consuming waste biomass as an inexpensive carbon source for the electrocatalyst support. Herein, we report the simple fabrication and in-depth characterization of electrocatalysts using lignin-derived activated char. The activated char (LAC) was functionalized with metal phthalocyanine (FePc and MnPc) via atmosphere-controlled pyrolysis to produce monometallic M-N-Cs (L\_Mn and L\_Fe) and bimetallic M1-M2-N-Cs (L\_FeMn) electrocatalysts. Raman spectroscopy and transmission electron microscopy (TEM) revealed a defect-rich architecture. XPS confirmed the coexistence of various nitrogen-containing active moieties. L\_Fe and L\_FeMn demonstrated appreciable ORR in both acidic and alkaline conditions whereas L\_FeMn helped in restricting the peroxide yield, particularly in alkaline media. L\_Fe and L\_FeMn demonstrated remarkable onset potential (Eonset) of ∼0.942 V (vs RHE) with an E1/2 of 0.874 V (vs RHE) in 0.1 M KOH. In acid, L\_FeMn had an Eonset of 0.817 V (vs RHE) and an E1/2 of ∼0.76 V (vs RHE). Finally, the L\_FeMn as a cathode electrocatalyst was integrated and tested in PEMFC and AEMFC. AEMFC demonstrated optimistic performance with a peak power density of 261 mW cm−2 at the current density of ∼577 mA cm−2.",

keywords = "Anion exchange membrane fuel cell, Lignin-derived char, Oxygen reduction reaction, Platinum group metal-free, Proton exchange membrane fuel cell",

author = "Mohsin Muhyuddin and Ariel Friedman and Federico Poli and Elisabetta Petri and Hilah Honig and Francesco Basile and Andrea Fasolini and Roberto Lorenzi and Enrico Berretti and Marco Bellini and Alessandro Lavacchi and Lior Elbaz and Carlo Santoro and Francesca Soavi",

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Muhyuddin, M, Friedman, A, Poli, F, Petri, E, Honig, H, Basile, F, Fasolini, A, Lorenzi, R, Berretti, E, Bellini, M, Lavacchi, A, Elbaz, L, Santoro, C & Soavi, F 2023, 'Lignin-derived bimetallic platinum group metal-free oxygen reduction reaction electrocatalysts for acid and alkaline fuel cells', Journal of Power Sources, vol. 556, 232416. https://doi.org/10.1016/j.jpowsour.2022.232416

TY - JOUR

T1 - Lignin-derived bimetallic platinum group metal-free oxygen reduction reaction electrocatalysts for acid and alkaline fuel cells

AU - Muhyuddin, Mohsin

AU - Friedman, Ariel

AU - Poli, Federico

AU - Petri, Elisabetta

AU - Honig, Hilah

AU - Basile, Francesco

AU - Fasolini, Andrea

AU - Lorenzi, Roberto

AU - Berretti, Enrico

AU - Bellini, Marco

AU - Lavacchi, Alessandro

AU - Elbaz, Lior

AU - Santoro, Carlo

AU - Soavi, Francesca

PY - 2023/2/1

Y1 - 2023/2/1

N2 - Metal-nitrogen-carbons (M-N-Cs) as a reliable substitution for platinum-group-metals (PGMs) for oxygen reduction reaction (ORR) are emerging candidates to rationalize the technology of fuel cells. The development of M-N-Cs can further be economized by consuming waste biomass as an inexpensive carbon source for the electrocatalyst support. Herein, we report the simple fabrication and in-depth characterization of electrocatalysts using lignin-derived activated char. The activated char (LAC) was functionalized with metal phthalocyanine (FePc and MnPc) via atmosphere-controlled pyrolysis to produce monometallic M-N-Cs (L_Mn and L_Fe) and bimetallic M1-M2-N-Cs (L_FeMn) electrocatalysts. Raman spectroscopy and transmission electron microscopy (TEM) revealed a defect-rich architecture. XPS confirmed the coexistence of various nitrogen-containing active moieties. L_Fe and L_FeMn demonstrated appreciable ORR in both acidic and alkaline conditions whereas L_FeMn helped in restricting the peroxide yield, particularly in alkaline media. L_Fe and L_FeMn demonstrated remarkable onset potential (Eonset) of ∼0.942 V (vs RHE) with an E1/2 of 0.874 V (vs RHE) in 0.1 M KOH. In acid, L_FeMn had an Eonset of 0.817 V (vs RHE) and an E1/2 of ∼0.76 V (vs RHE). Finally, the L_FeMn as a cathode electrocatalyst was integrated and tested in PEMFC and AEMFC. AEMFC demonstrated optimistic performance with a peak power density of 261 mW cm−2 at the current density of ∼577 mA cm−2.

AB - Metal-nitrogen-carbons (M-N-Cs) as a reliable substitution for platinum-group-metals (PGMs) for oxygen reduction reaction (ORR) are emerging candidates to rationalize the technology of fuel cells. The development of M-N-Cs can further be economized by consuming waste biomass as an inexpensive carbon source for the electrocatalyst support. Herein, we report the simple fabrication and in-depth characterization of electrocatalysts using lignin-derived activated char. The activated char (LAC) was functionalized with metal phthalocyanine (FePc and MnPc) via atmosphere-controlled pyrolysis to produce monometallic M-N-Cs (L_Mn and L_Fe) and bimetallic M1-M2-N-Cs (L_FeMn) electrocatalysts. Raman spectroscopy and transmission electron microscopy (TEM) revealed a defect-rich architecture. XPS confirmed the coexistence of various nitrogen-containing active moieties. L_Fe and L_FeMn demonstrated appreciable ORR in both acidic and alkaline conditions whereas L_FeMn helped in restricting the peroxide yield, particularly in alkaline media. L_Fe and L_FeMn demonstrated remarkable onset potential (Eonset) of ∼0.942 V (vs RHE) with an E1/2 of 0.874 V (vs RHE) in 0.1 M KOH. In acid, L_FeMn had an Eonset of 0.817 V (vs RHE) and an E1/2 of ∼0.76 V (vs RHE). Finally, the L_FeMn as a cathode electrocatalyst was integrated and tested in PEMFC and AEMFC. AEMFC demonstrated optimistic performance with a peak power density of 261 mW cm−2 at the current density of ∼577 mA cm−2.

KW - Anion exchange membrane fuel cell

KW - Lignin-derived char

KW - Oxygen reduction reaction

KW - Platinum group metal-free

KW - Proton exchange membrane fuel cell

UR - https://www.scopus.com/pages/publications/85142757508

U2 - 10.1016/j.jpowsour.2022.232416

DO - 10.1016/j.jpowsour.2022.232416

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AN - SCOPUS:85142757508

SN - 0378-7753

VL - 556

JO - Journal of Power Sources

JF - Journal of Power Sources

M1 - 232416

ER -

Lignin-derived bimetallic platinum group metal-free oxygen reduction reaction electrocatalysts for acid and alkaline fuel cells

Abstract

Bibliographical note

Funding

UN SDGs

Keywords

Access to Document

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