Junyi Gu, Yanan Qiang, Xuemei Mu, Zhihai Liu, Chao Zhang, Min Lai, Xiaobo Pan and Hao Zhao
{"title":"Enhanced photocatalytic hydrogen production through modification of B←N coordination units†","authors":"Junyi Gu, Yanan Qiang, Xuemei Mu, Zhihai Liu, Chao Zhang, Min Lai, Xiaobo Pan and Hao Zhao","doi":"10.1039/D4NJ01729C","DOIUrl":null,"url":null,"abstract":"<p >Low efficiency of photogenerated electron–hole separation has been a challenge for organic conjugated polymer photocatalysts. Our preceding studies have revealed that polymers containing B←N coordination bonds can form a localized built-in electric field that effectively promotes photogenerated charge separation. However, B←N coordination units are still scarce and require more examples to find regularities in their structural design. The systematic development and testing of B←N coordination units is necessary for the efficient development of subsequent polymers containing B←N coordination bonds. In this work, three conjugated polymers containing B←N coordination bonds, <strong>PBN–Ni</strong>, <strong>PBP–Ni</strong>, and <strong>PBS–Ni</strong>, were synthesized by changing the substituents of the boron atoms and introducing narrow-band thiophene units to form conjugate and energy band gradients. The energy band modulation and localized built-in electric field construction were both achieved as planned, while the bandgap and photogenerated charge transport capabilities caused performance discrepancies. The experimental results showed that <strong>PBN–Ni</strong> had a better photocatalytic hydrogen evolution (HER) performance, reaching 104.6 μmol h<small><sup>−1</sup></small> (<em>λ</em> > 420 nm). The optimal optical absorption edge of <strong>PBS–Ni</strong> was up to 643 nm, but the HER was lower, at 33.2 μmol h<small><sup>−1</sup></small> (<em>λ</em> > 420 nm, 1% Pt). <strong>PBP–Ni</strong> optimized some of the optical absorption efficiencies (511 nm) while ensuring the HER activity (96.6 μmol h<small><sup>−1</sup></small>, <em>λ</em> > 420 nm). This work tentatively explores the characterization of the B←N coordination bond-containing base units serving as photocatalysts and provides the basic model experience and data reference for the subsequent expansion of B←N coordination bond-containing units and the development of B←N coordination bond-containing copolymer systems.</p>","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"New Journal of Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/nj/d4nj01729c","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Low efficiency of photogenerated electron–hole separation has been a challenge for organic conjugated polymer photocatalysts. Our preceding studies have revealed that polymers containing B←N coordination bonds can form a localized built-in electric field that effectively promotes photogenerated charge separation. However, B←N coordination units are still scarce and require more examples to find regularities in their structural design. The systematic development and testing of B←N coordination units is necessary for the efficient development of subsequent polymers containing B←N coordination bonds. In this work, three conjugated polymers containing B←N coordination bonds, PBN–Ni, PBP–Ni, and PBS–Ni, were synthesized by changing the substituents of the boron atoms and introducing narrow-band thiophene units to form conjugate and energy band gradients. The energy band modulation and localized built-in electric field construction were both achieved as planned, while the bandgap and photogenerated charge transport capabilities caused performance discrepancies. The experimental results showed that PBN–Ni had a better photocatalytic hydrogen evolution (HER) performance, reaching 104.6 μmol h−1 (λ > 420 nm). The optimal optical absorption edge of PBS–Ni was up to 643 nm, but the HER was lower, at 33.2 μmol h−1 (λ > 420 nm, 1% Pt). PBP–Ni optimized some of the optical absorption efficiencies (511 nm) while ensuring the HER activity (96.6 μmol h−1, λ > 420 nm). This work tentatively explores the characterization of the B←N coordination bond-containing base units serving as photocatalysts and provides the basic model experience and data reference for the subsequent expansion of B←N coordination bond-containing units and the development of B←N coordination bond-containing copolymer systems.