Unravelling charge-transfer in Pd to pyrrolic-N bond for superior electrocatalytic performance

Lipipuspa Sahoo; Sanjit Mondal; A. Gloskovskii; Arunabhiram Chutia; Ujjal K. Gautam

doi:10.1039/d0ta12618g

Unravelling charge-transfer in Pd to pyrrolic-N bond for superior electrocatalytic performance

Lipipuspa Sahoo, Sanjit Mondal, A. Gloskovskii, Arunabhiram Chutia, Ujjal K. Gautam

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

19 Scopus citations

Abstract

Fuel-cells require large quantities of Pt for oxygen reduction reaction (ORR) to subvert the activity-loss during prolonged use. Pd can complement Pt in the near future by exhibiting a similar activity and stability in alkaline fuel-cells. Herein we show that by depositing Pd atom-by-atom on an N-doped reduced graphene oxide (NRGO), it is possible to create a strong bond between Pd and pyrrolic-fraction of the N-moieties. This bond further strengthens in the presence of an oxygen containing functional-group accompanied by a profound charge-transfer from the Pd 3d-orbitals to the 2p-orbitals of C, N and O, thereby lowering the Pd-3d binding-energy and the resulting Pd/NRGO exhibits a very high ORR activity (E_1/2= 0.93 Vvs.RHE) and stability (ΔE_1/2= 0.013 V after 15 000 cycles). Usually pyridinic-N is considered for imparting high-performance while N-doping creates nearly as many pyrrolic-N in graphene-substrates, the role of which is evidenced in this study.

Original language	English
Pages (from-to)	10966-10978
Number of pages	13
Journal	Journal of Materials Chemistry A
Volume	9
Issue number	17
DOIs	https://doi.org/10.1039/d0ta12618g
State	Published - 7 May 2021
Externally published	Yes

ASJC Scopus subject areas

General Chemistry
Renewable Energy, Sustainability and the Environment
General Materials Science

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

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10.1039/d0ta12618g

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title = "Unravelling charge-transfer in Pd to pyrrolic-N bond for superior electrocatalytic performance",

abstract = "Fuel-cells require large quantities of Pt for oxygen reduction reaction (ORR) to subvert the activity-loss during prolonged use. Pd can complement Pt in the near future by exhibiting a similar activity and stability in alkaline fuel-cells. Herein we show that by depositing Pd atom-by-atom on an N-doped reduced graphene oxide (NRGO), it is possible to create a strong bond between Pd and pyrrolic-fraction of the N-moieties. This bond further strengthens in the presence of an oxygen containing functional-group accompanied by a profound charge-transfer from the Pd 3d-orbitals to the 2p-orbitals of C, N and O, thereby lowering the Pd-3d binding-energy and the resulting Pd/NRGO exhibits a very high ORR activity (E1/2= 0.93 Vvs.RHE) and stability (ΔE1/2= 0.013 V after 15 000 cycles). Usually pyridinic-N is considered for imparting high-performance while N-doping creates nearly as many pyrrolic-N in graphene-substrates, the role of which is evidenced in this study.",

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T1 - Unravelling charge-transfer in Pd to pyrrolic-N bond for superior electrocatalytic performance

AU - Sahoo, Lipipuspa

AU - Mondal, Sanjit

AU - Gloskovskii, A.

AU - Chutia, Arunabhiram

AU - Gautam, Ujjal K.

PY - 2021/5/7

Y1 - 2021/5/7

N2 - Fuel-cells require large quantities of Pt for oxygen reduction reaction (ORR) to subvert the activity-loss during prolonged use. Pd can complement Pt in the near future by exhibiting a similar activity and stability in alkaline fuel-cells. Herein we show that by depositing Pd atom-by-atom on an N-doped reduced graphene oxide (NRGO), it is possible to create a strong bond between Pd and pyrrolic-fraction of the N-moieties. This bond further strengthens in the presence of an oxygen containing functional-group accompanied by a profound charge-transfer from the Pd 3d-orbitals to the 2p-orbitals of C, N and O, thereby lowering the Pd-3d binding-energy and the resulting Pd/NRGO exhibits a very high ORR activity (E1/2= 0.93 Vvs.RHE) and stability (ΔE1/2= 0.013 V after 15 000 cycles). Usually pyridinic-N is considered for imparting high-performance while N-doping creates nearly as many pyrrolic-N in graphene-substrates, the role of which is evidenced in this study.

AB - Fuel-cells require large quantities of Pt for oxygen reduction reaction (ORR) to subvert the activity-loss during prolonged use. Pd can complement Pt in the near future by exhibiting a similar activity and stability in alkaline fuel-cells. Herein we show that by depositing Pd atom-by-atom on an N-doped reduced graphene oxide (NRGO), it is possible to create a strong bond between Pd and pyrrolic-fraction of the N-moieties. This bond further strengthens in the presence of an oxygen containing functional-group accompanied by a profound charge-transfer from the Pd 3d-orbitals to the 2p-orbitals of C, N and O, thereby lowering the Pd-3d binding-energy and the resulting Pd/NRGO exhibits a very high ORR activity (E1/2= 0.93 Vvs.RHE) and stability (ΔE1/2= 0.013 V after 15 000 cycles). Usually pyridinic-N is considered for imparting high-performance while N-doping creates nearly as many pyrrolic-N in graphene-substrates, the role of which is evidenced in this study.

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Unravelling charge-transfer in Pd to pyrrolic-N bond for superior electrocatalytic performance

Abstract

ASJC Scopus subject areas

UN SDGs

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