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Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

ABSTRACT: Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN4C12, CoN3C10,porp and CoN2C5. The O2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0?V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O2-adsorption strength, we conclude that cobalt-based moieties bind O2 too weakly for efficient O2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.

SUBMITTER: Zitolo A

PROVIDER: S-EPMC5715157 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

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Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

Zitolo Andrea A Ranjbar-Sahraie Nastaran N Mineva Tzonka T Li Jingkun J Jia Qingying Q Stamatin Serban S Harrington George F GF Lyth Stephen Mathew SM Krtil Petr P Mukerjee Sanjeev S Fonda Emiliano E Jaouen Frédéric F

Nature communications 20171016 1

Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and elect ...[more]

PMID: 29038426

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Project description:In order to reduce fuel cell material cost and promote its application, it is urgent to develop non-noble metal materials to replace platinum as the cathode catalysts in fuel cells. The cobalt sulfide and nitrogen co-doped carbon (S-Co-N/C) materials with metal-organic frameworks as precursors have shown good oxygen reduction reaction (ORR) catalytic activity. Benefiting from the protection of catalytic active sites by sulfur atoms, the stability and alcohol-tolerance of the S-Co-N/C catalyst can be significantly improved. In order to fully understand the effect of the sulfurization process on the properties of the material, zeolite imidazole frameworks (ZIF)-8, and ZIF-67 are used as precursors to prepare a novel material of S-Co-N/C by using a sulfurization-pyrolysis method. Another S-Co-N/C material by using a pyrolysis- sulfurization method is prepared for comparison. The effects of the sulfurization process in the preparation on the morphology, chemical structure, specific surface area, and ORR catalytic activity of the final material are investigated. The experimental results show that the surface of the S-Co-N/C material tends to be rough due to the sulfurization reaction of the metal elements. The porosity of the material is reduced to some extent due to the remaining Zn elements in the final product. Interestingly, some carbon nanotubes are found to be generated on the surface of the S-Co-N/C material because of the synergistic effect of Zn and Co on the carbon material during the pyrolysis process, which is beneficial to accelerate the adsorption of oxygen on the S-Co-N/C surface and the electron transportation during the oxygen reduction reaction. In addition, the generated CoS during the sulfurization process can further protect the Co elements from agglomeration, which can effectively increase the ORR catalytic active sites in the final material. The S-Co-N/C material prepared by the sulfurization-pyrolysis method performs a superior ORR catalytic activity to the one synthesized by the pyrolysis-sulfurization method.

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Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

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Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

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