Sains Malaysiana 51(9)(2022): 2937-2954

http://doi.org/10.17576/jsm-2022-5109-16

Zirconium(IV)-BTC-Based MOF Modified with Nickel as a Catalyst for Hydrogenation of Citronellal

(Zirkonium(IV)-BTC-Berdasarkan MOF Terubah Suai dengan Nikel sebagai Pemangkin untuk Penghidrogenan Sitronela)

WITRI WAHYU LESTARI^1,*, ARIFTI NUR LAILY AQNA¹, FAUZAN IBNU PRIHADIYONO¹, RIANDY PUTRA¹, MAULIDAN FIRDAUS¹, VENANSIA AVELIA ROSARI¹, UBED SONAI FAHRUDIN ARROZI² & GRANDPRIX T. M. KADJA^3,4,5

¹Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sebelas Maret University, Jl. Ir Sutami No. 36A, Kentingan-Jebres, Surakarta, Central Java, Indonesia

²Department of Chemistry, Faculty of Mathematics and Science, State University of Malang, Jl. Semarang 5, Malang 65145, East Java, Indonesia

³Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung 40132, Indonesia

⁴Center for Catalysis and Reaction Engineering, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung 40132, Indonesia

⁵Research Center for Nano sciences and Nanotechnology, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung 40132, Indonesia

Diserahkan: 14 Januari 2022/Diterima: 19 April 2022

Abstract

This study is designed to determine the effect of nickel (Ni) metal bearing on zirconium(IV) benzene 1,3,5-tricarboxylate based MOF, [Zr₆O₄(OH)₄(O₂C₂H₃)₆(BTC)₂] (Zr-BTC) and its application as a catalyst in the citronellal hydrogenation. The synthesis of Zr-BTC was carried out under solvothermal condition, while the wet impregnation method was used to synthesize 2.5 wt.% Ni/Zr-BTC. The catalytic test of citronellal hydrogenation was performed in a batch reactor at 80 °C for 6 h with various hydrogen pressures. XRD characterization showed the suitability of the prominent peaks of Zr-BTC to the standard pattern, while Ni metal could not be detected clearly but was confirmed by EDX analysis. FTIR analysis showed a significant shift in the wavenumber from 1722 cm^-1 to 1567 cm^-1 indicating coordination of deprotonated ligands to the Zr⁴⁺ metal ions. Nickel loading reduced the surface area of Zr-BTC to 523 m²/g and the pore volume to 0.11 cc/g according to the nitrogen sorption isotherm. The catalytic tests showed that 30% Ni loading enhanced the activity and selectivity of Zr-BTC in citronellal hydrogenation, resulting in 62.1% yield of isopulegol (for batch reactor) and 14.1% yield of citronellol (for hydrogen balloon).

Keywords: Catalyst; citronellal; hydrogenation; MOFs; Ni/Zr-BTC

Abstrak

Kajian ini adalah untuk menentukan kesan galas logam nikel (Ni) ke atas zirkonium(IV) benzena 1,3,5-trikarboksilat berasaskan MOF, [Zr₆O₄(OH)₄(O₂C₂H₃)₆(BTC)₂] (Zr-BTC) dan penggunaannya sebagai pemangkin dalam penghidrogenan sitronela. Sintesis Zr-BTC telah dijalankan dalam keadaan solvoterma, manakala kaedah impregnasi basah digunakan untuk mensintesis 2.5 wt.% Ni/Zr-BTC. Ujian pemangkin hidrogenasi sitronela dilakukan dalam reaktor kelompok pada suhu 80 °C selama 6 jam dengan pelbagai tekanan hidrogen. Pencirian XRD menunjukkan puncak tajam pada Zr-BTC sepadan dengan puncak piawai, manakala logam Ni tidak dapat dikesan dengan jelas tetapi disahkan oleh analisis EDX. Analisis FTIR menunjukkan perubahan ketara pada nombor gelombang daripada 1722 cm^-1 kepada 1567 cm^-1 yang menunjukkan koordinasi ligan terdeprotonasi kepada ion logam Zr⁴⁺. Pertambahan nikel telah mengurangkan luas permukaan Zr-BTC kepada 523 m²/g dan isi padu liang kepada 0.11 cc/g mengikut isoterma penyerapan nitrogen. Ujian pemangkin pula mendedahkan bahawa penambahan 30% Ni meningkatkan aktiviti dan kepemilihan Zr-BTC dalam penghidrogenan sitronela, seterusnya menghasilkan 62.1% isopulegol (untuk reaktor kelompok) dan 14.1% sitronelo (untuk belon hidrogen).

Kata kunci: MOFs; Ni/Zr-BTC; pemangkin; penghidrogenan; sitronela

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^*Pengarang untuk surat-menyurat; email: witri@mipa.uns.ac.id