October 18, 2018 Journal article Open Access

Schwarz, Dana; Acharjya, Amitava; Ichangi, Arun; Kochergin, Yaroslav; Lyu, Pengbo; Opanasenko, Maksym V.; Tarábek, Jan; Vacek Chocholoušová, Jana; Vacek, Jaroslav; Schmidt, Johannes; Nachtigall, Petr; Thomas, Arne; Bojdys, Michael J.

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    "description": "<p>Crystalline and amorphous organic materials are an<br>\nemergent class of heterogeneous photocatalysts for the generation of<br>\nhydrogen from water, but a direct correlation between their structures<br>\nand the resulting properties has not been achieved so far. To make a<br>\nmeaningful comparison between structurally different, yet chemically<br>\nsimilar porous polymers, we present two porous polymorphs of a<br>\ntriazine-based graphdiyene (TzG) framework from a simple, one-pot<br>\nreaction using Cu(I) for TzG<sub>Cu</sub> and Pd(II)/Cu(I) for TzG<sub>Pd/Cu</sub> catalyzed<br>\nhomocoupling polymerization. The polymers form via irreversible<br>\ncoupling reactions and give rise to a crystalline (TzG<sub>Cu</sub>) and an<br>\namorphous (TzG<sub>Pd/Cu</sub>) polymorph. Notably, the crystalline and<br>\namorphous polymorphs are narrow-gap semiconductors with<br>\npermanent surface areas of 660 m<sup>2</sup> g<sup>-1</sup> and 392 m<sup>2</sup> g<sup>-1</sup>, respectively.<br>\nHence, both polymers are ideal heterogeneous photocatalysts for<br>\nwater splitting with some of the highest hydrogen evolution rates<br>\nreported thus far up to 972 &mu;mol h<sup>-1</sup> g<sup>-1</sup> with and 276 &mu;mol h<sup>-1</sup> g<sup>-1</sup><br>\nwithout Pt co-catalyst. We conclude, that crystalline order improves<br>\ndelocalisation, while the amorphous polymorph requires a co-catalyst<br>\nfor efficient charge transfer; this will need to be considered in future<br>\nrational design of polymer catalysts and organic electronics.</p>", 
    "license": {
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    "title": "Tuning the porosity and photocatalytic performance of triazinebased graphdiyene polymers via polymorphism", 
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        "title": "Layered functional materials - beyond 'graphene'", 
        "acronym": "BEGMAT", 
        "program": "H2020", 
        "funder": {
          "doi": "10.13039/501100000780", 
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          "name": "European Commission", 
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    "keywords": [
      "graphdiyene", 
      "photocatalysis", 
      "covalent organic frameworks", 
      "conjugated microporous polymers", 
      "semiconductors"
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    "publication_date": "2018-10-18", 
    "creators": [
      {
        "name": "Schwarz, Dana"
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        "orcid": "0000-0002-0998-171X", 
        "name": "Acharjya, Amitava"
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      {
        "orcid": "0000-0002-3094-4331", 
        "name": "Ichangi, Arun"
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      {
        "orcid": "0000-0002-9060-6350", 
        "name": "Kochergin, Yaroslav"
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      {
        "name": "Lyu, Pengbo"
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      {
        "name": "Opanasenko, Maksym V."
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      {
        "name": "Tar\u00e1bek, Jan"
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      {
        "name": "Vacek Chocholou\u0161ov\u00e1,  Jana"
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      {
        "name": "Vacek, Jaroslav"
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      {
        "name": "Schmidt, Johannes"
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      {
        "name": "Nachtigall, Petr"
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      {
        "affiliation": "0000-0002-2130-4930", 
        "name": "Thomas, Arne"
      }, 
      {
        "orcid": "0000-0002-2592-4168", 
        "affiliation": "Humboldt-Universit\u00e4t zu Berlin", 
        "name": "Bojdys, Michael J."
      }
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