Showcasing research from the laboratories of Bin Liu and

Qichun Zhang, Nanyang Technological University,
Singapore 639798, Singapore

As featured in:

A p-type Ti(IV)-based metal–organic framework with
visible-light photo-response
A new Ti(IV)-based porous metal–organic framework (MOF)
(NTU-9) with visible-light photo-response was reported. The
p-type characteristics and efficient dye photo-degradation results
demonstrated that Ti(IV)-based MOFs could be promising
visible-light photocatalysts for energy conversion and
environmental remediation.
See Liu, Zhang et al.,
Chem. Commun., 2014, 50, 3786.

www.rsc.org/chemcomm
Registered charity number: 207890

whose absorption reaches up to 750 nm. 50.2 However. Photoelectrochemical studies indicated that NTU-9 is photoactive under visible light illumination (k 4 400 nm) and acts as a p-type semiconductor. gray. The electronic structure and bandgap were further investigated by DFT calculations. we report a new Ti(IV)-based porous metal–organic framework (MOF) (NTU-9). For ESI and crystallographic data in CIF or other electronic format see DOI: 10. the Ti atom is octahedrally coordinated with six oxygen atoms from hydroxide and carboxylate groups. Moreover. which accounts for only 5% of the solar spectrum. Singapore 637459. Nanyang Technological University. H atoms are removed for clarity.edu.5-dihydroxyterephthalic acid) in acetic acid. Singapore. its large bandgap has limited its application only in the UV light range. low cost.858 Å while the a School of Materials Science and Engineering.sg b School of Chemical and Biomedical Engineering. Here. 3786 Received 12th December 2013. Exploring new visible-light-driven photocatalysts has been one of the most attractive topics to address energy problems and reduce environmental contamination. 1 (a) The coordination mode of the Ti atom in NTU-9. Color representation: red. Nanyang Technological University. some MOFs such as MOF-5. COMMUNICATION Cite this: Chem.ChemComm Published on 04 February 2014. CCDC 974959.1039/c3cc49440c www. The results demonstrated that Ti(IV)-based MOFs could be promising visible-light photocatalysts for energy conversion and environmental remediation. Singapore 637371.a Yanli Zhao. UIO-66.edu. Singapore † Electronic supplementary information (ESI) available: Experimental details.3 However. (b) The coordination of the DOBDC ligand in NTU-9. Singapore 639798. Single crystal XRD analysis reveals that NTU-9 crystallizes in the trigonal space group P-31c. Singapore. NTU-9 was obtained as red. E-mail: liubin@ntu. which displayed strong absorption in the visible region with a bandgap of 1.‡ As shown in Fig. Commun. titanium dioxide (TiO2) has become one of the most studied semiconductors for photocatalysis. 2014. This journal is © The Royal Society of Chemistry 2014 .1039/c3cc49440c 3786 | Chem. 50.5 Very recently.4 In fact. IR spectra. it is essential to extend the optical response of TiO2 into visible light through the modification of TiO2 with inorganic or organic species. (c) 1-D channels of NTU-9 viewed along the c-axis. To address these problems.c Bin Liu*b and Qichun Zhang*a DOI: 10. summary of crystal structure and refinement details of NTU-9. The bond length between Ti and the oxido oxygen atom is B1.b Pei-Zhou Li. 2014. we report a new porous Ti(IV)-based MOF structure (NTU-9). the surface areas.a Jianwei Miao. and MIL-88B(Fe) have already been demonstrated to have semiconductor properties for photoelectronics and photocatalysis. MIL-100(Fe). powder-XRD and TGA spectra of NTU-9. low toxicity and large abundance. hexagonal prism crystals by the reaction of Ti(i-OPr)4 (titanium isopropoxide) with H4DOBDC (2. the successful demonstration of MIL-1256a and its NH2-functionalized isostructure (MIL-125-NH2) in light-driven water splitting and CO2 reduction makes Ti-based MOFs more attractive as photocatalysts. metal–organic frameworks (MOFs) might be a possible solution because of their large surface areas and downsized catalytic centers (one metal or small metal-oxide cluster).rsc.org/chemcomm Here. Accepted 4th February 2014 View Article Online View Journal | View Issue A p-type Ti(IV)-based metal–organic framework with visible-light photo-response† Junkuo Gao. C. high efficiency. which shows p-type semiconductor behaviour. most of such composites suffer from either poor stability or fast recombination.72 eV. O.7 However.1 Because of its good photostability.. it is worthy to note that no other Ti(IV)-based porous MOF structure except MIL-1256a and MIL-916b have been reported. Nanyang Technological University. Downloaded by Nanyang Technological University on 24/06/2015 09:47:13. Commun.c Wen Yuan Teng.. Therefore. 1a. Ti. bandgaps and photoactivities of MOFs can be tuned by changing the organic ligands or metal centers.a Ling Yang.sg c School of Physical and Mathematical Sciences. 3786--3788 Fig. blue. E-mail: qczhang@ntu.

72 eV. S4. The photoelectrochemical properties of NTU-9 were studied in a three-electrode set-up. The conduction bands (CB) above Fermi energy are mostly made up of Ti 3d states.74 eV. This ‘designable’ character of MOFs could lead to the synthesis of more Ti(IV)-based MOF semiconductors with visible light activity. 3786--3788 | 3787 . Fig. After removing guests in the channels. the density of states (DOS) and the electronic band structure of NTU-9 were calculated using the density functional theory (DFT) in the CASTEP program. S2 in ESI†). S2 in ESI†). The calculated energy band gap for NTU-9 is 1. Crystalline NTU-9 is stable in air. The band structure illustrates that the interband transitions of NTU-9 are direct. which may exhibit a higher photonic efficiency compared with indirect band gap semiconductors such as TiO2. The connection between Ti(IV) atoms and DOBDC ligands forms a two dimensional (2-D) honeycomb-like layer. The framework {Ti2(HDODBC)2(H2DOBDC)}n is neutral. and the empty spaces in channels are occupied by 2-propanol molecules. The coordination geometries of the Ti center resemble the structure of [Ti(salicylate)3]2 ions. S4–S6 (ESI†). indicating the stronger bonding between Ti(IV) and O atoms. There exist one dimensional (1-D) channels about 11 Å  11 Å along the c-axis. 2 Diffuse reflectance spectra of NTU-9.8 Note that the Ti–O bonds in NTU-9 are much shorter than the metal–O bonds in MOF-749 which is constituted of divalent metal ions (such as Co2+. 1c). Downloaded by Nanyang Technological University on 24/06/2015 09:47:13.0 eV) is mainly contributed from the O 2p states mixed with a small amount of C 2p states. These layers are stacked along the c-axis. Thermogravimetric analysis (TGA) of NTU-9 revealed that most of the guest molecules in the channels were removed below 100 1C (Fig.037 Å. with minor contributions from the C 2p and O 2p states.0 eV) and the Fermi level (0. which are similar to the 1-D channels in MOF-74 (Fig. As shown in Fig.7% using PLATON. The absorption of NTU-9 was dramatically red-shifted when compared with TiO2 (3.. Details of the crystal structure and refinement data are provided in the ESI† (Table S1 in ESI†). Mg2+) and DOBDC ligands. the spectrum of NTU-9 shows a broad range of absorption in the visible region from 400 nm to 750 nm with an absorption peak centered at around 520 nm. The DOS results indicate the existence of charge transfer from the organic ligand to Ti(IV) atoms in NTU-9. The experimental powder XRD pattern for NTU-9 matches very well with the simulated one (generated on the basis of single crystal structure analysis). inset shows the photovoltage (illuminated open-circuit potential) responses of the NTU-9/FTO electrode. 2. Chem. 50. water and common organic solvents.9b All uncoordinated O atoms from the carboxylate groups point to the 1-D channels. Commun.2 eV for anatase and 3. 3 (a) Zero-bias photocurrent response of the NTU-9/FTO electrode upon chopped visible light illumination. whose VB is mainly formed by the overlapping of O 2p orbitals and CB is mainly constituted of the 3d states of Ti. the crystalline structure of NTU-9 was retained which was confirmed via the powder XRD pattern (Fig. Fe2+.View Article Online Published on 04 February 2014. S1 in ESI†). (b) Mott–Schottky plot of the NTU-9/FTO electrode measured at a frequency of 1000 Hz. The dominations of VB and CB by O and Ti atoms in NTU-9 are similar to that of TiO2. the valence Fig.74 eV) and VB maximum (0 eV) are located at the same k-point in the Brillouin zone (Fig.6 eV). and the reported Ti(IV)-based MOF MIL-125 (3. This journal is © The Royal Society of Chemistry 2014 ChemComm band (VB) of NTU-9 between the energy level ( 4. which matches the experimental data very well.0 for rutile).7c To understand the electronic structure of NTU-9. the solvent-accessible void in the structure of NTU-9 was calculated to be about 50. The flat-band potential of the NTU-9 is indicated by the intercept of the dashed lines.6 eV) and its isostructure MIL-125-NH2 (2. 3a shows the photocurrent Fig. The calculated bandgap of NTU-9 from the absorption onset is about 1. The small contributions of p atomic orbitals of carbon to the CB in NTU-9 may alter and further reduce the band gap by changing the degree of conjugation or functional group modification in the ligands.10 As depicted in Fig. ESI†). 2014. The CB minimum (1. The diffuse reflectance spectra were recorded on a PerkinElmer Lambda 750s UV-Vis spectrometer. which confirmed the phase purity of the bulk materials (Fig. After removal of the guest molecules (treated at 120 1C for 12 h under vacuum). Communication distance between Ti and the oxygen atom from the carboxylate group is B2.

Ed. we have reported a new Ti(IV)-based MOF. Chem. (c) M. 17652. Lee. (e) J. Garcia. M. Science. 3 (a) X. 11 (a) S. 1555. Li. O’Keeffe and O. M. Am. B. G. Y. Chem. Matter. Morikawa. 2012. K. Taga. 3. If we take the dielectric constant of NTU-9 to be B101 (a typical value for most of the MOFs). the Mott–Schottky measurement gives the flat-band potential of NTU-9 at around 0. X. Garcia. J. 11133. Segall. Q. C. 6608. L. K. Am.. Ed. S. 2002. E. 2014. (c) Y. 6354. Nature.. NTU-9 exhibited persistent high photoactivity and good photostability. D. Rosi. Wu. 2006. Am.. Lightfoot. T. deKrafft and W.. M. L.5 M Na2SO4 aqueous solution. Y. Chem. ‡ Data collection of crystals was carried out on a Bruker APEX II CCD diffractometer equipped with a graphite-monochromatized Mo-Ka radiation source (l = 0. 80. (c) E. W. 112. Garcia. (b) C. Hendon. Fontecave. C. 2012. the Mott–Schottky measurement was performed in 0. 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