Available online at http://ijcpe.uobaghdad.edu.iq and www.iasj.net Iraqi Journal of Chemical and Petroleum Engineering Vol. 24 No.2 (June 2023) 113 – 122 EISSN: 2618-0707, PISSN: 1997-4884 *Corresponding Author: Name: Mohammed Thamer Jaafar, Email: mohammed.thamer@uokerbala.edu.iq IJCPE is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License. Synthesis of Novel Porphyrin Derivatives and Investigate their Application in Sensitized Solar Cells Mohammed Thamer Jaafar a, b, *, Luma Majeed Ahmed b, and Rahman Tama Haiwal b a Department of Petroleum Engineering, College of Engineering, Kerbala University, Karbala, Iraq b Department of Chemistry, College of Science, Kerbala University, Karbala, Iraq Abstract Solar energy has significant advantages compared to conventional sources such as coal and natural gas, including no emissions, no need for fuel, and the potential for installation in a wide range of locations with access to sunlight. In this investigation, heterocyclic derivatives were synthesized from several porphyrin derivatives (4,4',4",4"'-(porphyrin-5,10,15,20-tetrayl) tetra benzoic acid) compound (3), obtained by reaction Pyrrole with 4-formyl benzoic acid. Subsequently, porphyrin derivative-component amides 5a, 5b, and 5c were produced by reacting compound (3) with amine derivatives at a 1:4 molar ratio. These derivatives exhibited varying sensitivities for utilization in solar cells, with compound 5a displaying the highest power conversion efficiency (PCE) at 1.37%, as determined by measuring the short circuit current (Jsc), open-circuit voltage (Voc), and fill factor (FF) (Jsc = 2.24 mA cm-2, Voc = 0.80 mV, FF = 76.5%). Meanwhile, compound 5c exhibited the lowest PCE at 0.94% (Jsc = 1.55 mA cm-2, Voc = 0.750 mV, FF = 76.4%). Keywords: Synthesis Porphyrin, Porphyrin Derivatives, power conversion efficiency, Solar Cells. Received on 28/02/2023, Received in Revised Form on 05/04/2023, Accepted on 06/04/2023, Published on 30/06/2023 https://doi.org/10.31699/IJCPE.2023.2.13 1- Introduction Greek porphyria, which means purple, is the source of the term porphyrin. They belong to a vast family of highly colored pigments with a substituted aromatic macrocycle ring that is either natural or synthetic in origin and are composed of four pyrrole rings connected by four methine bridges [1–6]. The study of porphyrins has recently attracted more and more attention. porphyrins are utilized in a wide range of devices and applications, including optoelectronic, luminescent, and molecular logic ones, photonic materials, solar energy harvesting systems, supramolecular self-assembly, and medicines. The porphyrins' various electrochemical and photophysical characteristics, as well as the exocyclic substituents on the macrocycle's capacity to fine-tune these properties, have an impact on these applications [7–11]. Porphyrins have a wide variety of beneficial properties, some of which include high stability, strong photon absorption, a highly conjugated plane, and a little energy difference exists between the lowest unoccupied molecular orbital (LUMO) and highest occupied molecule orbital (HOMO). These are just a few examples of the benefits that porphyrins offer. A porphyrin has an appropriate quantity of electrons due to its highly conjugated -electron skeleton and transitions often result in substantial absorption in the UV and visible range [12– 15]. Despite the abundance of described procedures, it is still difficult to synthesize porphyrins with specified functional patterns. Separations, purifications, and the scarcity of acceptable precursors all add to the challenges. Despite reports of synthetic approaches to different porphyrins, there is currently no supply of porphyrin building blocks with certain peripheral substituents [16– 18]. The solar cell, a promising source of renewable energy that transforms sunlight into electricity, has great promise for helping to address humanity's ongoing energy crisis. Due to its multiple benefits, including its capability to operate in an acoustically tranquil setting, and its absence of toxicity or greenhouse gas emissions, the field of solar energy technology is currently experiencing significant expansion. As opposed to other photovoltaic devices, dye- sensitized solar cells (DSSCs) stand out among other solar cells due to their tall efficiency, inexpensive, straightforward manufacturing processes, environmental friendliness, transparency, and excellent flexibility. Although DSSCs outperform conventional solar cells in the lab, their commercial applicability is determined by factors including efficiency, longevity, and cost. Traditional DSSCs are made up of a variety of important parts, the most essential of which are a nanocrystalline semiconductor oxide, a dye sensitizer, a redox electrolyte, and a counter electrode. Traditional DSSCs also include other elements. To lower manufacturing costs and achieve excellent cell performance, in-depth research on the http://ijcpe.uobaghdad.edu.iq/ http://www.iasj.net/ mailto:mohammed.thamer@uokerbala.edu.iq http://creativecommons.org/licenses/by-nc/4.0/ https://doi.org/10.31699/IJCPE.2023.2.13 M. T. Jaafar et al. / Iraqi Journal of Chemical and Petroleum Engineering 24,2 (2023) 113 - 122 114 individual DSSC components has recently been carried out. The performance of the cell is influenced by a variety of variables, including surface shape, particle size, TiO2 photoelectrode thickness, and dye type. Utilizing liquid electrolytes, a total solar conversion efficiency of more than 12% has been attained [19–22]. However, using liquid electrolytes in DSSCs has many drawbacks, including restricted solubility of inorganic salts like KI, NaI, and LiI, electrode corrosion, and short- term stability owing to organic solvent evaporation and leakage. In order to facilitate the reduction process (I-/I-3), the counter electrode, which receives its charge from the photo-oxidized dye, injects electrons into the electrolytes. Conventional conductive glasses, such as indium- or fluorine-doped tin oxide, provide a poor rate of reduction for the counter electrode in the absence of a catalyst; as a result, the counter electrode must be coated with a catalytic substance to speed up the process. Due to its better conductivity and strong electrocatalytic activity, platinum (Pt) is favored in this respect. However, because of the corrosive I-/I-3 redox electrolyte and the slow dissolution of platinum, which reduces its long-term stability, platinum is a highly costly, rare noble metal. These limitations prevent Pt electrodes from being used extensively in DSSCs. Therefore, it is crucial to create substitute noble-metal-free materials that can take the place of platinum as an electrocatalyst. It is feasible to achieve a high-power conversion efficiency with a very thin platinum film of 2 nm since the power conversion efficiency of DSSCs does not grow proportionally to an increase in the thickness of the platinum film [23–26]. As novel compounds, they have demonstrated success as photovoltaic materials by exhibiting responsiveness to solar cells. The achieved results indicate favorable prospects for utilizing newly synthesized porphyrin-based compounds in conjunction with TiO2 paste as an anode material. This work focused on the synthesis of some new substituted porphyrin derivative compounds (3) that start from Pyrrole with 4-forms benzoic acid and preparing amides derivatives from compound (3). The characterization of all prepared compounds will do and then test them as solar cells. 2- Experimental Part 2.1. Material and Instruments The chemicals employed in this investigation were procured from a variety of manufacturers, including Sigma Aldrich, and were utilized directly without any additional purification. To verify the identity of the resulting compounds, melting points were precisely determined utilizing a digital Electro Thermal Stuart SMP-30. Fourier transform infrared spectroscopy (SHIMADZU FTIR-8400S) was conducted and reported in cm-1 units. Nuclear magnetic resonance spectra were obtained in DMSO-d6 using a Bruker spectrometer, operating at 500 MHz for 1H NMR and 125 MHz for 13C NMR. ESI-mass spectra were obtained using an Agilent Technology (HP) instrument with electron ionization at 70 eV. 2.2. Preparation and Spectral Characterization of Porphyrin Derivatives 2.2.1. Synthesis of 4,4',4",4"'-(porphyrin-5,10,15,20- tetrayl) tetra benzoic acid (3) Pyrrole (4 mol) was added to a solution of substituted aldehyde (4-formyl benzoic acid) (4 mol) in propionic acid (20 mL), and the reaction mixture was refluxed for one hour in the dark after that. After that, the solution was filtered and washed with hot water. 2.2.2. Preparation of porphyrin derivatives 5a-c (General procedure) 1 mmol of SOCl2 was added to 1 mmol of 4,4’,4’’,4’’’-(porphyrin-5,10,15,20-tetrayl) tetra benzoic acid (TCPP). The mixture was stirred at 70 rpm for 30 minutes at environmental temperature, then DMF (5mL) was added with continuous stirring at the same temperature. The final solution was transferred to a round bottom flask volume (25 mL), 4 mmol of amines (a-c) were added to the last solution with reflex at 120 oC for (2-3) hours, and then 8 mmol of triethylamine (Et3N) was added with continuous reflex at 120 oC for 1huore. The black solution was added to ice crystal, filtration, and washed with ethanol. 2.3. Fabrication of the Working Electrodes (WE) Isopropanol and acetone were applied to the Fluorine- doped Tin Oxide (FTO) glass slides for a total of 10 minutes to fully clean them. All cleaned substrates are then DIW washed and dried using a hot air stream. TiO2 was used as an electrode in the fabrication of DSSCs, together with other photoanode materials. Every time, the paste produced from the photoanode materials was applied to the FTO substrates together with 0.2 g of TiO2 with 0.4 mL of (0.1 M) HNO3, and one drop of Triton X- 100 (C34H62O11, M.Wt. 646.67 g/ mol) In order to achieve the thin and symmetrical thickness indicated in Fig. 1, the produced paste is applied to an FTO-glass substrate using a glass rod. The sample is then dried for 10 minutes at 80 oC. In order to avoid dye photodegradation, the produced samples were then submerged in a porphyrin derivative- compensated amide solution for 2 hours in the dark after being annealed for 3 hours at 220 °C. The surface of the photoanode materials was cleaned with ethanol absolute to remove non-absorbed dye molecules [27]. Finally, As demonstrated in Fig. 2, the graphite electrode is created by employing a candle flame on a spotless FTO glass surface [28]. 2.4. Preparation of the Counter Electrode (CE) A drop of (0.1M) iodine solution was added between two prepared electrodes. A (0.1 M) iodine solution was M. T. Jaafar et al. / Iraqi Journal of Chemical and Petroleum Engineering 24,2 (2023) 113 - 122 115 prepared by combining 3.175 g of iodine (I2) with 10 g of potassium iodide (KI) in 25 mL of absolute ethanol. The solution is then maintained in an opaque container after shaking the flask until the iodine has fully dissolved [29]. In order to prevent the solution from leaking beyond the designated cell region, the counter electrode is then put on the working electrode and the solution is retained in an opaque container [30]. The J-V curve was used to compute the open-circuit voltage (Voc) and short-circuit current (Jsc). The following equations were used to calculate the solar cells' efficiency and fill factor (FF) [31, 32]. 𝐹𝐹 = 𝐽𝑚𝑎𝑥 𝑉𝑚𝑎𝑥 𝐽𝑆𝐶 𝑉𝑜𝑐 (1) 𝜂 = 𝐽𝑠𝑐 𝑉𝑜𝑐 𝐹𝐹 𝐼𝑜 (2) Where Io is the total incident irradiance, Vmax is the solar cell's maximum power point voltage, and Jmax is the maximum power point current. Fig. 1. FTO Glasses Fixed with Medical Tape Fig. 2. (A) FTO Glasses with Dye and (B) Graphite Counter Electrode 3- Results and Discussion 3.1. Synthesis and Spectroscopic Characterization of the Porphyrin Derivatives The product compound (3) as shown in Fig. 3 was diagnosed using the infrared spectrum by the appearance of NH, OH, and CO groups in carboxylic acid at radii of 3371, 3300, and 1674 cm-1, respectively. The 1H-NMR spectra of compound 3 showed a singlet signal at -2.29 (2H), which can be attributed to the N-H in the pyrrole group. The compound (3) was characterized by various techniques like FT-IR, 1H-NMR, and Mass spectroscopy (Fig. 4 – Fig. 6). Fig. 3. Scheme of Produced of Compound (3) (3) 4,4',4",4"'-(porphyrin-5,10,15,20-tetrayl) tetra benzoic acid Color: Black powder: Yield 21%, mp > 350°C Rf =0.85 (n-hexane/ethyl acetate) FT-IR (KBr, Cm- 1):3371(NH),3300-2400(OH),3043(C-H aromatic),1674(C=O), 1604 (C=N), 1573 (C=C),.1H NMR (500MHz, DMSO-d6) 𝛿H (ppm): 12.91(s,4H- COOH), 8.41-8.79(d, J = 7.6 Hz Pyrrole-8H),). 7.13-8.38 (m, 16 Ph-H), -2.29 (s,2NH), 13C NMR (500MHz, DMSO-d6) δ C 122.25,126.64,126.92,129.53,129.55, 130.57,130.57,130.61130.63,138.03,139.17,143.88,147.6 5,168.1 4., UV-Vis. Spectrum: (𝜆max), 419 nm.); EI–MS calcd exact mass (C48H30N4O8), 790.77; found, 790.6. The second step involved the reaction of compound (3) with a variety of amines to obtain (5a-c), as explained in Fig. 7. These compounds were investigated using the infrared spectrum by disappearing the carbonyl group and appearing the amide group. The Experimental part provides all of the porphyrin derivatives' complete spectrum information (MS, FT-IR, 1 H, and 13C NMR), as well as melting points. Compound (3) was reacted with a variety of amines in the second step to produce compound (5a-c), as displayed in Fig. 7. Using an infrared spectrum, these compounds were identified by the disappearance of the OH in carboxylic acid (3300) cm-1 and the appearance of the amide group (3420) cm-1. The Experimental section gives comprehensive spectral data (MS, FT-IR, 1H, and 13C NMR) and melting points for all porphyrin derivatives. All the new compounds were characterized by various techniques like FT-IR and 1H-NMR Mass spectroscopy (Fig. 8 – Fig. 12). (5-a) 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl) tetrakis(N- (benzo[d]thiazol-2-yl) benzamide) Color: Black powder: Yield 80%, mp > 350°C FT-IR (KBr, Cm-1):3425(NH Stretch),3055(C–H aromatic),1701(C=O), 1608 (C=N),1489(C=C), 636(C- S)., 1HNMR (500MHz, DMSO-d6): 𝛿H (ppm): 10,51 (s,4H-CONH), 8.66-8.11 (m 8H Pyrrole-H), 8.09-7.97 (m, 8 Ar-H,),7.84-7.87(m, 8 Ar-H), 7.71 (d, J = 8.1 Hz, 4H Ar-H), 7.45-7.16 (m 12H Ar-H), -2.29 (s,2NHint)., 13C NMR (500 MHz, DMSO-d6) δ C 120.03,120.93,122.2, 123.60,125.64,126.64,126.92,129.43,129.52,129.54,130.6 1,130.64,130.71,132.15,138.01,138.72,139.35,143.88,147 .65,150.32,156.83,159.77,166.95., UV-Vis. Spectrum: (𝜆max), 417nm.; Anal.Calcd for (C76H46N12O4S4): C, 69.18; H, 3.51; N, 12.74; O, 4.85; S, 9.72 found C, 69.01; (A) (B) M. T. Jaafar et al. / Iraqi Journal of Chemical and Petroleum Engineering 24,2 (2023) 113 - 122 116 H, 3.32; N, 12.48 %.,EI–MS calcd exact mass 1319.52; found, 1319.5. (5-b) 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl) tetrakis(N- (1H-benzo[d]imidazol-2-yl) benzamide) Color: Black powder: Yield 82%, mp > 350°C FT-IR (KBr, Cm-1):3421(NH Stretch),3036 (C–H aromatic),1705(C=O), 1624 (C=N),1485(C=C)., 1HNMR (500MHz, DMSO-d6): 𝛿H (ppm): 11.37 (s,4NH), 10.69 (s,4H-CONH), 8.86 -8.37 (m,8 Pyrrole-H), 8.10-7.12 (m, 32H Ar-H), -2.25 (s,2NH pyrrole), Anal.Calcd for (C76H50N16O4): C, 72.95; H, 4.03; N, 17.91; found C, 72.60; H, 4.21; N, 17.70 %., ESI–MS calcd exact mass 1251.34; found, 1251.22. (5-c) 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl) tetrakis(N- (4-carbamoylphenyl) benzamide) Color: Black powder: Yield 84%, mp > 350°C FT-IR (KBr, Cm-1): 3420-3395-(NH2), 3290 (NH), 3059 (C–H aromatic), 1697(C=O), 1600 (C=N),1484C=C),.1HNMR (500MHz, DMSO-d6): 𝛿H (ppm): 9.84 (s,4H-CONH), 8.67-8.64 (m, 8 Pyrrole-H), 8.15-7.31 (m, 32H Ar-H), 0693 (s,8NH2), - 1.99 (s,2NH)., Anal.Calcd for (C76H54N12O8): C, 72.26; H, 4.31; N, 13.30; O, 10.13; found C, 72.02; H, 4.15; N, 13.12%. Fig. 4. FT-IR Spectrum of Compound (3) Fig. 5. 1HNMR Spectrum of Compound (3) M. T. Jaafar et al. / Iraqi Journal of Chemical and Petroleum Engineering 24,2 (2023) 113 - 122 117 Fig. 6. Mass Spectrum of Compound (3) Fig. 7. Scheme of Prepared Compounds 5a, 5b, and 5c Fig. 8. FT-IR Spectrum of Compound (5a) M. T. Jaafar et al. / Iraqi Journal of Chemical and Petroleum Engineering 24,2 (2023) 113 - 122 118 Fig. 9. 1HNMR Spectrum of Compound (5a) Fig. 10. FT-IR Spectrum of Compound (5b) Fig. 11. 1HNMR Spectrum of Compound (5b) M. T. Jaafar et al. / Iraqi Journal of Chemical and Petroleum Engineering 24,2 (2023) 113 - 122 119 Fig. 12. 1HNMR Spectrum of Compound (5c) 3.2. DSSCs Test Findings JSC, Voc, FF, and PCE are shown in Fig. 13 together with the J-V curves for all produced compounds (Table 1). Based on the results in Table 1, the increased efficiencies (𝜂) for using prepared compounds are sequenced 𝜂5𝑎 > 𝜂5𝑏 > 𝜂5𝑐 .The efficiency of using compound 5a is large due to have it thiazole group, which is rich in electrons (N-S) that will inject lone pair electrons to LUMO of TiO2. On the other hand, compound 5b has an imidazole group (N-H) that has fewer lone pair electrons compared with compound 5a. Fig. 13. J-V Curve of DSSCs Sensitized by 5a,5b and 5c Table 1. Photovoltaic Characteristics for All Colors in a Typical Environment Dye )2-(mA.cm scJ (mV) ocV FF (%) PCE (%) 5a 2.24 0.806 76.5 1.3756 5b 2.01 0.775 76.6 1.2325 5c 1.55 0.750 76.4 0.9470 4- Conclusion This work is summarized: 1- A series of porphyrin derivatives were used as sensitized in solar cells after adsorbed on the TiO2 paste surface. This paste was poured on the FTO surface using Triton X-100 as linked material. All prepared derivatives were given the sensitivity to work as solar cells. 2- The maximum efficiency value was found for using derivative 5a which generates a power conversion efficiency (PCE) of 1.37%. 3- The 5c compound has the lowest PCE value 0.94% and that may be attributed to the smallest optical energy gap about (2.2eV) when compared to other prepared compounds. References: [1] H. 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Jaafar et al. / Iraqi Journal of Chemical and Petroleum Engineering 24,2 (2023) 113 - 122 122 ةلحساستخليق مشتقات البورفيرين الجديدة والتحقق من تطبيقها في الخاليا الشمسية ا 2رحمن طعمه هيول و ، 2، لمى مجيد احمد *، 2، 1محمد ثامر جعفر ، كلية الهندسة ، جامعة كربالء ، كربالء ، العراق نفطقسم هندسة ال 1 قسم الكيمياء ـ كلية العلوم ـ جامعة كربالء ـ كربالء ـ العراق 2 الخالصة الفحم والغاز الطبيعي، بما في ذلك عدم تمتلك الطاقة الشمسية مزايا هامة مقارنة بالمصادر التقليدية مثل وجود انبعاثات وعدم الحاجة إلى وقود وإمكانية التركيب في مجموعة واسعة من المواقع التي تتوفر فيها أشعة " 4"، 4'،4،4الشمس. وفي هذه الدراسة، تم تحضير مشتقات حلقية غير متجانسة من عدة مشتقات بورفيرين ) ، التي تم الحصول عليها بتفاعل بيرول 3تترايل( تترا حمض البنزويك( مركب -5،10،15،20-)بورفيرين -' من خالل 5c، و 5a ،5bفورميل. وفيما بعد، تم إنتاج مشتقات بورفيرين الجزيئية -4-مع حمض البنزويك . وقد أظهرت هذه المشتقات حساسيات متفاوتة 4: 1مع مشتقات األمين بنسبة مولية 3تفاعل المركب ٪، 1.37بنسبة (PCE) أعلى كفاءة تحويل الطاقة 5aخدام في الخاليا الشمسية، حيث عرض المركب لالست = Jsc) ، وعامل الملء(Voc) ، والجهد الدائري المفتوح(Jsc) طريق قياس التيار القصير الدائر وذلك عن ) FF) (2.24 0.80 ، 2مللي أمبير / سمVoc = 76.5، فولتFF = 5المركب ٪ بينما عرض c أدنى , .FF فولت = 0.750Voc ، 2مللي أمبير / سم = PCE 1.55Jsc =0.94 ٪ كفاءة تحويل بنسبة = 76.4٪. ، الخاليا الشمسية.، كفاءة تحويل الطاقة، مشتقات البورفيرينتخليق البورفيرين :دالةالكلمات ال