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Photocathodic hydrogen evolution from catalysed nanoparticle films prepared from stable aqueous dispersions of P3HT and PCBM
摘要： Photo-assisted hydrogen evolution is achieved on photocathodes comprising of nanoparticles of poly(3-hexylthiophene) (npP3HT) and nanoparticles of phenyl-C61-butyric acid methyl ester (npPCBM) onto which ultra-low loadings of Pt nanoparticles are deposited. The nanoparticles, npP3HT and npPCBM, are prepared individually via miniemulsion using surfactants of opposite head group polarity. Aqueous dispersions of npP3HT:npPCBM, devoid of organic solvent, are cast conformally onto ITO-coated glass to yield water-insoluble bulk-heterojunction films. Pt is deposited photoelectrochemically onto ITO/npP3HT:npPCBM photocathodes and found to nucleate preferentially on PCBM nanoparticles. ITO/npP3HT:npPCBM/Pt photocathodes produce 65 μA/cm2 photocurrent under 100 mW/cm2 of visible light at 0.0 VSHE and liberate H2 gas. The photocurrents observed for electrodes prepared using npP3HT:npPCBM are twice as large, and the onset potential is ～0.4 V more positive than analogous photocathodes cast from nanoparticles each comprising an intimate blend of P3HT and PCBM. These are encouraging results for large scale synthesis of organic photoelectrochemical devices, given the simplicity of the photoelectrode, i.e., prepared from aqueous solutions and devoid of vacuum-deposited films such as charge transport layers and protective films.
关键词： Polymer nanoparticle,Photoelectrochemistry,P3HT: PCBM bulk-heterojunction,Solar hydrogen generation,Organic semiconductor,Mini-Emulsion
更新于2025-09-23 15:23:52
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Effective quenching and excited-state relaxation of a Cu(I) photosensitizer addressed by time-resolved spectroscopy and TDDFT calculations
摘要： Homogenous photocatalytic systems based on copper photosensitizers are promising candidates for noble metal free approaches in solar hydrogen generation. To improve their performance, a detailed understanding of the individual steps is needed. Here, we study the interaction of a heteroleptic copper (I) photosensitizer with an iron catalyst by time-resolved spectroscopy and ab initio calculations. The catalyst leads to rather efficient quenching of the 3MLCT state of the copper complex, with a bimolecular rate being about three times smaller than the collision rate. Using control experiments with methyl viologen, an appearing absorption band is assigned to the oxidized copper complex demonstrating that an electron transfer from the sensitizer to the iron catalyst occurs and the system reacts along an oxidative pathway. However, only about 30% of the quenching events result in an electron transfer while the other 70% experience deactivation indicating that the photocatalytic performance might suffer from geminate recombination.
关键词： Solar hydrogen generation,Time-resolved spectroscopy,Ab initio calculations,Copper photosensitizers,Electron transfer
更新于2025-09-04 15:30:14