Synthesis of metal organic frameworks

based on lanthanum metal and perylene

ligand as photocatalyst for hydrogen gas
production
Cite as: AIP Conference Proceedings 2243, 020034 (2020); https://doi.org/10.1063/5.0005000
Published Online: 04 June 2020

A. Zulys, Q. A’yun and J. Gunlazuard

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© 2020 Author(s).
 Synthesis of Metal Organic Frameworks Based on
Lanthanum Metal and Perylene Ligand as Photocatalyst for
Hydrogen Gas Production
A. Zulysa), Q. A’yun, and J. Gunlazuard

Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Indonesia, Depok, 16424,
Indonesia
a)
Corresponding author: zulys@ui.ac.id

Abstract. Lanthanum-Metal Organic Frameworks (La-MOFs) have been successfully synthesized based on perylene-
3,4,9,10-tetracarboxylic dyes and ion lanthanum (La3+) as metal organic linkers using solvothermal methods. The
absence of absorption at wavenumber 1700 cm-1 as vibration stretching v(C=O) from La-MOFs, indicates that the oxygen
atom from ligand can coordinate with the lanthanum metal ion. This indicates that La-MOFs has been successfully
formed. Peak intensity of strong and sharp from X-ray diffraction indicates the high crystallinity of La-MOFs. La-MOFs
possesses a HOMO-LUMO band gap of 2.686 eV determined by UV-Vis spectroscopy with absorbed edge at 462 nm,
which present effective photocatalytic activity for hydrogen gas production in the process of water splitting under UV-
Vis irradiation. The results of cyclic voltammetry from La-MOFs obtained a reduction potential value (LUMO) of -
2.0735 V vs. NHE which is more negative than the H+/H2 reduction potential, it can be concluded that La-MOFs have
potential thermodynamic requirements for the reduction of H+/H2. The production of hydrogen gas obtained from La-
MOFs reached 4112.784 µmol in 4 hours.

INTRODUCTION
The problem of the energy crisis throughout the world and environmental problems caused by the increasing use
of limited fossil fuels has been a concern of researchers in the search for clean and renewable energy sources.
Therefore, other alternatives are needed to replace fossil fuels with other fuels that are cleaner and renewable.
Hydrogen is a renewable and environmentally friendly energy source that has the potential to replace fossil fuels [1].
One method that can be used to produce hydrogen is the photocatalytic water splitting with semiconductors to
produce hydrogen [1]. Major advancements have been made since Fujishima and Honda in 1972 converted solar
energy using TiO2 photocatalysts for water splitting to H2 and O2 [2]. The use of semiconductor catalysts has
received much attention because this technology has great potential, as well as large economic and environmental
interests for H2 fuel production which is clean from water using solar energy [1]. The research triggered the
development of semiconductor photocatalysis for various environmental and energy applications [1]. Photocatalysis
plays an important role in many fields, such as the synthesis of clean chemicals, environmental remediation (e.g.
degradation of organic dyes, reduction of heavy metal ions in wastewater, and inhibition of air pollution), energy
regeneration (e.g. separation of water into H2 and O2) [1].
Semiconductors are considered to be one of the most promising photocatalysts for various photoredox reactions,
due to appropriate bandgap, low cost, high chemical stability, and environmental friendliness [2]. Some
semiconductors include TiO2, CdS, CdSe, ZnO, Fe2O3, besides that MOFs can also act as semiconductors in
photocatalysts [2]. Extensive MOFs have been extensively studied as photocatalysts for the production of hydrogen
gas from water and have been proven to be alternative semiconductor photocatalyst materials and metal complexes
[1]. Metal Organic Frameworks (MOFs) or known as coordination polymers, are crystalline compounds consisting
of an unlimited number of lattices [3]. These lattices consist of a secondary building unit (SBU) composed of metal

The 8th International Conference of the Indonesian Chemical Society (ICICS) 2019
AIP Conf. Proc. 2243, 020034-1–020034-7; https://doi.org/10.1063/5.0005000
Published by AIP Publishing. 978-0-7354-2002-1/$30.00

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ions/clusters and an organic linker, which are connected to one another through coordination bonds with moderate
bond strength [3]. MOFs have several characteristics such as large surface area, homogeneous active sites and
tunable functionality, so MOFs are successfully applied in various fields, such as gas storage, separation, sensors
and catalysts, and several other applications. The use of MOFs in the catalyst has made several increasing efforts to
explore the potential of MOFs as a new class of photocatalysts [3]. MOFs have several characteristics such as large
surface area, homogeneous active sites and tunable functionality so that they can increase light absorption in the
photocatalytic process [3].
A general approach has been used to attempt to obtain active photocatalyst MOFs for hydrogen production [7].
One strategy is to combine light harvesting units into MOFs, for example, Ti-based MOF (TLMOF-NH2) [4] and Zr-
based MOF (UiO-66-NH2) [5] used as photocatalysts for hydrogen production. By loading the amino group on the
linker framework, the absorption of this MOF photocatalyst can be extended to the visible light region to a certain
extent. In addition, [6] Porphyrin-based Al-MOF showed excellent evolution of photocatalytic hydrogen under
visible light with Pt nanoparticles as co-catalyst and MV2+(Methyl viologen N,N'-dimethyl-4,4'-bipyridinium) as
acceptors electron. Another strategy is modification of post synthesis of MOFs with photosensitizers or catalysts to
improve photocatalytic performance, such as Pt(bpydc)Cl, [Ru(dcbpy)(bpy)2]2+ and [Fe2S2]. When this light
absorbing metal complex is doped into MOFs, a very active photocatalytic MOF with visible light response is
generated [7]. Recently, dye-sensitized Pt@UiO-66(Zr) was synthesized by Rhodamine B which was absorbed or
added directly to hydrogen production in the presence of triethanolamine [7]. With the presence of MOFs light
harvesting mentioned above, it might also be wondered whether organic dyes or ligands such as dyes can be applied
as linkers to build metal organic frameworks by reaction with metal ions, where the advantages of efficient light
sensitization and photocatalytic sites can be incorporated into the frame and will be more effective for light
harvesting [8]. Sun, et al. 2016 successfully synthesized Gd-MOFs-based dye-like azo-carboxylic acid with extra
stability for different pH solutions. Due to the exact energy level of frameworks and excellent light harvest from
ligands similar to dyes, the only Gd-MOF without the aid of co-catalysts, shows prominent photocatalytic activity
for hydrogen production under UV radiation - Visible with 530 nm adsorption wavelength and has a bandgap of
2.35 eV. After loading Ag as a co-catalyst, photocatalytic activity increased to 1.5 times the value given by the Gd-
MOF [9].
Based on the background described, we applied the strategy of constructing dye-based MOFs and utilizing them
for hydrogen generation. In this study, 3,4,9,10-perylene tetracarboxylic was chosen as an organic linker and light
harvester units by reaction with La3+ ions. As a result, La-MOFs exhibited good performance in hydrogen evolution
without the presence of co-catalyst.

EXPERIMENTAL STUDIES

Materials
Distilled water, Perylene-3,4,9,10-Tetracarboxylic Dianhydride 97% and La(NO3)3.6H2O 99.9% were purchased
from Sigma Aldrich production, Sulfuric Acid 98% (H2SO4), N,N-dimethylformamide (DMF), Ethanol (C2H5OH),
Sodium Hydroxide (NaOH), and Methanol (CH3OH) were purchased from Merck.

Preparation of Na-Perylene Ligand from perylene-3,4,9,10-tetracharboxylate anhydrate

(PTCDA)
PTCDA (0.5 g, 1.27 mmol) was deposited in 50 mL of distilled water and then added NaOH (0.356 g, 8.9 mmol)
while stirring rapidly. The greenish solution produced was then filtered and the filtrate obtained was added with
excess ethanol to obtain yellow precipitate. The precipitated Na4-PTC was then filtered and washed by ethanol to
pH 6-7 and dried at room temperature (in a desiccator).

Synthesis of La-MOFs with the Solvothermal Method

La(NO3)3.6H2O (0.33 mmol, 0.1429 g) dissolved with distilled water as much as 4 mL, and added by Na4-PTC
(0.25 mmol, 0.1291 g) which has been dissolved in DMF (4 mL) and H2O (11 mL), then mixed with stirring for 1
hour, then transferred to Teflon-autoclave to be heated for 24 hours at a temperature of 170°C. After the reaction

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time, the temperature was reduced by 5° C/15 minutes, then filtered after it was washed with ± 5 mL of distilled
water and DMF, then dried in an oven at a temperature of 50° C – 60° C for 24 hours. The results obtained were
weighed, crushed and put into vial bottles. The yields obtained were then weighed.

Photocatalytic Activity of La-MOFs for Hydrogen Gas Production

The photocatalytic experiments were carried out in a 200 mL pyrex reactor. The photocatalyst was dispersed in
100 mL of 10% methanol aqueous solution. Before irradiation, the system was purged for at least 30 min to remove
dissolved oxygen. Then, the resulting mixtures were irradiated for 4 h with 150 W Mercury lamp and stirred at room
temperature. After the reaction, gas evolution was analyzed by Shimadzu gas chromatograph with a TCD. The
resulting hydrogen peak is in the form of area and concentration then calculated quantitatively the amount of
hydrogen gas (H2) produced.

RESULTS AND DISCUSSION

Synthesis of Lanthanum-Metal Organic Frameworks (La-MOFs)

La-MOFs synthesis was carried out using the solvothermal method in the liquid phase using DMF and distilled
water solvents. The ratio of reactant molar ratio 0.33: 0.25 was used with a reaction time of 24 hours. The
solvothermal method is expected to provide better precursor solubility. In this study, lanthanum (III) nitrate
hexahydrate (La(NO3)3.6H2O) was chosen as a source of lanthanum metal ions. Lanthanum in the form of nitrate
salt has a large solubility in distilled water.

Characterization of La-MOFs
Fourier Transform Infra-Red (FTIR)

Figure 1 shows the FTIR spectra of PTCDA (Perylene-3,4,9,10-Tetracarboxylic dianhydride), Na4-PTC

(Tetrasodium; Perylene-3,4,9,10-Tetracarboxylic), and La-MOFs. Based on the FTIR spectra, we can identify the
functional groups produced, at wave numbers 1774 cm-1 (s) and 1302 cm-1 (s) identified as stretching vibrations of
closed chain (cyclic) C=O anhydride groups in PTCDA no longer appearing on the Na4-PTC FTIR spectrum. In the
Na4- PTC FTIR spectrum shows the absorption that appears at wave numbers 1594 cm-1 (s) and 1435 cm-1 (s) which
are identified as stretching vibrations of the group (—COO—), confirming that there is a sodium carboxylic group
which is conjugated to the perylene ring [10]. Stretching vibration -C=O carboxylic at wave numbers 1725-1700 cm-
1
does not appear in the IR La-MOFs spectrum. This shows that there has been a deformation of the ligand structure
which is characterized by the appearance of stretching asymmetry and symmetry at wave numbers 1554 and 1436
cm-1 [11]. The separated band between these vibration modes indicates that the –COO– of PTC is coordinated to
La3+. In the FTIR spectrum of La-MOFs, the absorption that appears at wave number 1584 cm-1 (s) is identified as
the asymmetric stretching vibration (—COO) of the Na4-PTC ligand. The uptake that appears at wave number 419
cm-1 (m) is identified as a vibration v(La—O), which confirms the coordination between the lanthanide metal ion
and oxygen v(Ln—O) appearing at 400 - 470 cm-1.

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 FIGURE 1. FTIR spectra of PTCDA, Na4PTC, and La-MOFs

UV-Vis Diffuse Reflectance Spectroscopy (DRS)

Figure 2 (a) shows the absorbance spectrum of La-MOFs and the band gap energy curve of La-MOFs, at a
wavelength of 400 nm the spectrum increases sharp absorbance, this indicates that the electrons in the valence band
are activated and excited by absorbing the photons given at a wavelength of 400 nm. The absorbance spectrum of
La-MOFs (0.33: 0.25) is at a wavelength of 461.4904 nm. The conversion of wavelength to energy can be done
through the Planck's equation, with the formula Eg = 1240/λ, using the formula, the gap energy of La-MOFs can be
calculated, from the calculation of the gap energy obtained at 2.687 eV. From the DRS UV-Vis data, the reflectance
measurements of a solid material are obtained. The percent reflectance data obtained at a wavelength of 200-800
nm, is converted to energy quantities using the theory of Kubelka Munk. This amount of energy is called the
bandgap energy of a material. Slit energy from La-MOFs (0.33: 0.25) is obtained by connecting the value of E (eV)
to (FR)2 as seen in Figure 2 (b). The gap energy value is obtained at 2.686 eV. This gap energy value can be said to
be almost no difference with the calculation results using wavelengths through the Planck's equation.

FIGURE 2. (a) Spectrum of La-MOFs absorbance; (b) band gap La-MOFs energy curve

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 Cyclic Voltammetry (CV)

La-MOF analysis using cyclic voltammetry was carried out by mixing carbon powder with La-MOFs and stirring
until homogeneous and then added paraffin. The paste formed is then transferred to the Teflon bar which has been
inserted into a copper bar and dried and then used as a working electrode in the process of testing cyclic
voltammetry. In cyclic voltammetry, a platinum (Pt) rod is used as a counter electrode. Ag/AgCl is used as a
reference electrode and H2SO4 1 M as an electrolyte solution with measurements at room temperature and a scan
rate of 50 mV s-1. Cyclic voltammetry was used to determine the suitability of the HOMO (High Occupied
Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) values of La-MOFs to meet the
thermodynamic requirements for La-MOFs water splitting with the requirement to be more negative than the
reduction potential H+/H2.

FIGURE 3. CV curve of La-MOFs

La-MOFs synthesis results with a ratio of molar ratio metal: ligand 0.33: 0.25 has a band gap of 2.686 eV with
the results of cyclic voltammetry shown in Figure 3 with an oxidation potential (HOMO-High Occupied Molecular
Orbital) of 0.4125 V vs Ag/AgCl (0.6125 V vs NHE) and if the gap energy obtained is 2.686 eV then the reduction
potential (LUMO-Lowest Unoccupied Molecular Orbital) is -2.0735 V vs NHE where the La-MOFs reduction
potential value is more negative than the reduction potential H+/H2 at pH 7 (-0.41 V) it can be concluded that La-
MOFs have the potential for thermodynamic requirements for the reduction of H+/H2.

X-Ray Diffraction (XRD)

XRD characterization was carried out to see the crystallinity of La-MOFs. Metal Organic Frameworks are known
as compounds that have high crystallinity. The sharp diffraction peaks in Figure 4 diffractogram pattern La-MOFs
(0.33: 0.25) indicate good crystallinity. La-MOFs (0.33: 0.25) have diffraction peaks at 2-theta at 6.363; 9.229;
9.998; 12.691; 18.349; 18.922; 21.248; 21.615; 23.433; 28.993. The most prominent peak was observed around 6°
which corresponds to the (011) plane, and this reveals the improvement crystallinity. The phenomenon is similar to
the previously result in MOFs synthesis [12], to determine the structure and size of crystals can be tested using X-
Ray Crystallography.

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 FIGURE 4. Diffractogram pattern La-MOFs

Photocatalytic Activity of La-MOFs

Figure 5 is the result of a photocatalytic test of La-MOFs with a mass of 0.02 g which was suspended into a
reactor containing 90 mL of water and 10 mL of methanol. From zero to thirty minutes, it can be seen that the
profile of hydrogen gas production tends to be low. This shows that the system is still in a phase of adjustment
(catalyst activation). In the first hour, the total production of hydrogen produced was 741.529 µmol, indicating that
the catalyst was activated. There was an increase in total hydrogen production which can be observed in the picture.
The second hour was obtained 1473.236 µmol. Towards the third hour, a significant increase in total hydrogen
production was 3864.790 µmol. This can be said to be the optimum time for hydrogen gas production if the La-
MOFs mass used 0.02 g. In the third hour leading to the fourth hour, there was an increase in total hydrogen
production which was not too significant at 4112.784 µmol.

FIGURE 5. Photocatalytic H2 production under UV-Vis light irradiation of dye based La-MOFs

CONCLUSION
In summary, Lanthanum-Metal Organic Frameworks (La-MOFs) have been successfully synthesized based on
perylene-3,4,9,10-tetracarboxylic dyes and ion lanthanum (La3+) as metal organic linkers using solvothermal
methods. There is no absorption at wavenumber 1700 cm-1 as stretching vibration v(C=O) for La-MOFs, indicating
the oxygen atom from the ligand can coordinate with lanthanum metal ions. This indicates that La- MOFs have been
successfully formed. The strong and sharp diffraction intensity of the X-ray peak indicates the high crystallinity of
La-MOFs. The results of cyclic voltammetry from La-MOFs obtained a reduction potential value (LUMO) of -

020034-6
2.0735 V vs. NHE which is more negative than the H+/H reduction potential, it can be concluded that La-MOFs
have potential thermodynamic requirements for the reduction of H+/H2. The production of hydrogen gas obtained
from La-MOFs reached 4112.784 µmol for 4 hours.

ACKNOWLEDGEMENT
This work was financially supported by HIBAH PITTA 2019 University of Indonesia.

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