Ning Zhang,
Kaifu Zhang,
Wei Zhou,
Baojiang Jiang,
Kai Pan,
Yang Qu* and
Guofeng Wang*
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of The People’s Republic of China, Heilongjiang University, Harbin 150080, P. R. China. E-mail: copy0124@126.com; wanggf75@gmail.com
First published on 1st December 2015
An undesirable phase transformation was overcome and pure phase orthorhombic MgTi2O5 nanocrystals were facilely prepared. The concentration of metal ions and the reaction temperature are the two factors that were found to affect the phase transformation of the magnesium titanates. The as-prepared pure phase MgTi2O5 nanocrystals possessed a high crystallinity and were 20 nm in diameter. They exhibited excellent photocatalytic hydrogen production activity (418 μmol h−1), and high apparent quantum efficiency (62.5% at 313 nm and 50.6% at 365 nm, respectively). Significantly, a “solar-to-hydrogen” efficiency of 0.52% was obtained. This may be attributed to the pure phase crystals and large surface area, which favored charge transfer and promoted photo-induced charge separations which is proven using photoelectrochemical measurements.
Alkali titanates with the formula M2TinO2n+1 have a unique layered and ilmenite or tunnel-like crystal structure, and have attracted increasing attention due to their more negative conduction band and high photocatalytic activity.4,5 Hereinto, MgTi2O5 possesses a suitable electronic structure and conduction/valence band position, that matches well with the redox potential of splitting water into hydrogen and oxygen molecules. MgTi2O5 has a theoretical band gap energy of approximately 3.4 eV, and contains Ti4+, a d0 metal ion which has the potential activity for water splitting.6 However, pure orthorhombic phase MgTi2O5 is very hard to prepare because the two main magnesium titanates, MgTiO3 and MgTi2O5, are associated minerals.7–10 These two phase transformations may be caused by possible crystallography incompatibilities, which may cause undesired secondary phases as often happened in the conventional solid state method to prepare magnesium titanates.11 However, pure phase materials are beneficial to photocatalysis because they reduce impurities and lead to fast charge transport from bulk to surface. Moreover, the synthesis of pure phase titanates is significant to, not only the properties themselves, but also to the inside study of their electronic energy structure. M. Morimoto reported the synthesis of uniformly porous MgTi2O5 with a narrow pore-size distribution at 1000–1200 °C and it showed excellent thermal expansion behavior.13 Recently, Deng and Chen et al. prepared a novel hybrid MgTi2O5–C nanocomposite from an in situ carbonization process of a cheap single molecule precursor with unique morphology that exhibited improved lithium ion battery properties.12 So, developing methods to prepare pure phase MgTi2O5 is significant to enhance its properties.
Generally speaking, if the phase transformation could be controlled or the MO6 units were “fixed”, pure phase magnesium titanates could be prepared. Luckily, some works have demonstrated that the concentration of metal ions can affect the phases of the products.14,15 Moreover, it was found in our previous works that parts of bivalent metals are easy to coordinate with some organic ligands (ethylene glycol) to form metal glycolates. Metal oxides or ilmenites were prepared using further calcinations. This means that pure phase MgTi2O5 could be prepared by fixing Mg2+ and Ti4+ using ethylene glycol and then calcination.
Hence, we report the facile synthesis of pure phase MgTi2O5 nanocrystals for H2 production. Different to the traditional method, we develop an organic ligand coordinated polymerization method. Ethylene glycol (EG) acts as a ligand to coordinate with Mg2+ and Ti4+ to form MgO6 and TiO6 units that are linked by EG, this can fix the cation distortion to avoid phase transformation and forms pure phase MgTi2O5 when calcined in air.
In addition, all of the data in this work, especially the photocatalytic activities and electrochemical measurements, were tested at least three times to confirm the reproducibility, to ensure the scientific and scrupulous treatment of our work.
The presence of the pure phase could be proven using the XRD patterns in Fig. 1a, as all of the diffraction peaks can be indexed to pure orthorhombic phase MgTi2O5 (JCPDS 35-0792). No other impurity peaks such as TiO2, MgTiO3 and Mg2TiO4 were detected. In the XRD patterns of the samples that were synthesized under other conditions, mixed-phase MgTi2O5/MgTiO3 (MMT) and rhombohedral phase MgTiO3 (JCPDS 06-0494) emerged (as shown in Fig. S1†). The X-ray Energy Dispersive Spectrometer (EDS) results in Fig. 1b show that the sample of PMT contains the three elements Mg, Ti and O. The Raman spectrum in Fig. S2† gives further evidence of MgTi2O5 nanocrystals, as the Raman shifts at 661 cm−1 and 797 cm−1 may be attributed to the vibrations of the O atoms and 159 cm−1, 218 cm−1 and 266 cm−1 may be attributed to the anti-symmetric breathing and twisting vibrations of the O octahedral, according to previous works.17,18
The XPS results in Fig. 2 demonstrate that the Mg and Ti are +2 and +4 without alterable valence states, and the atom ratios of them are also approximately two. According to the results of the XRD, assisted by EDS and XPS, it could be confirmed that pure orthorhombic phase MgTi2O5 was successfully prepared.
The optical absorptions of the pure MgTi2O5 nanocrystals and commercial MgTi2O5 were conducted with a UV-vis absorption spectrometer, as shown in Fig. S3a.† Obviously, both the PMT and CMT show photoabsorption in the UV light region (λ < 400 nm). It should be noted that there are some impurities in the CMT, which is consistent with the results of the XRD (Fig. S3b†). The band gaps (Eg) of the pure MgTi2O5 nanocrystals and commercial MgTi2O5 were calculated to be about 3.45 eV from the onset of the absorption edges.
The morphology of PMT is nanocrystalline with the small size TEM and HRTEM images in Fig. 3a–c showing that the nanocrystals are uniform, well dispersed and the average size is about 20–30 nm. The aggregated nanoparticles form many pores which enhance the surface area and are beneficial to photocatalysis. It is well known that the photocatalytic performance is related to the BET surface area. N2 adsorption–desorption isotherms and corresponding BJH pore size distribution plots of the pure MgTi2O5 nanocrystals and commercial MgTi2O5 were performed, as shown in Fig. S4.† The BET surface areas for the prepared and pure MgTi2O5 nanocrystals, mixed phase MgTi2O5/MgTiO3 and commercial MgTi2O5 are 64.94, 69 and 2.95 m2 g−1, respectively. The HRTEM image clearly shows an interplanar spacing of 0.34 nm, corresponding to the (101) plane of MgTi2O5. The high quality crystallinity and the pure phase are positive to charge transfer and separation.19–21
The as-prepared magnesium titanates are regarded as potential photocatalysts for H2 evolution. Fig. 4a shows the H2 evolution from the prepared pure phase MgTi2O5, mixed-phase MgTi2O5/MgTiO3, and commercial MgTi2O5 under UV light irradiation. It can clearly be seen that the pure phase MgTi2O5 (PMT) displays the highest H2 evolution efficiency, which is up to 418 μmol h−1 (average over three hours), which is much higher than that of the mixed-phase one and the commercial one. It is important that the samples with different surface areas play significant roles, compared to PMT and CMT. However, the surface areas of PMT and MMT-4 are similar, but their efficiencies are very different, which means that there are also other factors affecting the activity. The time dependent H2 evolution curves in Fig. 4b show that the pure phase MgTi2O5 can sustainably produce H2 over time. After recycling five times, the photocatalyst retains its catalytic efficiency, with a decline of about only 10%. This illustrates that the pure phase MgTi2O5 possesses high H2 production efficiency and stability. The crystal structure didn’t change after recycling five times, which can be seen in the XRD pattern in Fig. S5.†
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Fig. 4 Photocatalytic H2 production of the different samples (a), time dependent H2 evolution and cycle experiment (b) and apparent quantum efficiency (c) of PMT. |
In order to demonstrate the relationship between light energy and efficiency, we tested and calculated the apparent quantum efficiency of the MgTi2O5 nanocrystals, which is 62.5% and 50.6% at 313 nm and 365 nm, respectively. This is assessed using the UV-vis absorbance shown in Fig. 4c. This means that the pure phase MgTi2O5 in this work is a UV responsive photocatalyst and UV light is dominant in the photocatalytic efficiency. Significantly, the “solar-to-hydrogen” conversion efficiency (STH) of MgTi2O5 is 0.52%, the computing method for this was followed from a previous report.22
Photoelectrochemical (PEC) performance is a useful technique to demonstrate the charge separation and estimate the water splitting properties.23,24 The PEC properties of PMT were tested, CMT was also tested for contrast. A linear sweep voltammogram of the MgTi2O5 material shows a photocurrent density of 103 μA cm−2, which is almost four times higher than that of the commercial MgTi2O5 material (21 μA cm−2), under UV light irradiation, as shown in Fig. 5a. To further investigate the photocurrent responses of PMT and CMT, transient photocurrents of the samples were carried out during repeated on/off illumination cycles at 0.7 V (vs. Ag/AgCl). Both of the samples showed prompt and reproducible photocurrent responses upon each illumination (Fig. 5b). The transient photocurrent density of PMT is 100 μA cm−2, which is greatly enhanced compared to that of CMT (20 μA cm−2). The transient photocurrent responses match well with the linear sweep voltammograms and display the stability of the magnesium titanate materials.
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Fig. 5 Liner sweep voltage (a) and transient photocurrent (b) of pure phase MgTi2O5 (PMT) and commercial MgTi2O5 (CMT). |
The photogenerated charge transfer and separation need to overcome the impedance of the interface.25,26 The electrochemical impedance measurements show smaller interfacial resistance for PMT than for CMT, not only in the dark but also under illumination, indicating a more efficient charge separation (Fig. 6a). Mott–Schottky plots could be used to reflect the type of semiconductors, the flat band and the charge density. Fig. 6b demonstrates that both PMT and CMT are n-type semiconductors from the positive slopes. The slope of the plot is inversely proportional to the charge density, the smaller it is, the higher the charge density. PMT showed a substantially smaller slope on the Mott–Schottky plot than CMT, illustrating that PMT possesses higher charge density. Thus, PMT has smaller interface impedance and higher charge density, and also higher photocurrent density. These results give good evidence that PMT is beneficial for charge transfer and separation, possibly due to the pure phase crystal structure and large surface area. Based on the results above, we speculate that the enhancement is caused by (i) the pure phase structure that has the effect of eliminating the harmful impurities of TiO2 or Mg2TiO4 (mismatched electronic band structure); (ii) the large surface area, which is due to the small nanoparticles compared to the commercial sample. It may also be concerned with defects, because many nanomaterials have more or less defects but we have no direct evidence. However, it is believed that this topic of defects in pure phase materials would inspire future interest to focus on the deep mechanism.
Footnote |
† Electronic supplementary information (ESI) available: Quantum efficiency calculations, Raman, UV-vis, N2 adsorption–desorption isotherm curves and XRD before/after reactions. See DOI: 10.1039/c5ra20992g |
This journal is © The Royal Society of Chemistry 2015 |