Pd Supported IRMOF-3: Heterogeneous, Efficient and Reusable Catalyst for Heck Reaction


IRMOF-3 with a high surface area prepared by a hydrothermal method was used for deposition of Pd(OAc)2 on IRMOF-3 particles. The final catalyst was characterized with FT-IR, nitrogen physisorption, thermogravimetry, scanning electron microscopy, transmission electron microscopy combined with energy dispersive X-ray analysis, wide angle X-ray diffraction spectroscopy and X-ray photoelectron spectroscopy. The prepared porous catalyst was effectively used in the Heck coupling reaction in the presence of an organic base. The reaction parameters such as the type of base, amounts of catalyst and solvents, temperature were optimized. The catalyst was then easily separated, washed, and reused 4 times without significant losses of catalytic activity.

Graphical Abstract


Recently metal–organic frameworks (MOFs), porous materials of a crystalline structure comprising bridged organic ligands and metal centers, have been attracted significant attention in gas sorption average owing to their large pore volumes and surface areas. Several studies have been reported on MOFs utilization as heterogeneous catalysts [1,2,3,4], in gas storage [5], separation [6], drug delivery [7], and sensing [8, 9]. These materials have been explored because of their intrinsic high surface area, tunable pores, and various functionalities [10].

The IRMOF series based on MOF-5 was synthesized possessing octahedral clusters with carboxylate linear linkers. IRMOF-1 formed an oxide-centered Zn4O tetrahedron by six carboxylate edges giving the octahedral shape that reticulates into a three dimensional (3D) cubic porous system. The IRMOFs pore size and structure depend on the functional groups on the linkers. When the linkers have different functional groups such as bromo, amino, n-propoxy, n-pentoxy, cyclobutyl, and fused benzene, effective structures ranging from IRMOF-2 through IRMOF-7 (Fig. 1) can be synthesized [11]. Each of the different type of IRMOFs has a specific single-crystal X-ray diffraction spectroscopy (XRD) pattern.

Fig. 1

Structure of IRMOF materials

A high flexibility of these compounds allows synthesis of several types of MOFs with ultrahigh surface area and high thermal stability. For example, in the case of MOF-5 decomposition of the structure happens at as high temperature region as between 350 and 400 °C [12]. In terms of the framework structure, the MOFs have different types such as extra-high porosity frameworks IRMOF-1, square channels (MOF-2), hexagonally packed cylindrical channels (MOF-74), MOF-177, interpenetration (IRMOF-11), alkyl- and amino-functionalized pores (IRMOFs-6 and -3) and pores decorated with open metal sites (MOF-505 and Cu3 (BTC)2) [13]. Babarao et al. studied storage and separation of CO2 and CH4 with silicalite, C168 schwarzite, and IRMOF-1 [14]. The authors compared the materials and reported that IRMOF-1 has a considerably higher adsorption volume than other adsorbents, while the adsorption selectivity of CO2 over CH4 was found to be similar. IRMOF-14 and IRMOF-16 being nontoxic were found to afford high-loading capacity for drug delivery. The results showed that the hydrogen atom with a hydroxyl moiety in the organic linker of IRMOF-14 and IRMOF-16 is the key for hydrogen bonding and acid–base interactions with Tamoxifen [15]. Phan et al. synthesized a highly porous IRMOF-3 from the reaction of zinc nitrate hexahydrate and 2-amino-1,4-benzenedicarboxylic acid by a solvothermal technique. This catalyst was used for the Paal–Knorr reaction of benzyl amine with 2,5-hexanedione confirming that IRMOF-3 is an efficient heterogeneous catalyst to form 1-benzyl-2,5-dimethyl-1H-pyrrole as the major product [16].

Several techniques have been developed for coupling of C–C bond, which can be exemplified by Heck [17], Suzuki [18], Negishi [19], Sonogashira [20], Kumada [21], and Stille[22] coupling reactions, etc. Various metals such as palladium, rhodium, ruthenium, copper, zinc, tin, magnesium, etc [23]. have been used. One of the fundamental transformations in organic chemistry is the Heck reaction used for reacting substituted halobenzenes and vinyl halides with olefins (Scheme 1). In general, the reaction of alkyl halides with olefins is not satisfactory, because of a premature β-hydrogen elimination and slow oxidative addition rates [24]. Challenges to enhance the scope of enantioselective Heck reactions have been very recently well documented [25]. Kong et al. reported palladium-catalyzed intramolecular asymmetric enantioselective Heck reactions in the presence of diboron–water as a hydride source [26]. Bao et al. described palladium-catalyzed enantioselective Narasaka–Heck reaction in the presence of an achiral bidentate phosphine ligand with direct C–H alkylation of arenes [27].

Scheme 1

Scheme of the Heck reaction

A highly effective tool for deposition of various metals including palladium and platinum is chemical vapor deposition of organometallic compounds. Sabo et al. deposited palladium into a highly porous metal–organic framework MOF-5 by palladium acetoacetate in CHCl3 solution via the “incipient wetness” impregnation and studied catalytic behavior in styrene hydrogenation. Park et al. prepared a highly dispersed palladium (II) in a defective metal-organic framework for C-H activation and functionalization of naphthalene [28].

In this work deposition of palladium acetate on the surface of IRMOF-3 was performed to develop a highly active and reusable heterogeneous catalyst for the Heck coupling reaction.



Zinc nitrate hexahydrate, 2-aminoterephthalic acid, Pd(OAc)2, iodobenzene, ethyl acrylate and bases were obtained from Sigma Aldrich and used without further purification. Other solvents and chemicals were of laboratory grade, obtained from Alfa and used without further purification.

Preparation of IRMOF-3

In order to synthesize IRMOF-3, zinc nitrate hexahydrate (3.720 g, 12.5 mmol) and 2-aminoterephthalic acid (0.750 g, 4.15 mmol) were dissolved in dry DMF (100 mL). The mixture was placed into an autoclave heated at 100 °C for 24 h, following by slow cooling to room temperature. The solid products after filtration were washed three times with DMF. For removal of DMF from the pores immersion two times into CH2Cl2 for 12 h was done [29, 30].

Preparation of IRMOF-3-Pd

Activated IRMOF-3 particles (1.000 g) were dispersed in CH2Cl2 (30 mL), following by addition of Pd(OAc)2 (50 mg) and stirring for 24 h. Thereafter, the solid catalyst was separated by centrifugation and washed several times with CH2Cl2 and dried under vacuum at 150 °C for 24 h to give IRMOF-3-Pd (3.5 wt% Pd detected by ICP-OES) [31]. The procedure for the catalyst synthesis is given in Scheme 2.

Scheme 2

Preparation of IRMOF-3-Pd


The functional groups on the solid compounds were investigated by infrared spectroscopy (ATI Mattson FTIR). The specific surface area and pore volume were determined by N2 adsorption/desorption using a Sorptometer 1900 apparatus (Carlo-Erba Instruments). The morphology and crystal size distribution were studied by a scanning electron microscope (Zeiss Leo 1530 Gemini) equipped with a Thermo-NORAN vantage X-ray detector. Elemental analysis was performed with the same instrument. The IRMOF-3 and IRMOF-3-Pd size distributions images were obtained by transmission electron microscopy (TEM) using by EFTEM, LEO 912 OMEGA, LaB6 filament, 120 kV. Thermogravimetry (TGA) curves were recorded on a CAHN D-200 instrument for the powder samples (scanning rate 10 °C/min to 600 °C). The content of palladium in the catalyst was determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES), using an Optima 4300 DV optical atomic emission spectrometer. The XRD measurements were carried out on a Bruker AXS D8 Discover instrument equipped with a Cu Kα X-ray source and scintillator point detector. The samples were scanned in the 1°–70° 2θ range, with an increment of 0.04° and at a scan speed of 8 s per point. The progress of the reaction was analyzed by GC equipped with FID system using HP 6890 Series with HP-5, 5% phenyl methyl siloxane capillary column (30.0 m × 320 µm, 0.25 µm). The injector temperature was 280 °C, while the gas flow was 9.5 mL/min. Hexadecane was used as an internal standard.

Heck Coupling Reaction

The reaction was performed at 120 °C in the 14 mL round bottom vial with stirrer. The reaction mixture contained 0.2 mmol of iodobenzene, 0.3 mmol of methyl acrylate, 0.3 mmol of triethylamine (Et3N), 0.001 g of IRMOF-3-Pd as a catalyst (0.165 mol% Pd to aryl halide) and 0.5 mL DMA (dimethylacetamide) as a solvent. The reaction progress was followed by TLC and after completion analyzed with GC. The catalyst was separated from the reaction mixture by filtration and then it was washed with DMA and ethyl acetate.

Results and Discussion

Catalyst Characterization

IRMOF-3 was studied using different characterization techniques. In the FT-IR spectra characteristic bands revealed the presence of functional organic groups on IRMOF-3 and IRMOF-3-Pd as shown in Fig. 2. The peaks of asymmetric and symmetric stretching vibrations of amino groups are visible at 3477 and 3355 cm−1. The strong bands at 1662–1382 cm−1 are related to symmetrical and asymmetrical O–C=O vibrations of dicarboxylate and C=C in the benzene ring. A strong peak at 1255 cm−1 is assigned to C−N stretching. The aromatic C−H bending at 1103 and 833 cm−1 also appeared in the spectra of IRMOF-3 [32, 33].

Fig. 2

FT-IR spectra for IRMOF-3 (black line) and IRMOF-3-Pd (blue line)

The SEM images show that the IRMOF-3 is highly crystalline displaying well-shaped cubic crystals (Fig. 3a–c). After deposition of palladium acetate on the surface, the cubic structures have been partially destroyed (Fig 3d, e).

Fig. 3

SEM images for IRMOF-3 (a to c) and IRMOF-3-Pd (d and e)

In order to identify the elemental composition of IRMOF-3-Pd EDX at random points on the surface of the catalyst was performed (Fig. 4). The EDX results indicate that palladium deposited on catalyst are at least to some extent ligated with chlorines that originates from CH2Cl2 that was used during catalyst preparation.

Fig. 4

EDX analysis of IRMOF-3-Pd

The measurements confirmed the presence of palladium, zinc, oxygen, nitrogen and carbon in the supported catalyst. The weight % and atomic % of different components are shown in Table 1.

Table 1 The weight % and atomic % of elements in the catalyst

Transmission electron microscopy (TEM) was performed to determine the MOF particle size. The porous structure of the IRMOF-3 is clearly visible in the TEM images (Fig. 5a, b). After deposition of palladium acetate on IRMOF-3, palladium (II) has been converted into metallic palladium, which is visible as the metal clusters with the size below ca. 6 nm (Fig. 5c). These clusters tend to grow. After four Heck cycles they formed much bigger agglomerates (Fig 5d) which probably caused drop of the activity.

Fig. 5

TEM images for fresh IRMOF-3-Pd (a to c) and used (d)

The nitrogen adsorption-desorption isotherms for IRMOF-3 is shown in Fig. 6. The BET surface area for IRMOF-3 was calculated to be 996 m2/g. After deposition of palladium on the surface of IRMOF-3 the surface area was diminished to 810 m2/g. The Pd loading was optimized to keep IRMOF-3 structure and high porosity.

Fig. 6

Nitrogen physisorption diagram of IRMOF-3

Low angle X-ray diffraction (XRD) patterns of IRMOF-3 and IRMOF-3-Pd are presented in Fig. 7a. Diffraction peaks of the supporting material (Fig. 7a—black pattern) were observed at 2θ = 6.8, 9.8 and 13.8 which is in agreement with the structure of IRMOF-3 [34]. After palladium deposition the intensity of peaks has been slightly decreased but they were still present showing that the crystal structure of IRMOF-3 is preserved (Fig. 7a—red pattern). However, after the reaction only the peak of a lower intensity at the 2θ = 9.8 indicating that framework was preserved only to a certain extent (Fig. 7b).

Fig. 7

XRD patterns of IRMOF-3, IRMOF-3-Pd (a) and IRMOF-3-Pd recycled (b)

The thermogravimetric analysis (Fig. 8) reflects the thermal stability of IRMOF-3. The IRMOF-3 exhibited two main weight losses, the first one (app. 7%) in the temperature range below 400 °C, corresponding to the loss of water from the pores of metal organic frameworks as well as aromatic groups and unreacted molecules. A second more prominent mass loss of 27% above 400 °C is related to decomposition of the organic frameworks.

Fig. 8

TGA thermograms of IRMOF-3

X-ray photoelectron spectroscopy (XPS) analysis, giving information on the metal oxidation state, is presented in Fig. 9a, which displays that the fresh catalyst contains palladium in the form of Pd(II) having the characteristic 3d5/2 and 3d3/2 peaks at 337.6 and 342.9 eV binding energies. After the reaction (Fig. 9b) all Pd was converted to the metallic Pd(0) form with binding energies at 335.7 and 340.9 eV, in agreement with TEM analysis. Besides these peaks, an additional peak at around 343.8 eV was observed, being evidently more prominent in the spectra of the recycled catalyst. It can be speculated that this peak originates from Pd forming an alloy with zinc which can result in significant electron disorder similar to previous reports [35, 36].

Fig. 9

XPS spectra of the fresh and recycled IRMOF-3-Pd

Optimization of Reaction Conditions

The reaction conditions were optimized by conducting the coupling reaction of iodobenzene and methyl acrylate, as model substances, and changing the reaction parameters including the base type, the solvent, the catalyst amount and reaction temperature. The results are summarized in Table 2. Methyl acrylate is typically added in excess [37] to compensate evaporation, moreover unreacted iodobenzene in the reaction mixture causes high leaching of palladium from the catalyst [38]. Experiments with various solvents (entry 1–10) revealed that dimethylacetamide (DMA) was the most efficient solvent (entry 1, 3.6% yield). After a careful screening of different bases (entries 11 to 18), Et3N was found to give the highest yield of the coupling product (entry 15, 88.8% yield). Solubility of the inorganic bases is very poor in the organic systems, while triethylamine is miscible in the slurry of the Heck reaction. This is the main reason for high conversion in the presence of triethylamine as a base [39]. Additionally, commonly used Heck solvents such as DMF and NMP are tested with Et3N base to avoid any uncertainty with choice of solvent/base system (entries 19, 20). The effect of Pd loading was investigated showing that the highest activity was observed by using 0.165 mol% of palladium (entry 21, 5.2% yield). Based on plotted results for different catalyst amounts (Fig. 10a) the reaction order in the catalyst was calculated to be 0.70. A deviation from first order kinetics is expected due to formation of inactive palladium dimers when a relatively high Pd to halide ratio is used. Smaller amounts of palladium than used in the current work would probably lead to the first order reaction, however, such small amounts are very difficult to handle experimentally. The reaction order in the catalyst determined in the current work is in good agreement with a recently published kinetic study by Bures, who reported the values of 0.55–0.86 depending on Pd loading [40]. Furthermore, by increasing the reaction temperatures (entries 25 to 28) reaction rate increases linearly which is explained typically by Arrhenius type dependence of the rate constants on temperature as well as by a faster redisposition of Pd on the catalyst at elevated temperature [41]. The apparent activation CPd energy (Fig. 10b) was calculated to be 18.4 kJ/mol.

Table 2 Optimization of conditions for Heck reaction
Fig. 10

Rate of the reaction between iodobenzene and methyl acrylate as a function of catalyst concentration (a) and temperature (b)

Without any catalyst the reaction between iodobenzene and methyl acrylate did not give any product (Entry 24).

In Table 3, the catalytic activity of the IRMOF-3-Pd in the Heck cross-coupling reaction of iodobenzene with methyl acrylate is compared with some catalysts reported in the literature. As can be seen, IRMOF-3-Pd is more effective than the previously studied catalysts for the Heck reaction. It should be also noted that the values of TOF presented for IRMOF-3-Pd (Table 3, entry 6), as well as for some other entries in the same Table (entries 1–3) certainly underestimate the real catalytic activity especially during the initial period, as they are calculated at 100% conversion.

Table 3 Comparison of the prepared catalyst with other catalysts for Heck cross-coupling reactions from iodobenzene with methyl acrylate

Catalyst recyclability is one of the important factors in catalysis. In this respect, leaching of palladium, stability and reusability of supported IRMOF-3-Pd was studied in the Heck cross-coupling reaction of iodobenzene and methyl acrylate as a model substrate under optimal conditions. In order to reuse the catalyst, the IRMOF-3-Pd was separated by centrifuge after each cycle, washed with diethyl ether and ethyl acetate. A certain decline in activity can be seen (Fig. 11), which most probably can be attributed to palladium agglomeration (Fig. 5d) and leaching. In the first cycle 17% of Pd leached in the mixture of the reaction. Such leaching is in line with the current mechanistic views on the Mizoroki-Heck reaction with heterogeneous catalysts [44,45,46] suggesting that the reaction involves dissolution of Pd from the support with subsequent redeposition of formed Pd species in the solution. The latter colloidal type of species are thus considered catalytically active.

Fig. 11

Recycling of IRMOF-3-Pd for the Heck cross-coupling under optimal conditions. The reaction mixture contained 0.2 mmol of iodobenzene, 0.3 mmol of methyl acrylate, 0.3 mmol of Et3N, 0.001 g of IRMOF-3-Pd as a catalyst (0.165 mol% Pd to aryl halide) and 0.5 mL DMA (dimethylacetamide) as a solvent


In the present study, IRMOF-3 was prepared by a hydrothermal method and after deposition of palladium acetate, was used as a heterogeneous catalyst for the Heck cross-coupling reaction. IRMOF-3 and IRMOF-3-Pd were characterized by FT-IR, nitrogen physisorption, transmission electron microscopy (TEM), scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX), broad angle X-ray diffraction spectroscopy (XRD) and X-ray photoelectron spectroscopy (XPS). The results have demonstrated that the IRMOF-3 is a suitable support for deposition of palladium acetate, which can efficiently catalyze the Heck reaction between iodobenzene and methyl acrylate.


  1. 1.

    Bhattacharjee S, Yang D-A, Ahn W-S (2011) A new heterogeneous catalyst for epoxidation of alkenesvia one-step post-functionalization of IRMOF-3 with a manganese(ii) acetylacetonate complex. Chem Commun 47:3637–3639

    Article  CAS  Google Scholar 

  2. 2.

    Dhakshinamoorthy A, Asiri A, Garcia H (2015) Mmetal–organic frameworks catalyzed C–C and C-heteroatom coupling reactions. Chem Soc Rev 44:1922–1947

    Article  CAS  PubMed  Google Scholar 

  3. 3.

    Dhakshinamoorthy A, Li Z, Garcia H (2018) Catalysis and photocatalysis by metal organic frameworks. Chem Soc Rev 47:8134–8172

    Article  CAS  PubMed  Google Scholar 

  4. 4.

    Chughtai A, Ahmad N, Younus H, Laypkov A, Verpoort F (2015) Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations. Chem Soc Rev 44:6804–6849

    Article  CAS  PubMed  Google Scholar 

  5. 5.

    DeSantis D, Mason JA, James BD, Houchins C, Long JR, Veenstra M (2017) Techno-economic analysis of metal–organic frameworks for hydrogen and natural gas storage. Energy Fuels 31:2024–2032

    Article  CAS  Google Scholar 

  6. 6.

    Addicoat M, Bennett T, Chapman K, Denysenko D, Dincă M, Doan H, Easun T, Eddaoudi M, Farha O, Gagliardi L, Haase F, Hajiahmadi Farmahini A, Hendon C, Jorge M, Kitagawa S, Lamberti C, Lee J-SM, Leus K, Li J, Lin W, Liu X, Lloyd G, Lu C, Ma S, Perez JPH, Ranocchiari M, Rosi N, Stassen I, Ting V, van der Veen M, Van Der Voort P, Vande Velde CML, Volkmer D, Vornholt S, Walsh A, Yaghi OM (2017) New directions in gas sorption and separation with MOFs: general discussion. Faraday Disc 201:175–194

    Article  CAS  Google Scholar 

  7. 7.

    Xie Y, Liu X, Ma X, Duan Y, Yao Y, Cai Q (2018) Small titanium-based MOFS prepared with the introduction of tetraethyl orthosilicate and their potential for use in drug delivery. ACS Appl Mater Interf 10:13325–13332

    Article  CAS  Google Scholar 

  8. 8.

    Schönfeld F, Meyer LV, Mühlbach F, Zottnick SH, Müller-Buschbaum K (2018) Optical isotherms as a fundamental characterization method for gas sensing with luminescent MOFs by comparison of open and dense frameworks. J Mater Chem C 6:2588–2595

    Article  Google Scholar 

  9. 9.

    Assen AH, Yassine O, Shekhah O, Eddaoudi M, Salama KN (2017) MOFs for the sensitive detection of ammonia: deployment of fcu-MOF thin films as effective chemical capacitive sensors. ACS Sensors 2:1294–1301

    Article  CAS  PubMed  Google Scholar 

  10. 10.

    Wei J-Z, Wang X-L, Sun X-J, Hou Y, Zhang X, Yang D-D, Dong H, Zhang F-M (2018) Rapid and large-scale synthesis of IRMOF-3 by electrochemistry method with enhanced fluorescence detection performance for TNP. Inorg Chem 57:3818–3824

    Article  CAS  PubMed  Google Scholar 

  11. 11.

    Eddaoudi M, Kim J, Rosi N, Vodak D, Wachter J, O’Keeffe M, Yaghi OM (2002) Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295(5554):469–472

    Article  CAS  PubMed  Google Scholar 

  12. 12.

    Britt D, Tranchemontagne D, Yaghi OM (2008) Metal–organic frameworks with high capacity and selectivity for harmful gases. Proc Natl Acad Sci USA 105:11623–11627

    Article  PubMed  Google Scholar 

  13. 13.

    Millward AR, Yaghi Millward OM (2005) Metal–organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature. J Am Chem Soc 127:17998–17999

    Article  CAS  PubMed  Google Scholar 

  14. 14.

    Babarao R, Hu Z, Jiang J, Chempath S, Sandler SI (2007) Storage and separation of CO2 and CH4 in silicalite, C168 Schwarzite, and IRMOF-1: a comparative study from Monte Carlo simulation. Langmuir 23:659–666

    Article  CAS  PubMed  Google Scholar 

  15. 15.

    Koukaras EN, Montagnon T, Trikalitis P, Bikiaris D, Zdetsis AD, Froudakis GE (2014) Toward efficient drug delivery through suitably prepared metal–organic frameworks: a first-principles study. J Phys Chem C 118:8885–8890

    Article  CAS  Google Scholar 

  16. 16.

    Phan NTS, Nguyen TT, Luu QH, Nguyen LTL (2012) Paal-Knorr reaction catalyzed by metal–organic framework IRMOF-3 as an efficient and reusable heterogeneous catalyst. J Mol Catal A 363–364:178–185

    Article  CAS  Google Scholar 

  17. 17.

    Go H, Shun I, Yasuhiro U (2018) A palladium NNC-pincer complex as an efficient catalyst precursor for the Mizoroki-Heck Reaction. Adv Synth Catal 360:1833–1840

    Article  CAS  Google Scholar 

  18. 18.

    Zhou X, Guo X, Jian F, Wei G (2018) Highly efficient method for Suzuki reactions in aqueous media. ACS Omega 3:4418–4422

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. 19.

    Rejc L, Gómez-Vallejo V, Alcázar J, Alonso N, Andrés JI, Arrieta A, Cossío FP, Llop J (2018) Negishi coupling reactions with [11 C] CH 3 I: a versatile method for efficient 11 C-C bond formation. Chem Commun 54:4398–4401

    Article  CAS  Google Scholar 

  20. 20.

    Liu Q, Xu M, Zhao J, Yang Z, Qi C, Zeng M, Xia R, Cao X, Wang B (2018) Microstructure and catalytic performances of chitosan intercalated montmorillonite supported palladium (0) and copper (II) catalysts for Sonogashira reactions. Int J Biol Macromol 113:1308–1315

    Article  CAS  PubMed  Google Scholar 

  21. 21.

    Qi X, Sun H, Li X, Fuhr O, Fenske D (2018) Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions. Dalton Trans 47:2581–2588

    Article  CAS  PubMed  Google Scholar 

  22. 22.

    Gao J, Wang W, Zhang S, Xiao S, Zhan C, Yang M, Lu X, You W (2018) Distinction between PTB7-Th samples prepared from Pd (PPh 3) 4 and Pd 2 (dba) 3/P (o-tol) 3 catalysed stille coupling polymerization and the resultant photovoltaic performance. J Mater Chem A 6:179–188

    Article  CAS  Google Scholar 

  23. 23.

    Shi S, Nawaz KS, Zaman MK, Sun Z (2018) Advances in enantioselective C–H activation/Heck reaction and Suzuki reaction. Catalysts 8:90

    Article  CAS  Google Scholar 

  24. 24.

    Kurandina D, Rivas M, Radzhabov M, Gevorgyan V (2018) Heck reaction of electronically diverse tertiary alkyl halides. Org Lett 20:357–360

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  25. 25.

    Minatti A, Zheng X, Buchwald SL (2007) Synthesis of chiral 3-substituted indanones via an enantioselective reductive-Heck reaction. J Org Chem 72:9253–9258

    Article  CAS  PubMed  Google Scholar 

  26. 26.

    Wangqing K, Qian W, Jieping Z (2017) Water as a hydride source in palladium-catalyzed enantioselective reductive Heck reactions. Angew Chem Int Ed Engl 56:3987–3991

    Article  CAS  Google Scholar 

  27. 27.

    Xu B, Qian W, Jieping Z (2017) Palladium-catalyzed enantioselective Narasaka-Heck reaction/direct C–H alkylation of arenes: Iminoarylation of alkenes. Angew Chem Int Ed Engl 56:9577–9581

    Article  CAS  Google Scholar 

  28. 28.

    Park T-H, Hickman AJ, Koh K, Martin S, Wong-Foy AG, Sanford MS, Matzger AJ (2011) Highly dispersed palladium(II) in a defective metal-organic framework: application to C–H activation and functionalization. J Am Chem Soc 133:20138–20141

    Article  CAS  PubMed  Google Scholar 

  29. 29.

    Servalli M, Ranocchiari M, Van Bokhoven JA (2012) Fast and high yield post-synthetic modification of metal-organic frameworks by vapor diffusion. Chem Commun 48:1904–1906

    Article  CAS  Google Scholar 

  30. 30.

    Xamena FXL, Cirujano FG, Corma A (2012) An unexpected bifunctional acid base catalysis in IRMOF-3 for Knoevenagel condensation reactions. Microporous Mesoporous Mater 157:112–117

    Article  CAS  Google Scholar 

  31. 31.

    Yuanbiao H, Tao M, Ping H, Dongshuang W, Zujin L, Rong C (2013) Direct C-H bond arylation of indoles with aryl boronic acids catalyzed by palladium nanoparticles encapsulated in mesoporous metal-organic framework. ChemCatChem 5:1877–1883

    Article  CAS  Google Scholar 

  32. 32.

    Wang X-L, Fan H-L, Tian Z, He E-Y, Li Y, Shangguan J (2014) Adsorptive removal of sulfur compounds using IRMOF-3 at ambient temperature. Appl Surf Sci 289:07–113

    Google Scholar 

  33. 33.

    Wang S, Bromberg L, Schreuder-Gibson H, Hatton TA (2013) Organophophorous ester degradation by chromium(III) terephthalate metal-organic framework (MIL-101) chelated to N,N-dimethylaminopyridine and related aminopyridines. ACS Appl Mater Interf 5:1269–1278

    Article  CAS  Google Scholar 

  34. 34.

    Zhou X, Zhang Y, Yang X, Zhao L, Wang G (2012) Functionalized IRMOF-3 as efficient heterogeneous catalyst for the synthesis of cyclic carbonates. J Mol Catal A 361–362:12–16

    Article  CAS  Google Scholar 

  35. 35.

    Rodriguez J, Kuhn M (1996) Interaction of Zinc with transition-metal surfaces: electronic and chemical perturbations induced by bimetallic bonding. J Phys Chem 100:381–389

    Article  CAS  Google Scholar 

  36. 36.

    Fasana A, Braichovic L (1982) Chemically driven diffusion of Pd in the surface region of Zn(0001): an ultraviolet photoemission investigation. Surf Sci 120:239–250

    Article  CAS  Google Scholar 

  37. 37.

    Liang L, Nie L, Jiang M, Bie F, Shao L, Qi C, Zhang XM, Liu X (2018) Palladium immobilized on in situ cross-linked chitosan superfine fibers for catalytic application in an aqueous medium. New J Chem 42:11023–11030

    Article  CAS  Google Scholar 

  38. 38.

    Zhao F, Bhanage BM, Shirai M, Arai M (2000) Heck reactions of iodobenzene and methyl acrylate with conventional supported palladium catalysts in the presence of organic and/and inorganic bases without ligands. Chem Eur J 6:843–848

    Article  CAS  PubMed  Google Scholar 

  39. 39.

    Liu G, Hou M, Song J, Jiang T, Fan H, Zhang Z, Han B (2010) Immobilization of Pd nanoparticles with functional ionic liquid grafted onto cross-linked polymer for solvent-free Heck reaction. Green Chem 12:65–69

    Article  CAS  Google Scholar 

  40. 40.

    Burés J (2016) A simple graphical method to determine the order in catalyst. Angew Chem Int Ed Engl 55:2028–2031

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  41. 41.

    Rosol M, Moyano A (2005) 1′-Carbopalladated-4-ferrocenyl-1,3-oxazolines as catalysts for Heck reactions: further evidence in support of the Pd(0)/Pd(II) mechanism. J Organomet Chem 690:2291–2296

    Article  CAS  Google Scholar 

  42. 42.

    Cassez A, Kania N, Hapiot F, Fourmentin S, Monflier E, Ponchel A (2008) Chemically modified cyclodextrins adsorbed on Pd/C particles: new opportunities to generate highly chemo- and stereoselective catalysts for Heck reaction. Catal Commun 9:1346–1351

    Article  CAS  Google Scholar 

  43. 43.

    Han W, Liu N, Liu C, Jin ZL (2010) A ligand-free Heck reaction catalyzed by the in situ-generated palladium nanoparticles in PEG-400. Chin Chem Lett 21:1411–1414

    Article  CAS  Google Scholar 

  44. 44.

    Phan NTS, van der Sluys M, Jones CW (2006) On the nature of the active species in palladium catalyzed Mizoroki-Heck and Suzuki-Miyaura couplings—homogeneous or heterogeneous catalysis. A critical review. Adv Synth Catal 348:609–679

    Article  CAS  Google Scholar 

  45. 45.

    Asrtruc D (2007) Palladium nanoparticles as efficient green homogeneous and heterogeneous carbon–carbon coupling precatalysts: a unifying view. Inorg Chem 46:1884–1894

    Article  CAS  Google Scholar 

  46. 46.

    Glasnov TN, Findenig S, Kappe CO (2009) Heterogeneous versus homogeneous palladium catalysts for ligandless Mizoroki–Heck reactions: a comparison of batch/microwave and continuous-flow processing. Chem Eur J 15:1001–1010

    Article  CAS  PubMed  Google Scholar 

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Open access funding provided by Abo Akademi University (ABO). This work is part of the activities at the Åbo Akademi University Johan Gadolin Process Chemistry Centre within the Centre of Excellence Programme appointed by ÅAU, Finland. In Sweden the Bio 4 Energy programme is acknowledged.

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Correspondence to Dmitry Yu. Murzin.

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Nuri, A., Vucetic, N., Smått, JH. et al. Pd Supported IRMOF-3: Heterogeneous, Efficient and Reusable Catalyst for Heck Reaction. Catal Lett 149, 1941–1951 (2019). https://doi.org/10.1007/s10562-019-02756-0

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  • Metal–organic-frameworks
  • IRMOF-3-Pd
  • Heck reaction