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Efficient hydrogen production and photocatalytic

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Cite this: Catal. Sci. Technol., 2013,

reduction of nitrobenzene over a visible-light-responsive
3, 2092
metal–organic framework photocatalyst†
Takashi Toyao,a Masakazu Saito,a Yu Horiuchi,*a Katsunori Mochizuki,b
Masatoshi Iwata,b Hideyuki Higashimurab and Masaya Matsuoka*a

Received 1st April 2013,
Accepted 24th April 2013
DOI: 10.1039/c3cy00211j
www.rsc.org/catalysis
Efficient hydrogen production and photocatalytic reduction of nitrobenzene were achieved by using a
Pt-deposited amino-functionalised Ti(IV) metal–organic framework (Pt/Ti-MOF-NH2) under visible-light
irradiation. XRD and N2 adsorption measurements revealed that crystalline microporous structures were formed
and maintained even after the Pt deposition. The photocatalytic activity for the visible-light-promoted hydrogen
production was improved through the optimization of the deposition amount of Pt as a cocatalyst. The
optimised amount of Pt was determined to be 1.5 wt%. The results of in situ ESR measurements clearly indicate
that the reaction proceeds through the electron transfer from the organic linker to deposited Pt as a cocatalyst
by way of titanium-oxo clusters. In addition, the Pt/Ti-MOF-NH2 photocatalyst was found to catalyse
photocatalytic reduction of nitrobenzene under visible-light irradiation. It was also confirmed that the catalyst
can be reused at least three times without significant loss of its catalytic activity.

Introduction Metal–organic frameworks (MOFs) also called porous coordina-

In recent years, various kinds of photocatalysts have been widely
investigated for applications in air and water purification, hazardous
waste elimination and the production of clean energy resources.1–5
Among them, enormous attention has been paid to photocatalytic
hydrogen production from water which is a promising way to
produce hydrogen as a potential clean energy source. In addition,
the development of a new process using photocatalysts for the
organic transformations has also been studied as an important
way to pursue environmentally benign and green chemistry.
However, most of the photocatalysts operate only under irradia-
tion by UV-light, consequently, only 3–5% of the solar energy
reaching the earth can be utilized. Because of this limitation,
development of an efficient system for light energy conversion
into chemical energy is one of the urgent subjects for research
from the viewpoint of the utilization of abundant sunlight.6–9
a
Department of Applied Chemistry, Graduate School of Engineering, Osaka
Prefecture University, 1-1, Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan.
E-mail: horiuchi@chem.osakafu-u.ac.jp, matsumac@chem.osakafu-u.ac.jp;
Fax: +81-72-254-9910; Tel: +81-72-254-9288
b
Advanced Materials Research Laboratory, Sumitomo-Chemical Co., Ltd., 6,
Kitahara, Tsukuba, Ibaraki 300-3294, Japan
† Electronic supplementary information (ESI) available: BET surface areas, XAFS
spectra, XRD patterns and FT-IR spectra before and after the photocatalytic
reduction reactions. See DOI: 10.1039/c3cy00211j
tion polymers (PCPs) have been of great interest due to their
beneficial properties such as extremely high surface areas,
well-ordered porous structures and structure designability.10–12
Taking advantage of these interesting properties, MOFs are widely
studied for many potential applications to gas storage,13–18
molecular sieving19–23 and catalysis.24–28 Additionally, an
increasing number of studies have been explored in recent
years to indicate that MOFs serve as platforms for integrating
different molecular functional components to achieve light
harvesting29–34 and to drive various photocatalytic reactions
such as H2 production,35–37 O2 production,38 carbon dioxide
reduction39 and organic transformations.40 Compared to other
photocatalytic systems, the MOF photocatalyst-catalysed systems
have advantages that various combinations of metal-oxo clusters
and bridging organic linkers allow for fine-tuning and rational
design of these photocatalysts at the molecular level, and further-
more, intrinsic porosity of MOFs facilitates the diffusion of
substrates and products through the open framework structures.
We have previously reported the synthesis of a visible-light-
responsive Ti-based MOF photocatalyst (Ti-MOF-NH2) by
employing 2-amino-benzenedicarboxylic acid as an organic
linker.41–43 Ti-MOF-NH2 promotes photocatalytic H2 production
from water containing sacrificial electron donors under visible-
light irradiation. It is also noteworthy that the reaction proceeds
through the light absorption by its organic linker and the following

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Paper
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Fig. 1 Schematic illustration of photocatalytic hydrogen production reaction
over Ti-MOF-NH2 under visible-light irradiation (l > 420 nm).
electron transfer to the catalytically active titanium-oxo cluster
as described in Fig. 1.
Although the visible-light-responsive MOF photocatalysts were
successfully developed, however, the improvement of photocatalytic
activities is still needed and the use should be expanded for various
catalytic reactions not only the H2 production reaction but also
other reactions such as organic transformations.
In the present study, we have prepared Ti-MOF-NH2 with differ-
ent loading amounts of Pt as a cocatalyst and investigated their
photocatalytic activities for the hydrogen production reaction. The
role of the deposited Pt was evaluated by in situ electron spin reso-
nance (ESR) measurements. Furthermore, the developed visible-
light-responsive MOF photocatalyst system was applied to photo-
catalytic reduction of nitrobenzene under visible-light irradiation.
Experimental
Materials
Tetrapropyl orthotitanate (TPOT) was purchased from Tokyo Kasei
Kogyo Co., Ltd. 2-Amino-benzenedicarboxylic acid (H2BDC-NH2;
C8H7NO4), 1,4-benzenedicarboxylic acid (H2BDC; C8H6O4),
N0 N-dimethylformamide (DMF; (CH3)2NCHO), methanol (CH3OH),
triethanolamine (TEOA; C6H15NO3), nitrobenzene (C6H5NO2) and
acetonitrile (CH3CN) were purchased from Nacalai Tesque Inc.
Hydrogen hexachloroplatinate(IV) hexahydrate (H2PtCl66H2O)
was purchased from Kishida Chemicals Co., Ltd.
Catalyst preparation
Ti-MOF-NH2 was synthesized on the basis of a method for the
preparation of MIL-125 (Ti-MOF) previously reported by M.
Dan-Hardi et al.,44 with the exception of using H2BDC-NH2 in place
of H2BDC as an organic linker. The mixture of TPOT, H2BDC-NH2,
DMF and methanol was subject to react under solvothermal condi-
tions in a Teflon-lined stainless steel autoclave for 48 h at 423 K
under autogenous pressure. The precipitate was filtrated, washed
repeatedly with DMF and dried at room temperature overnight.
Finally, the obtained powder sample was dried under vacuum for
1 h at 423 K to remove the residual H2BDC-NH2. For comparison,
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the conventional Ti-MOF was also prepared by using H2BDC as
an organic linker.
Pt deposition on Ti-MOF-NH2 as a cocatalyst was performed by
employing a photodeposition method. A suspension containing
Ti-MOF-NH2 (0.4 g), 0.039 M H2PtCl6 methanol solution
(0.55–2.2 mL), DMF (20 mL) and methanol (20 mL) was
irradiated with UV light from a 100 W high-pressure Hg lamp
at 5 mW cm2 for 3 h with continuous stirring. The obtained
precipitate was centrifuged, washed repeatedly with DMF and
dried in air at room temperature overnight. Finally the obtained
powder sample was dried under vacuum at 423 K for 1 h, yielding
Pt(X)/Ti-MOF-NH2, where X = 0.5, 1.0, 1.5 and 2.0 wt%.
General methods
Standard y–2y X-ray diffraction (XRD) data were recorded on a
Shimadzu X-ray diffractometer XRD-6100 using Cu Ka radiation
(l = 1.5406 Å). Specific surface areas were estimated from the
amount of N2 adsorption at 77 K using the BET (Brunauer–
Emmett–Teller) equilibrium equation. Diffuse reflectance UV-vis
spectra were obtained using a Shimadzu UV-vis recording spectro-
photometer 2200A. X-ray absorption fine structure (XAFS) spectra
were recorded at the BL-01B1 facility of the Photon Factory at
Spring-8 at the Japan Synchrotron Radiation Research Institute
(JASRI). The Pt L3 edge XAFS spectra were measured in the
fluorescence mode using a Si(111) double-crystal monochromator
at room temperature. Transmission electronic microscope (TEM)
images were taken using JEM-2000FX operating under 200 kV
accelerating voltage. Electron spin resonance (ESR) spectra were
recorded using a JEOL JES-RE-2X at 77 K. Prior to the measure-
ments, the sample immersed in an aqueous solution containing
0.01 M TEOA (2 mL) was added an in situ cell, evacuated at 77 K to
remove dissolved oxygen and then irradiated with visible light
having a wavelength of l > 420 nm from a Xe lamp (500 W;
San-Ei Electric Inc. XEF-501S) with a cut-off filter for 3 h at room
temperature. FT-IR measurements were carried out in the trans-
mission mode using a FT-IR spectrometer (JASCO FT-IR 660 Plus).
Self-supporting pellets of the samples diluted with KBr were loaded
in a specially constructed IR cell, which was equipped with CaF2
windows. After the pellets were evacuated at 473 K for 30 min, the
spectra were measured at room temperature.
Photocatalytic hydrogen production reaction
The photocatalyst (10 mg) and 0.01 M aqueous TEOA solution
(2 mL) were added to a Pyrex reaction vessel connected to a
vacuum line. The resulting mixture was evacuated at 77 K
to remove dissolved oxygen. Subsequently, the sample was
irradiated with the 500 W Xe lamp through a cut-off filter
(l > 420 nm) with stirring at room temperature. After the reaction,
the resulting gas was analyzed by using a gas chromatograph (GC)
of Shimadzu GC-12A with a thermal conductivity detector
equipped with a packed column (MS-5A).
Photocatalytic reduction of nitrobenzene
The photocatalyst (25 mg) and 4 mL of acetonitrile containing
nitrobenzene (0.1 mmol) and TEOA (1.0 mmol) were added to a
Pyrex reaction vessel. The vessel was sealed with a rubber
Catal. Sci. Technol., 2013, 3, 2092--2097 2093

Catalysis Science & Technology
septum, followed by 15 min of Ar bubbling. The reaction
mixture was irradiated with visible light having a wavelength
of l > 420 nm from the 500 W Xe lamp with a cut-off filter
(l > 420 nm) at room temperature. The progression of the
reaction was monitored using a GC (Shimadzu GC-14B with
a flame ionization detector) equipped with an InertCaps1
capillary column.
Reusability of the photocatalyst was studied as follows. After
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the first run, the photocatalyst was washed three times with
methanol, dried at 323 K in air and reused for the next run. The
above procedure was repeated three times.
Results and discussion
Diffuse reflectance UV-vis spectra of Ti-MOF-NH2 and Ti-MOF,
along with those of H2BDC-NH2 and H2BDC as reference
samples were obtained. Although Ti-MOF absorbs only UV
light, Ti-MOF-NH2 can absorb visible light up to around
500 nm owing to the organic linker unit (BDC-NH2), that is, a
MOF with visible-light absorption characteristics was success-
fully prepared by using H2BDC-NH2 as the organic linker.41–43
XRD patterns of Ti-MOF-NH2 before and after the photo-
deposition of Pt are shown in Fig. 2. Ti-MOF-NH2 exhibited the
same pattern observed for Ti-MOF, indicating the successful
formation of the MIL-125 structure, even using H2BDC-NH2 as the
organic linker. In addition, the characteristic peaks of the bulk
titanium dioxide phases such as anatase and rutile were not
detected in their diffraction patterns, suggesting that Ti-species
in Ti-MOF-NH2 do not form aggregated species but form titanium-
oxo clusters consisting of the MIL-125 framework. It was also found
that the diffraction patterns remained nearly unchanged even after
the photodeposition of Pt species regardless of the deposition
amount. This finding indicates that the photodeposition process
does not influence the structure of Ti-MOF-NH2.
To evaluate the pore structure and specific surface area, N2
adsorption measurements were performed before and after the
photodeposition of Pt species (Fig. S1 in the ESI†). A specific
surface area of Ti-MOF-NH2 was determined to be 1101 m2 g1
by using the BET method based calculation on its N2 adsorp-
tion isotherm. This result revealed that Ti-MOF-NH2 has large
Fig. 2 XRD patterns of Ti-MOF-NH2 and Pt(X)/Ti-MOF-NH2.
2094 Catal. Sci. Technol., 2013, 3, 2092--2097
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specific surface areas derived from its microporous structures.
After the photodeposition of Pt, its specific surface area
remained almost unchanged, suggesting the MOF structure
was preserved after the Pt deposition. This result is in good
agreement with the results of XRD measurements. The com-
bined results coming from XRD and BET specific surface area
measurements reveal that the MOF structure was maintained
even after the photodeposition process.
XAFS measurements were carried out to clarify the states of
the deposited Pt on Ti-MOF-NH2 (Fig. S2, ESI†). The edge
positions and shapes of the XANES spectra of Pt(X)/Ti-MOF-
NH2 are intermediate form between those of Pt foil and H2PtCl6
as reference samples. In the FT-EXAFS spectra of Pt(X)/Ti-MOF-
NH2, two peaks were observed at ca. 1.9 Å and 2.5 Å (without
phase-shift correction) assignable to Pt–Cl or –O and Pt–Pt
bonds, respectively.45 These results suggest that the deposited
Pt exist as mixed states of metal and ion on Ti-MOF-NH2. In
addition, TEM observations were also carried out for Pt(X)/
Ti-MOF-NH2. However, Pt nanoparticles were not observed
because of extremely small quantity of deposited Pt.
In order to investigate effectiveness of the Pt deposition
on Ti-MOF-NH2 as a cocatalyst, the photocatalytic hydrogen
production from aqueous solution containing TEOA (triethanol-
amine) as a sacrificial electron donor was carried out under
visible-light irradiation (l > 420 nm) at room temperature.
The results under the irradiation of visible light for 3 h are
presented in Fig. 3. The yields of evolved hydrogen increase
upon an increase in the Pt loading amount and achieve
a maximum when the loading amount is 1.5 wt%. Pt(1.5)/
Ti-MOF-NH2 gave 15.5 mmol of hydrogen after 3 h of visible-
light irradiation. In general, it is well-known that Pt, which
exists as a metal but not ion or oxide, plays major roles as
cocatalysts in hydrogen production.46 Pt cocatalysts accelerate
the hydrogen production reactions by trapping the photogen-
erated electrons, inducing efficient charge separation. There-
fore, it is expected that Pt metal behaves as cocatalysts in the
Pt(1.5)/Ti-MOF-NH2 catalyzed system.
Fig. 4 shows the time course of the hydrogen production
reaction catalysed by Pt(1.5)/Ti-MOF-NH2 with intermittent
evacuation and exposure to atmospheric conditions every 3 h.
Fig. 3 Photocatalytic hydrogen production under visible-light irradiation
(l > 420 nm) over Ti-MOF-NH2 and Pt(X)/Ti-MOF-NH2.
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Fig. 4 Time course of photocatalytic hydrogen production under visible-light

Fig. 5 ESR spectra observed at 77 K for Ti-MOF-NH2 (solid line) and Pt(1.5)/
irradiation (l > 420 nm) over Pt(1.5)/Ti-MOF-NH2 for a total of 9 h with
Ti-MOF-NH2 (dotted line) immersed in aqueous 0.01 M TEOA solution after
intermittent evacuation and exposure to atmospheric conditions every 3 h.
visible-light irradiation (l > 420 nm). The suspension was degassed under vacuum
at 77 K and irradiated with visible light for 3 h at room temperature, followed by
spectrum acquisition at 77 K.
Pt(1.5)/Ti-MOF-NH2 achieved steady hydrogen production with-
out significant loss of photocatalytic activity over at least three
cycles. In contrast, Pt/Ti-MOF showed no photocatalytic activity essential and stimulating research subjects.50–52 Photochemical
under the same conditions. The results obtained from several excitation can be conducted at room temperature without the use
control reactions revealed that the light irradiation as well as of harmful reagents, which results in environmentally benign and
the presence of Pt(1.5)/Ti-MOF-NH2 and TEOA as a sacrificial energy saving processes.53,54 From this point of view, the visible-
electron donor are essential for the progression of the reaction. light-responsible MOF (Pt(1.5)/Ti-MOF-NH2) was applied to photo-
For the elucidation of the role in the Pt deposited as a catalytic reduction of nitrobenzene under visible-light irradiation
cocatalyst, the charge separation characteristics of Pt-deposited (l > 420 nm). Fig. 6 shows the time courses of the amounts of
and -undeposited Ti-MOF-NH2 were investigated by in situ ESR nitrobenzene, nitrosobenzene and aniline. The amounts of nitro-
measurements. For the measurements, Pt(1.5)/Ti-MOF-NH2 or benzene monotonously decreased along with photoirradiation time
Ti-MOF-NH2 was immersed in a solution of 0.01 M aqueous TEOA and the amount of aniline increased. In addition, nitrosobenzene
solution, and the suspension was evacuated at 77 K. This was was also obtained as an intermediate product of the reaction.49 For
followed by irradiation of visible light (l > 420 nm) for 3 h at room comparison of the photocatalytic activities of Pt(1.5)/Ti-MOF-NH2,
temperature. After irradiation, the ESR spectrum was recorded at the initial reaction rates for Pt(1.5)/Ti-MOF-NH2 and Ti-MOF-NH2
77 K. As shown in Fig. 5, the ESR spectrum after visible-light were determined to be 3.3 and 2.3 mmol h1, respectively (on
irradiation contains signals, whose parameters are characteristic of the basis of the nitrobenzene conversion). Pt(1.5)/Ti-MOF-NH2
paramagnetic Ti3+ centers in a distorted rhombic oxygen ligand exhibited higher photocatalytic activity than Ti-MOF-NH2,
field (gx = 1.994, gy = 1.958 and gz = 1.904). It has already been indicating that deposited Pt efficiently acts as a cocatalyst in
reported that the ESR spectrum after visible-light irradiation this system. It was also confirmed that selectivities of the
contains the signal assigned to Ti3+ species.41 This result suggests reaction are almost the same regardless of the presence of Pt
that visible light promotes transfer of photogenerated electrons
from the excited BDC-NH2 group to the conduction band of
titanium-oxo cluster, resulting in the formation of Ti3+ species
for Ti-MOF-NH2. In the case of Pt(1.5)/Ti-MOF-NH2, the intensity in
the ESR signal due to the Ti3+ species was small as compared to
that of Pt-undeposited Ti-MOF-NH2 after visible-light irradiation. It
is well-known that the photogenerated electrons were efficiently
transferred from TiO2 to the Pt species over Pt/TiO2 systems,47,48
preventing the formation of the Ti3+ species and electron–hole
recombination. The increased amount of evolved hydrogen on
Pt(1.5)/Ti-MOF-NH2 can, thus, be ascribed to the suppression of
the electron–hole recombination due to electron trapping by Pt,49
i.e., the transfer of the electrons from titanium-oxo cluster to Pt
deposited on Ti-MOF-NH2. In addition, it was also observed that
the signals assigned to Ti3+ species disappear after exposure to air,
indicating the reoxidation of generated Ti3+ species to Ti4+ species. Fig. 6 Time course of photocatalytic reduction of nitrobenzene (K) to nitroso-
The design of effective photocatalysts for the synthesis of benzene (m) and aniline (’) under visible-light irradiation (l > 420 nm) in the
specialty chemicals under visible-light irradiation is one of the presence of TEOA over Pt(1.5)/Ti-MOF-NH2.

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Fig. 7 Wavelength-dependent apparent quantum yield for the photocatalytic Fig. 8 Recycling tests for photocatalytic reduction of nitrobenzene under visible-
reduction of nitrobenzene reaction over Pt(1.5)/Ti-MOF-NH2. The apparent light irradiation (l > 420 nm) over Pt(1.5)/Ti-MOF-NH2. Reaction conditions:
quantum yields were determined on the basis of the conversion of nitrobenzene. catalyst (25 mg), acetonitrile containing 0.1 mmol of nitrobenzene and 1.0 mmol
of TEOA (4 ml), Xe lamp (500 W) light source with a cutoff filter, Pyrex reaction
vessel, room temperature, 72 h.
species. On the other hand, no reaction took place in the
absence of visible-light irradiation, Pt(1.5)/Ti-MOF-NH2
and TEOA as a sacrificial electron donor, that is, Pt(1.5)/ toward the photocatalytic reduction of nitrobenzene under
Ti-MOF-NH2 acts as a visible-light responsive photocatalyst in visible-light irradiation.
this system. In addition, the reaction did not proceed when
using Pt(1.5)/Ti-MOF or a physical mixture of Pt(1.5)/Ti-MOF
and H2BDC-NH2 as a photocatalyst. This fact indicates that the Conclusions
coordination networks of Ti-oxo clusters and BDC-NH2 units
A visible-light-responsive metal–organic framework (MOF)
are key factors for the progression of the reaction.
photocatalyst was developed by employing 2-amino-benzenedi-
To further confirm the reaction mechanism, the wavelength
carboxylic acid as an organic linker. The synthesized amino-
dependence of apparent quantum efficiency was investigated,
functionalized Ti-based MOF (Ti-MOF-NH2) exhibited efficient
as shown in Fig. 7. The trend of the apparent quantum yield
photocatalytic activities for hydrogen production reaction from
matches well with that of the absorption spectrum. This result
aqueous solution containing TEOA as a sacrificial electron
suggests that the reaction proceeds through the light absorp-
donor under visible-light irradiation. Pt deposition successfully
tion by its organic linker and the following electron transfer to
enhanced the photocatalytic activities, indicating that Pt species
the catalytically active titanium-oxo cluster, as displayed in
efficiently act as a cocatalyst. The optimal amount of Pt deposition
Fig. 1. Therefore, it can be considered that nitrobenzene was
was determined to be 1.5 wt%. ESR investigations suggested that
reduced over Pt deposited on Ti-oxo clusters and TEOA was
deposited Pt play an important role in realizing the efficient charge
sacrificially oxidized over BDC-NH2 groups under visible-light
separation of the photogenerated electrons and holes, leading
irradiation. It is not fully understood what oxidation products
to the high photocatalytic performance of Pt(1.5)/Ti-MOF-NH2.
were produced in this system. However, it was at least con-
In addition, Pt(1.5)/Ti-MOF-NH2 also catalysed photocatalytic
firmed that CO2 was not evolved as the oxidation products.
reduction of nitrobenzene to nitrosobenzene and aniline under
Finally, the reusability of Pt(1.5)/Ti-MOF-NH2 was investi-
visible-light irradiation (l > 420 nm) and could be reused at
gated, as shown in Fig. 8. The catalyst after the reaction for 72 h
least three times without significant loss of photocatalytic
was washed with methanol, dried under vacuum, and then
activity. These findings will lead to highly active photocatalysts
reused for the next run. The results of recycling tests indicated
in solar energy utilization.
no significant loss of photocatalytic activities even after three
cycles. Moreover, XRD and FT-IR measurements were performed
before and after four cycles of the reaction to investigate the Acknowledgements
stability of Pt(1.5)/Ti-MOF-NH2 (Fig. S3 and S4 in the ESI†). The
diffraction peaks corresponding to the MIL-125 structure were The present work is supported by a Grant-in-Aid for Scientific
maintained even after the four cycles of the reaction. FT-IR Research (KAKENHI) from Ministry of Education, Culture,
spectra of Pt(1.5)/Ti-MOF-NH2 both before and after four cycles Sports, Science and Technology of Japan (No. 21550192). T. T.
of the reaction exhibit two absorption bands at around 3382 thanks the JSPS Research Fellowships for Young Scientists. The
and 3470 cm1 which are attributed to the symmetrical and X-ray absorption measurements were performed at the BL-01B1
asymmetrical stretching vibrations of free amino groups (–NH2), facility of Spring-8 at the Japan Synchrotron Radiation Research
respectively. This fact demonstrates that the organic linker with Institute (JASRI) (No. 2012A1310) and at the BL-7C facility of the
amino group stably exist during the reaction. From these results, Photon Factory at the National Laboratory for High-Energy
it was found that Pt(1.5)/Ti-MOF-NH2 possesses high durability Physics (No. 2011G556).

2096 Catal. Sci. Technol., 2013, 3, 2092--2097 This journal is c The Royal Society of Chemistry 2013

Paper
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