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 LESTARI1,*, ARIFTI NUR LAILY AQNA1, FAUZAN IBNU PRIHADIYONO1, RIANDY PUTRA1, MAULIDAN FIRDAUS1, VENANSIA AVELIA ROSARI1, UBED SONAI FAHRUDIN ARROZI2 & GRANDPRIX T. M. KADJA3,4,5

 

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

 

 

   

 

   

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