Selective visible-light-driven CO2 reduction on a p-type dye-sensitized NiO photocathode.
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ABSTRACT:
SUBMITTER: Bachmeier A
PROVIDER: S-EPMC4241363 | biostudies-other | 2014 Oct
REPOSITORIES: biostudies-other
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Project description:The thin-layer-stacked dye-sensitized NiO photocathodes decorated with palladium nanoparticles (nPd) can be used for the visible-light-driven selective reduction of CO2, mostly to CO, at potentials starting as low as 0 V vs. RHE (compared to -0.6 V in the dark for electrocatalysis). The photosensitization of NiO by the organic dye P1, with a surface coverage of 1.5 × 10-8 mol cm-2, allows the hybrid material to absorb light in the 400-650 nm range. In addition, it improves the stability and the catalytic activity of the final material decorated with palladium nanoparticles (nPd). The resulting multi-layered-type photocathode operates according to the electron-transfer-cascade mechanism. On the one hand, the photosensitizer P1 plays a central role as it generates excited-state electrons and transfers them to nPd, thus producing the catalytically active hydride material PdH x . On the other hand, the dispersed nPd, absorb/adsorb hydrogen and accumulate electrons, thus easing the reductive electrocatalysis process by further driving the separation of charges at the photoelectrochemical interface. Surface analysis, morphology, and roughness have been assessed using SEM, EDS, and AFM imaging. Both conventional electrochemical and photoelectrochemical experiments have been performed to confirm the catalytic activity of hybrid photocathodes toward the CO2 reduction. The recorded cathodic photocurrents have been found to be dependent on the loading of Pd nanoparticles. A sufficient amount of loaded catalyst facilitates the electron transfer cascade, making the amount of dye grafted at the surface of the electrode the limiting parameter in catalysis. The formation of CO as the main reaction product is postulated, though the formation of traces of other small organic molecules (e.g. methanol) cannot be excluded.
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Project description:The p-block semiconductors are regarded as a new family of visible-light photocatalysts because of their dispersive and anisotropic band structures as well as high chemical stability. The bismuth oxide halides belong to this family and have band structures and dispersion relations that can be engineered by modulating the stoichiometry of the halogen elements. Herein, we have developed a new visible-light photocatalyst Bi24O31Cl10 by band engineering, which shows high dye-sensitized photocatalytic activity. Density functional theory calculations reveal that the p-block elements determine the nature of the dispersive electronic structures and narrow band gap in Bi24O31Cl10. Bi24O31Cl10 exhibits excellent visible-light photocatalytic activity towards the degradation of Rhodamine B, which is promoted by dye sensitization due to compatible energy levels and high electronic mobility. In addition, Bi24O31Cl10 is also a suitable photoanode material for dye-sensitized solar cells and shows power conversion efficiency of 1.5%.
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Project description:The visible-light responsive Cu(I)-complex photosensitizers were developed by introducing various aromatic substituents at the 4,7-positions of a 2,9-dimethyl-1,10-phenanthroline (dmp) ligand in a heteroleptic CuI(dmp)(DPEphos)+-type complexes (DPEphos = [2-(diphenylphosphino)phenyl]ether) for photocatalytic CO2 reduction. Introducing biphenyl groups (Bp-) on the dmp ligand enhanced the molar extinction coefficient (ε) of the metal-to-ligand charge transfer (MLCT) band in the visible region (ε = 7,500 M-1cm-1) compared to that of the phenyl (Ph-)-containing analog (ε = 5,700 M-1cm-1 at λmax = 388 nm). However, introducing 4-R-Ph- groups (R = the electron-withdrawing groups NC-, or NO2-) led to a red shift in the band to λmax = 390, 400, and 401 nm, respectively. Single-crystal X-ray analysis showed the Ph- groups were twisted because of the steric repulsion between the 2,6-protons of the Ph- groups and 5,6-protons of the dmp ligand. The result strongly indicated that the π-conjugation effect of the 4-R-Ph- groups is so weak that the lowering of the energy of the dmp π* orbitals is small. However, when 4-R-ph- was substituted by a 5-membered heterorings, there was a larger red shift, leading to an increase in the ε value of the MLCT absorption band. Thus, the substitution to 2-benzofuranyl- groups resulted in visible-light absorption up to 500 nm and a shoulder peak at around 420 nm (ε = 12,300 M-1cm-1) due to the expansion of π-conjugation over the substituted dmp ligand. The photocatalytic reaction for CO2 reduction was tested using the obtained CuI complexes as photosensitizers in the presence of a Fe(dmp)2(NCS)2 catalyst and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as a sacrificial reductant, which showed improved CO generation.
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