Synthesis and Characterization of Copper Impregnated Mesoporous Carbon as Heterogeneous Catalyst for Phenylacetylene Carboxylation with Carbon Dioxide

Putri Nurul Amalia(1), Iman Abdullah(2*), Dyah Utami Cahyaning Rahayu(3), Yuni Krisyuningsih Krisnandi(4)

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(4) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 1642, Indonesia
(*) Corresponding Author


Carbon dioxide (CO2) is a compound that can potentially be used as a carbon source in the synthesis of fine chemicals. However, the utilization of CO2 is still constrained due to its inert and stable nature. Therefore, the presence of a catalyst is needed in CO2 conversion. This study aims to synthesize copper impregnated mesoporous carbon (Cu/MC) as a catalyst for phenylacetylene carboxylation reaction with CO2 to produce phenylpropiolic acid. The synthesis of mesoporous carbon was performed via the soft template method. The as-synthesized Cu/MC material was characterized by FTIR, SAA, XRD, and SEM-EDX. BET surface area analysis of mesoporous carbon showed that the material has a high surface area of 405.8 m2/g with an average pore diameter of 7.2 nm. XRD pattern of Cu/MC indicates that Cu has been successfully impregnated in the form of Cu(0) and Cu(I). Phenylacetylene carboxylation reaction with CO2 was carried out by varying reaction temperatures (25, 50, and 75 °C), amount of catalyst (28.6, 57.2, and 85.8 mg), type of base (Cs2CO3, K2CO3, and Na2CO3), and variation of support. The reaction mixtures were analyzed by HPLC and showed that the highest phenylacetylene conversion of 41% was obtained for the reaction at 75 °C using Cs2CO3 as a base.


carbon dioxide; mesoporous carbon; copper; catalyst; phenylacetylene; carboxylation reaction

Full Text:

Full Text PDF


[1] Wu, Z., Sun, L., Liu, Q., Yang, X., Ye, X., Hu, Y., and Huang, Y., 2017, A Schiff base-modified silver catalyst for efficient fixation of CO2 as carboxylic acid at ambient pressure, Green Chem., 19 (17), 2080–2085.

[2] Yu, B., Xie, J.N., Zhong, C.L., Li, W., and He, L.N., 2015, Copper(I)@carbon-catalyzed carboxylation of terminal alkynes with CO2 at atmospheric pressure, ACS Catal., 5 (7), 3940–3944.

[3] Wang, X., Nakajima, M., and Martin, R., 2015, Ni-catalyzed regioselective hydrocarboxylation of alkynes with CO2 by using simple alcohols as proton sources, J. Am. Chem. Soc., 137 (28), 8924–8927.

[4] Doi, R., Abdullah, I., Taniguchi, T., Saito, N., and Sato, Y., 2017, Nickel-catalyzed hydrocarboxylation of ynamides with CO2 and H2O: Observation of unexpected regioselectivity, Chem. Commun., 53 (55), 7720–7723.

[5] Doi, R., Okano, T., Abdullah, I., and Sato, Y., 2019, Nickel-catalyzed b-carboxylation of ynamides with carbon dioxide, Synlett, 30 (9), 1048–1052.

[6] Williams, C.M., Johnson, J.B., and Rovis, T., 2008, Nickel-catalyzed reductive carboxylation of styrenes using CO2, J. Am. Chem. Soc., 130 (45), 14936–14937.

[7] Börjesson, M., Moragas, T., and Martin, R., 2016, Ni-catalyzed carboxylation of unactivated alkyl chlorides with CO2, J. Am. Chem. Soc., 138 (24), 7504–7507.

[8] Boogaerts, I.I.F., Nolan, S.P., 2010, Carboxylation of C–H bonds using N-heterocyclic carbene gold(I) complexes, J. Am. Chem. Soc., 132 (26), 8858–8859.

[9] Steinmann, S.N., Michel, C., Schwiedernoch, R., Wu, M., and Sautet, P., 2016, Electro-carboxylation of butadiene and ethene over Pt and Ni catalysts, J. Catal., 343, 240–247.

[10] Shah, D.J., Sharma, A.S., Shah, A.P., Sharma, V.S., Athar, M., and Soni, J.Y., 2019, Fixation of CO2 as a carboxylic acid precursor by microcrystalline cellulose (MCC) supported AgNPs: A more efficient, sustainable, biodegradable and eco-friendly catalyst, New J. Chem., 43 (22), 8669–8676.

[11] Song, J., Liu, Q., Liu, H., and Jiang, X., 2018, Recent Advances in palladium-catalyzed carboxylation with CO2, Eur. J. Org. Chem., 2018 (6), 696–713.

[12] Whang, H.S., Lim, J., Choi, M.S., Lee, J., and Lee, H., 2019, Heterogeneous catalysts for catalytic CO2 conversion into value-added chemicals, BMC Chem. Eng., 1 (1), 9.

[13] Bondarenko, G.N., Dvurechenskaya, E.G., Magommedov, E.S., and Beletskaya, I.P., 2017, Copper(0) nanoparticles supported on Al2O3 as catalyst for carboxylation of terminal alkynes, Catal. Lett., 147 (10), 2570–2580.

[14] Zhang, X., Zhang, W.Z., Ren, X., Zhang, L.L., and Lu, X.B., 2011, Ligand-free Ag(I)-catalyzed carboxylation of terminal alkynes with CO2, Org. Lett., 13 (9), 2402–2405.

[15] Yu, D., Tan, M.X., and Zhang, Y., 2012, Carboxylation of terminal alkynes with carbon dioxide catalyzed by poly(N-heterocyclic carbene)-supported silver nanoparticles, Adv. Synth. Catal., 354 (6), 969–974.

[16] Wang, W.H., Jia, L., Feng, X., Fang, D., Guo, H., and Bao, M., 2019, Efficient carboxylation of terminal alkynes with carbon dioxide catalyzed by ligand‐free copper catalyst under ambient conditions, Asian J. Org. Chem., 8 (8), 1501–1505.

[17] Liang, C., and Dai, S., 2006, Synthesis of mesoporous carbon materials via enhanced hydrogen-bonding interaction, J. Am. Chem. Soc., 128 (16), 5316–5317.

[18] Wang, X., Liang, C., and Dai, S., 2008, Facile synthesis of ordered mesoporous carbons with high thermal stability by self assembly of resorcinol-formaldehyde and block copolymers under highly acidic conditions, Langmuir, 24 (14), 7500–7505.

[19] Cao, J.M., Cao, Y.L., Chang, X., Zheng, M.B., Liu, J.S., and Ji, H.M., 2005, Synthesis of silver nanoparticles within ordered CMK-3 mesoporous carbon, Stud. Surf. Sci. Catal., 156, 423–426.

[20] Li, J.G., Tsai, C.Y., and Kuo, S.W., 2014, Fabrication and characterization of inorganic silver and palladium nanostructures within hexagonal cylindrical channels of mesoporous carbon, Polymers, 6 (6), 1794–1809.

[21] Prasiwi, A.D., Trisunaryanti, W., Triyono, Falah, I.I., Santi, D., and Marsuki, M.F., 2019, Synthesis of mesoporous carbon from Merbau wood (Intsia spp.) by microwave method as Ni catalyst support for α-cellulose hydrocracking, Indones. J. Chem., 19 (3), 575–582.

[22] Pamungkas, A.Z., Abdullah, I., and Krisnandi, Y.K., 2019, Synthesis and characterization of Ni nanoparticles supported on nitrogen-doped mesoporous carbon, IOP Conf. Ser.: Mater. Sci. Eng., 496, 012003.

[23] Liu, J., Wang, Z., Yan, X., and Jian, P., 2017, Metallic cobalt nanoparticles imbedded into ordered mesoporous carbon: A non-precious metal catalyst with excellent hydrogenation performance, J. Colloid Interface Sci., 505, 789–795.

[24] Liu, X., Lan, G., Su, P., Qian, L., Reina, T.R., Wang, L., Li, Y., and Liu, J., 2020, Highly stable Ru nanoparticles incorporated in mesoporous carbon catalysts for production of γ-valerolactone, Catal. Today, 351, 75–82.

[25] Şahin, N.E., Comminges, C., Valant, A.L., Kiener, J., Parmentier, J., Napporn, T.W., Melinte, G., Ersen, O., and Kokoh, K.B., 2018, One‐pot soft‐template synthesis of nanostructured copper‐supported mesoporous carbon FDU‐15 electrocatalysts for efficient CO2 reduction, ChemPhysChem, 19 (11), 1371–1381.

[26] Liu, L., Zhang, H., Wang, G., Du, J., Zhang, Y., Fu, X., and Chen, A., 2017, Synthesis of mesoporous carbon nanospheres via ‘‘pyrolysis-deposition’’strategy for CO2 capture, J. Mater. Sci., 52 (16), 9640–9647.

[27] Ardhyarini, N., and Krisnandi, Y.K., 2017, Carbon dioxide capture by activated methyl diethanol amine impregnated mesoporous carbon, AIP Conf. Proc., 1862 (1), 030090.

[28] Pal, N., and Bhaumik, A., 2013, Soft templating strategies for the synthesis of mesoporous materials: Inorganic, organic–inorganic hybrid and purely organic solids, Adv. Colloid Interface Sci., 189-190, 21–41.

[29] Hosseini, S., Bayesti, I., Marahel, E., Babadi, F.E., Abdullah, L.C., and Choong, T.S.Y., 2015, Adsorption of carbon dioxide using activated carbon impregnated with Cu promoted by zinc, J. Taiwan Inst. Chem. Eng., 52, 109–117.

[30] Kooti, M., and Matouri, L., 2010, Fabrication of nanosized cuprous oxide using Fehling’s solution, Sci. Iran., Trans. F, 17 (1), 73–78.

[31] Górka, J., Zawislak, A., Choma, J., and Jaroniec, M., 2008, KOH activation of mesoporous carbons obtained by soft-templating, Carbon, 46 (8), 1159–1161.

[32] Yuan, Z., 2014, Applications of bases in transition metal catalyzed reactions, Postdoc J., 2 (3), 17–28.

[33] Dingyi, Y., and Yugen, Z., 2011, The direct carboxylation of terminal alkynes with carbon dioxide, Green Chem., 13 (5), 1275–1279.

[34] Piccin, J.S., Dotto, G.L., and Pinto, L.A.A., 2011, Adsorption isotherms and thermochemical data of FD&C Red no 40 binding by chitosan, Braz. J. Chem. Eng., 28 (2), 295–304.

[35] Ayawei, N., Ebelegi, A.N., and Wankasi, D., 2017, Modelling and interpretation of adsorption isotherms, J. Chem., 2017, 3039817.

[36] Wu, Z., Liu, Q., Yang, X., Ye, X., Duan, H., Zhang, J., Zhao, B., and Huang, Y., 2017, Knitting aryl network polymers-incorporated Ag nanoparticles: A mild and efficient catalyst for the fixation of CO2 as carboxylic acid, ACS Sustainable Chem. Eng., 5 (11), 9634–9639.


Article Metrics

Abstract views : 2895 | views : 2670

Copyright (c) 2020 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.