Biochar as heterogeneous support for immobilization of Pd as efficient and reusable biocatalyst in C–C coupling reactions

Abstract

Biochar is a stable and carbon-rich solid which has a high density of carbonyl, hydroxyl and carboxylic acid functional groups on its surface. In this work, the surface of biochar nanoparticles (BNPs) was modified with 3-choloropropyltrimtoxysilane and further 2-(thiophen-2-yl)-1H-benzo[d]imidazole was anchored on its surface. Then, palladium nanoparticles were fabricated on the surface of the modified BNPs and further the catalytic application was studied as recyclable biocatalyst in carbon-carbon coupling reactions such as Suzuki-Miyaura and Heck-Mizoroki cross-coupling reactions. The structure of the catalyst was characterized using scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, X-ray diffraction and atomic absorption spectroscopy. The catalyst can be reused several times without a decrease in its catalytic efficiency.In addition to the several advantages reported, application of biochar as catalyst support for the first time is a major novelty of the present work. 1 H NMR (400 MHz, CDCl 3 ): δ H = 10.09 (s, 1H), 7.99-7.97 (d, J = 8 Hz, 2H), 7.79-7.77 (d, J = 8 Hz, 2H), 7.68-7.66 (d, J = 8 Hz, 2H), 7.53-7.49 (t, J = 8 Hz, 2H), 7.47-7.43 (t, J = 8 Hz, 1H) ppm. 2.5.4 | [1,1′-Biphenyl]-3-carbaldehyde 1 H NMR (400 MHz, CDCl 3 ): δ H = 10.12 (s, 1H), 8.40 (s, 1H), 8.15-8.14 (d, J = 2 Hz, 1H), 7.91-7.87 (td, J = 4 Hz, J = 2 Hz, 1H), 7.68-7.65 (m, 2H), 7.62-7.57 (dd, J = 12 Hz, J = 4 Hz, 1H), 7.53-7.49 (t, J = 8 Hz, 2H), 7.45-7.43 (m, 1H) ppm. 2.5.5 | 3,4-Difluoro-1,1′-biphenyl 1 H NMR (400 MHz, CDCl 3 ): δ H = 7.56-7.54 (d, J = 8 Hz, 2H), 7.49-7.45 (t, J = 8 Hz, 2H), 7.44-7.38 (m, 2H), 7.34-7.31 (m,1H), 7.28-7.21 (m, 1H) ppm. 2.5.6 | Butyl 3-(4-methylphenyl)acrylate 1 H NMR (400 MHz, CDCl 3 ): δ H = 7.70-7.66 (d, J = 16 Hz, 1H), 7.46-7.44 (d, J = 8 Hz, 2H), 7.22-7.20 (d, J = 8 Hz, 2H), 6.44-6.40 (d, J = 16 Hz, 1H), 4.25-4.21 (t, J = 8 Hz, 2H), 2.39 (s, 3H), 1.75-1.68 (quint, J = 8 Hz, 2H), 1.51-1.42 (sextet, J = 8 Hz, 2H), 1.01-0.97 (t, J = 8 Hz, 3H) ppm. | Butyl 3-(4-methoxyphenyl)acrylate

Cu–citric acid metal–organic framework: Synthesis, characterization and catalytic application in Suzuki–Miyaura cross‐coupling reaction and oxidation of sulfides

“…As shown in Scheme 3, this catalyst provided a good selectivity in the coupling of PhB (OH) 2 with 1-bromo-4-chlorobenzene. [36] 2 210 93 43-45 42-43 [37] 3 310 90 82-85 82-85 [36] 4 220 86 62-64 62-65 [36] 5 320 84 43-45 42-43 [37] 6 300 85 71-73 69-72 [38] 7 290 81 50-52 51-53 [39] 8 80 89 111-113 111-114 [22] 9 420 80 Oil Oil [38] 10 540 77 67-68 66-68 [17] 11 480 85 111-112 111-114 [22] a Reaction conditions: Aryl halide (1 mmol), phenylboronic acid (1. The cyclic mechanism of Suzuki-Miyaura reaction in the presence of Cu-CA-MOF has been shown in the Scheme 4 based on the authentic reported mechanisms.…”

“…Some reasons that led to the broadly implement Suzuki-Miyaura reaction is the usage of this C-C bond formation reaction in many fields such as pharmaceuticals, agrochemicals, natural products and chemical industries, Besides, the products obtained from this coupling reaction are non-toxic and less expensive. [1][2][3][4][5] It's worthy to note that C-C coupling reactions usually performed in the presence of Pd containing catalysts, [17][18][19][20][21] which are very expensive in costs. Meanwhile, Cu containing catalysts are of interest, because of their nontoxicity nature and costeffective preparation's methods.…”

Green Synthesis of Pd Nanoparticles for Sustainable and Environmentally Benign Processes

“…In 2019, biochar from dried chicken manure was prepared by Hajjami and co-workers [164]. Surface modified biochar was used as a support to immobilize PdNPs by using NaBH 4 as the reducing agent.…”

Stabilization of ruthenium on biochar-nickel magnetic nanoparticles as a heterogeneous, practical, selective, and reusable nanocatalyst for the Suzuki C–C coupling reaction in water

“…[18][19][20][21] C-C bond formation was chosen here as it is a powerful tool in organic chemistry for the preparation of many natural products, biologically active compounds, hydrocarbons, and advanced materials. [22][23][24] Another principle of green chemistry is the use of safe, available, and environmentally friendly solvents, such water, ethanol, PEG, and ionic liquids. Among these, water is the cheapest and safest solvent available.…”