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Palladium Nanoparticles Tethered in Amine-Functionalized Hypercrosslinked Organic Tubes As an Efficient Catalyst for Suzuki Coupling in Water

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Palladium Nanoparticles Tethered in Amine-Functionalized Hypercrosslinked Organic Tubes As an Efficient Catalyst for Suzuki Coupling in Water catalysts Article Palladium Nanoparticles Tethered in Amine-Functionalized Hypercrosslinked Organic Tubes as an Efficient Catalyst for Suzuki Coupling in Water Arindam Modak 1,2, Jing Sun 1, Wenjun Qiu 1 and Xiao Liu 1,* 1 Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China; [email protected] (A.M.); [email protected] (J.S.); [email protected] (W.Q.) 2 Indian Association for the Cultivation of Science, Jadavpur, Kolkata-700032, India * Correspondence: [email protected]; Tel./Fax: +86-22-2789-0859 Academic Editor: Ioannis D. Kostas Received: 7 September 2016; Accepted: 14 October 2016; Published: 20 October 2016 Abstract: It is highly desirable to design functionalized supports in heterogeneous catalysis regarding the stabilization of active sites. Pd immobilization in porous polymers and henceforth its application is a rapidly growing field. In virtue of its’ scalable synthesis and high stability in reaction conditions, amorphous polymers are considered an excellent scaffold for metal mediated catalysis, but the majority of them are found as either agglomerated particles or composed of rough spheres. Owing to several important applications of hollow organic tubes in diverse research areas, we aimed to utilize them as support for the immobilization of Pd nanoparticles. Pd immobilization in nanoporous polymer tubes shows high activity in Suzuki cross coupling reactions between aryl halides and sodium phenyl trihydroxyborate in water, which deserves environmental merit. Keywords: porous organic tubes; heterogeneous catalysis; Suzuki coupling in water 1. Introduction Porous organic polymers (POPs) are emerging as next-generation support materials for heterogeneous catalysis [1–6]. Cheap and readily available organic precursors, tailorable functionality arising from diverse building blocks, are generally advantageous for making high surface area POPs, which are not only used as “support” for metal-mediated catalysis, but also possess significant applications in diverse research, owing to the advantages of densely packed organic groups [7–9]. Therefore, it is customary to mention that the inherent advantages of having organic units in POPs is tremendous, as a support for metal complexes/nanoparticles or as a catalyst because of the virtue of having an electronic interaction between the organic units in POPs and metal nanoparticles. In fact, the main advantage of POPs with its competitive porous support viz. metal organic frameworks (MOFs) [10] and periodic mesoporous organosilica (PMOs) [11,12] is its stability in drastic reaction conditions, which has been immensely highlighted as POPs have shown usability in water medium for catalysis. Considering adverse environmental impact, using volatile organic solvent for catalysis is a serious concern, which should be replaced by water as an environmentally more demanding. However, reactions using water as the only solvent is frequently encountered as fatal because of the moisture sensitive organic precursors, catalysts, and intermediates. Therefore, it is highly challenging to develop water-compatible catalysts that could be stable, active, and reusable for a number of times without being deteriorated [13,14]. In this context, a Suzuki–Miyaura cross coupling reaction in Catalysts 2016, 6, 161; doi:10.3390/catal6100161 www.mdpi.com/journal/catalysts Catalysts 2016, 6, 161 2 of 11 Catalysts 2016, 6, 161 2 of 11 boronicwater as acid/salt an eco-friendly [15]. Pd solvent‐catalyzed is meritorious Suzuki–Miyaura because cross of its coupling high stability reactions and goodhave solubility significant of importancephenyl boronic in organic acid/salt chemistry, [15]. Pd-catalyzed pharmaceuticals Suzuki–Miyaura research, drug cross discovery, coupling reactions and development have significant as an elegantimportance tool for in organicC–C bond chemistry, formation pharmaceuticals reactions, mainly research, because drug of the discovery, wide availability and development of starting as materialsan elegant and tool relatively for C–C bondmild formationreaction conditions reactions, [16,17]. mainly Although because of a the majority wide availability of research of has starting been donematerials in homogeneous and relatively conditions mild reaction using conditionseither organic/water [16,17]. Although as solvent, a majority it suffers of from research the formation has been ofdone Pd black in homogeneous as an inactive conditions catalytic using species. either Again, organic/water the use of triphenyl as solvent, phosphine it suffers fromfor stabilization the formation of Pdof Pdintermediates black as an under inactive homogeneous catalytic species. conditions Again, often the encounters use of triphenyl toxicity/poison phosphine [18]. for In stabilization this regard, highof Pd surface intermediates area heterogeneous under homogeneous catalysts conditions possess oftentremendous encounters applications toxicity/poison in fine [18 chemical]. In this industries,regard, high owing surface to its area repetitive heterogeneous usability, catalysts tailorability possess of tremendous surface modification applications for instabilization fine chemical of activeindustries, sites, and owing so on. to its Pd repetitive‐grafted heterogeneous usability, tailorability catalysts ofcomprising surface modification porous silica, for zeolite, stabilization MOFs, andof active polymers sites, are and hereby so on. reported Pd-grafted as solid heterogeneous‐supported catalysts catalysts for comprising Suzuki reaction, porous but silica, few zeolite, show considerableMOFs, and polymersrecyclability are and hereby stability reported in a water as solid-supported medium [19–21]. catalysts On the other for Suzuki hand, microporous reaction, but POPsfew show are considerablegenerally formed recyclability through and stabilityprecipitation in a waterpolymerization medium [19 –as21 ].agglomerated On the other hand,solid particles/irregularmicroporous POPs flakes, are generally instead formedof any well through defined precipitation nanostructure polymerization [22]. Nevertheless, as agglomerated POPs having solid uniformparticles/irregular morphology flakes, of hollow instead tubes/fibers of any well are defined still nanostructurescarce; moreover, [22]. their Nevertheless, application POPs is merely having limiteduniform to morphology device manufacturing of hollow tubes/fibers [23]. Recently, are still Modak scarce; moreover,and Bhaumik their reported application interesting is merely microporouslimited to device polymer manufacturing tubes (PP‐1, [23 PP].‐ Recently,2, PP‐3; PPs) Modak that and are Bhaumikuniform and reported show interesting high heterogeneity microporous for onepolymer‐pot tandem tubes (PP-1, catalysis PP-2, PP-3;[24]. PPs)However, that are PPs uniform could and also show be high interesting heterogeneity as support for one-pot for tandemmetal nanoparticles’catalysis [24]. owing However, to their PPs amine could alsofunctionality; be interesting therefore, as support we investigated for metal nanoparticles’ its activity for owingSuzuki– to Miyauratheir amine cross functionality; coupling reactions. therefore, weThe investigated catalysis in its water activity might for Suzuki–Miyaura be advantageous, cross since coupling the hydrophobicreactions. The 4‐ catalysistritylaniline in water‐based might tubes be are advantageous, stable and prevent since the the hydrophobic active sites from 4-tritylaniline-based agglomeration andtubes inactivation. are stable andHopefully, prevent this the research active sites can provide from agglomeration tremendous scientific and inactivation. interest in Hopefully, the utilization this ofresearch highly canfunctionalized provide tremendous porous organic scientific tubes/fibers interest in as the support utilization of nanoparticles. of highly functionalized porous organic tubes/fibers as support of nanoparticles. 2. Results and Discussion 2. Results and Discussion 2.1. Synthesis and Characterization of Pd/PP‐3 Tubes 2.1. Synthesis and Characterization of Pd/PP-3 Tubes The amine‐functionalized hypercrosslinked polymer (PP‐3) is formed through a one‐pot The amine-functionalized hypercrosslinked polymer (PP-3) is formed through a one-pot polymerization condensation using 4‐Tritylaniline as starting precursor, dimethoxymethane (DMM) polymerization condensation using 4-Tritylaniline as starting precursor, dimethoxymethane (DMM) as as linker and FeCl3 as catalyst/mediator (Scheme 1). linker and FeCl3 as catalyst/mediator (Scheme1). SchemeScheme 1. 1.SchematicSchematic representation representation for for the the formation formation of ofPd/PP Pd/PP-3‐3 from from a 4 a‐tritylaniline 4-tritylaniline precursor. precursor. TheThe resulting resulting light light brown brown precipitate precipitate shows shows a a unique unique hollow hollow tube tube shaped shaped morphology morphology as as shown shown inin both both scanning scanning electron electron microscopy microscopy (SEM) (SEM) and and transmission transmission electron electron microscopy microscopy (TEM) (TEM) images images (Figure(Figure 11).). Unlike other tube-shapedtube‐shaped porous polymers, synthesis of PP PP-3‐3 is performed in relatively mildmild conditions conditions utilizing utilizing FeCl FeCl33 asas a a cheap cheap and and non non-harmful‐harmful chemical chemical [23,25]. [23,25]. The The size size of of the the organic organic tubestubes are are found found to to be be ~5–7 ~5–7
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