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Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution
The design of active and selective co-catalysts constitutes one of the major challenges in developing heterogeneous photocatalysts for energy conversion applications. This work provides a comprehensive insight into thermally induced bottom-up generation and transformation of a series of promising Cu...
Autores principales: | , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8492008/ https://www.ncbi.nlm.nih.gov/pubmed/34707872 http://dx.doi.org/10.1039/d1ta05561e |
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author | Schubert, Jasmin S. Kalantari, Leila Lechner, Andreas Giesriegl, Ariane Nandan, Sreejith P. Alaya, Pablo Kashiwaya, Shun Sauer, Markus Foelske, Annette Rosen, Johanna Blaha, Peter Cherevan, Alexey Eder, Dominik |
author_facet | Schubert, Jasmin S. Kalantari, Leila Lechner, Andreas Giesriegl, Ariane Nandan, Sreejith P. Alaya, Pablo Kashiwaya, Shun Sauer, Markus Foelske, Annette Rosen, Johanna Blaha, Peter Cherevan, Alexey Eder, Dominik |
author_sort | Schubert, Jasmin S. |
collection | PubMed |
description | The design of active and selective co-catalysts constitutes one of the major challenges in developing heterogeneous photocatalysts for energy conversion applications. This work provides a comprehensive insight into thermally induced bottom-up generation and transformation of a series of promising Cu-based co-catalysts. We demonstrate that the volcano-type HER profile as a function of calcination temperature is independent of the type of the Cu precursor but is affected by changes in oxidation state and location of the copper species. Supported by DFT modeling, our data suggest that low temperature (<200 °C) treatments facilitate electronic communication between the Cu species and TiO(2), which allows for a more efficient charge utilization and maximum HER rates. In contrast, higher temperatures (>200 °C) do not affect the Cu oxidation state, but induce a gradual, temperature-dependent surface-to-bulk diffusion of Cu, which results in interstitial, tetra-coordinated Cu(+) species. The disappearance of Cu from the surface and the introduction of new defect states is associated with a drop in HER performance. This work examines electronic and structural effects that are in control of the photocatalytic activity and can be transferred to other systems for further advancing photocatalysis. |
format | Online Article Text |
id | pubmed-8492008 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-84920082021-10-25 Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution Schubert, Jasmin S. Kalantari, Leila Lechner, Andreas Giesriegl, Ariane Nandan, Sreejith P. Alaya, Pablo Kashiwaya, Shun Sauer, Markus Foelske, Annette Rosen, Johanna Blaha, Peter Cherevan, Alexey Eder, Dominik J Mater Chem A Mater Chemistry The design of active and selective co-catalysts constitutes one of the major challenges in developing heterogeneous photocatalysts for energy conversion applications. This work provides a comprehensive insight into thermally induced bottom-up generation and transformation of a series of promising Cu-based co-catalysts. We demonstrate that the volcano-type HER profile as a function of calcination temperature is independent of the type of the Cu precursor but is affected by changes in oxidation state and location of the copper species. Supported by DFT modeling, our data suggest that low temperature (<200 °C) treatments facilitate electronic communication between the Cu species and TiO(2), which allows for a more efficient charge utilization and maximum HER rates. In contrast, higher temperatures (>200 °C) do not affect the Cu oxidation state, but induce a gradual, temperature-dependent surface-to-bulk diffusion of Cu, which results in interstitial, tetra-coordinated Cu(+) species. The disappearance of Cu from the surface and the introduction of new defect states is associated with a drop in HER performance. This work examines electronic and structural effects that are in control of the photocatalytic activity and can be transferred to other systems for further advancing photocatalysis. The Royal Society of Chemistry 2021-09-06 /pmc/articles/PMC8492008/ /pubmed/34707872 http://dx.doi.org/10.1039/d1ta05561e Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Schubert, Jasmin S. Kalantari, Leila Lechner, Andreas Giesriegl, Ariane Nandan, Sreejith P. Alaya, Pablo Kashiwaya, Shun Sauer, Markus Foelske, Annette Rosen, Johanna Blaha, Peter Cherevan, Alexey Eder, Dominik Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution |
title | Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution |
title_full | Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution |
title_fullStr | Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution |
title_full_unstemmed | Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution |
title_short | Elucidating the formation and active state of Cu co-catalysts for photocatalytic hydrogen evolution |
title_sort | elucidating the formation and active state of cu co-catalysts for photocatalytic hydrogen evolution |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8492008/ https://www.ncbi.nlm.nih.gov/pubmed/34707872 http://dx.doi.org/10.1039/d1ta05561e |
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