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LETTERS

PUBLISHED ONLINE: 29 APRIL 2012 | DOI: 10.1038/NMAT3312

A red metallic oxide photocatalyst
Xiaoxiang Xu, Chamnan Randorn† , Paraskevi Efstathiou and John T. S. Irvine*

Kubelka¬Munk (a.u.)

0.6
0.5
Absorbance (a.u.)

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, Sr1−x NbO3 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.
If the stoichiometric cubic strontium niobate (SrNbO3 ) perovskite could be prepared, it would be an archetypal d 1 oxide and
it might be expected to exhibit interesting electronic properties
such as metallicity. Electronic band structure calculations in this
and previous studies on this composition clearly indicate a metallic
structure, with the Fermi level located within the conduction band
(Supplementary Fig. S1)1 .
The stoichiometric SrNbO3 phase with cubic perovskite
structure has proved difficult to realize2 , possibly indicative of
a charge disproportionation phenomenon distorting the cubic
lattice; however, cubic perovskites are readily achieved in nonstoichiometric compositions. The series Sr1−x NbO3−δ yields cubic
perovskites for 0.1 < x < 0.25 (refs 3,4), for example with unit
cell parameters of 4.019 Å (x = 0.2) and 4.027 Å (x = 0.1). A
series of strongly coloured red materials with absorption energy
gaps around 1.9 eV (estimated from an absorption tail to 700 nm)
were synthesised for 0.1 ≤ x ≤ 0.2 in this study (Fig. 1). The
Fermi level of these materials might be expected to have a small
positive shift as Nb in the structure increases its formal oxidation
state compared with stoichiometric SrNbO3 , and a decrease in
energy gap is observed as x increases. These materials were single
phase according to X-ray powder diffraction analysis and electron
microscopy examination. Thermogravimetric analysis showed that
the phase was stable against oxidation in air up to 300 ◦ C and
confirmed that δ was generally small.
Not only are these materials strongly coloured, they have
high electronic conductivity, exhibiting a conductivity of
3 × 103 S cm−1 for x = 0.2 (Supplementary Table S1). Conductivity
decreased slightly on increasing the temperature from 82 K
to ambient (Supplementary Fig. S2), consistent with previous
studies that showed such an expected metallic signature
with conductivity decreasing with temperature2,4,5 . A positive
temperature coefficient of resistance (αt = 2.047 × 10−4 K−1 ) is

0.4
0.3

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Energy (eV)

Sr0.9NbO3

0.2

Sr0.85NbO3
0.1

Sr0.8NbO3

0
200

300

400

500
600
Wavelength (nm)

700

800

900

Figure 1 | Ultraviolet–visible absorbance spectra (converted from diffuse
reflectance spectra) for Sr1−x NbO3 (x = 0.1, 0.15 and 0.2). Kubelka–Munk
transformation of the absorption curves is shown in the top inset. Typical
sintered pellets (Sr0.9 NbO3 ) are shown in the bottom inset.

calculated from the slope of the curve. Thus, these materials are
red metallic oxides.
Materials can only be strongly coloured if they strongly absorb
light, which must promote electrons to create electron–hole pairs.
In a semiconductor or insulator, this is well understood as an
electron transition from the essentially occupied valence band to an
essentially unoccupied conduction band. In a metallic conductor,
the terms valence and conduction band are less easy to apply.
It is reasonable to consider the partially occupied band as the
conduction band, but the valence band (VB) no longer equates
with the highest occupied band. It is therefore better to describe
the band below the conduction band (CB) as the highest fully
occupied band and that above it as the lowest unoccupied band,
termed as B−1 and B1 , respectively, in Fig. 2. Transitions that might
be associated with photon absorption could be conceived as either
being from B−1 to CB or alternatively CB to B1 , that is, either
involving transitions to or from the partially occupied conduction
band. In the case of the metallic oxides Sr1−x NbO3 (0.1 ≤ x ≤ 0.2),
the absorption energy gaps (∼1.9 eV) observed in ultraviolet–visible
absorbance spectra are smaller than the indirect bandgap energy
(2.38 eV) predicted by theoretical calculations for B−1 to CB in
the related stoichiometric phase. As the Fermi level is calculated
to be some 1 eV above the conduction band edge1 and bandgaps
obtained from density functional theory (DFT) calculations are
typically underestimated, especially for semiconductors; it seems
unlikely that the transition is from an occupied level to the
conduction band (B−1 to CB). Therefore, it seems that the transition
is most probably from the conduction band to a higher level
unoccupied band (CB to B1 ). DFT calculations on the related

School of Chemistry, EaSTChem, University of St Andrews, St Andrews, Fife KY16 9ST, UK. † Present address: Department of Chemistry, Faculty of Science,
Chiang Mai University, Muang, Chiang Mai 50200, Thailand. *e-mail: jtsi@st-andrews.ac.uk.
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One of the features of the high-temperature synthesis is that large particles are produced.025 M) with 0. Bands below and above the conduction band (CB) are labelled as B−1 and B1 . indicating that both the improved surface area and the presence of co-catalyst contribute to this enhancement. This can be overcome by ball milling the powders after synthesis and loading a suitable co-catalyst such as Pt.nature.1 g catalyst.9 µmol h−1 g−1 after ball milling and loading with 1 wt% Pt (Supplementary Fig. All rights reserved . suggesting the overpotentials for water splitting at this oxide were large enough to hinder the process. Typical time courses of H2 evolution in aqueous oxalic acid solution (0. Typical time courses of O2 evolution in aqueous silver nitrate solution (0. however. therefore blocking photons from reaching the surface. 12). with the ‘holes’ remaining in the conduction band below (CB. One of the most interesting properties of semiconductors where charge carriers can be created by irradiation is photocatalysis of reactions such as water splitting7–11 . However. Supplementary Fig. The maximum difference in energy between photogenerated holes and electrons is around 1. The gradual decay of O2 production is due to the reduced Ag that covers the surface of Srx NbO3 particles. the small surface areas of the product will limit photocatalytic performance. S5).5 ± 0.3.5562 m2 g−1 after ball milling) in accord with the large decrease in particle size (Supplementary Fig. the physical properties of which will closely correlate with those of the bulk materials.8NbO3 0 0 1 2 3 Time (h) 4 5 Figure 3 | Photocatalytic performance of as-prepared strontium niobates under visible light irradiation.1038/NMAT3312 LETTERS B1 Energy CB Ef B–1 Figure 2 | Schematic of band structure for a metallic conductor. 1). only about 0. The surface areas of the ball-milled powders increased considerably (from 0.8 eV at 0 point) to the absorption energy gaps observed (∼1. In both cases. This is an increase by a factor of 4.8NbO3 0 0 5 10 Time (h) 15 20 2 Sr0. the absence of significant electric field would mean that recombination could not be avoided.9 eV).005 M) with 0.9NbO3 Sr0.NATURE MATERIALS DOI: 10. ‘SrNbO3 ’ suggest that this type of transition is associated with a similar energy (∼1.com/naturematerials © 2012 Macmillan Publishers Limited. The photocatalytic properties of these red metallic oxides were therefore investigated and they were shown to be photocatalytically active using visible light for oxidation and reduction water splitting processes (Fig. Electron–hole pairs can be created by interband transitions where electrons are excited from the conduction band into the unoccupied energy levels in the higher band.6 eV more than the difference in potential between water oxidation and reduction.85 eV.9NbO3 Sr0. Similar milling treatments of these phases without co-catalyst addition increased performance by a factor of 3. From a the band calculations on the hypothetical SrNbO3 (ref. especially if the carriers could be rapidly transferred6 .2 g catalyst. On the other hand. S4). 596 NATURE MATERIALS | VOL 11 | JULY 2012 | www.5 µmol h−1 g−1 photocatalyst to 44. The hydrogen production rate was increased from 10. the created electrons would be located in the B1 band. a.23 eV at 300 K. were not necessary to promote either oxidation or reduction processes. Unfortunately.2805 m2 g−1 to 11. These transitions seem to be between bands with predominant Nb character and are associated with an intense colour and sharp absorption (Fig. the high conductivity implies high carrier mobility and this might allow carrier separation. sacrificial elements were used to facilitate the reverse processes. b. one might assume that even when such electron–hole pairs are created in a highly conducting. As the effective oxidation state of Nb in strontium niobate is close to four (as confirmed by thermogravimetric analysis b 14 40 12 10 O2 (µmol) H2 (µmol) 30 20 8 6 4 10 Sr0. Possible transitions associated with photon absorption are marked by arrows. metallic material. S1). Direct water splitting without the aid of sacrificial elements was not achieved. 3). catalyst additives such as Pt (ref. The strontium niobate photocatalyst was also found to be active for the oxidative process of methylene blue decolourization (Supplementary Fig. which is 1.8 ± 5. which significantly enhanced photoactivity. 1). S3).

For methylene blue degradation. Static calculations were done with a 9 × 9 × 9 Monkhorst-Pack k-point grid16 . No hydrogen was detected under control experimental conditions. 13).2 g sample powders were suspended in 200 ml oxalic acid aqueous solution (0. then once the two photocarriers have been created. The d. Photoelectrochemical process involving the combination of a semiconductor photoelectrode and a metallic counter electrode. The number of moles of product significantly exceeded the number of moles of photoatalyst present. Red Ox+ Physical characterization. Particle size analysis was performed on Mastersizer 2000 Particle Size Analyser (Malvern Instruments). morphology (by scanning electron microscopy). and X-ray photoelectron spectroscopy. Visible light irradiation was generated by a 250 W iron-doped metal halide ultraviolet–visible lamp with an ultraviolet cut-off filter (λ ≥ 420 nm. Photocatalytic processes occurring on a single photocatalyst. All rights reserved 597 . 2 ml aliquots were sampled at various time intervals and the initial pH value was kept at 7. In a photoelectrochemical cell. four-probe technique according to a previously reported method12 . Photocatalytic reactions. c. Incident radiation was generated using a CuKα1 source (λ = 1. Diffuse reflectance spectra were collected on an ultraviolet–visible spectrophotometer (JASCO-V550). Supplementary Fig. The evolved gases under irradiation were then examined using an online gas chromatograph (Agilent 3000 Micro Gas Chromatograph). even when sacrificial oxalate was present and the light source was masked. Cambridge UK).2) were synthesised by calcination of homogenized Sr4 Nb2 O9 .1 ≤ x ≤ 0. Borosilicate Coated Glass HM07. The temperature during irradiation was controlled at about 25 ◦ C by means of a water bath to remove infrared radiation and heat. Methods Ox Material synthesis. ref. These Theoretical calculations. 0. To measure H2 or O2 evolution.025 M) or 200 ml silver nitrate solution (0. this was not found to be a significant process under the investigated conditions. Activity was maintained over several photoreduction cycles with no detectable change in the colouration.000 s at each step.6 eV) arising from adventitious carbon. the photoreduction and photooxidation processes involve independent redox reactions of the photocarriers (Fig. The powders were then heated at 180 ◦ C for 2 h for the decomposition of H2 PtCl6 . 4b). Photocatalytic activity was evaluated by monitoring the degradation of methylene blue as well as examining the H2 or O2 evolution in various aqueous solutions (oxalic acid or silver nitrate solutions). The photoactivity of the samples was then evaluated by monitoring the intensity of the strongest absorption peak of methylene blue at 665 nm on a Perkin Elmer Lambda 35 ultraviolet/visible spectrometer along with irradiation time. 4c).com/naturematerials © 2012 Macmillan Publishers Limited. Theoretical calculations were carried out using the density functional theory implemented in the Vienna ab initio simulation package (VASP.03 Å was used for the simulations. with the induced potential within the particle driving the counter process (that is. Crystal structures were examined by X-ray diffraction analysis of powders on a SToe STADI/P powder diffractometer.1 g or 0.c.5 g l−1 ) was first kept in a dark condition for 2 h to reach absorption equilibrium before irradiation. Strontium niobates Sr1−x NbO3 (0. 4). NATURE MATERIALS | VOL 11 | JULY 2012 | www. Nb and Nb2 O5 mixtures in a flowing Ar atmosphere at 1400 ◦ C for 20 h. The mechanism of operation of this metallic photocatalyst may be considered as being between that of a photoelectrocatalyst and that of a photocatalyst (Fig.54056 Å). Spin polarization was also taken into account in this calculation. S7. it is reasonable to suggest that photogenerated electrons drive the initial photoreduction process. electronic conductivity values were measured on sintered pellets by a d. oxidation state (by X-ray photoelectron spectroscopy) and crystal structure of the catalyst (by X-ray diffraction analysis. this we term as a metallic photocatalyst (Fig. X-ray photoelectron spectroscopy was performed on a Thermo Escalab 250 using a monochromatic Al Kα X-ray source. The induced potential in the electrochemical circuit then drives the secondary redox process at the metal counter electrode (Fig. which also demonstrates that the surface and bulk states are similar.0. it might be expected to chemically reduce water. a. Pt was loaded onto the specimen by an impregnation method: the proper amount of H2 PtCl6 aqueous solution was impregnated into the sample powders and then evaporated at 90 ◦ C until dry. In the case of the photoactive metallic oxide. The step size for data collection was 0. The Perdew. Burke and Ernzerhof (PBE) exchange–correlation functional within the generalized gradient approximation14 and the projector augmented-wave pseudopotential15 were adopted. The absorbance was transformed by the Kubelka–Munk method. b. The suspension (0. UQG (optic). c Red– B1 Red hν CB Ox Ox+ Figure 4 | Schematic of possible photocatalytic-type processes to drive solar redox processes. If we consider a normal semiconductor photocatalyst. 4a). Experiments were performed on samples with or without Pt as a co-catalyst. and these photocarriers drive the primary redox process. photoelectrons or holes are generated in a semiconductor photoelectrode. The suspensions were sealed in a home-made photoreactor purged with pure Ar as a protective gas.nature. confirming photocatalytic behaviour.02◦ with a collection time 1. however.1 g sample powders were suspended in 200 ml of methylene blue aqueous solution (1 × 10−4 M) under air bubbling.005 M) under visible light irradiation. A cubic cell with a = 4. All geometry structures were fully relaxed until the forces on each atom were less than 0. S6).NATURE MATERIALS DOI: 10. Details of the synthesis can be found in the Supplementary Information. 0.1038/NMAT3312 LETTERS a Red– CB Red hν Ox VB Ox+ b CB hν VB Red– e– results conclusively prove that this metallic conductor can be used as a photocatalyst. A plane-wave basis set with an energy cutoff of 500 eV was employed. Supplementary Figs S5. the oxidation). S8 and S9).01 eV Å−1 . Vaseline was used to mount the powders onto the holder.c. Photocatalytic process occurring at the partially filled conduction band of a metallic oxide particle with the counter process occurring at a higher band. All binding energies were referenced to the C 1s peak (284.

133. J.. D. Ridgley. Maeda. performed the synthesis and collected data with C. 8. A. Rev. Hoffman (Caltech) and P.. & Fitzgerald. & Arakawa. S. J. Chinese Academy of Science) for assistance with reflectance measurements and X-ray photoelectron spectroscopy measurements. Nature Mater.90). G. 8. B 47. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Synthesis and crystal structure of the distorted perovskite Sr0.nature.. 13. Bull. thanks Sasol UK and Energy Technology Partnership (ETP) for studentship support. & Yu. 625–627 (2001). All rights reserved . B 13. Additional information The authors declare no competing financial interests. S. S. G. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. C. Reprints and permissions information is available online at www.nature. 11. First-principles calculations of the elastic and electronic properties of the cubic perovskites SrMO3 (M = Ti. © 2012 Macmillan Publishers Limited. S. 217–225 (2008). 5147–5154 (2008). Mater. Lett. B. Mater. H. V.E. 16.. 6. J. X. 14. Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst.. F. Sugiyama. Sayama.E.75 ≤ x ≤ 0. Shein. K. Phys. 77. Chem. 9. K.R. J. A. Author contributions X. Sunshine. 15.. Photocatalyst releasing hydrogen from water–enhancing catalytic performance holds promise for hydrogen production by water splitting in sunlight. 6132–6136 (1955). F. Supplementary information accompanies this paper on www. & Yamauchi. K. L. Z. Res. letting you access read them immediately. Solid State Sci. Zr and Nb) in comparison with SrSnO3 . J. J. Perdew. J. Synthesis and transport-properties of Srx NbO3 (0. H. 10. B 59. 8. D. 26.S. J. et al. Mao. Chen. Siegrist. 85–90 (1991). Chem. P. & Pack. M. Burke. Konysheva. Hessen. Ni (University of Science & Technology of China) for theoretical calculations. et al. Robertson (Robert Gordon University) for helpful discussions.T. Soc.X. J.. K. T. A.. Kresse. 3. 12. J. & Joubert. S. Chem. Phys. Ye. Monkhorst. 746–750 (2011). Rev. The preparation of a strontium–niobium bronze with the perovskite structure. Inorganic materials as catalysts for photochemical splitting of water. 7. 1758–1775 (1999). T. 7264–7267 (2011). and J. & Furthmuller. J. Peng.. 5. E. 11169–11186 (1996). P. Früchtl and M. Crystallization of reduced strontium and barium niobate perovskites from borate fluxes. Evolution of conductivity. Matsuura.com/naturematerials. 35–54 (2008). H. Nature 414. N.com/reprints. 5188–5192 (1976). Generalized gradient approximation made simple. R. 10.. X. A. Phys. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Frame. Photocatalytic water oxidation with nonsensitized IrO2 nanocrystals under visible and UV light. 1033–1038 (1998). Nature 440. K. G.nature. 4. Liu..1038/NMAT3312 LETTERS Received 13 May 2011. H. & Ernzerhof. 18. Osterloh. A. B. 77.com/naturematerials All in-text references underlined in blue are linked to publications on ResearchGate. & Jimenez. et al.97 NbO3 determined by high resolution powder neutron diffraction. 2849–2853 (1993). M. 3865–3868 (1996). D. Rev. L. P. & Irvine. Chem. E.NATURE MATERIALS DOI: 10. analysed the results and wrote the paper.. Isawa. Mater. G.I. 76–80 (2009). Irvine. published online 29 April 2012 References 1. Acknowledgements We thank the Engineering and Physical Sciences Research Council (EPSRC) and National Science Foundation (NSF) for financial support and G. Special points for Brillouin-zone integrations. Am. Rev. & Ivanovskii. Buehl (St Andrews). 2. Rev. J. & Ward. structure and thermochemical stability of lanthanum manganese iron nickelate perovskites. B 54. Mater. Kozhevnikov. I. Zou. Wang. Kresse. Chem. V. R. R. H.I.. 295 (2006). accepted 23 March 2012. Phys. 598 NATURE MATERIALS | VOL and 11 | JULY 2012 | www. From ultrasoft pseudopotentials to the projector augmented-wave method. and P. T. S. Science 331. Correspondence and requests for materials should be addressed to J. 20. H. Phys. Am. Soc. Nozaki.T.S. Liu (Institute of Metal Research. Y.