Alyaa S. SHIDDIQAH, Iman ABDULLAH, Yuni K. KRISNANDI

Selective hydrogenation of diphenylacetylene using NiCo nanoparticles supported on mesoporous carbon as catalyst

Hydrogenation of alkynes to alkenes is an important procedure in the synthesis of organic compounds. In this study, selective hydrogenation was carried out on diphenylacetylene as a model of alkyne compounds using $NaBH_4$ as a hydrogen source and NiCo bimetallic nanoparticles supported on mesoporous carbon (NiCo/MC) as a catalyst. The mesoporous carbon was prepared using the soft-templated method from phloroglucinol and formaldehyde as precursors while the NiCo/MC catalyst was synthesized using a wet impregnation method. Based on surface area analysis, it was found that the pore diameters of MC, Ni/MC, and NiCo/MC were 12.8 nm, 13.4 nm, and 12.7 nm respectively, which indicated the mesoporous size of the materials. TEM analysis also confirmed the formation of nanoparticles on mesoporous carbon with the average size similar to the pore structure of the support, thus indicating the incorporation of the metals on the support. The hydrogenation reaction of diphenylacetylene was carried out with variations in reaction time and temperature. GCMS analysis of the products showed that the optimum conditions were obtained over NiCo/MC catalyst at 50 °C for 4 h with a diphenylacetylene conversion of 71.5% and a selectivity of 87.1% for the formation of cis-stilbene.

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1. Ritleng V, Sirlin C, Pfeffer M. Ru-, Rh-, and Pd-catalyzed C-C bond formation involving C-H activation and addition on unsaturated substrates: Reactions and mechanistic aspects. Chemical Reviews 2002; 102 (5): 1731–1769. doi: 10.1021/cr0104330
2. Kani I, Unver H (2020). Bimetallic Ni(II) complex with carboxylate bridging for homogeneous hydrogenation of alkenes with NaBH4.Polyhedron 2020; 187. doi: 10.1016/j.poly.2020.114649
3. Özkar S, Zahmakiran M. Hydrogen generation from hydrolysis of sodium borohydride using Ru(0) nanoclusters as catalyst. Journal of Alloys and Compounds 2005; 404–406: 728–731. doi: 10.1016/j.jallcom.2004.10.084
4. Wen X, Shi X, Qiao X, Wu Z, Bai G. Ligand-free nickel-catalyzed semihydrogenation of alkynes with sodium borohydride: a highly efficient and selective process for cis-alkenes under ambient conditions. Chemical Communications 2017; 53 (39): 5372–5375. doi: 10.1039/c7cc02140b
5. Murugesan K, Bheeter CB, Linnebank PR, Spannenberg A, Reek JNH et al. Nickel-Catalyzed Stereodivergent Synthesis of E- and Z-Alkenes by Hydrogenation of Alkynes. ChemSusChem 2019; 12 (14): 3363–3369. doi: 10.1002/cssc.201900784
6. Alruqi SS, Al-Thabaiti SA, Khan Z. Iron-nickel bimetallic nanoparticles: surfactant assisted synthesis and their catalytic activities. Journal of Molecular Liquids 2019; 282: 448-455. doi: 10.1016/j.molliq.2019.03.021
7. Rodiansono R., Dewi AM, Husain S, Nugroho A, Sutomo S. Selective Conversion of 2-Methylfuran to 1,4-Pentanediol Catalyzed by Bimetallic Ni-Sn Alloy. Bulletin of Chemical Reaction Engineering & Catalysis 2019; 14 (3): 529-541. doi: 10.9767/bcrec.14.3.4347.529-541
8. Seethapathy V, Sudarsan P, Pandey AK, Pandiyan A, Kumar THV et al. Synergistic effect of bimetallic Cu:Ni nanoparticles for the efficient catalytic conversion of 4-nitrophenol. New Journal of Chemistry 2019; 43: 3180-3187. doi: 10.1039/C8NJ05649H
9. Khairani NS, Abdullah I, Krisnandi YK. Synthesis and characterization of NiZn/mesoporous carbon as heterogeneous catalyst for carboxylation reaction of acetylene with CO2. AIP Conference Proceedings 2020; 2242 (1): 040039. doi: 10.1063/5.0007890
10. Gallo A, Snider JL, Sokaras D, Nordlund D, Kroll T et al. $Ni_5 Ga_3 catalysts for CO_2$ reduction to methanol: Exploring the role of Ga surface oxidation/reduction on catalytic activity. Applied Catalysis B: Environmental 2020; 267: 118369. doi: 10.1016/j.apcatb.2019.118369
11. Pei GX, Liu XY, Wang A, Su Y, Li L et al. Selective hydrogenation of acetylene in an ethylene-rich stream over silica supported Ag-Ni bimetallic catalysts. Applied Catalysis A: General 2017; 545: 90-96. doi: 10.1016/j.apcata.2017.07.041
12. Bian Z, Das S, Wai MH, Hongmanorom P, Kawi S. A Review on Bimetallic Nickel-Based Catalysts for $CO_2$ Reforming of Methane. ChemPhysChem 2017; 18 (22): 3117-3134. doi: 10.1002/cphc.201700529
13. Yang L, Yu S, Peng C, Fang X, Cheng Z et al. Semihydrogenation of phenylacetylene over nonprecious Ni-based catalysts supported on AlSBA-15. Journal of Catalysis 2019; 370: 310–320. doi: 10.1016/j.jcat.2019.01.012
14. Ridwan M, Suhanda D, Aziz I, Abdullah I. Dehydrogenatıon of hydrazine hydrate using NiCo bimetallic catalyst supported on naturalzeolite (ZA), Z-NaY, Z-HY, $Al_2O_3 and TiO_2$. Rasayan Journal of Chemistry 2021; 14 (3): 1821-1828. doi: 10.31788/RJC.2021.1436319
15. Pal N, Bhaumik A. Soft templating strategies for the synthesis of mesoporous materials: Inorganic, organic-inorganic hybrid and purely organic solids. Advances in Colloid and Interface Science 2013; 189–190: 21–41. doi: 10.1016/j.cis.2012.12.002
16. Afriani A, Abdullah I, Krisnandi YK. Synthesıs of $NiCl_2$ impregnated mesoporous carbon and its adsorption activity on $CO_2$. AIP Conference Proceedings 2021; 2349: 020048. doi: 10.1063/5.0051524
17. Abdullah I, Andriyanti R, Nurani DA, Krisnandi YK. Nickel-phenanthroline complex supported on mesoporous carbon as a catalyst for carboxylation under CO2 atmosphere. Bulletin of Chemical Reaction Engineering & Catalysis 2021; 16 (1): 111-119. doi: 10.9767/ bcrec.16.1.9733.111-119
18. Pamungkas AZ, Abdullah I, Krisnandi YK. Synthesis and characterization of Ni nanoparticles supported on nitrogen-doped mesoporous carbon. IOP Conference Series 2019; 496: 012003. doi:10.1088/1757-899X/496/1/012003
19. Amalia PN, Abdullah I, Rahayu DUC, Krisnandi YK. Synthesis and Characterization of Copper Impregnated Mesoporous Carbon as Heterogeneous Catalyst for Phenylacetylene Carboxylation with Carbon Dioxide. Indonesian Journal of Chemistry 2021; 21 (1): 77-87. doi: 10.22146/ijc.52778
20. Zawislak A, Choma J, Jaroniec M. Adsorption and structural properties of soft-templated mesoporous carbons obtained by carbonization at different temperatures and KOH activation. Applied Surface Science 2010; 256: 5187–5190. doi: 10.1016/j.apsusc.2009.12.092
21. Sulistianti I, Krisnandi YK, Moenandar I. Study of $CO_2$ adsorption capacity of mesoporous carbon and activated carbon modified by triethylenetetramine (TETA). IOP Conference Series: Materials Science and Engineering 2017; 188, 012041. doi: 10.1088/1757- 899X/188/1/012041
22. He X, Xu Y, Yao X, Zhang C, Pu Y et al. Large exchange bias and enhanced coercivity in strongly-coupled Ni/NiO binary nanoparticles. RSC Advances 2019; 9 (52): 30195–30206. doi: 10.1039/C9RA03242H
23. García T, Murillo R, Agouram S, Dejoz A, Lázaro MJ et al. Highly dispersed encapsulated AuPd nanoparticles on ordered mesoporous carbons for the direct synthesis of $H_2O_2$ from molecular oxygen and hydrogen. Chemical Communications 2012; 48 (43): 5316–5318. doi: 10.1039/c2cc14667c
24. Netskina OV, Tayban ES, Rogov VA, Ozerova AM, Mukha SA et al. Solid-state NaBH4 composites for hydrogen generation: Catalytic activity of nickel and cobalt catalysts. International Journal of Hydrogen Energy 2021; 46 (7): 5459-5471. doi: 10.1016/j.ijhydene.2020.11.078
25. Egeberg A, Dietrich C, Kind C, Popescu R, Gerthsen D et al. Bimetallic $NiIr_4 and NiOs_4$ alloy nanoparticles and their catalytic performance in hydrogenation reactions. ChemCatChem 2017; 9 (18): 3534-3543. doi: 10.1002/cctc.201700168
26. Deng X, Bai R, Chai Y, Hu Z, Guan N et al. Homogeneous-like alkyne selective hydrogenation catalyzed by cationic nickel confined in zeolite. Chinese Chemical Society Chemistry 2021; 3: 1101-1114. doi: 10.31635/ccschem.021.202100820
27. Murugesan K, Alshammari AS, Sohail M, Beller M, Jagadeesh RV. Monodısperse nickel-nanoparticles for stereo- and chemoselective hydrogenation of alkynes to alkenes. Journal of Catalysis 2019; 370: 372-377. doi: 10.1016/j.jcat.2018.12.018