We describe efficient visible- and near-infrared (vis/NIR) light-driven photocatalytic properties of hybrids of CuO and plasmonic Cu arrays. The CuO/Cu arrays were prepared simply by allowing a Cu half-shell array to stand in an oxygen atmosphere for 3 h, which was prepared by depositing Cu on two-dimensional colloidal crystals with a diameter of 543 or 224 nm. The localized surface plasmon resonances (LSPRs) of the arrays were strongly excited at 866 and 626 nm, respectively, at which the imaginary part of the dielectric function of Cu is small. The rate of photodegradation of methyl orange was 27 and 84 times faster, respectively, than that with a CuO/nonplasmonic Cu plate. The photocatalytic activity was demonstrated to be dominated by Cu LSPR excitation. These results showed that the inexpensive CuO/Cu arrays can be excellent vis/NIR-light-driven photocatalysts based on the efficient excitation of Cu LSPR.

We demonstrated the usefulness of Cu light-harvesting plasmonic nanoantennae for the development of inexpensive and efficient artificial organic photoelectric conversion systems. The systems consisted of the stacked structures of layers of porphyrin as a dye molecule, oxidation-suppressing layers, and plasmonic Cu arrayed electrodes. To accurately evaluate the effect of Cu nanoantenna on the porphyrin photocurrent, the production of CuO by the spontaneous oxidation of the electrode surfaces, which can act as a photoexcited species under visible light irradiation, was effectively suppressed by inserting the ultrathin linking layers consisting of 16-mercaptohexadecanoic acid, titanium oxide, and poly(vinyl alcohol) between the electrode surface and porphyrin molecules. The reflection spectra in an aqueous environment of the arrayed electrodes, which were prepared by thermally depositing Cu on two-dimensional colloidal crystals of silica with diameters of 160, 260, and 330 nm, showed clear reflection dips at 596, 703, and 762 nm, respectively, which are attributed to the excitation of localized surface plasmon resonance (LSPR). While the first dip lies within the wavelengths where the imaginary part of the Cu dielectric function is moderately large, the latter two dips lie within a region of a quite small imaginary part. Consequently, the LSPR excited at the red region provided a particularly large enhancement of porphyrin photocurrent at the Q-band (ca. 59-fold), compared to that on a Cu planar electrode. These results strongly suggest that the plasmonic Cu nanoantennae contribute to the substantial improvement of photoelectric conversion efficiency at the wavelengths, where the imaginary part of the dielectric function is small.

We succeeded in controlling the wavelength range in which the photocurrent of porphyrin is enhanced by tuning as well as expanding the wavelength ranges in which the localized surface plasmon resonance (LSPR) occurs. We fabricated photoelectric conversion systems consisting of 5,10,15,20-tetrakis(p-carboxyphenyl)porphyrin (TCPP) and silver nanoprisms with small (SAgPRs) and large (LAgPRs) aspect ratios as plasmonic nano-antennae. Their photocurrents were much larger than those from TCPP-modified Ag planar electrodes at the specific wavelengths corresponding to their LSPR bands (SAgPRs: 460-610 nm; LAgPRs: 610-690 nm). The maximum enhancement factors (EFs) for the SAgPRs and the LAgPRs were 37 and 35, respectively. In order to enhance the photocurrents, we expanded the LSPR bands by the combined use of SAgPRs and LAgPRs. The system consisting of the mixture (MAgPRs) showed enhancement of the photocurrent over the entire Q-band region (480-690 nm). Finally, the total EFs of the photocurrents were evaluated by irradiation with AM1.5G sunlight through a long-pass filter of 480 nm and the results revealed that the EFs were in the order of MAgPRs > SAgPRs > LAgPRs. Furthermore, the system showed stability without loss of the enhancement property for at least 10 min under the solar irradiation.

We demonstrate up to ∼630-fold enhancement of the photocurrent from a porphyrin monolayer on a plasmonic Ag-array electrode showing plasmon absorption in the Q-band region relative to that on a planar Ag electrode. The photocurrent obtained by the Q-band excitation in the plasmonic electrodes even exceeded that obtained by the Soret-band excitation in a normal, nonplasmonic electrode.

Plasmon‐induced charge separation (PICS) at plasmonic metal‐semiconductor interfaces has been used for photovoltaics, photocatalysis, and many other photofunctional materials and devices. In most of those cases, dispersed and disordered metal nanoparticle ensembles have been used. We prepared two‐dimensionally ordered and interconnected Au halfshell arrays on SiO2@TiO2 core‐shell nanosphere colloidal crystals and exploited them for PICS. The present system exhibits broad light absorption over the visible to near‐infrared (NIR) range, leading to wide photoelectrochemical responses. Here we report that this system is characterized not only by localized and propagating surface plasmons but also by light propagation through the colloidal crystals, which enhances plasmonic light harvesting. Effects of the SiO2 core size were examined, and the middle‐sized cores were found to be optimum for efficient PICS processes because of strong electric field at the photoelectrode.