Tailorable synthesis of porous organic polymers decorating ultrafine palladium nanoparticles for hydrogenation of olefins

Article abstract of DOI:10.1021/cs501731w

Two 1,2,3-triazolyl-containing porous organic polymers (CPP-C and CPP-Y) were readily synthesized through click reaction and Yamamoto coupling reaction, respectively. The effects of synthetic methods on the structures and properties of CPP-C and CPP-Y were investigated. Their chemical compositions are almost identical, but their physical and texture properties are different from each other. Ultrafine palladium nanoparticles can be effectively immobilized in the interior cavities of CPP-C and CPP-Y. The interactions between polymers and palladium are verified by IR, solid-state NMR, XPS, and EDS. Their catalytic performances are evaluated by hydrogenation of olefins. Pd@CPP-Y exhibits higher catalytic activity and recyclability than Pd@CPP-C. Hot filtration and the three-phase test indicate that hydrogenation functions in a heterogeneous pathway. (Figure Presented).

Full text of DOI:10.1021/cs501731w

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Article
Tailorable Synthesis of Porous Organic Polymers Decorating
Ultrafine Palladium Nanoparticles for Hydrogenation of Olefins
Ruihu Wang
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/cs501731w • Publication Date (Web): 28 Dec 2014
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Tailorable Synthesis of Porous Organic Polymers Decorating
Ultrafine Palladium Nanoparticles for Hydrogenation of
Olefins
Journal: ACS Catalysis
Manuscript ID: cs-2014-01731w.R1
Manuscript Type: Article
Date Submitted by the Author: 25-Dec-2014
Complete List of Authors: Li, Liuyi; Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences,
Zhao, Huaixia; Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences,
Wang, Ruihu; Fujian Institute of Research on the Structure of
Matter,Chinese Academy of Sciences ,
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Tailorable Synthesis of Porous Organic Polymers
Decorating Ultrafine Palladium Nanoparticles for
Hydrogenation of Olefins
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Liuyi Li,†,‡ Huaixia Zhao†,‡ and Ruihu Wang*†,‡
†State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of
Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China
‡ Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Chinese Academy of
Sciences, Fuzhou, Fujian, 350002, China
ABSTRACT. Two 1,2,3ꢀtriazolylꢀcontaining porous organic polymers (CPPꢀC and CPPꢀY) were
readily synthesized through click reaction and Yamamoto coupling reaction, respectively. The
effects of synthetic methods on the structures and properties of CPPꢀC and CPPꢀY were
investigated. Their chemical compositions are almost identical, but their physical and texture
properties are different from each other. Ultrafine palladium nanoparticles can be effectively
immobilized in the interior cavities of CPPꢀC and CPPꢀY. The interactions between polymers
and palladium are verified by IR, solidꢀstate NMR, XPS and EDS. Their catalytic performances
are evaluated by hydrogenation of olefins. Pd@CPPꢀY exhibits higher catalytic activity and
recyclability than Pd@CPPꢀC. Hot filtration and threeꢀphase test indicate that hydrogenation
functions in a heterogeneous pathway.
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KEYWORDS: Click reaction, Porous organic polymers, Palladium nanoparticles,
Heterogeneous catalysis, Hydrogenation.
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1. INTRODUCTION
The synthesis of supported metal nanoparticles (NPs) has attracted considerable attention
because of their potential applications in energy conversion, environmental remediation and
catalysis.1, 2 Ultrafine metal NPs usually exhibit unique properties distinct from those in largeꢀ
size NPs and bulk metal counterparts, and are thought to be more reactive in catalysis.3ꢀ5 but they
are prone to aggregate during catalytic reactions owing to high surface energy, leading to the loss
of catalytic activity.6, 7 By serving as unique host matrices, MOFs have been reported to be a
family of ideal supports for the immobilization and stabilization of ultrafine metal NPs,8ꢀ10 which
results in the catalytic systems with high selectivities and catalytic activities.11ꢀ13 However, the
reversible nature of metalꢀcoordination chemistry usually makes them unstable enough in most
of liquidꢀphase catalysis. Taking into account the similarity to MOFs, porous organic polymers
(POPs) also can serve as a promising platform for incorporating metal NPs within the pores of
POPs.14ꢀ21 Spatial control of catalytically active sites in POPs can be tuned and modified through
vast choice of organic building blocks and synthetic diversity, which endows them potential for
catalysis.22ꢀ24 Generally, the porous structure of POPs play an important role in catalysis,25 which
are highly dependent on the geometry and size of monomers as well as the synthetic method of
POPs.26ꢀ29 The intensive efforts have been focused on the construction of functionalized POPs by
judicious selection of building blocks, in which functional groups, such as triazolyl, imine, urea
and salen, not only can serve as linkages of POPs, but also are favorable for stabilization of
metal ions and NPs.30ꢀ33 For example, a twoꢀdimensional imineꢀbased POF (Pd/COFꢀLZU1) has
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been reported to support palladium ions and NPs through the confinement of polymer and
coordination of imine to palladium, and excellent catalytic activity and recyclability were shown
in the SuzukiꢀMiyaura coupling reaction.34 However, studies on the effects of synthetic methods
on the structures , properties and applications of target POPs are rare.35
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Click reaction of organic azides and terminal alkynes has become a common coupling
procedure in many interdisciplines owing to its superior reliability and modular synthesis.36ꢀ38
Recently, several 1,2,3ꢀtriazoylꢀcontaining POPs have been prepared through Click reaction, 39, 40
and have been explored as sorbents for gas storage41ꢀ43 and supports of metal nanoparticles (NPs)
for heterogeneous catalysis.21, 44, 45It is known that homoꢀcoupling reactions of rigid monomers
are more controllable than crossꢀcoupling reactions. Nickelꢀmediated Yamamoto coupling
reaction is one of efficient methods for arylꢀaryl homoꢀcoupling of arylꢀhalogenide compounds.46
Several POPs with high surface area have been synthesized through Yamamoto coupling
reaction.47ꢀ52 Among them, PAFꢀ1 and PPNꢀ4, which were prepared by selfꢀcondensation of
tetrakis(4ꢀbromophenyl)methane and tetrakis(4ꢀbromophenyl)silane, respectively, possess the
ultrahigh BET surface area of 5640 and 6461 m2 gꢀ1, respectively.53, 54 As a result, it will be
interesting to compare the performances of 1,2,3ꢀtriazoylꢀcontaining POPs from Click crossꢀ
coupling reaction and Yamamoto homoꢀcoupling reaction. As a continuation of our studies in
Clickꢀbased porous organic polymers (CPPs),21, 49 herein, we report the effects of synthetic
methods on the structures and properties of 1,2,3ꢀtriazoylꢀcontaining POPs, CPPꢀC and CPPꢀY,
which were synthesized via click reaction and Yamamoto coupling reaction, respectively. In
comparison with CPPꢀC, CPPꢀY exhibits superior performances in gas sorption, immobilization
of ultrafine palladium nanoparticles (NPs) and hydrogenation of olefins.
2.
EXPERIMENTAL SECTION
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1ꢀazidoꢀ4ꢀbromobenzene,55
4,4'ꢀdiazidobiphenyl,55
1,3,5,ꢀ
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General
Information:
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triethynylbenzene,56 Merrifield resin supported 5ꢀhexenꢀ1ꢀol and Merrifield resin supported 1ꢀ
hexanol57 were prepared according to literature methods. Other chemicals were commercially
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available and used without further purification. H and C NMR spectra were recorded on a
Bruker AVANCE III NMR spectrometer at 400 and 100 MHz, respectively, using
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tetramethylsilane (TMS) as an internal standard. Solidꢀstate C CP/MAS NMR was performed
on a Bruker SB Avance III 500 MHz spectrometer with a 4ꢀmm doubleꢀresonance MAS probe.
IR spectra were recorded with KBr pellets using PerkinꢀElmer Instrument. Raman spectra were
recorded on a Renishaw inVia system by using 633 nm laser. Thermogravimetric analysis (TGA)
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was carried out on NETZSCH STA 449C by heating samples from 30 to 700 C in a dynamic
nitrogen atmosphere with a heating rate of 10 °Cꢁminꢀ1. Powder Xꢀray diffraction (XRD) patterns
were recorded in the range of 2θ = 5ꢀ85o on a desktop Xꢀray diffractometer (RIGAKUꢀMiniflex
II) with Cu Kα radiation (λ = 1.5406 Å). Nitrogen adsorption and desorption isotherms were
measured at 77 K using a Micromeritics ASAP 2020 system, and the samples were degassed at
100 oC for 10 h before the measurements. Surface areas were calculated from the adsorption data
using BrunauerꢀEmmettꢀTeller (BET). The pore size distribution curves were obtained from the
adsorption branches using nonꢀlocal density functional theory (NLDFT) method. Fieldꢀemission
scanning electron microscopy (SEM) was performed on a JEOL JSMꢀ7500F operated at an
accelerating voltage of 3.0 kV. Transmission electron microscope (TEM) images were obtained
on TECNAI G2 F20. Xꢀray photoelectron spectroscopy (XPS) measurements were performed on
a Thermo ESCALAB 250 spectrometer, using nonꢀmonochromatic Al Kα xꢀrays as the
excitation source and choosing C 1s (284.6 eV) as the reference line. Inductively coupled plasma
spectroscopy (ICP) was measured on Jobin Yvon Ultima2. Gas chromatography (GC) was
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performed on a Shimadzu GCꢀ2014 equipped with a capillary column (RTXꢀ5, 30 m×0.25 ꢂm)
using a flame ionization detector. Elemental analyses were performed on an Elementar Vario
MICRO Elemental analyzer.
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Synthesis of 1,3,5-tris(1-(4-bromophenyl)-1H-1,2,3-triazol-4-yl)benzene: Sodium ascorbate
(120 mg, 0.6 mmol) was added to a suspension of 1ꢀazidoꢀ4ꢀbromobenzene (790 mg, 4.0 mmol),
1,3,5,ꢀtriethynylbenzene (150 mg, 1.0 mmol) and CuSO4·5H2O (75 mg, 0.3 mmol) in tꢀ
BuOH/H2O (10/10 mL). The reaction mixture was stirred at room temperature for 24 h. The
precipitate was isolated by filtration and washed successively with H2O (20 mL) and methanol
(10 mL). The crude product was further purified by flash column chromatography on silica gel
using cyclohexane/CH2Cl2 (2:1) as eluent to give target product as a yellow solid. Yield: 0.3 g
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(40 %). 1H NMR (400 MHz, DMSOꢀd6):
NMR (100 MHz, DMSOꢀd6):
δ
9.50 (s, 3H), 8.54 (s, 3H), 8.20ꢀ8.65 (m, 12H); C
δ
146.7, 136.2, 133.4, 131.9, 122.3, 121.9, 121.0; IR (KBr, cmꢀ1):
3097 (w), 2970 (vw), 2335 (vw), 2271 (vw), 1897 (vw), 1615 (w), 1497 (vs), 1395 (m), 1320
(w), 1233 (m), 1074 (m), 1039 (s), 1014(m), 986 (s), 882 (w), 825 (s), 781 (m), 719 (w), 507
(vw).
Synthesis of CPP-C: To a solution of 4,4'ꢀdiazidobiphenyl (0.58 g, 2.4 mmol), CuSO4·5H2O
(120 mg, 0.5 mmol) and 1,3,5,ꢀtriethynylbenzene (0.24 g, 1.6 mmol) in DMF (100 mL), sodium
ascorbate (95 mg, 0.5 mmol) was added under N2 atmosphere. The stirring mixture was heated to
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100 C and maintained at the temperature for 3 days. The precipitate was isolated by filtration,
rinsed with DMF (2 x 30 mL) and methanol (2 x 30 mL), and then redispersed in saturated
EDTAꢀ2Na solution (20 mL) at room temperature for 12 h. After filtered and washed with
excess H2O and methanol, the resultant material was purified by Soxhlet extraction using THF,
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dried in vacuo at 80 C for 12 h to afford CPPꢀC as a brown powder. Yield: 0.68 g (83%). IR
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(KBr, cmꢀ1): 3402 (m), 3137 (w), 3058 (w), 2926 (vw), 2097 (w), 1608 (s), 1506 (vs), 1458 (vw),
1399 (m), 1328 (vw), 1231 (m), 1108 (w), 1042 (s), 988 (m), 883 (w), 825 (s), 779 (m), 528 (w);
Elemental analysis calculated (%) for (C10H6N3)n: C 71.42, H 3.60, N 24.99. Found: C 65.25, H
4.64, N 20.62.
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Synthesis of CPP-Y: To a solution of bis(1,5ꢀcycloctadiene)nickel(0) (1.6 g, 5.8 mmol) and
2,2′ꢀbipyridyl (0.9 g, 5.8 mmol) in dehydrated DMF (40 mL), 1,5ꢀcycloctadiene (0.6 g, 5.8
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mmol) was added, and the mixture was heated at 80 C for 1 h. 1,3,5ꢀTris(1ꢀ(4ꢀbromophenyl)ꢀ
1Hꢀ1,2,3ꢀtriazolꢀ4ꢀyl)benzene (1.2 g, 1.6 mmol) in dehydrated DMF (60 mL) was added to the
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resultant purple solution at 80 C. The mixture was stirred at 80 C for 3 days to obtain the deep
purple suspension. After cooling to room temperature, the concentrated HCl was added to the
mixture until it turned to a green suspension. After filtration, the residue was washed with H2O
(2 x 30 mL), and then redispersed in saturated EDTA solution (20 mL) at room temperature for 3
h. After filtered and washed with excess H2O and methanol, the resultant material was purified
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by Soxhlet extraction using THF, dried in vacuo at 80 C for 12 h to afford CPPꢀY as a brown
powder. Yield: 0.69 g (81 %). IR (KBr, cmꢀ1): 3428 (m), 2967 (w), 2927 (w), 2345 (w), 1608 (s),
1504 (vs), 1385 (m), 1321 (vw), 1228 (m), 1106 (vw), 1042 (s), 988 (w), 883 (vw), 825 (m), 780
(w), 530 (vw); Elemental analysis calculated (%) for (C10H6N3)n: C 71.42, H 3.60, N 24.99.
Found: C 60.17, H 4.66, N 20.12.
Synthesis of Pd@CPP-C and Pd@CPP-Y: To a solution of Pd(OAc)2 (81 mg, 0.36 mmol) in
dichloromethane (100 mL), CPPꢀC or CPPꢀY (200 mg) was added. After stirring at 60 oC for 24
h, the precipitate was isolated by filtration. The resultant solid was purified by Soxhlet extraction
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with dichloromethane, dried in vacuo at 80 C for 12 h to give a brown solid, and then reduced
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in a stream of H2/N2 (10% H2, 100 mL/minꢀ1) at 200 C for 4 h to afford Pd@CPPꢀC and
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Pd@CPPꢀY. Pd contents in Pd@CPPꢀC and Pd@CPPꢀY were determined by ICP analysis, they
are 0.386 and 0.645 mmol gꢀ1, respectively.
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Hydrogenation of olefin: A highꢀpressure reactor was charged with olefin (2 mL) and
Pd@CPPꢀC or Pd@CPPꢀY (1/5000 equivalent of Pd per olefin mol) in ethanol (2 mL). The
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reactor was sealed and purged with hydrogen at 0 C to remove air. Hydrogen was introduced
into the reactor at the constant pressure, the reactor was placed into the preheated oil bath with
the agitation speed 1000 rpm. After a suitable reaction time, the reactor was placed in ice water
and gas was released. The products were analyzed using GC. The structures of the products were
confirmed by comparison with GC retention time of commercial materials and literature NMR
spectroscopic data. Solventꢀfree hydrogenation was carried out following the same method
described above except the absence of ethanol.
Recyclability test for hydrogenation of olefin: After hydrogenation of neat 1ꢀhexene, the
liquid was isolated by decantation. After washing twice with nꢀhexane and drying in vacuo at
room temperature for 0.5 h, the recovered gray solid was reused directly for the next run.
3.
RESULTS AND DISCUSSION
Scheme 1. Synthesis of CPPꢀC and CPPꢀY as well as schematic illustration of Pd@CPPꢀC and
Pd@CPPꢀY.
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Following the synthetic route outlined in Scheme 1, CPPꢀC was readily prepared by copperꢀ
catalyzed click reaction of 1,3,5ꢀtriethynylbenzene with 4,4'ꢀdiazidobiphenyl, while CPPꢀY was
synthesized by click reaction of 1,3,5ꢀtriethynylbenzene and 4ꢀbromophenyl azide, followed by
nickleꢀmediated Yamamoto coupling reaction. Both CPPꢀC and CPPꢀY are brown powders, they
are insoluble in water and common organic solvents.
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IR, solidꢀstate 13C NMR and XPS spectra of CPPꢀC and CPPꢀY are close to each other owing
to their similar chemical structure. In IR spectrum of CPPꢀC, the formation of 1,2,3ꢀtriazolyl
linkage is clearly confirmed by the disappearance of characteristic peaks of terminal alkynyl and
azide groups at 3281 and 2112 cmꢀ1, respectively, and the concomitant emergence of
characteristic peaks of 1,2,3ꢀtriazolyl group at 1610 and 3133 cmꢀ1 (Figure S1a).40 The
preservation of characteristic peaks of 1,2,3ꢀtriazolyl group and the absence of CꢀBr peak at 1073
cmꢀ1 in IR spectrum of CPPꢀY show successful homoꢀcoupling of 1,3,5ꢀtris(1ꢀ(4ꢀbromophenyl)ꢀ
1,2,3ꢀtriazol)benzene (Figure S1b).39 In solidꢀstate 13C NMR spectra of CPPꢀC and CPPꢀY, the
peak at 147 ppm is ascribed to C4 carbon of 1,2,3ꢀtriazolyl ring, and the broad signals at 110ꢀ140
ppm correspond to aromatic carbon atoms (Figure 1b).42 XPS survey spectra show the presence
of C, N and O in CPPꢀC and CPPꢀY (Figure S2). The N 1s regions of CPPꢀC and CPPꢀY are
deconvoluted into two peaks. One peak around 401.29 eV is ascribed to N2 atom of 1,2,3ꢀ
triazolyl, and the other peak around 399.64 eV corresponds to N1 and N3 atoms (Figure 2a).58, 59
Their intensity ratio of the relative peak areas is close to 1:2, which is the same as the ratio of
nitrogen content in 1,2,3ꢀtriazolyl ring. Elemental analyses of CPPꢀC and CPPꢀY show that the
experimental values of C and N are slightly lower than the corresponding theoretical values. The
deviations are mainly ascribed to the inclusion of guest molecules in the POPs,39, 60 which is
further confirmed by weight loss before 120 oC in TGA curves (Figure S3). XRD analyses reveal
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CPPꢀC and CPPꢀY are amorphous due to kinetic irreversibility of reaction processes (Figure S4).
SEM spectra show that they are composed of granular particles. The particle size of CPPꢀY is in
the range of 100ꢀ300 nm, which is larger than that in CPPꢀC (below 100 nm) (Figure S5).
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Figure 1. IR spectra (a) and solidꢀstate 13C NMR spectra (b) for CPPꢀC, CPPꢀY, Pd@CPPꢀC and
Pd@CPPꢀY.
Figure 2. (a) N 1s spectra for CPPꢀC, CPPꢀY, Pd@CPPꢀC and Pd@CPPꢀY; (b) Pd 3d XPS
spectra for Pd@CPPꢀC and Pd@CPPꢀY.
The porosities of CPPꢀC and CPPꢀY were investigated by N2 adsorption/desorption at 77 K.
As shown in Figure S6, the isotherm for CPPꢀY shows rapid N2 uptake at low relative pressure
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(P/P0<0.1), which is typical for microporous materials. The hysteresis is probably attributed to
deformation and/or swelling of the polymer at 77 K by N2.61 CPPꢀC exhibits similar isotherm
shape, but its gas uptakes at low relative pressures are drastically reduced. BET surface area of
CPPꢀC and CPPꢀY are 156 and 408 m2 gꢀ1, respectively, and their total pore volumes are 0.19
and 0.25 cm3 gꢀ1, respectively. Interestingly, appreciable amounts of CO2 adsorption were also
observed owing to the combination of microporous character and nitrogenꢀrich 1,2,3ꢀtriazolyl
group in the polymers. CO2 capture amounts at 273 K and 1 atm in CPPꢀC and CPPꢀY are 70.2
and 87.5 mg gꢀ1, respectively. The isosteric heat of adsorption (Qst) at low coverage of CPPꢀC
and CPPꢀY are 34.2 and 28.7 kJ molꢀ1, respectively, suggesting the binding affinity of CO2 with
the nitrogenꢀrich polymers (Figure S6c and S6d).43 CPPꢀC shows a slightly higher Qst than CPPꢀ
Y at the zero coverage, which can be attributed to smaller micropore size of CPPꢀC than CPPꢀ
Y.35 CPPꢀY gives 3.52 mmol gꢀ1 H2 adsorption at 1.1 bar and 77 K, which is higher than 2.89
mmol gꢀ1 in CPPꢀC (Figure S6e), which is correlated directly with the surface area and
microporous volume of CPPꢀY and CPPꢀC.39
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Considering the confinement of POPs and coordination ability of 1,2,3ꢀtriazolyl moieties,32, 34,
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palladium NPs inside CPPꢀC and CPPꢀY were investigated. As shown in Scheme 1, the
facile treatment of CPPꢀC and CPPꢀY with palladium acetate in dichloromethane, and
subsequent reduction in a stream of H2/N2 gave rise to gray Pd@CPPꢀC and Pd@CPPꢀY,
respectively. Transmission electron microscope (TEM) images show ultrafine palladium NPs are
uniformly distributed in Pd@CPPꢀC and Pd@CPPꢀY (Figure 3), and their average sizes are
1.69±0.33 and 1.39±0.31 nm, respectively, which are small enough to be accommodated in the
interior cavities of CPPꢀ1 and CPPꢀ2. No obvious characteristic peaks of palladium NPs were
observed in XRD patterns of Pd@CPPꢀC and Pd@CPPꢀY, revealing that the particles are too
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small and/or well dispersed in the polymers (Figure S4). EDS analyses exhibit that Pd@CPPꢀC
and Pd@CPPꢀY are composed of C, N, O and Pd (Figure S7). ICP analyses show Pd contents in
Pd@CPPꢀC and Pd@CPPꢀY are 0.386 and 0.645 mmol gꢀ1, respectively. The palladium loading
in CPPꢀC and CPPꢀY is in good agreement with their surface area.
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Figure 3. TEM images for Pd/CPPꢀC (a, b) and Pd/CPPꢀY (c, d).
In solidꢀstate 13C NMR spectra of Pd@CPPꢀC and Pd@CPPꢀY, signals of aromatic carbons at
110ꢀ150 ppm are similar to those in CPPꢀC and CPPꢀY, confirming the integrity of their
backbone after palladium loading (Figure 1). In XPS spectra, the appearance of characteristic
binding energy peaks of Pd 3d further confirms successful incorporation of palladium (Figure
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S2). Pd 3d spectra present two sets of doublet peaks corresponding to Pd 3d5/2 and Pd 3d3/2. Pd
3d5/2 peaks at 335.72 and 335.75 eV are attributed to Pd0 species in Pd@CPPꢀC and Pd@CPPꢀY,
respectively, while the peaks at 337.41 and 337.28 eV are related to Pd2+ species in Pd@CPPꢀC
and Pd@CPPꢀY, respectively (Figure 2b). The ratios of Pd0/Pd2+ in Pd@CPPꢀC and Pd@CPPꢀY
are 0.86 and 0.36, respectively. In comparison with N1s XPS spectra of CPPꢀC and CPPꢀY, a
slight upshift of N1s characteristic peaks in N1s XPS spectra of Pd@CPPꢀC and Pd@CPPꢀY
was observed owing to the weak coordination of nitrogen atoms to palladium (Figure 2a). BET
surface areas for Pd@CPPꢀC and Pd@CPPꢀY are decreased to 43 and 70 m2 gꢀ1, respectively,
and their total pore volumes are lowered to 0.11 and 0.07 cm3 gꢀ1 , respectively (Figure S6a and
S6b). The considerable decrements in BET surface area and pore volumes as well as the
increment of pore width have further demonstrated successful incorporation of palladium NPs in
the interior cavities of the polymers.65ꢀ67 Despite the significant decrement in surface area and
pore volume, Pd@CPPꢀC and Pd@CPPꢀY show hydrogen uptake of 2.10 and 1.87 mmol gꢀ1,
respectively.18, 68
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Figure 4. (a) Kinetic profiles of 1ꢀhexene conversion and nꢀhexane formation for Pd@CPPꢀC
and Pd@CPPꢀY, (b) reusability of Pd@CPPꢀC and Pd@CPPꢀY. Reaction conditions: the molar
ratio of 1ꢀhexene to Pd is 5000, 1.0 atm of H2, 25 °C, 2h.
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It is known that ultrafine palladium NPs possess a high surfaceꢀtoꢀvolume ratio, and provide a
large number of available active sites per unit area for substrates in catalysis. As a result,
ultrafine palladium NPs are thought to be more reactive than bulk palladium. 69, 70 The catalytic
performances of Pd@CPPꢀC and Pd@CPPꢀY were initially investigated by using hydrogenation
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of neat 1ꢀhexene under 1 atm of H2 at 25 C with olefin/Pd molar ratio of 5000. As shown in
Figure 4, kinetic profiles of hydrogenation of 1ꢀhexene show that Pd@CPPꢀC and Pd@CPPꢀY
present high conversion in 30 min. A full selectivity of nꢀhexane was achieved after 90 min and
60 min in Pd@CPPꢀC and Pd@CPPꢀY, respectively. Not all of 1ꢀhexene is simultaneously
transformed into nꢀhexane, which was attributed to the inherent competition between
isomerization and hydrogenation of 1ꢀhexene by using palladium NPs (Figure S8).71, 72 From the
proposed mechanism in Scheme S1, the olefinꢀpalladium intermediate can either undergo a
reductive elimination to form hexane or βꢀH elimination to form hexene isomers. The surface
hydrogen species on palladium play a crucial role in hydrogenation and isomerization of alkenes,
but only volumeꢀabsorbed hydrogen atoms is prone to react with olefinꢀpalladium intermediate
to form alkane.73 The faster rate of isomerization than hydrogenation during the early stages of
the reaction is a natural consequence of the fact that hydrogen atoms have to diffuse from the
surface into the cluster volume. The kinetic profiles of the conversion of 1ꢀhexene as well as the
formation of intermediated products and nꢀhexane indicate that ultrafine palladium NPs in
Pd@CPPꢀY show a higher selectivity for hydrogenation over isomerization than that in
Pd@CPPꢀC and commercial Pd@C, suggesting that the diffusion of hydrogen from the surface
into the cluster of the palladium particles can be facilitated by using ultrafine palladium NPs.
The catalytic recyclabilities of Pd@CPPꢀC and Pd@CPPꢀY were also evaluated. For
Pd@CPPꢀC, an obvious decrement of catalytic activity was observed in the consecutive
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reactions. For examples, the yields of nꢀhexane were decreased to 87% and 64% in the second
and fourth runs, respectively. However, Pd@CPPꢀY could be used at least seven times without
significant loss of catalytic activity. To explore the difference of the two catalytic systems, the
resultant powders containing palladium species were isolated after the consecutive reaction and
were examined by TEM. As shown in Figure 5, a certain degree of aggregations of palladium
NPs on the external surface of Pd@CPPꢀC and Pd@CPPꢀY were observed after the fourth run
and the seventh run, respectively, whereas the sizes in majority of the particles are slightly larger
than that in fresh samples. These observations indicate that 1,2,3ꢀtriazoyl on the surface of
polymers cannot completely prevent the aggregation of external surface NPs through Ostwald
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ripening. However, palladium NPs in the interior cavities can be effectively restricted by the
confinement interaction of the polymer backbone and the coordination interaction between 1,2,3ꢀ
triazoyl and palladium NPs. In comparison with Pd@CPPꢀC, Pd@CPPꢀY exhibits more
restriction against NPs aggregation and superior catalytic activity, which are ascribed to its
relatively higher surface area and larger pore volume. It should be mentioned that no catalytic
activity was detected when control experiment for hydrogenation of 1ꢀhexene was performed in
the presence of CPPꢀY, suggesting the palladium NPs is crucial for smooth implement of
hydrogenation. XPS analyses show that Pd/N molar ratios of fresh Pd@CPPꢀC and Pd@CPPꢀY
are 0.048 and 0.071, respectively, while Pd/N molar ratios of the used Pd@CPPꢀC and
Pd@CPPꢀY are 0.056 and 0.076, respectively, which are slightly higher than that of their
respective fresh samples.75 The increments are possibly ascribed to the migration of palladium
from the interior pore to the surface of polymers during hydrogenation, which are consistent with
the results of TEM analysis.
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Figure 5. TEM images for Pd@CPPꢀC after the fourth run (a, b), and Pd@CPPꢀY after the
seventh run (c, d).
To further investigate catalytic performances of Pd@CPPꢀY, other olefins were tested. As
shown in Figure 6a, complete conversion of 1ꢀoctene was achieved in 4h, which was much
slower than that of 1ꢀhexene, suggesting that the reactivity of olefins was significantly affected
by the chain length of alkenes. Hydrogenation rate of transꢀ2ꢀoctene was slower than 1ꢀoctene
owing to its bulkily steric hindrance. Similar to hydrogenation of 1ꢀhexene, hydrogenation of
styrene to ethyl benzene also gave a full conversion in 30 min, which probably resulted from πꢀπ
interactions between styrene and aromatic framework of POPs as well as the coordination of
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styrene to the accessible surface of ultrafine palladium NPs. 76 However, when cyclohexene was
employed as a substrate, 30% yield of cyclohexane was achieved in 1h, and was only increased
to 40% in 4h, which was much lower than that of 1ꢀhexene. Interestingly, 2ꢀnorbornene was fully
hydrogenated in 2h, which was much faster than cyclohexene, probably because of relatively
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small bond angle of double bond and considerable strain in the skeleton of 2ꢀnorbornene.
However, hydrogenation of (S)ꢀ(ꢀ)ꢀlimonene only gave 5% conversion after 4h, probably
because its large size is unfavorable to access active sites of palladium NPs inside cavity of the
polymers. The competition reactions were also performed using a mixture of equimolar styrene
and (S)ꢀ(ꢀ)ꢀlimonene as substrates. In comparison with hydrogenation of neat styrene and (S)ꢀ(ꢀ)ꢀ
limonene, a full conversion of styrene was also observed in 30 min, while the conversion of (S)ꢀ
(ꢀ)ꢀlimonene was increased from 5 to 34% after 4h (Figure 6b). The increment occurred after a
nearly full conversion of styrene to ethylbenzene, which are probably attributed that the swelling
behavior of surface pores in Pd@CPPꢀY in the presence of ethylbenzene enables (S)ꢀ(ꢀ)ꢀ
limonene to enter into the pores of polymer, and ultimately promoting the contact between (S)ꢀ(ꢀ
)ꢀlimonene and active sites in polymers.24, 80, 81
It is known that palladium particles in Pd@C are located on the outer surface of carbon, and
catalytic reactions occur on the surface of Pd@C. The control experiments of hydrogenation of
1ꢀhexene and 1ꢀoctene were investigated using commercial Pd@C. The kinetic profile showed
that hydrogenation of 1ꢀoctene was slightly slower than 1ꢀhexene in the presence of Pd@C
(Figure S9), which was similar to those from Pd@CPPꢀY. In comparison with Pd@CPPꢀY,
Pd@C showed a slightly lower catalytic activity in hydrogenation of 1ꢀhexene, but the catalytic
activity in hydrogenation of 1ꢀoctene was slightly higher, suggesting that the dispersion of
palladium NPs and the property of supports have important effects on hydrogenation of olefins.82
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Figure 6. Kinetic profiles for hydrogenation of olefins (a) and hydrogenation of mixture of
styrene and (S)ꢀ(ꢀ)ꢀlimonene (b) catalyzed by Pd@CPPꢀY. Reaction conditions: the molar ratio
of olefin to Pd is 5000, 1.0 atm of H2, 25 °C.
To confirm hydrogenation of olefins was indeed catalyzed by palladium NPs in the polymer
backbone instead of the leached palladium species, hot filtration and threeꢀphase test were
performed. After hydrogenation of 1ꢀhexene was run for 10 min, Pd@CPPꢀY was removed from
the reaction mixture by filtration, and the filtrate was continued to react for 4h, negligible
changes in conversion and selectivity were observed (Figure 6a). ICP analysis of the filtrate
shows that palladium leaching is 0.12 ppm, which is insignificant with respect to 0.65 mmol gꢀ1
of fresh Pd@CPPꢀY. Threeꢀphase test is usually considered to be a useful proof for the detection
of homogeneously catalytic active metal species. 83, 84 The threeꢀphase test was conducted using
Merrifield resinꢀsupported (Oꢀlinked) 1ꢀhexenol as an alkene substrate.52 After hydrogenation,
Pd@CPPꢀY can be facilely separated from Merrifield resin by centrifugation (Figure S10), no
obvious conversion of resinꢀbound substrate was observed (Figure 7).
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Figure 7. Raman spectra of Merrifield resin (black), 5ꢀhexenꢀ1ꢀol supported on Merrifield resin
(green), attempted hydrogenation of 5ꢀhexenꢀ1ꢀol supported on Merrifield resin by Pd@CPPꢀY
(red), 1ꢀhexanol supported on Merrifield resin (purple).
It is known that viscosity of reaction media and physical accessibility of the substrates into the
catalytic sites have important effects on hydrogenation of olefins, hydrogenation was also
performed in ethanol solution. Pd@CPPꢀY showed higher activity than Pd@CPPꢀC in
hydrogenation of 1ꢀhexene (Figure S11), which was consistent with that under solventꢀfree
conditions. Similar variation trends in conversion profiles were observed in hydrogenation of 1ꢀ
octene, transꢀ2ꢀoctene, styrene and 2ꢀnorbornene using Pd@CPPꢀY (Figure S12). Besides, the
catalytic activities in ethanol were much faster than those under neat conditions. The promotion
was mainly ascribed to the decrement of viscosity of olefins in ethanol solution, accelerating the
accessibility of the catalytically active sites to olefin molecules .
4. CONCLUSIONS
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CPPꢀC and CPPꢀY containing 1,2,3ꢀtriazolyl linkages have been prepared by click reaction and
Yamamoto coupling reaction, respectively. Their structures and properties can be finely tuned by
proper choice of synthetic methods. Ultrafine palladium NPs with uniform distribution are
facilely incorporated inside the pores of CPPꢀC and CPPꢀY. The confinement interaction of the
polymer backbone in conjunction with coordination interaction between 1,2,3ꢀtriazoyl and
palladium NPs result in good stabilization of palladium NPs. Both Pd@CPPꢀC and Pd@CPPꢀY
exhibit excellent catalytic activities in hydrogenation of olefins. Pd@CPPꢀY presents higher
catalytic activity and recyclability than Pd@CPPꢀC. In summary, this study not only expands the
library of clickꢀbased POPs, but also provides a useful strategy for the construction of new POPꢀ
based catalytic systems with tunable reactivity and stability.
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ASSOCIATED CONTENT
Supporting Information. The details of the preparation of materials and their characterizations,
and NMR spectra for catalytic products. This material is available free of charge via the Internet
at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
* ruihu@fjirsm.ac.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
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The authors acknowledge 973 Program (2011CBA00502), National Natural Science
Foundation of China (21273239, 21471151, 21403238) and Major Project of Fujian Province
(2014H0053).
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Two 1,2,3ꢀtriazolylꢀcontaining porous organic polymers (CPPꢀC and CPPꢀY) were readily
synthesized through click reaction and Yamamoto coupling reaction, respectively. Ultrafine
palladium NPs with uniform distribution are facilely incorporated inside the pores. The chemical
compositions of CPPꢀC and CPPꢀY are almost identical, but palladium nanoparticles show
different structures and catalytic performances.
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84x47mm (300 x 300 DPI)
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