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Water oxidation electrocatalysis using ruthenium coordination oligomers adsorbed on multiwalled carbon nanotubes

Nature Chemistry volume 12, pages 1060–1066 (2020)Cite this article

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Abstract

Photoelectrochemical cells that utilize water as a source of electrons are one of the most attractive solutions for the replacement of fossil fuels by clean and sustainable solar fuels. To achieve this, heterogeneous water oxidation catalysis needs to be mastered and properly understood. The search continues for a catalyst that is stable at the surface of electro(photo)anodes and can efficiently perform this reaction at the desired neutral pH. Here, we show how oligomeric Ru complexes can be anchored on the surfaces of graphitic materials through CH–π interactions between the auxiliary ligands bonded to Ru and the hexagonal rings of the graphitic surfaces, providing control of their molecular coverage. These hybrid molecular materials behave as molecular electroanodes that catalyse water oxidation to dioxygen at pH 7 with high current densities. This strategy for the anchoring of molecular catalysts on graphitic surfaces can potentially be extended to other transition metals and other catalytic reactions.

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Fig. 1: NMR characterization of the coordination oligomers.
Fig. 2: STM of 15 on HOPG.
Fig. 3: Oligomer–surface interaction by 2D GIWAXS.
Fig. 4: Theoretical analysis based on DFT/MM.
Fig. 5: XAS at the surface of the electrodes.
Fig. 6: Water oxidation electrocatalytic performance of 15@CNT@GC.

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Data availability

All data generated during this study, experimental details together with additional, analytic, spectroscopic, electrochemical, X-ray scattering, microscopy and DFT data are included in this article or in the Supplementary Information. Data for Figs. 1–6 are available as source data with this paper. Data for Supplementary Figs. are available from the corresponding author on reasonable request.

The crystal data parameters of 1 and 2 and all information related to the structures can be found in the deposited CIF/Checkcif-files. CCDC 1945004 (1) and 1945005 (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.

A data set collection of computational results is available as source data with this paper and can be accessed at ioChem-BD repository via https://doi.org/10.19061/iochem-bd-1-180. Source data are provided with this paper.

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Acknowledgements

Md.A.H. acknowledge funding from AGAUR with grant nos 2016FI_B 01011 and 2014 SGR-915. F.M. and A.d.A. acknowledge funding from MINECO (CTQ2017-87792-R). A.d.A. thanks MINECO for a FPI fellowship (BES-2015-073012). J.L. thanks the Alexander von Humboldt Foundation for financial support. D.M. acknowledges support by the Severo Ochoa Excellence programme (SEV-2016-0686) from the Instituto IMDEA Nanociencia, the Acciones de Dinamización “Europa Investigacion” grant (EIN2019-103399) and the Spanish Ministerio de Ciencia, Innovación y Universidades grant (PID2019-111086RA-I00). X.S. acknowledges funding from MINECO/FEDER (PID2019-104171RB-I00). A.L. acknowledges support from the Ministerio de Ciencia e Innovación, FEDER and AGAUR through grants: PID2019-111617RB-I00 and 2017-SGR-1631. XAS experiments were performed at the CLAESS beamline at the ALBA Synchrotron under proposal No. 2016091818 and 2017092493 with the collaboration of ALBA staff and additionally used resources of the sector 20 beamline at the APS at Argonne National Laboratory. Sector 20 beamline at APS is operated by the US DOE (Contract No. DE-AC02-06CH11357) and the Canadian Light Source. Synchrotron X-ray scattering experiments were performed at NCD-SWEET beamline at the ALBA synchrotron with the collaboration of ALBA staff (Proposal 2020014050).

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  1. These authors contributed equally: Md Asmaul Hoque, Marcos Gil-Sepulcre.

Authors and Affiliations

  1. Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona, Spain

    Md Asmaul Hoque, Marcos Gil-Sepulcre, Adiran de Aguirre, Roc Matheu, Yuanyuan Shi, Jordi Benet-Buchholz, Feliu Maseras, Carolina Gimbert-Suriñach & Antoni Llobet

  2. Institute for Molecules and Materials, Radboud University, Nijmegen, The Netherlands

    Johannes A. A. W. Elemans

  3. Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia), Madrid, Spain

    Dooshaye Moonshiram

  4. Institute of Functional Nano & Soft Materials (FUNSOM), Collaborative Innovation Center of Suzhou Nanoscience and Technology, Suzhou, China

    Yuanyuan Shi & Mario Lanza

  5. Departament de Química, Universitat Autonoma de Barcelona, Barcelona, Spain

    Xavier Sala, Feliu Maseras & Antoni Llobet

  6. NCD-SWEET beamline, ALBA synchrotron light source, Barcelona, Spain

    Marc Malfois & Eduardo Solano

  7. Max-Planck-Institut für Eisenforschung GmbH, Düsseldorf, Germany

    Joohyun Lim, Alba Garzón-Manjón & Christina Scheu

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  1. Md Asmaul Hoque
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Contributions

Md.A.H. and M.G.-S. performed the synthesis, characterization and electrochemical experiments and coordinated the tasks with all authors. These authors contributed equally to this work. J.A.A.W.E. performed the STM experiments. D.M. performed the XANES and EXAFS measurements and data analysis. Y.S. prepared the samples for XANES and EXAFS experiments. J.B.-B. performed the single crystal X-ray structure determinations. M.M. and E.S. performed and analysed the synchrotron scattering experiments. J.L., A.G.-M. and C.S. designed, carried out and analysed electron microscopy experiments. F.M. designed the computational part. A.d.A. performed the theoretical calculations. C.G.-S. supervised the project. A.L. conceived the idea of the project and wrote the paper with input from other authors. All authors contributed to the design of experiments, analysis of the results and preparation of the manuscript.

Corresponding authors

Correspondence to Mario Lanza, Feliu Maseras, Carolina Gimbert-Suriñach or Antoni Llobet.

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Supplementary information

Supplementary Information

Supplementary methods, Figs. 1–48, computational methods.

Supplementary Data 1

Supplementary Data 1.

Supplementary Data 2

Supplementary Data 2.

Supplementary Data 3

Supplementary Data 3.

Source data

Source Data Fig. 1

This file contains raw NMR data for Fig. 1.

Source Data Fig. 3

Figure_3D.xlsx – Excel file with source data for Fig. 3d.

Source Data Fig. 4

Coordinates for this figure.

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Figure_5.xlsx – Excel file with source data for Fig. 5.

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Excel file with source data for Fig. 6.

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Hoque, M.A., Gil-Sepulcre, M., de Aguirre, A. et al. Water oxidation electrocatalysis using ruthenium coordination oligomers adsorbed on multiwalled carbon nanotubes. Nat. Chem. 12, 1060–1066 (2020). https://doi.org/10.1038/s41557-020-0548-7

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