Xiaoxiang Xu

A red metallic oxide photocatalyst

Light absorption across the bandgap in semiconductors is exploited in many important applications such as photovoltaics, light emitting diodes and photocatalytic conversion. Metals differ from semiconductors in that there is no energy gap separating occupied and unoccupied levels; however, it is still possible to excite electrons between bands. This is evidenced by materials with metallic properties that are also strongly coloured. An important question is whether such coloured metals could be used in light harvesting or similar applications. The high conductivity of a metal would preclude sufficient electric field being available to separate photocarriers; however, the high carrier mobility in a metal might also facilitate kinetic charge separation. Here we clearly demonstrate for the first time the use of a red metallic oxide, Sr(1-x)NbO(3) as an effective photocatalyst. The material has been used under visible light to photocatalyse the oxidation of methylene blue and both the oxidation and reduction of water assisted by appropriate sacrificial elements.

Photocatalytic Hydrogen Production over Chromium Doped Layered Perovskite Sr2TiO4

Layered semiconductor photocatalysts have been found to exhibit promising performance levels, probably linked to their interlayer framework that facilitates separation of charge carriers and the reduction/oxidation reactions. Layered titanates, however, generally demonstrate activities under UV irradiation, and therein lies the strong desire to extend their activity into the visible light region. Here, we investigated a series of layered perovskite by doping Sr2TiO4 with Cr and/or La in the hope to improve their visible light responses. Their crystal structures and other physicochemical properties were systematically explored. Our results show that La and Cr can be successfully accommodated in the layered structure and Cr is an efficient dopant for the extension of visible light absorbance. Much enhanced photocatalytic hydrogen evolution was observed after doping and was found to be composition-dependent. The highest hydrogen production rate approaches 97.7 μmol/h for Sr2Ti0.95Cr0.05O4-δ under full range irradiation (λ ≥ 250 nm) and 17 μmol/h for Sr2Ti0.9Cr0.1O4-δ under visible light irradiation (λ ≥ 400 nm), corresponding to an apparent quantum efficiency of 0.16% and 0.05%, respectively. Theoretical calculation reveals that the improved optical and photocatalytic properties are owing to a newly formed spin-polarized valence band from Cr 3d orbitals. The decreased unit cell parameters, reduced band gaps as well as anisotropic properties of layered architectures are likely the reasons for a better activity. Nevertheless, instability of these compounds in the presence of moisture and CO2 was also noticed, suggesting that protective atmospheres are needed for the storage of these photocatalysts.

On the Existence of A‐Site Deficiency in Perovskites and Its Relation to the Electrochemical Performance

The low range of A-site deficiency in perovskite structures with Ni cations was verified by neutron powder diffraction, transmission electron microscopy, and thermogravimetric analysis. A thermodynamic approach has been utilized, for the first time, to predict the extent of A-site deficiencies within the perovskite structure, introducing simple prediction criteria that could be adopted for designing advanced materials.

Efficient Photocatalytic Oxygen Production over Nitrogen‐Doped Sr4Nb2O9 under Visible‐Light Irradiation

Photocatalytic water splitting is an appealing process for solar energy conversions yet it is often limited by the slow oxidation of water to oxygen half‐reaction. Here we performed an investigation on N‐doped Sr4Nb2O9 as a water oxidation photocatalyst. Our results show that N doping is an effective approach to improve the visible‐light response of Sr4Nb2O9. Efficient photocatalytic oxygen production was observed after N doping, and the highest production rate of ∼27 μmol h−1 under visible‐light irradiation corresponds to an apparent quantum efficiency of ∼0.31 %. Clear anodic photocurrent can be generated under visible‐light illumination, and the flat‐band potential was determined to be ∼−1.25 V vs. Ag/AgCl at pH 7. Theoretical calculations reveal that N doping introduces additional valence bands and is responsible for the visible‐light response. Variations in light absorption and photo‐oxidation performance can be controlled by modifying these valence band positions using different nitridation temperatures.

Bismuth and chromium co-doped strontium titanates and their photocatalytic properties under visible light irradiation

Modification of prototype perovskite compound SrTiO3 by introducing foreign elements has been an appealing means to endow this wide band gap semiconductor with visible light responses. Here we systematically investigated a series of Sr1-xBixTi1-xCrxO3 solid solution compounds prepared by two different synthetic routes, namely, solid state reactions and the hydrothermal method. Their crystal structures as well as other physicochemical properties were explored. Our results showed that a number of important factors such as microstructures, crystallinity, light absorbance and surface compositions etc. are all strongly correlated with the synthetic methods used. The hydrothermal method is generally helpful for morphology controls as well as avoiding Cr(6+) defects and Sr segregation at the surface, thereby contributing to a high photocatalytic activity. Better performance normally occurs in samples with a high crystallinity and free of defects like Bi(5+). Theoretical calculations suggest that Cr plays an important role in band gap reduction and photocatalytic reactions, while Bi only acts as a constituent cation for the perovskite structure and does not significantly alter the electronic structures near the Fermi level. Our findings have revealed how synthetic routes are relevant to the final photocatalytic properties of a compound, and therefore comparisons among various photocatalysts have to include concerns about their preparation history.

Role of Oxygen Defects on the Photocatalytic Properties of Mg-Doped Mesoporous Ta3N5

Tantalum nitride (Ta3 N5 ) highlights an intriguing paradigm for converting solar energy into chemical fuels. However, its photocatalytic properties are strongly governed by various intrinsic/extrinsic defects. In this work, we successfully prepared a series of Mg-doped mesoporous Ta3 N5 using a simple method. The photocatalytic and photoelectrochemical properties were investigated from the viewpoint of how defects such as accumulation of oxygen and nitrogen vacancies contribute to the catalytic activity. Our findings suggest that Mg doping is accompanied by an accumulation of oxygen species and a simultaneous elimination of nitrogen vacancies in Ta3 N5 . These oxygen species in Ta3 N5 induce delocalized shallow donor states near the conduction band minimum and are responsible for high electron mobility. The superior photocatalytic activity of Mg-doped Ta3 N5 can then be understood by the improved electron-hole separation as well as the lack of nitrogen vacancies, which often serve as charge-recombination centers.

Role of surface composition upon the photocatalytic hydrogen production of Cr-doped and La/Cr-codoped SrTiO3

Abstract Surface properties play a vital role in many heterogeneous catalytic reactions, particularly in photocatalytic water splitting, where photo-generated electron and holes must migrate to and be transferred at the very top surface of a photocatalyst. Here, we carried out a detailed investigation on the role of surface composition towards photocatalytic hydrogen production of perovskite-based materials, namely, Cr-doped and La/Cr-codoped SrTiO3. Our findings showed that a depletion of B site cations occurred at the surface of these high-temperature annealed samples and a severe diminishing of B site cations took place after introducing La cations at the A site. Although the presence of La helps to improve surface alkalinity and inhibit the formation of detrimental Cr6+ species, La/Cr-codoped sample showed a poor photocatalytic activity. Such a correlation between surface composition and photocatalytic activity suggests that surface tailoring or composition control is highly necessary in the design and development of these perovskite-based photocatalysts. Since surface rearrangements can be kinetically hindered at low temperatures, low temperature synthetic methods are therefore strongly preferred during the synthesis of these perovskite-based photocatalysts.

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge.

Ultrathin Lanthanum Tantalate Perovskite Nanosheets Modified by Nitrogen Doping for Efficient Photocatalytic Water Splitting

Ultrathin nitrogen-doped perovskite nanosheets LaTa2O6.77N0.15- have been fabricated by exfoliating Dion-Jacobson-type layered perovskite RbLaTa2O6.77N0.15. These nanosheets demonstrate superior photocatalytic activities for water splitting into hydrogen and oxygen and remain active with photon wavelengths as far as 600 nm. Their apparent quantum efficiency under visible-light illumination (λ ≥ 420 nm) approaches 1.29% and 3.27% for photocatalytic hydrogen and oxygen production, being almost 4-fold and 8-fold higher than bulk RbLaTa2O6.77N0.15. Their outstanding performance likely stems from their tiny thickness (single perovskite slab) that essentially removes bulk charge diffusion steps and extends the lifetime of photogenerated charges. Theoretical calculations reveal a peculiar 2D charge transportation phenomenon in RbLaTa2O6.77N0.15; thus, exfoliating RbLaTa2O6.77N0.15 into LaTa2O6.77N0.15- nanosheets has limited impact on charge transportation properties but significantly enhances the surface areas which contributes to more reaction sites.

Homologous Compounds ZnnIn2O3+n (n = 4, 5, and 7) Containing Laminated Functional Groups as Efficient Photocatalysts for Hydrogen Production

Strong visible light absorption and high charge mobility are desirable properties for an efficient photocatalyst, yet they are hard to be realized simultaneously in a single semiconductor compound. In this work, we demonstrate that these properties coexist in homologous compounds ZnnIn2O3+n (n = 4, 5, and 7) with a peculiar layered structure that combines optical active segment and electrical conductive segment together. Their enhanced visible light absorption originates from tetrahedrally or trigonal-bipyramidally coordinated In atoms in Zn(In)O4(5) layers which enable p-d hybridization between In 4d and O 2p orbitals so that valence band minimum (VBM) is uplifted with a reduced band gap. Theoretical calculations reveal their anisotropic features in charge transport and functionality of different constituent segments, i.e., Zn(In)O4(5) layers and InO6 layers as being for charge generation and charge collection, respectively. Efficient photocatalytic hydrogen evolution was observed in these compounds under full range (λ ≥ 250 nm) and visible light irradiation (λ ≥ 420 nm). High apparent quantum efficiency ∼2.79% was achieved for Zn4In2O7 under full range irradiation, which is almost 5-fold higher than their parent oxides ZnO and In2O3. Such superior photocatalytic activities of these homologous compounds can be understood as layer-by-layer packing of charge generation/collection functional groups that ensures efficient photocatalytic reactions.