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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  <identifier identifierType="URL">https://zenodo.org/record/1471618</identifier>
  <creators>
    <creator>
      <creatorName>Schwarz, Dana</creatorName>
      <givenName>Dana</givenName>
      <familyName>Schwarz</familyName>
      <affiliation></affiliation>
    </creator>
    <creator>
      <creatorName>Acharjya, Amitava</creatorName>
      <givenName>Amitava</givenName>
      <familyName>Acharjya</familyName>
      <nameIdentifier nameIdentifierScheme="ORCID" schemeURI="http://orcid.org/">0000-0002-0998-171X</nameIdentifier>
    </creator>
    <creator>
      <creatorName>Ichangi, Arun</creatorName>
      <givenName>Arun</givenName>
      <familyName>Ichangi</familyName>
      <nameIdentifier nameIdentifierScheme="ORCID" schemeURI="http://orcid.org/">0000-0002-3094-4331</nameIdentifier>
    </creator>
    <creator>
      <creatorName>Kochergin, Yaroslav</creatorName>
      <givenName>Yaroslav</givenName>
      <familyName>Kochergin</familyName>
      <nameIdentifier nameIdentifierScheme="ORCID" schemeURI="http://orcid.org/">0000-0002-9060-6350</nameIdentifier>
    </creator>
    <creator>
      <creatorName>Lyu, Pengbo</creatorName>
      <givenName>Pengbo</givenName>
      <familyName>Lyu</familyName>
    </creator>
    <creator>
      <creatorName>Opanasenko, Maksym V.</creatorName>
      <givenName>Maksym V.</givenName>
      <familyName>Opanasenko</familyName>
    </creator>
    <creator>
      <creatorName>Tarábek, Jan</creatorName>
      <givenName>Jan</givenName>
      <familyName>Tarábek</familyName>
    </creator>
    <creator>
      <creatorName>Vacek Chocholoušová,  Jana</creatorName>
      <givenName>Jana</givenName>
      <familyName>Vacek Chocholoušová</familyName>
    </creator>
    <creator>
      <creatorName>Vacek, Jaroslav</creatorName>
      <givenName>Jaroslav</givenName>
      <familyName>Vacek</familyName>
    </creator>
    <creator>
      <creatorName>Schmidt, Johannes</creatorName>
      <givenName>Johannes</givenName>
      <familyName>Schmidt</familyName>
    </creator>
    <creator>
      <creatorName>Nachtigall, Petr</creatorName>
      <givenName>Petr</givenName>
      <familyName>Nachtigall</familyName>
    </creator>
    <creator>
      <creatorName>Thomas, Arne</creatorName>
      <givenName>Arne</givenName>
      <familyName>Thomas</familyName>
      <affiliation>0000-0002-2130-4930</affiliation>
    </creator>
    <creator>
      <creatorName>Bojdys, Michael J.</creatorName>
      <givenName>Michael J.</givenName>
      <familyName>Bojdys</familyName>
      <nameIdentifier nameIdentifierScheme="ORCID" schemeURI="http://orcid.org/">0000-0002-2592-4168</nameIdentifier>
      <affiliation>Humboldt-Universität zu Berlin</affiliation>
    </creator>
  </creators>
  <titles>
    <title>Tuning the porosity and photocatalytic performance of triazinebased graphdiyene polymers via polymorphism</title>
  </titles>
  <publisher>Zenodo</publisher>
  <publicationYear>2018</publicationYear>
  <subjects>
    <subject>graphdiyene</subject>
    <subject>photocatalysis</subject>
    <subject>covalent organic frameworks</subject>
    <subject>conjugated microporous polymers</subject>
    <subject>semiconductors</subject>
  </subjects>
  <dates>
    <date dateType="Issued">2018-10-18</date>
  </dates>
  <resourceType resourceTypeGeneral="Text">Journal article</resourceType>
  <alternateIdentifiers>
    <alternateIdentifier alternateIdentifierType="url">https://zenodo.org/record/1471618</alternateIdentifier>
  </alternateIdentifiers>
  <relatedIdentifiers>
    <relatedIdentifier relatedIdentifierType="DOI" relationType="IsIdenticalTo">10.1002/cssc.201802034</relatedIdentifier>
  </relatedIdentifiers>
  <rightsList>
    <rights rightsURI="https://creativecommons.org/licenses/by-nc-nd/4.0/legalcode">Creative Commons Attribution Non Commercial No Derivatives 4.0 International</rights>
    <rights rightsURI="info:eu-repo/semantics/openAccess">Open Access</rights>
  </rightsList>
  <descriptions>
    <description descriptionType="Abstract">&lt;p&gt;Crystalline and amorphous organic materials are an&lt;br&gt;
emergent class of heterogeneous photocatalysts for the generation of&lt;br&gt;
hydrogen from water, but a direct correlation between their structures&lt;br&gt;
and the resulting properties has not been achieved so far. To make a&lt;br&gt;
meaningful comparison between structurally different, yet chemically&lt;br&gt;
similar porous polymers, we present two porous polymorphs of a&lt;br&gt;
triazine-based graphdiyene (TzG) framework from a simple, one-pot&lt;br&gt;
reaction using Cu(I) for TzG&lt;sub&gt;Cu&lt;/sub&gt; and Pd(II)/Cu(I) for TzG&lt;sub&gt;Pd/Cu&lt;/sub&gt; catalyzed&lt;br&gt;
homocoupling polymerization. The polymers form via irreversible&lt;br&gt;
coupling reactions and give rise to a crystalline (TzG&lt;sub&gt;Cu&lt;/sub&gt;) and an&lt;br&gt;
amorphous (TzG&lt;sub&gt;Pd/Cu&lt;/sub&gt;) polymorph. Notably, the crystalline and&lt;br&gt;
amorphous polymorphs are narrow-gap semiconductors with&lt;br&gt;
permanent surface areas of 660 m&lt;sup&gt;2&lt;/sup&gt; g&lt;sup&gt;-1&lt;/sup&gt; and 392 m&lt;sup&gt;2&lt;/sup&gt; g&lt;sup&gt;-1&lt;/sup&gt;, respectively.&lt;br&gt;
Hence, both polymers are ideal heterogeneous photocatalysts for&lt;br&gt;
water splitting with some of the highest hydrogen evolution rates&lt;br&gt;
reported thus far up to 972 &amp;mu;mol h&lt;sup&gt;-1&lt;/sup&gt; g&lt;sup&gt;-1&lt;/sup&gt; with and 276 &amp;mu;mol h&lt;sup&gt;-1&lt;/sup&gt; g&lt;sup&gt;-1&lt;/sup&gt;&lt;br&gt;
without Pt co-catalyst. We conclude, that crystalline order improves&lt;br&gt;
delocalisation, while the amorphous polymorph requires a co-catalyst&lt;br&gt;
for efficient charge transfer; this will need to be considered in future&lt;br&gt;
rational design of polymer catalysts and organic electronics.&lt;/p&gt;</description>
  </descriptions>
  <fundingReferences>
    <fundingReference>
      <funderName>European Commission</funderName>
      <funderIdentifier funderIdentifierType="Crossref Funder ID">10.13039/501100000780</funderIdentifier>
      <awardNumber awardURI="info:eu-repo/grantAgreement/EC/H2020/678462/">678462</awardNumber>
      <awardTitle>Layered functional materials - beyond 'graphene'</awardTitle>
    </fundingReference>
  </fundingReferences>
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