The search for active semiconductor photocatalysts that directly split water under visible-light irradiation remains one of the most challenging tasks for solar-energy utilization. Over the past 30 years, the search for such materials has focused mainly on metal-ion substitution as in In(1-x)Ni(x)TaO(4) and (V-,Fe- or Mn-)TiO(2) (refs 7,8), non-metal-ion substitution as in TiO(2-x)N(x) and Sm(2)Ti(2)O(5)S(2) (refs 9,10) or solid-solution fabrication as in (Ga(1-x)Zn(x))(N(1-x)O(x)) and ZnS-CuInS(2)-AgInS(2) (refs 11,12). Here we report a new use of Ag(3)PO(4) semiconductor, which can harness visible light to oxidize water as well as decompose organic contaminants in aqueous solution. This suggests its potential as a photofunctional material for both water splitting and waste-water cleaning. More generally, it suggests the incorporation of p block elements and alkali or alkaline earth ions into a simple oxide of narrow bandgap as a strategy to design new photoelectrodes or photocatalysts.

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Monoclinic clinobisvanite bismuth vanadate is an important material with wide applications. However, its electronic structure and optical properties are still not thoroughly understood. Density functional theory calculations were adopted in the present work, to comprehend the band structure, density of states, and projected wave function of BiVO(4). In particular, we put more emphasis upon the intrinsic relationship between its structure and properties. Based on the calculated results, its molecular-orbital bonding structure was proposed. And a significant phenomenon of optical anisotropy was observed in the visible-light region. Furthermore, it was found that its slightly distorted crystal structure enhances the lone-pair impact of Bi 6s states, leading to the special optical properties and excellent photocatalytic activities.

In this study, 3D-photonic crystal design was utilized to enhance incident photon-to-electron conversion efficiency (IPCE) of WO(3) photoanodes. Large-area and high-quality WO(3) photonic crystal photoanodes with inverse opal structure were prepared. The photonic stop-bands of these WO(3) photoanodes were tuned experimentally by variation of the pore size of inverse opal structures. It was found that when the red-edge of the photonic stop-band of WO(3) inverse opals overlapped with the WO(3) electronic absorption edge at E(g) = 2.6-2.8 eV, a maximum of 100% increase in photocurrent intensity was observed under visible light irradiation (λ > 400 nm) in comparison with a disordered porous WO(3) photoanode. When the red-edge of the stop-band was tuned well within the electronic absorption range of WO(3), noticeable but less amplitude of enhancement in the photocurrent intensity was observed. It was further shown that the spectral region with a selective IPCE enhancement of the WO(3) inverse opals exhibited a blue-shift in wavelength under off-normal incidence of light, in agreement with the calculated stop-band edge locations. The enhancement could be attributed to a longer photon-matter interaction length as a result of the slow-light effect at the photonic stop-band edge, thus leading to a remarkable improvement in the light-harvesting efficiency. The present method can provide a potential and promising approach to effectively utilize solar energy in visible-light-responsive photoanodes.

The development of efficient photocatalytic material for converting solar energy to hydrogen energy as viable alternatives to fossil-fuel technologies is expected to revolutionize energy shortage and environment issues. However, to date, the low quantum yield for solar hydrogen production over photocatalysts has hindered advances in the practical applications of photocatalysis. Here, we show that a carbon nitride intercalation compound (CNIC) synthesized by a simple molten salt route is an efficient polymer photocatalyst with a high quantum yield. We found that coordinating the alkali metals into the C-N plane of carbon nitride will induce the un-uniform spatial charge distribution. The electrons are confined in the intercalated region while the holes are in the far intercalated region, which promoted efficient separation of photogenerated carriers. The donor-type alkali metal ions coordinating into the nitrogen pots of carbon nitrides increase the free carrier concentration and lead to the formation of novel nonradiative paths. This should favor improved transport of the photogenerated electron and hole and decrease the electron-hole recombination rate. As a result, the CNIC exhibits a quantum yield as high as 21.2% under 420 nm light irradiation for solar hydrogen production. Such high quantum yield opens up new opportunities for using cheap semiconducting polymers as energy transducers.

Visible light-induced degradation of rhodamine B (RhB) and eosin Y (EO) in a heterogeneous TiO(2) P-25/EO/RhB system was investigated in the present work. The results showed that the photodegradation of RhB is enhanced significantly when EO is introduced into the P-25/RhB system. Under optimal conditions (50 mg P-25, 20 mg L(-1) EO), RhB (4 mg L(-1)) almost decomposed completely after 35 min of visible light irradiation, though EO was photodegraded simultaneously. The possible photodegradation mechanism was studied by the examination of active species HO*, O(2)(*-) anions, or dye radical cations through adding their scavengers such as methanol, t-butanol, benzoquinone, EDTA, and the I(-) anion. In addition, the electron paramagnetic resonance (EPR) spin trapping technique was also used to monitor the active oxygen species formed in the photocatalytic process. Combined with the contrastive experiments under different atmospheres (N(2)-purged or air) and in different systems, it can be deduced that dissolved O(2) plays a crucial role in dye photodegradation and the O(2)(*-) anion is possibly the major active oxygen species. The low degradation rate with the introduction of EDTA or I(-) indicated that dye radical cations also play a part in photodegradation. Furthermore, except for the dye-sensitized photodegradation on the P-25 surface, reaction in bulk solution also occurs in this system, leading to effective photodegradation of RhB.

Surface exfoliation: A Ta3 N5 photoanode prepared by a thermal oxidation and nitridation method shows a high solar photocurrent. This photocurrent is currently the highest achieved by a Ta3 N5 photoanode. The photocurrent is obtained mainly because of facile thermal and mechanical exfoliation of the surface passivation layer of the Ta3 N5 photoanode.