Sains Malaysiana 54(6)(2025): 1535-1549

http://doi.org/10.17576/jsm-2025-5406-09

 

Synthesis and Characterization of 5,15 A_2-Type Porphyrin, Metalloporphyrin and Preliminary Study on Carbon Dioxide Adsorption

(Sintesis dan Pencirian Porfirin Jenis 5,15 A₂, Metaloporfirin dan Kajian Awal tentang Penjerapan Karbon Dioksida)

 

NUUR HAZIQAH MOHD RADZUAN¹, ZAITUN GHAZALI¹, NURUL IZZATY HASSAN¹, MOHD BAKRI BAKAR², SITI AISHAH HASBULLAH¹ & MUNTAZ ABU BAKAR^1,*

 

¹Department of Chemical Sciences, Faculty of Science & Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

²Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 84600 Pagoh, Johor, Malaysia

 

Diserahkan: 9 Januari 2025/Diterima: 26 April 2025

 

Abstract

Porphyrins are among the most extensively studied compounds in chemistry due to their remarkable stability, optical, and photophysical properties. In recent years, advancements in their diverse applications have driven the exploration of porphyrins with different functional groups, allowing for more specific applications. Nowadays, a greater focus is being placed on the development of materials for capturing and converting carbon dioxide (CO₂) into value-added products. Despite their promising features, the application of porphyrins in carbon dioxide adsorption has been hindered by their initially low adsorption capacity compared to other traditional porous materials, such as microporous carbons and zeolites. Modifications to porphyrins, such as the introduction of diverse functional groups and the incorporation of metal centers are promising, as they may enhance the CO₂ adsorption performance of porphyrin-based materials. Therefore, this study focuses on the synthesis of 5,15 A₂-type porphyrin and its metalloporphyrin derivatives, along with a preliminary evaluation of synthesized porphyrin’s carbon dioxide adsorption ability. The synthesized porphyrins were characterized via nuclear magnetic resonance spectroscopy (NMR) and UV-visible spectroscopy. The yield for porphyrin varied from 23% to 35%, while metalloporphyrin achieved a yield of 99%. A preliminary study of carbon dioxide adsorption ability of porphyrin and metalloporphyrin showed that the insertion of metal into the center of porphyrin macrocyclic ring enhances the binding affinity and improves adsorption capacity. The Freundlich isotherm showed the presence of heterogeneous adsorption sites and possible multilayer adsorption of CO₂ onto the porphyrin’s surface. Additionally, due to the ability of metalloporphyrin to adsorb CO₂, metalloporphyrin has the potential to serve as a building block for the integration of porphyrin into hybrid materials such as metal-organic frameworks (MOFs) and covalent-organic framework (COFs), by enhancing their structural stability and CO₂ performance.

Keywords: Carbon dioxide adsorption; covalent-organic frameworks (COFs); metalloporphyrin; metal-organic frameworks (MOFs); 5,15-A₂-porphyrin

 

Abstrak

Porfirin merupakan antara sebatian yang paling banyak dikaji dalam bidang kimia kerana kestabilannya yang luar biasa serta sifat optik dan fotofizikal yang menonjol. Dalam beberapa tahun kebelakangan ini, kemajuan dalam pelbagai aplikasi telah mendorong penerokaan porfirin dengan kumpulan berfungsi yang berbeza, kerana perbezaan ini boleh membawa kepada aplikasi khusus yang berlainan. Pada masa kini, tumpuan yang lebih besar diberikan kepada pembangunan bahan untuk menangkap dan menukar karbon dioksida kepada produk yang mempunyai nilai tambah. Walaupun porfirin berpotensi sebagai bahan penjerap disebabkan ciri yang dimiliki, penggunaannya dalam penjerapan karbon dioksida masih terhad disebabkan kapasiti penjerapan yang rendah pada peringkat awal berbanding dengan bahan yang mempunyai kadar liang yang tinggi seperti karbon mikropori dan zeolit. Bagi mengatasi kekangan ini, pengubahsuaian terhadap struktur porfirin seperti memperkenalkan kumpulan berfungsi yang pelbagai dan menyepadukan pusat logam perlu diberi penekanan. Hal ini kerana pengubahsuaian ini berpotensi meningkatkan prestasi penjerapan karbon dioksida bagi bahan berasaskan porfirin. Oleh itu, kajian ini memberi tumpuan kepada sintesis porfirin jenis A₂-5,15, terbitan metaloporfirin dan penilaian awal terhadap keupayaan penjerapan karbon dioksida. Porfirin yang disintesis telah dicirikan menggunakan Spektroskopi NMR dan Spektroskopi UV-Vis. Hasil perolehan porfirin adalah antara 23% hingga 35%, manakala metaloporfirin mencapai hasil sebanyak 99%. Kajian awal terhadap penjerapan karbon dioksida bagi porfirin A₂-5,15 dan metaloporfirin menunjukkan bahawa penyepaduan pusat logam meningkatkan keupayaan pengikatan karbon dioksida dan menambah baik kapasiti penjerapan. Model isoterma Freundlich menunjukkan kehadiran tapak penjerapan heterogen dan kemungkinan berlakunya penjerapan berbilang lapisan karbon dioksida pada permukaan porfirin. Selain itu, disebabkan kebolehan metaloporfirin untuk menjerap karbon dioksida, metaloporfirin berpotensi untuk digunakan sebagai blok binaan untuk menghasilkan bahan hibrid seperti rangka logam-organik (MOF) dan rangka organik-kovalen (COF) bagi meningkatkan kestabilan struktur dan kecekapan penjerapan karbon dioksida.

Kata kunci: Metaloporfirin; penjerapan karbon dioksida; rangka logam-organik (MOF); rangka organik-kovalen (COF); 5,15-A₂-porfirin

 

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*Pengarang untuk surat-menyurat; email: muntaz@ukm.edu.my