Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution
Abstract The donor–acceptor (D–A) dye 4‐(bis‐4‐(5‐(2,2‐dicyano‐vinyl)‐thiophene‐2‐yl)‐phenyl‐amino)‐benzoic acid (P1) has been frequently used to functionalize NiO photocathodes and induce photoelectrochemical reduction of protons when coupled to a suitable catalyst. Photoinduced twisting of the P1...
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Wiley
2024-10-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202403454 |
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| author | Kaijian Zhu Ainoa Paradelo Rodríguez Maria B. Brands Titus deHaas Francesco Buda Joost N.H. Reek Guido Mul Annemarie Huijser |
| author_facet | Kaijian Zhu Ainoa Paradelo Rodríguez Maria B. Brands Titus deHaas Francesco Buda Joost N.H. Reek Guido Mul Annemarie Huijser |
| author_sort | Kaijian Zhu |
| collection | DOAJ |
| description | Abstract The donor–acceptor (D–A) dye 4‐(bis‐4‐(5‐(2,2‐dicyano‐vinyl)‐thiophene‐2‐yl)‐phenyl‐amino)‐benzoic acid (P1) has been frequently used to functionalize NiO photocathodes and induce photoelectrochemical reduction of protons when coupled to a suitable catalyst. Photoinduced twisting of the P1 dye is steered on NiO by co‐adsorption of tetradecanoic acid (C14, myristic acid (MA)). Density Functional Theory and time‐resolved photoluminescence studies confirm that twisting lowers the energy levels of the photoexcited D–A dye. The apolar environment provided by the MA suppresses photoinduced D–A twisting, retards charge recombination following photoinduced charge separation between P1 and NiO, and provides a larger electrochemical potential increasing the photocurrent. Very interestingly, co‐adsorption of MA induces H2 evolution upon photoexcitation without the presence of an H2 evolution catalyst. Based on prior art, the formation of H2 is assigned to the dissolution of Ni2+, followed by reduction and re‐deposition of Ni nanoparticles acting as the catalytically active site. It propose that only excited P1 with suppressed twisting provides the sufficient electrochemical potential to induce deposition of Ni nanoparticles. The work illustrates the importance of understanding the effects of photoinduced intramolecular twisting and highlights the promise of designing twisting‐limited D–A dyes to create efficient solar fuel devices. |
| format | Article |
| id | doaj-art-bd2b4139491841a1ab67222eb2fdfe78 |
| institution | OA Journals |
| issn | 2198-3844 |
| language | English |
| publishDate | 2024-10-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-bd2b4139491841a1ab67222eb2fdfe782025-08-20T02:11:59ZengWileyAdvanced Science2198-38442024-10-011140n/an/a10.1002/advs.202403454Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 EvolutionKaijian Zhu0Ainoa Paradelo Rodríguez1Maria B. Brands2Titus deHaas3Francesco Buda4Joost N.H. Reek5Guido Mul6Annemarie Huijser7PhotoCatalytic Synthesis Group MESA+ Institute for Nanotechnology University of Twente P.O. Box 217 Enschede 7500 AE The NetherlandsPhotoCatalytic Synthesis Group MESA+ Institute for Nanotechnology University of Twente P.O. Box 217 Enschede 7500 AE The Netherlandsvan ‘t Hoff Institute for Molecular Sciences University of Amsterdam Science Park 904 Amsterdam 1098 XH The NetherlandsLeiden Institute of Chemistry Leiden University P.O. Box 9502 Leiden 2300 RA The NetherlandsLeiden Institute of Chemistry Leiden University P.O. Box 9502 Leiden 2300 RA The Netherlandsvan ‘t Hoff Institute for Molecular Sciences University of Amsterdam Science Park 904 Amsterdam 1098 XH The NetherlandsPhotoCatalytic Synthesis Group MESA+ Institute for Nanotechnology University of Twente P.O. Box 217 Enschede 7500 AE The NetherlandsPhotoCatalytic Synthesis Group MESA+ Institute for Nanotechnology University of Twente P.O. Box 217 Enschede 7500 AE The NetherlandsAbstract The donor–acceptor (D–A) dye 4‐(bis‐4‐(5‐(2,2‐dicyano‐vinyl)‐thiophene‐2‐yl)‐phenyl‐amino)‐benzoic acid (P1) has been frequently used to functionalize NiO photocathodes and induce photoelectrochemical reduction of protons when coupled to a suitable catalyst. Photoinduced twisting of the P1 dye is steered on NiO by co‐adsorption of tetradecanoic acid (C14, myristic acid (MA)). Density Functional Theory and time‐resolved photoluminescence studies confirm that twisting lowers the energy levels of the photoexcited D–A dye. The apolar environment provided by the MA suppresses photoinduced D–A twisting, retards charge recombination following photoinduced charge separation between P1 and NiO, and provides a larger electrochemical potential increasing the photocurrent. Very interestingly, co‐adsorption of MA induces H2 evolution upon photoexcitation without the presence of an H2 evolution catalyst. Based on prior art, the formation of H2 is assigned to the dissolution of Ni2+, followed by reduction and re‐deposition of Ni nanoparticles acting as the catalytically active site. It propose that only excited P1 with suppressed twisting provides the sufficient electrochemical potential to induce deposition of Ni nanoparticles. The work illustrates the importance of understanding the effects of photoinduced intramolecular twisting and highlights the promise of designing twisting‐limited D–A dyes to create efficient solar fuel devices.https://doi.org/10.1002/advs.202403454donor–acceptor dyedye‐sensitized photocathodeH2 evolutionmolecular twistingTICT |
| spellingShingle | Kaijian Zhu Ainoa Paradelo Rodríguez Maria B. Brands Titus deHaas Francesco Buda Joost N.H. Reek Guido Mul Annemarie Huijser Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution Advanced Science donor–acceptor dye dye‐sensitized photocathode H2 evolution molecular twisting TICT |
| title | Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution |
| title_full | Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution |
| title_fullStr | Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution |
| title_full_unstemmed | Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution |
| title_short | Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution |
| title_sort | limiting molecular twisting upgrading a donor acceptor dye to drive h2 evolution |
| topic | donor–acceptor dye dye‐sensitized photocathode H2 evolution molecular twisting TICT |
| url | https://doi.org/10.1002/advs.202403454 |
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