Thiocarbohydrazide-cross-linked pectin: A promising support material for palladium nanoparticles in the water-mediated Suzuki-Miyaura cross-coupling reaction and the catalytic reduction of 4-nitrophenol

Abstract

Suzuki-Miyaura reaction is a classic palladium-catalyzed reaction for forming Csp2-Csp2 bonds. However, the leaching of Pd species and using organic solvents are two important problems that adversely affect their performance, reusability, and greenness. Considering the abundant resources, cheapness, and availability of pectin (Pec), a Pec-based catalyst for the Suzuki reaction in pure water as a non-toxic reaction medium was developed for the first time. In this regard, Pec was chosen as a benign support and cross-linked by thiocarbohydrazide (TCH) to prepare Pec-TCH. The Pec-TCH acted as an efficient reducing and stabilizing agent for in-situ fabrication of Pd(0) nanoparticles. The heterogeneous and air-stable Pec-TCH-Pd(0) nanoparticles were thoroughly characterized. The results exhibited a significant catalytic activity (up to 99%) and reusability (at least 7 times) for in-water Suzuki-Miyaura cross-coupling reaction. The use of TBAB as a phase-transfer catalyst improved the yield of Suzuki reaction since it prevented the problems related to the immiscibility of water and aryl halides as well as the gelation of catalyst. The catalyst was also utilized for water-mediated 4-nitrophenol reduction to 4-aminophenol with NaBH4 which showed excellent activity (k = 9.2 × 10−3 s−1). A very good compatibility with iodobenzene, bromobenzene, and chlorobenzene was observed for the Suzuki reaction. Because of various binding sites such as amino, hydroxyl, carbonyl and thiocarbonyl groups, negligible leach of Pd nanoparticles was observed, as shown by ICP-MS after runing 7th of reusability studies. Moreover, the leaching, mercury poisoning, and large-scale tests showed its potential for industrial applications.