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Research Article | | Peer-Reviewed

Synthesis and Characterization of Highly Efficient Cu-BTC MOF, ([Cu3(C9H3O6)2].3H2O{18H2O}) Photocatalyst for the Adsorptive Transformation of Coloured Organic Pollutants in Water

Aba Akebi Atta-Eyison,  Ruphino Zugle*
Published in Modern Chemistry (Volume 12, Issue 3)
Received: 30 July 2024     Accepted: 26 August 2024     Published: 11 September 2024
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Abstract

Photocatalysis has garnered significant attention for its potential in environmental remediation, energy conversion, and sustainable chemistry. Metal-organic frameworks (MOFs) have emerged as promising photocatalytic materials due to their tunable structures, high surface areas, and unique optical properties. Among them, a newly synthesized copper-benzene-1, 3, 5-tricarboxylic acid (Cu-BTC) MOF, [Cu3(C9H3O6)2].3H2O{18H2O} has shown remarkable potential as a photocatalyst. In this work, the synthesis and characterization of a novel [Cu3(C9H3O6)2].3H2O{18H2O} for its photocatalytic applications is described. The synthesis of [Cu3(C9H3O6)2].3H2O{18H2O} was achieved through a solvothermal method employing Copper (II) Nitrate trihydrate and benzene-1, 3, 5-tricarboxylic acid as precursors in a suitable solvent. The synthesized [Cu3(C9H3O6)2].3H2O{18H2O}) was characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), Scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS), Single crystal and Thermogravimetric (TGA) analysis. The photocatalytic activity of ([Cu3(C9H3O6)2].3H2O{18H2O}) was evaluated in the transformation of Lissamine green SF (LGSF) and Tetraethylrhodamine (TeRh) under solar light irradiation. The intermediate compounds obtained during the transformation of LGSF under photocatalysis were detected using a gas chromatography-mass spectrometer (GC-MS). The recyclability of [Cu3(C9H3O6)2].3H2O{18H2O}was investigated to demonstrate its stability, robustness and potential for practical applications. Conclusively, the [Cu3(C9H3O6)2].3H2O{18H2O} was proven to be an effective catalyst in the mineralization of LGSF and TeRh.

Published in Modern Chemistry (Volume 12, Issue 3)
DOI 10.11648/j.mc.20241203.11
Page(s) 47-59
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

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Copyright © The Author(s), 2024. Published by Science Publishing Group
Previous article
Keywords

Metal-organic Frameworks, Solvothermal Synthesis, Characterization, Adsorption, Light Irradiation

1. Introduction
Copper (Cu) is one of the prevailing transition metal elements used as a metal centre for metal-organic frameworks (MOFs). Copper is abundant, less expensive, non-toxic and has amazing complexation strength
[3, 4]
. Copper-based MOFs are, therefore, easy to synthesize due to the remarkable complexation property of copper
[5, 6]
. The d9 system of Cu (II) complexes leads to diversified structural geometries. Geometries such as square planar, tetrahedral, octahedral, trigonal planar, square pyramidal and trigonal bipyramid have been found
[7-12]
. Copper is one of the first transition elements to be used with benzene-1, 3, 5- tricarboxylic acid to synthesize HKUST-1 ([Cu3(BTC)23H2O]n), which has served as a standard for adsorption studies for many years
[13, 14]
. After the discovery of the promising adsorption property of HKUST-1, numerous research into the synthesis of copper-base MOFs using different synthetic techniques including hydrothermal, solvothermal, microwave, and sonochemical techniques with varying parameters have been investigated for different applications with a recent focus on photocatalysis
[15-21]
.
Copper-base MOFs as photocatalysts should have the ability to capture light and have a light excitation period that produces charge separation. An efficient electron-hole separation is obtained in MOFs by the transfer of photogenerated electrons from the organic ligands onto the surfaces of metal clusters through ligand-to-metal charge transfer (LMCT)
[22-25]
. The amount of energy absorbed by MOF for excitation (Eabs) is directly related to the band gap (Eg) between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of ligands and the energy necessary to transfer the photogenerated electrons from the LUMO of the ligands to the LUMO of the metal clusters (ELMCT)
[22, 24, 26-28]
. Charge separation is better when Eg is constant with ELMCT approaching zero or negative. This condition results in a smaller absorbed excitation energy (Eabs) to enhance visible light absorption.
[29-32]
.
In a photocatalytic mineralization process, the HOMO/LUMO in MOFs performs a similar function as the conduction and valence band (CB/VB) in semiconductors
[33-36]
. During photocatalysis, ligand-to-metal charge transfer (LMCT) occurs. Electrons then transit from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO)
[37-40]
of the metal. The transition of electrons from the HOMO leaves holes in the HOMO. The transitioned election in the LUMO is trapped by oxygen molecules reducing it to yield superoxide radical (•O2-). This radical is a strong oxidant which can react rapidly with adsorbed pollutants. The strong oxidative ability of the holes (h+) generated in the HOMO enables the direct adsorption of pollutants and the oxidation of the surface hydroxyl group or water to generate hydroxyl radicals (•OH). The hydroxyl radicals (•OH) formed are also a strong oxidant which is capable of reacting eagerly with surface-adsorbed pollutants. The activity of these generated radicals and holes can lead to pollutant mineralization
[41-44]
.
Recently, the use of Cu-BTC MOFs as photocatalysts for the mineralization of pollutants in water has been keenly investigated
[45-55]
. A comprehensive analysis has been conducted to highlight the wide range of advantageous characteristics exhibited by Cu-BTC MOF, establishing it as a highly versatile material with applications across various domains. Emphasis has been placed on its reactivity, the significance of the metal ion, and its recent potential in effectively tackling the removal of hazardous textile dye pollutants from wastewater effluent. Drawbacks such as low stability and low turnout in photocatalytic performance have, however, been observed. The photocatalytic performance of Cu-BTC is usually enhanced by hydrogen peroxide activity to generate sufficient radicals for the photocatalytic mineralization process
[45, 46]
. Additionally, most studies into the use of Cu-BTC MOFs as photocatalysts involve the modification of Cu-BTC MOFs into composites through post-synthesis to improve their stability and photocatalytic performance
[47-55]
. The low stability and low turnout in the photocatalytic performance of Cu-BTC MOFs may highly relate to inappropriate synthetic processes. The choice of reaction conditions, the duration and kinetics of the synthesis process as well as the ratio of metal ions to organic ligands during synthesis is critical. It is, therefore, vital to optimize the synthetic processes for Cu-BTC MOFs. As a result of this emerging exploitation, research into the synthesis of a highly effective stable copper MOF photocatalyst using the solvothermal synthetic technique to transform organic dyes into less toxic compounds in water was intended.
2. Materials and Methods
2.1. Materials
Copper (II) nitrate trihydrate (98-103%, Sigma Aldrich), Benzene- 1, 3, 5- tricarboxylic acid (H3BTC) (95%, Aldrich Chemistry), Ultrapure water (100%,), methanol (99.9%, Daejung Chemicals and Metals Co. LTD), ethanol (99.6% J. T. Baker), Lissamine green SF (65%, Paskem Finechemical Industries) and Tetraethylrhodamine (≥95%, Paskem Finechemical Industries). The chemicals were used as obtained.
2.2. Synthesis of [Cu3(C9H3O6)2].3H2O{18H2O}
The synthesis of the Cu-BTC MOF, ([Cu3(C9H3O6)2].3H2O{18H2O}), was a modification of the synthetic procedure reported in previous works
[57, 58]
. A 60 mL solution (15 mL ethanol /45 mL ultrapure water) containing 3.5 mmol 1, 3, 5-benzene tricarboxylic acid ((H3BTC) and 5 mmol of Copper (II) Nitrate trihydrate was heated at 120 °C for 18 hours in Teflon liner autoclave. The acquired compound was filtered, washed thoroughly with methanol and dried in the oven at 70°C overnight to acquire a blue crystal product.
2.3. Characterization
Various test were done to characterize H3BTC and [Cu3(C9H3O6)2].3H2O{18H2O}. Functional groups were identified by Fourier transform infrared (FTIR) analysis using the Bruker Alpha Spectrometer. The crystallinity was investigated using an Empyrean X-ray Diffractometer. The surface morphology and elemental analysis were analyzed using ZEISS EVO MA 15 SEM-EDS. The topology of [Cu3(C9H3O6)2].3H2O{18H2O} through Single Crystal analysis was done using Rigaku 007VHF diffractometer. The thermal stability of the [Cu3(C9H3O6)2].3H2O{18H2O} was examined using the SDT Q600 V20.9 System under a nitrogen atmosphere. The data for the various characterizations have been referenced
[1]
. A band gap analysis was performed by measuring the UV-visible absorption of [Cu3(C9H3O6)2].3H2O{18H2O} using the T70 UV/VIS Spectrometer by PG Instruments Ltd.
2.4. Photo-Transformation Test
The photocatalytic activity of the synthesized [Cu3(C9H3O6)2].3H2O{18H2O} was studied on Lissamine green SF (LGSF) and Tetraethylrhodamine (TeRh). For each photocatalytic activity, a 150 mL beaker containing 100 mL of sample pollutant solution and [Cu3(C9H3O6)2].3H2O{18H2O} as catalyst was stirred in the dark for an hour to achieve adsorption/desorption equilibrium and then under solar light for 180 min. During the photocatalytic activity, a 5 mL aliquot was drawn at 30 min intervals to observe the absorbance.
2.5. Adsorption Study
The quantities of pollutants adsorbed on the surfaces of [Cu3(C9H3O6)2].3H2O{18H2O} at a given time t, and at equilibrium, are obtained using equation (1) and equation (2).
qt=(Ci- Ct)m ×V(1)
qe=(Ci- Ce)m×V(2)
Where; qt(mg/g) is the adsorption capacity of [Cu3(C9H3O6)2].3H2O{18H2O} at a given time, qe(mg/g) is the adsorption capacity of [Cu3(C9H3O6)2].3H2O{18H2O} at equilibrium, Ci (mg/L) = initial concentration of pollutant in solution, Ct(mg/L) = concentration of pollutant in solution at time t, Ce (mg/L) = concentration of pollutant in solution at equilibrium, V is the volume of solution (L) and m is the mass (g) of [Cu3(C9H3O6)2].3H2O{18H2O}. The pollutant percentage removal efficiency was calculated using Equation (3)
Pollutant removal efficiency (%) =Ci- CtCi ×100%(3)
2.6. Transformed Compound Determination Test
SHIMADZA GC-MS QP 2020 was used to identify intermediate compounds from the transformed pollutants
[2]
. For the gas chromatogram (GC), a DB-5ms column of 30 m × 0.25 mm, 0.25 μm film thickness was employed. An injection pot temperature of 250°C and splitless injection mode were employed with helium as the carrier gas. For the mass spectrometer (MS), the ion source temperature was 210 °C. It was run on scan mode with start m/z 50.00 to m/z 1030.
3. Results
3.1. Characterization
To investigate the link between the metal and the ligand, Fourier transform infrared (FTIR) spectrum of H3BTC (a) and that of the [Cu3(C9H3O6)2].3H2O{18H2O} (b) was investigated as shown in Figure 1. A shift of broadband to the left is observed for [Cu3(C9H3O6)2].3H2O{18H2O} compared to that observed in H3BTC. The broadband between 3650 cm−1 to 2840 cm-1 could be due to the presence of the OH group from water molecules adsorbed on the surface of the [Cu3(C9H3O6)2].3H2O{18H2O} from its’ hydrate salt
[59-61]
. The intense bands from 1370 cm-1 to 1609 cm-1 could be associated with the asymmetric and symmetric vibrational stretch of the carboxylate (COO-) groups found in the [Cu3(C9H3O6)2].3H2O{18H2O}
[61, 62]
. The bands between 1100 cm−1 to 680 cm−1 relate to the in and out of plane vibrations of CH in the benzene ring found in H3BTC and [Cu3(C9H3O6)2].3H2O{18H2O}
[60, 62, 63]
. The bands at 660 cm−1 and 480 cm−1 in [Cu3(C9H3O6)2].3H2O{18H2O} (b) could be a result of Cu–O bending and stretching vibrations similar to reports related to copper complexes
[59, 64]
.
Figure 1. FTIR of (a) H3BTC and (b) [Cu3(C9H3O6)2].3H2O{18H2O}.
Crystallinity study of (a) H3BTC (a) and [Cu3(C9H3O6)2].3H2O{18H2O} (b) through X-ray diffraction (XRD) analysis is shown in Figure 2 referenced in research data. The obtained XRD result of [Cu3(C9H3O6)2].3H2O{18H2O} (b) indicates the formation of well-resolved peeks with main diffraction peaks at 6.70°, 9.48°, 11.62°, 13.43°, 16.50°, 17.48o, 19.05°, 20.21o, 24.16o, 25.97 o, 29.35o, 35.50o and 39.28o which indicate a high degree of crystallinity. The diffraction peaks 6.70o, 9.48o, 11.62o, 13.43o and 29.35o were identifiable to similar angles for H3BTC (a).
Figure 2. XRD of (a) H3BTC (b) ([Cu3(C9H3O6)2].3H2O{18H2O}).
The morphology and elemental analysis of H3BTC (a) and [Cu3(C9H3O6)2].3H2O{18H2O} (b) using scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS) is as shown in Figure 3. It is observed that H3BTC shows a close-packed arrangement with a cuboid-shaped morphology. The EDS spectrum revealed the presence of carbon (C) copper and oxygen (O) with atomic percentages of 64.62 % for carbon and 35.38 % for oxygen. SEM-EDS images of [Cu3(C9H3O6)2].3H2O{18H2O} exhibited cubic crystal particles with trapezoid shapes. The EDS spectrum revealed the presence of carbon (C), copper (Cu) and oxygen (O) with atomic percentages of 58.22 % for carbon, 34.21 % for oxygen and 7.57% for copper (C).
Topology analysis of [Cu3(C9H3O6)2].3H2O{18H2O} through Single crystal XRD is shown in Figure 4. The [Cu3(C9H3O6)2].3H2O{18H2O} had a unit formula C6H16CuO11 and crystallizes in the Fm-3m space group with a grown view of each unit [Cu3(C9H3O6)2].3H2O{18H2O} (a) consisting of an assembly of two linked copper atoms (Cu1) forming coordinates with four carboxylate oxygen atoms (O1) each and one oxygen atom (O2) each from coordinated H2O molecule
[65, 66]
. The unit assembly forms a cubic crystal system with a trapezoid shape having a size dimension of 0.10×0.09×0.07 mm3 with a bond length of a = 26.2891(3) Å, b = 26.2891(3) Å, c = 26.2891(3) Å and bond angle, a = b = g = 90°. A water mask of V = 18168.8(6) Å3 was obtained for a void per unit cell. The coordination of the carboxylate oxygen, water oxygen and copper develops into a highly porous 3D network of metal-organic framework shown in Figure 4(b) having four pore centres.
Figure 3. SEM-EDS of (a) H3BTC and (b) [Cu3(C9H3O6)2].3H2O{18H2O}.
Figure 4. Single crystal XRD of (a) A grown view of [Cu3(C9H3O6)2].3H2O{18H2O} (b) A 3D network of [Cu3(C9H3O6)2].3H2O{18H2O}.
Thermogravimetric analysis (TGA) of [Cu3(C9H3O6)2].3H2O{18H2O} is shown in Figure 5. Two main weight loss steps and corresponding rate of change of weight loss exothermic peaks were observed. The first weight loss percentage of 23.63% with a corresponding rate of change of weight loss of 7.31 %/min observed between 50°C and 200°C relates to the elimination of water molecules and organic solvents remaining in the [Cu3(C9H3O6)2].3H2O{18H2O}
[58, 67]
. A large percentage loss of 37.71% and a correspondingly high rate of change of weight loss of 22.64 %/min observed between 350°C and 400°C indicates the decomposition of [Cu3(C9H3O6)2].3H2O{18H2O} due to the removal of ligand molecule from [Cu3(C9H3O6)2].3H2O{18H2O}
[67, 68]
. A slight decrease in the percentage weight loss observed in the range of 400–800 °C indicates the formation of copper oxide formed after the decomposition of the [Cu3(C9H3O6)2].3H2O{18H2O}
[58, 59]
. The decomposition of [Cu3(C9H3O6)2].3H2O{18H2O} around 400°C indicates it is thermally stable and will only disintegrate above 300°C.
Figure 5. TGA-DSC of [Cu3(C9H3O6)2].3H2O{18H2O}.
The UV-visible absorption spectrum of [Cu3(C9H3O6)2].3H2O{18H2O} in Figure 6 shows a maximum absorption wavelength of 386 nm. The Eg was subsequently calculated using Equation (4)
[69, 70]
.
Eg=1240λg(4)
Where, Eg = band gap energy of photocatalyst in electron volt (eV) and λg = absorption edge of photocatalyst in nanometers (nm). Eg = 2.67 eV was observed. Schottky barrier height (ΦB) at equilibrium with graphical definition as the difference between the interfacial conduction band edge (EC) and Fermi level (EF)
[71, 72]
was recorded as 0.32ev.
Figure 6. Uv-Visible absorption spectrum of [Cu3(C9H3O6)2].3H2O{18H2O}.
3.2. Photo-Transformation Test
The photocatalytic ability of [Cu3(C9H3O6)2].3H2O{18H2O} for the transformation of Lissamine green SF (LGSF) and Tetraethylrhodamine (TeRh) which resulted in their removal from water is shown in Figure 7. Over 80% pollutant removal was observed using [Cu3(C9H3O6)2].3H2O{18H2O} as photocatalyst. The percentage of LGSF (92.56%) removal was however higher than that of TeRh (85.43%) removal.
Figure 7. Photoactivity of [Cu3(C9H3O6)2].3H2O{18H2O} (Optimum parameters: [Pollutant] = 0.20 g/L;[Cu3(C9H3O6)2].3H2O{18H2O} Loading = 0.10 g/L; Solution pH = 6; Percentage error = 5%; Number of repeated experiment =3).
This indicates [Cu3(C9H3O6)2].3H2O{18H2O} is photoactive with efficient charge separation to generate radicals through an oxidation-reduction process during photolysis to mineralize LGSF and TeRh as indicated in Figure 8.
Figure 8. Band structure and Photocatalytic mechanism of [Cu3(C9H3O6)2].3H2O{18H2O}on LGSF and TeRh.
A review of previously published literature on the photocatalytic degradation of organic dyes has shown that [Cu3(C9H3O6)2].3H2O{18H2O} demonstrates comparable efficiency to what has been reported in Table 1. The results indicate that [Cu3(C9H3O6)2].3H2O{18H2O} exhibits higher efficiency than HKUST-1 and MOF-199 in the mineralization of LGSF and TeRh pollutants (200 ppm), using a catalyst concentration of 100 mg/L (0.10 g/L). The efficiency of [Cu3(C9H3O6)2].3H2O{18H2O} in the mineralization of TeRh (Rhodamine B) can be compared to composites like TiO2@HKUST-1, ZnO@HKUST-1, Ag/HKUST-1/ g-C3N4, and HKUST-1/PMS/Vis which require higher catalyst concentrations or lower pollutant concentrations. The unique properties of [Cu3(C9H3O6)2].3H2O{18H2O}, such as remarkable thermal stability, a large surface area, and substantial pore volume, contribute to its exceptional performance. The presence of Cu2+ ions, which are redox active, enhances its photocatalytic effectiveness by participating in both oxidation and reduction reactions. Additionally, [Cu3(C9H3O6)2].3H2O{18H2O}maintains its structural integrity during the adsorption and desorption of water. Furthermore, the synthesis procedure for [Cu3(C9H3O6)2].3H2O{18H2O}is simple, making it a promising candidate for various photocatalytic applications.
Table 1. Summary of reported photodegradation of dyes by Cu-BTC and Cu-BTC composites.

Cu-BTC, Cu-BTC based Photocatalyst

Pollutants

Pollutant concentration (ppm)

Catalyst loading (mg/L)

Irradiation time (min)

Efficiency (%)

Ref

HKUST-1

Rhodamine B, Methylene blue

10

120

5.8, 53

46

MOF-199

Methylene blue

5

40

300

88.96

45

HKUST-1/PMS/Vis

Rhodamine B, Methylene blue

10

120

95

46

GO/ ZIF-8/HKUST-1

Congo red

50

500

60

91

47

CuO@HKUST− 1

Methylene blue

55

833.3

180

98

48

Cu-H3-btc–Ag2O

Orange G

4.5

440

80

68.96

49

TiO2@HKUST-1

Rhodamine B

300

120

95.20

50

HKUST-1(Cu)/polymer

Acid Black

15

45

96

73

ZnO@HKUST-1

Rhodamine B

20

320

45

97.4

51

Ag/Ag3PO4/HKUST-1

Biotrack 405 Blue caspase-3 dye (PBS)

1000

80

87

52

Ag/HKUST-1/ g-C3N4

Rhodamine B

0.5

500

90

87.4

53

TiO2@HKUST-1

Methylene blue

20

500

60

91

54

GO− CS@Cu3(btc)2

Methylene blue

10

500

60

98

55
The UV-visible absorption spectra of LGSF (640 nm) and TeRh (560 nm) are as shown in Figure 9. A gradual reduction of peaks at 30 min time intervals for 180 min was observed. This gradual reduction demonstrated that the pollutants were being removed from the sample solution.
Figure 9. Uv-visible absorption spectra of (a) Lissamine Green SF (LGSF) at 640 nm and (b) Tetraethylrhodamine (TeRh) at 560 nm under mineralization.
The structures of the intermediates observed for the removal of LGSF and TeRh from water after gas chromatography-mass spectroscopy (GC-MS) analysis are shown in Table 2. LGSF (749.893 g/mol) was disintegrated into fragment compounds such as Phenol, 2, 2'-methylenebis [6-(1, 1-dimethylethyl)-4-methyl (m/z 340), 2, 6-di-tert-butyl-4-(2, 4, 6-trimethyl benzyl) phenol (m/z 338), 3-Phenyl-2-ethoxypropylphthalimide (m/z 309), 13-Tetradecenyl acetate (m/z 256), Phenol, 2, 4-bis(1, 1-dimethylethyl)-5-methyl (m/z 220) and Fumaric acid-ethyl-2-methylallyl ester (m/z 198). Fragment compounds observed for TeRh (479.02 g/mol) include 1, 2-benzene dicarboxylic acid, bis(2-ethylhexyl) ester (m/z 390), Dodecanoic acid, 4-nitrophenyl ester (m/z 321), 15-Hydroxypentadecanoic acid (m/z 258), 6-Hydroxy-4, 4, 5, 7-tetramethyl-2-chromanone (m/z 220) and 2, 5-Dimethyl-1, 5-hexadiene-3, 4-diol (m/z 142).
Table 2. Summary of Intermediates after 180 min Photoactivity on LGSF and TeRh.

Lissamine green

(LGSF)

Intermediates Percentage

(m/z 340)

(m/z 338)

(m/z 309)

(m/z 220)

(m/z 256)

(m/z 198)

Time

30

(84%)

(96%)

(64%)

(49%)

--

--

60

(61%)

(62%)

(41%)

(46%)

(59%)

(13%)

90

(21%)

(52%)

(34%)

(93%)

(74%)

(21%)

120

(13%)

(23%)

(42%)

(71%)

(84%)

(62%)

150

(17%)

(11%)

--

(67%)

(91%)

(89%)

180

--

--

--

(31%)

(71%)

(97%)

Tetraethylrhodamine

(TeRh)

Intermediates Percentage

(m/z 390)

(m/z 321)

(m/z 220)

(m/z 258)

(m/z 142)

Time

30

(97%)

(54%)

(71%)

(13%)

--

60

(34%)

(66%)

(51%)

(37%)

(21%)

90

(21%)

(42%)

(23%)

(42%)

(26%)

120

(18%)

(35%)

--

(78%)

(73%)

150

(11%)

(19%)

(62%)

(74%)

(82%)

180

--

--

(19%)

(93%)

(97%)
3.3. Reusability of [Cu3(C9H3O6)2].3H2O{18H2O}
That [Cu3(C9H3O6)2].3H2O{18H2O} was observed in Figure 10 to be relatively stable with no considerable loss of activity over three cycles of the photocatalytic activity on Lissamine green SF (LGSF). This stability indicates its potential application for wastewater treatment.
Figure 10. Cycle Test of [Cu3(C9H3O6)2].3H2O{18H2O} on Pollutants (Percentage error = 5%).
Figure 11. XRD of [Cu3(C9H3O6)2].3H2O{18H2O} before (a) and after (b) Cycle photocatalytic transformation test.
The X-ray diffraction (XRD) result of [Cu3(C9H3O6)2].3H2O{18H2O}before and after the cycle activity is shown in Figure 11. Similar diffraction peaks were observed after the cycle test confirming the stability of [Cu3(C9H3O6)2].3H2O{18H2O}. There was however a slight shift in diffraction peaks after the three-cycle activity which may have resulted in the slight decrease in photoactivity as observed in Figure 10.
SEM image of [Cu3(C9H3O6)2].3H2O{18H2O} before and after the cycle activity is shown in Figure 12. Cubic crystal particles with trapezoid shapes similar to the morphology before the cycle was observed although closely packed. The closely packed morphology may be a result absorption of moisture.
Figure 12. SEM of [Cu3(C9H3O6)2].3H2O{18H2O} before (a) and after (b) Cycle photocatalytic transformation test.
4. Conclusion
The key innovation of this work lies in the synthesis and characterization of the [Cu3(C9H3O6)2].3H2O{18H2O} MOF and its application as a photocatalyst. The researchers hypothesized that the unique structural properties, high surface area, and optical properties of the MOF would contribute to its exceptional photocatalytic performance. The work aimed to explore the potential of [Cu3(C9H3O6)2].3H2O{18H2O} in environmental remediation and sustainable chemistry. The newly synthesized [Cu3(C9H3O6)2].3H2O{18H2O} MOF demonstrated remarkable potential as a photocatalyst for the mineralization of LGSF and TeRh under solar light irradiation. The study contributes to the field of photocatalysis by introducing a novel MOF material with high surface area, and unique optical properties. The work presents improvements in terms of photocatalytic activity and provides a foundation for future research aimed at optimizing the synthesis process, understanding the mechanism of action, and exploring practical applications.
Abbreviations

CB

Conduction Band

EDS

Energy Dispersive X-ray Spectroscopy

FTIR

Fourier Transform Infrared

HOMO

Highest Occupied Molecular Orbital

LMCT

Ligand-to-Metal Charge Transfer

LUMO

Lowest Unoccupied Molecular Orbital

MOF

Metal-organic Framework

SEM

Scanning Electron Microscope

TGA

Thermogravimetric

UV

Ultraviolet

VB

Valence Band

XRD

X-Ray Diffraction
Acknowledgements
The authors would like to thank the University of Cape Coast Chemistry Department laboratory for providing the necessary facilities and resources to carry out this study. The authors would like to acknowledge Dr Samuel Tetteh a Senior Lecturer at the Department of Chemistry, University of Cape Coast, Ghana and James Orton a Crystallographer at the National Crystallography Service, University of Southampton, UK, for their assistance in the deposition of the crystal structure of the synthesized metal-organic framework.
The crystal structure of [Cu3(C9H3O)2].3H2O{18H2O} determined has been deposited with a CCDC 2277633. https://doi.org/10.5517/ccdc.csd.cc2gg212.
Author Contributions
Aba Akebi Atta-Eyison: Data curation, Formal Analysis, Investigation, Methodology, Resources, Writing – original draft
Ruphino Zugle: Conceptualization, Resources, Supervision, Writing – review & editing
Conflicts of Interest
The authors declare no conflicts of interest.
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    Atta-Eyison, A. A., Zugle, R. (2024). Synthesis and Characterization of Highly Efficient Cu-BTC MOF, ([Cu3(C9H3O6)2].3H2O{18H2O}) Photocatalyst for the Adsorptive Transformation of Coloured Organic Pollutants in Water. Modern Chemistry, 12(3), 47-59. https://doi.org/10.11648/j.mc.20241203.11

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    Atta-Eyison, A. A.; Zugle, R. Synthesis and Characterization of Highly Efficient Cu-BTC MOF, ([Cu3(C9H3O6)2].3H2O{18H2O}) Photocatalyst for the Adsorptive Transformation of Coloured Organic Pollutants in Water. Mod. Chem. 2024, 12(3), 47-59. doi: 10.11648/j.mc.20241203.11

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    Atta-Eyison AA, Zugle R. Synthesis and Characterization of Highly Efficient Cu-BTC MOF, ([Cu3(C9H3O6)2].3H2O{18H2O}) Photocatalyst for the Adsorptive Transformation of Coloured Organic Pollutants in Water. Mod Chem. 2024;12(3):47-59. doi: 10.11648/j.mc.20241203.11

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  • @article{10.11648/j.mc.20241203.11,
  author = {Aba Akebi Atta-Eyison and Ruphino Zugle},
  title = {Synthesis and Characterization of Highly Efficient Cu-BTC MOF, ([Cu3(C9H3O6)2].3H2O{18H2O}) Photocatalyst for the Adsorptive Transformation of Coloured Organic Pollutants in Water
},
  journal = {Modern Chemistry},
  volume = {12},
  number = {3},
  pages = {47-59},
  doi = {10.11648/j.mc.20241203.11},
  url = {https://doi.org/10.11648/j.mc.20241203.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.mc.20241203.11},
  abstract = {Photocatalysis has garnered significant attention for its potential in environmental remediation, energy conversion, and sustainable chemistry. Metal-organic frameworks (MOFs) have emerged as promising photocatalytic materials due to their tunable structures, high surface areas, and unique optical properties. Among them, a newly synthesized copper-benzene-1, 3, 5-tricarboxylic acid (Cu-BTC) MOF, [Cu3(C9H3O6)2].3H2O{18H2O} has shown remarkable potential as a photocatalyst. In this work, the synthesis and characterization of a novel [Cu3(C9H3O6)2].3H2O{18H2O} for its photocatalytic applications is described. The synthesis of [Cu3(C9H3O6)2].3H2O{18H2O} was achieved through a solvothermal method employing Copper (II) Nitrate trihydrate and benzene-1, 3, 5-tricarboxylic acid as precursors in a suitable solvent. The synthesized [Cu3(C9H3O6)2].3H2O{18H2O}) was characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), Scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS), Single crystal and Thermogravimetric (TGA) analysis. The photocatalytic activity of ([Cu3(C9H3O6)2].3H2O{18H2O}) was evaluated in the transformation of Lissamine green SF (LGSF) and Tetraethylrhodamine (TeRh) under solar light irradiation. The intermediate compounds obtained during the transformation of LGSF under photocatalysis were detected using a gas chromatography-mass spectrometer (GC-MS). The recyclability of [Cu3(C9H3O6)2].3H2O{18H2O}was investigated to demonstrate its stability, robustness and potential for practical applications. Conclusively, the [Cu3(C9H3O6)2].3H2O{18H2O} was proven to be an effective catalyst in the mineralization of LGSF and TeRh.
},
 year = {2024}
}

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  • TY  - JOUR
T1  - Synthesis and Characterization of Highly Efficient Cu-BTC MOF, ([Cu3(C9H3O6)2].3H2O{18H2O}) Photocatalyst for the Adsorptive Transformation of Coloured Organic Pollutants in Water

AU  - Aba Akebi Atta-Eyison
AU  - Ruphino Zugle
Y1  - 2024/09/11
PY  - 2024
N1  - https://doi.org/10.11648/j.mc.20241203.11
DO  - 10.11648/j.mc.20241203.11
T2  - Modern Chemistry
JF  - Modern Chemistry
JO  - Modern Chemistry
SP  - 47
EP  - 59
PB  - Science Publishing Group
SN  - 2329-180X
UR  - https://doi.org/10.11648/j.mc.20241203.11
AB  - Photocatalysis has garnered significant attention for its potential in environmental remediation, energy conversion, and sustainable chemistry. Metal-organic frameworks (MOFs) have emerged as promising photocatalytic materials due to their tunable structures, high surface areas, and unique optical properties. Among them, a newly synthesized copper-benzene-1, 3, 5-tricarboxylic acid (Cu-BTC) MOF, [Cu3(C9H3O6)2].3H2O{18H2O} has shown remarkable potential as a photocatalyst. In this work, the synthesis and characterization of a novel [Cu3(C9H3O6)2].3H2O{18H2O} for its photocatalytic applications is described. The synthesis of [Cu3(C9H3O6)2].3H2O{18H2O} was achieved through a solvothermal method employing Copper (II) Nitrate trihydrate and benzene-1, 3, 5-tricarboxylic acid as precursors in a suitable solvent. The synthesized [Cu3(C9H3O6)2].3H2O{18H2O}) was characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), Scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS), Single crystal and Thermogravimetric (TGA) analysis. The photocatalytic activity of ([Cu3(C9H3O6)2].3H2O{18H2O}) was evaluated in the transformation of Lissamine green SF (LGSF) and Tetraethylrhodamine (TeRh) under solar light irradiation. The intermediate compounds obtained during the transformation of LGSF under photocatalysis were detected using a gas chromatography-mass spectrometer (GC-MS). The recyclability of [Cu3(C9H3O6)2].3H2O{18H2O}was investigated to demonstrate its stability, robustness and potential for practical applications. Conclusively, the [Cu3(C9H3O6)2].3H2O{18H2O} was proven to be an effective catalyst in the mineralization of LGSF and TeRh.

VL  - 12
IS  - 3
ER  -

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Author Information

  • Aba Akebi Atta-Eyison

    Industrial and Health Sciences Department, Takoradi Technical University, Takoradi, Ghana

    Research Fields: Chemistry, Coordination chemistry, Catalysis, Analytical Chemistry, Organic Chemistry, Environmental Chemistry

    Contact Email

    http://orcid.org/0000-0002-3736-5383

  • Ruphino Zugle

    Department of Chemistry, University of Cape Coast, Cape Coast, Ghana

    Research Fields: Chemistry, Analytical Chemistry, Organic Chemistry, Coordination Chemistry, Catalysis, Environmental Chemistry

    Contact Email

    http://orcid.org/0000-0002-7976-8068

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  • Abstract
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  • Document Sections

    1. 1. Introduction
    2. 2. Materials and Methods
    3. 3. Results
    4. 4. Conclusion
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  • Abbreviations
  • Acknowledgements
  • Author Contributions
  • Conflicts of Interest
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