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    • 专利摘要:
    Porous conjugated polymers, materials that comprise them, method of preparation and use thereof. Porous conjugated polymers (PCP) formed by repeating units comprising a core comprising at least one aryl group, the core being attached to at least three branches, wherein each branch comprises a structure of formula I or a structure of formula II, wherein the substituents are defined as in the description. The present invention also relates to hybrid materials comprising a PCP as defined in the present invention and an inorganic semiconductor, as well as methods of preparing the same. The invention also makes reference to the use of PCPs and hybrid materials as photocatalysts. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2684052A1
    申请号:ES201730445
    申请日:2017-03-28
    公开日:2018-10-01
    发明作者:Alba GARCÍA SÁNCHEZ；Carmen GARCÍA LÓPEZ；Patricia REÑONES BRASA；Fernando FRESNO；Marta Liras Torrente；Victor A. DE LA PEÑA O'SHEA
    申请人:Fund Imdea Energia；Fundacion Imdea Energia；
    IPC主号:
    专利说明:

    POROUS CONJUGATED POLYMERS, MATERIALS THAN THOSEUNDERSTAND, METHOD OF PREPARATION AND USE OF THE SAME
    DESCRIPTION The present invention relates to porous conjugated polymers, as well as to hybrid materials comprising said polymers. The process of preparing both polymers and hybrid materials and the use of these as photocatalysts is also an object of the present invention.
    STATE OF THE TECHNIQUE Photocatalysis is based on the promotion of electrons from their fundamental energy level to a higher one when a substance (the photocatalyst, generally, but not necessarily, a broadband semiconductor) is irradiated with wavelength light adequate. These excited electrons, together with the positive (hollow) charges they leave at the fundamental level, can react with electron acceptor and donor species, respectively, thus catalyzing oxidation-reduction reactions. The scientific and technological implications of this principle are widely recognized today, since they give rise to applications in different fields such as the elimination of contaminants, the inactivation of bacteria, the production of fuels and the synthesis of value-added products without the need for high temperatures and pressures, and using light as a source of energy. Artificial photosynthesis is a field of research within photocatalysis that attempts to mimic the natural photosynthesis of plants in order to convert carbon dioxide and water into fuels and chemicals, using a light source, such as the Sun . (Chem. Commun. 52 (2015) 35–59). The processes of CO2 photoreduction and hydrogen production from water are included in this research field. The development of new photocatalyst materials that improve both processes is one of the most promising areas within this field. A wide variety of materials have been used as photocatalysts in both processes and their impact on invention patents has been analyzed in 2014 by Protti et al. (Phys. Chem. Chem. Phys. 16 (2014) 19790–19827), being the inorganic semiconductors and, especially, the TiO2, the most important both for the number of contributions and for the


    results obtained (ACS Catal. 6 (2016) 7485í7527). There are several examples of the use of catalysts of organic nature, generally small molecules used as sensitizers, and a linear polymer based on bipyridine complexed to Ru (II) (JPS5730727 (A)) is described. On the other hand, the use of a polyaniline semiconductor polymer to prepare a composite material with TiO2 and its subsequent use in artificial photosynthesis, in particular in CO2 photoreduction (Chem. Commun. 51 (2015) 13654-13657) ). One of the drawbacks of the materials described to date is that they have very high rates of recombination of photogenerated electrons, which causes low yields in photocatalytic processes. Hybrid materials based on the mixture of two inorganic semiconductors improve these photocatalytic processes because the synergy between both materials results in an improvement in the separation of charges produced by the action of light, associated with an increase in production and a greater control of selectivity. The microporous conjugated polymers, "conjugated microporous polymers", whose acronym in English is CMP, are a subclass of porous materials that are related to structures such as zeolites, metal-organic networks and organic covalent networks. Although in a first stage the design of these materials was focused on the synthesis of microporous systems, the great textural versatility of the selected monomers and the polymers obtained allows the synthesis of multimodal materials with an intrinsic porosity control that includes the range of The micro to the pores. This characteristic allows not only a control in the diffusion of the reagents but also in the selectivity to certain products. CMPs possess many of the properties to inorganic semiconductors such as conductivity, mechanical stiffness and insolubility. The CMPs are synthesized through the covalent bond of conjugated molecule fragments, acquiring a three-dimensional structure thanks to the formation of ʌ-ʌ bonds that favor their stacking (Chem. Soc. Rev. (2013) 42, 8012). CMPs have applications in storage and separation of gas streams, catalysis, light absorption and emission devices, sensors and storage of electrical energy (Polymer Int. 63 (2013) 381). Their photophysical properties can be modulated depending on the nature of the starting monomers. In WO2009022187 reference is already made


    to this type of polymers, where CMPs formed exclusively from aryl units without heteroatoms are described for the first time. Recently, the use of both non-porous conjugated polymers (Angew. Chem. - Int. Ed. 55 (2016) 1792-1796) and microporous conjugated polymers (J. Am. Chem. Soc. 138 (2016) 7681 has been described –7686., Chem. Commun. 52 (2016) 10008–10011 and Angew. Chem. - Int. Ed. 55 (2016) 9202–9206) as photocatalysts for hydrogen production. As an improved alternative to the photocatalysts known in the state of the art, the present invention provides new photocatalyst materials based on porous conjugated polymers (with micro and mesopores), which are highly efficient in the production of solar fuels and value-added products. by artificial photosynthesis, that is, in processes of hydrogen production from water as well as CO2 reduction. In particular, the present invention describes new porous conjugated polymers containing the structural unit known as BOPHY, disclosed in WO2015077427A1, or the fused dithiothiophene type structural unit, whose acronym is DTT (Bull. Korean Chem. Soc. 29 (2008 ) 891–893 and RSC Adv. 5 (2015) 65192–65202), as well as new hybrid materials comprising said porous conjugated polymers.
    DESCRIPTION OF THE INVENTION In a first aspect, the present invention relates to porous conjugated polymers (PCPs) comprising repeated units comprising:
    - a core comprising at least one aryl group and
    - branches, where each branch comprises a structure of formula I or a structure of formula II:
    where R1 and R2 each independently represent H, C1-C4 alkyl, -Ph, PhOCH3, -SO3, -COOR7, -PO3, -NO2, -NH2, -C {CH, -SH, -SCOCH3;R7 is selected from H and C1-C4 alkyl,


    and where R1 and R2 are placed in positions 2 and 4 or 1 and 4 or 2 and 3 respectively in structure (I)
    5 where R1 ', R2', R3 ', R4', R5 'and R6' each independently represents H, C1-C4 alkyl, -Ph, -PhOCH3, -SO3, -COOR7 ', -PO3, -NO2, NH2 , -C {CH, -SH, -SCOCH3; R7 ’is selected from H and C1-C4 alkyl and where the nucleus is linked to at least three branches through bonds
    10 -C-C- or triple-C {C- links between the aryl or aryl group of the nucleus and the structure of formula I or the structure of formula II, and where each branch is linked to two nuclei. In this way, two adjoining units share one of its ramifications. That is, one unit joins another unit through a branch that both
    15 units share. Schematically, in the case that each core is attached to three branches, it could be represented as follows:
    20 where A would represent a nucleus and B a branch. Each unit AB3 joins other units AB3 sharing the branches B. In the same way, in the case that each core is linked to more branches, each unit ABn would join other units ABn sharing the branches B, where n is the number of branches B attached to each core A.
    Another aspect of the present invention relates to an organic-inorganic hybrid material comprising a PCP, as defined above, and an inorganic semiconductor.


    A third aspect of the present invention relates to the method of preparing a PCP defined in the first aspect of the present invention. A fourth aspect of the present invention relates to the method of preparing the organic-inorganic hybrid material comprising a PCP and an inorganic semiconductor. A final object of the present invention relates to the use of PCPs, defined in the present invention or of the hybrid materials mentioned above as photocatalysts, preferably in artificial photosynthesis, that is, in processes of hydrogen production from water as well. as CO2 reduction in the presence of water. In the present invention the term "aryl" refers to an aromatic carbocyclic chain, having from 6 to 12 carbon atoms, being able to be single or multiple ring, in the latter case with separate and / or condensed rings. The aryl groups are, for example but not limited to, phenyl, naphthyl, diphenyl, etc. Preferably the aryl group is a phenyl. The aryl group present in the nuclei may be substituted or unsubstituted. The aryl may optionally carry one or more substituents. Optionally, at least one of said substituents can be, for example, amino, C1-C4 alkyl, haloalkyl (for example trifluoromethyl), azide, fluorine, C1-C4 alkenyl, hydroxyl, thiol, ester, amide, urethane, carbonate, acetate, ether, thioether. The term "alkyl" refers, in the present invention, to aliphatic, linear or branched chains, having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl, sec-butyl. The alkyl groups may be optionally substituted by one or more substituents such as hydroxyl, azide, carboxylic acid or a substituted or unsubstituted group selected from amino, amido, carboxylic ester, ether, thiol, acylamino or carboxamido. In the present invention, semiconductor means that material whose conductivity is comprised between that of the conductive materials and that of the insulators and in which the charge density of electric current can be changed by external factors. Throughout the description and claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components
    or steps. For those skilled in the art, other objects, advantages and characteristics of


    The invention will be derived partly from the description and partly from the practice of the invention. DETAILED DESCRIPTION OF THE INVENTION
    In a first aspect, the present invention relates, as mentioned in the previous section, to porous conjugated polymers (PCPs) comprising repeated units which, in turn, comprise:
    - a core comprising at least one aryl group and
    - branches, where each branch comprises a structure of
    10 formula I or a structure of formula II:
    Where R1 and R2 each independently represent H, C1-C4 alkyl, -Ph, PhOCH3, -SO3, -COOR7, -PO3, -NO2, -NH2, -C {CH, -SH, -SCOCH3; R7 is selected from H and C1-C4 alkyl, and where R1 and R2 are located in positions 2 and 4 or 1 and 4 or 2 and 3 respectively in structure (I),
    C1-C4, -Ph, -PhOCH3, -SO3, -COOR7 ’, -PO3, -NO2, -NH2, -C {CH, -SH, -SCOCH3;R7 ’is selected from H and C1-C4 alkyl;and where the core is attached to at least three branches through linkssingle -C-C- or triple-C {C- bonds between the aryl group or aryls of the nucleus and the


    structure of formula I or structure of formula II and where each branch isattached to two cores.Then, each core is attached to at least three branches and each branch,comprising a structure of formula I or of formula II, is attached to two
    5 cores Preferably, R1 and R2 in formula (I) are in positions 2 and 3 respectively. The aryl group present in the nuclei may be substituted or unsubstituted. The aryl may optionally carry one or more substituents. Optionally, at least one
    10 of said substituents can be, for example, amino, C1-C4 alkyl, haloalkyl (for example trifluoromethyl), azide, fluorine, C1-C4 alkenyl, hydroxyl, thiol, ester, amide, urethane, carbonate, acetate, ether, thioether . In addition, the cores may have several aryl groups and may have several configurations, for example, they may include three aryl groups, preferably
    Phenyl, attached to a central nitrogen atom or to another central phenyl group or may include four phenyl groups attached to a central carbon atom. Preferably, the conjugated polymers of the present invention have a specific surface area greater than 10 m2g-1 and more preferably greater than 100
    2-1
    mg
    The PCPs described in the present invention have pore sizes 1-50 nm, preferably less than 2 nm. Both parameters (specific surface area and pore size) are determined from their adsorption isotherms of N2. In a preferred embodiment, the PCPs of the present invention have cores attached to three branches. Preferably, the nuclei attached to three
    25 branches are selected from the following:
    In another preferred embodiment, the PCPs of the present invention have cores attached to four branches.


    Preferably, the nuclei attached to four branches are selected from the following:
    Where R8 can be H, methyl or halogen selected from fluorine, chlorine, bromine or iodine. Another aspect of the present invention relates to an organic-inorganic hybrid material comprising a porous conjugated polymer, as defined in the present invention, and at least one inorganic semiconductor. In the organic-inorganic hybrid material, the polymer or polymeric macroparticles are surrounded by inorganic semiconductor nanoparticles. However, the polymer in hybrid materials does not affect the crystalline structure of the inorganic semiconductor. The polymer can be in any proportion in the hybrid material. Preferably between 0.1-99.9% by weight with respect to the hybrid material. More preferably, the PCP is in the hybrid material in a proportion of 1, 5, 10 or 15% by weight with respect to said material. Preferably, inorganic semiconductors are compounds formed by the combination of at least one non-metallic element and / or at least one metallic element. Among the possible inorganic semiconductors used are the following compounds: TiO2, TiSi, ZnO, NaTaO3, NaNbO3, SnO2, In2O3, Fe2O3, 25 WO3, InP, C3N4, GaN, BN, ZnS, CdS, ZnSe, CdSe, CdTe, BiWO6 , BiVO4. Preferably the inorganic semiconductor is TiO2. The inorganic compounds may be doped or additive with different metallic and / or non-metallic elements, or by two non-metallic elements, in addition to organometallic compounds containing metallic elements. For example, they can be doped with Fe, Sn, Nb, Cr, N, C, P ... or include additives


    as metal nanoparticles (for example, from Au, Ag, Pt, Pd, Ru, Re, Cu, Fe, Ni,Co, ...), or compounds and alloys thereof.Another aspect of the present invention relates to the method of preparing thePCPs of the present invention.PCPs are obtained by coupling in the presence of Pd (0) or Pd (II) of ahalogenated dithiothiophene (DDT) monomer of formula I ’:
    where R1 and R4 or R1 and R2 or R3 and R4 are halogens selected from fluorine, chlorine bromine or iodine and the rest of the substituents R3 and R2, R3 and R4 or R1 and R2 are independently H, C1-C4 alkyl, -Ph, - PhOCH3, -SO3, -COOR7, -PO3, -NO2, NH2, -C {CH, -SH, -SCOCH3; R7 is selected from H and C1-C4 alkyl,
    or of a halogenated monomer of formula II ’:
    where R1 ', R2', R3 ', R4', R5 'and R6' each independently represents H, C1-C4 alkyl, -Ph, -PhOCH3, -SO3, -COOR7 ', -PO3, -NO2, -NH2 , -C {CH, -SH, -SCOCH3; R7 ’is selected from H and C1-C4 alkyl; where X is a halogen selected from fluorine, chlorine bromine or iodine, with a second monomer comprising at least one aryl group and further comprising: -at least three terminal alkyne substituents, or -at least three substituents derived from boronic acid (- B (OH) 2) or boronic ester (-B (ORaRb)), where Ra and Rb each independently represent a C1C4 alkyl or Ra and Rb can form a C3-C7 carbocycle optionally substituted with C1-C4 alkyl groups.


    The monomer comprising at least one aryl group will give rise to the PCP nuclei and the monomers of formula I 'or II' will give rise to the branches that bind to said nuclei.
    5 In the event that the aryl monomer comprises at least three terminal alkyne substituents in its structure, during coupling the bond with the halogen in the monomer of formula I 'or II' is replaced by a bond to the terminal alkyne of the monomer of aryl In the case that the aryl monomer comprises at least three substituents
    10 derivatives of boronic acid or boronic ester, during coupling, C-C bonds are formed between the halogen-linked carbons in the monomer of formula I 'or II' and the carbons attached to the boron atom in the aryl monomer. Because the monomer comprising at least one aryl group has a plurality of terminal alkyne groups (at least three) or a plurality of
    15 groups derived from boronic acid or ester (at least three), said monomer is capable of reacting with at least three monomers of formula I ’or II’. Likewise, because the monomer of formula I 'or II' comprises two halogen atoms, said monomer is capable of reacting with two aryl monomers. In this way, a three-dimensional polymer network is formed.
    The aryl group present in the aryl monomer may optionally contain more than one unsubstituted or substituted aryl group. The aryl may optionally carry one or more substituents. Optionally, at least one of said substituents may be, for example, amino, C1-C4 alkyl, haloalkyl (for example trifluoromethyl), azide, halogen, C1-C4 alkenyl, hydroxyl,
    Thiol, ester, amide, urethane, carbonate, acetate, ether, thioether. In addition, the monomers that will give rise to the PCP nuclei may comprise several aryl groups and may have various configurations, for example, they may include three aryl groups, preferably phenyl, attached to a central nitrogen atom or another phenyl central group or may include four phenyl groups attached to
    30 a central carbon atom. Preferably, the monomer comprising at least one aryl group is one of the following:



    where R8 can be H, methyl or halogen selected from fluorine, chlorine, bromine or iodine and where Y is preferably:
    In the same monomer, the "Y" substituents are all the same, that is, a monomer has three or four terminal alkynes, or three or four substituents
    10 boronic acid derivatives or three or four substituents derived from boronic ester. If the aromatic compound is functionalized with terminal alkynes, the coupling reaction that takes place is a Shonogashira type reaction (K. Sonogashira, Y. Tohda, N. Hagihara Tetrahedron Lett. 16 (1975) 4467-4470).
    Said reaction takes place in the presence of a catalyst of Pd (0) and a copper cocatalyst. Preferably, the catalyst is a phosphine of Pd (0), for example, tetrakis- (triphenylphosphine) palladium and the copper cocatalyst is preferably copper iodide (CuI). The reaction takes place in the presence of a solvent such as dimethylformamide (DMF) or acetonitrile and in the presence of a base.
    20 such as triethylamine. The reaction temperature is preferably between 80-120 ° C and can be reached by thermal means or using microwave radiation.


    In the event that the aromatic compound is replaced by boronic groups or boronic ethers, the coupling that takes place with the haluroaromatic is based on the Suzuki reaction (N. Miyaura; K. Yamada, A. Suzuki, Tetrahedron Lett. 20 ( 1979) 3437-3440) and takes place in the presence of a Pd (0) catalyst, preferably tetrakis- (triphenylphosphine) palladium or a Pd (II) catalyst, preferably palladium diacetate, in the presence of a base (generally K2CO3, NaOtBu, Cs2CO3, K3PO4, etc). As the solvent, toluene, tetrahydrofuran, dioxane, dimethylformamide and even water or mixtures thereof with water are usually used, but it is not limited thereto. The reaction temperature is marked by the solvent system chosen and can be reached thermally or using microwave radiation. The present invention also relates to porous conjugated polymers obtained by any of the procedures indicated above. Another aspect of the present invention relates to the method of preparing the hybrid material comprising a PCP, as described in the present invention, and at least one inorganic semiconductor. The method of preparing the hybrid material includes the realization of a mixture of a PCP and an inorganic semiconductor, where the PCP is preferably in varying amounts between 0.1 and 99.9% by weight with respect to the mixture. Preferably, the mixing is carried out by stirring the components of the hybrid material (PCP and inorganic semiconductor) in an organic solvent (such as acetonitrile, methanol, etc.), or mixtures of organic solvents and water (such as, for example, acetonitrile / water), for a time that can range between 1 and 300 min, with subsequent removal of the solvent. Preferably, once the solvent is removed, a grinding of the hybrid material obtained in a mortar is carried out. Among the possible inorganic semiconductors used are the following compounds: TiO2, TiSi, ZnO, NaTaO3, NaNbO3, SnO2, In2O3, Fe2O3, WO3, InP, C3N4, GaN, BN, ZnS, CdS, ZnSe, CdSe, CdTe, BiWO6, BiVO4. Preferably the inorganic semiconductor is TiO2. In a preferred embodiment of the invention and prior to the preparation of the hybrid based on a PCP and an inorganic semiconductor, the inorganic semiconductor is subjected to a heat treatment for the elimination of possible


    impurities and stabilization thereof, which varies between 100 ° C and 1000 ° C and is carried out in times between 2 h and 5 days. The organic-inorganic hybrid materials described in the present invention have proved useful as photocatalysts, preferably in artificial photosynthesis, that is, in processes of hydrogen photoproduction from water as well as CO2 photoreduction. The results of the evaluation of hybrid materials as heterogeneous photocatalysts in hydrogen production processes from water in the presence of a sacrificial agent (such as methanol, ethanol, ethanolamine, triethylamine, sulfite / sulfide mixtures, etc.) and in absence of metals, show a substantial improvement with respect to the activity of the inorganic semiconductor material, as well as a great photostability that allows its reuse in various cycles and long reaction times. The sacrificial agent is a molecule that acts as an electron donor in a photoinduced electron transfer process, which also does not restore itself in a subsequent reduction process and, therefore, is destroyed in an irreversible chemical reaction. The results of the evaluation of the hybrid materials as heterogeneous photocatalysts in CO2 reduction in the presence of water or other reducing agent such as, for example, methanol, ethanol, ethanolamine, triethylamine, sulfite / sulfide mixtures, etc., show a substantial improvement with respect to to the activity of semiconductor inorganic material. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES Figure 1. A) Solid state 13C-CP / MAS NMR spectra of the CMPDTT-1 (below) and CMPDTT-2 (above) polymers recorded at a rotation speed of 10kHz. B) Fourier transform infrared (FTIR) spectra of the CMPDTTs polymer networks: CMPDTT-1 (above) and CMPDTT-2 (below) synthesized in Example 1 of the present invention. C) Nitrogen adsorption isotherms at 77 K (adsorption with full symbols and desorption with empty symbols) of CMPDTT-1 polymers (circles) and CMPDTT


    2 (squares). Inserted figure: pore distribution of both samples using DFT, CMPDTT-1 (circles) and CMPDTT-2 (squares) as the calculation method. D) Thermogravimetric (TGA) analysis of CMPDTT-1 (circles) and CMPDTT-2 (square) polymers under argon current (empty symbols) and under air current (full symbols). Figure 2. (a) Images taken using scanning electron microscopy (SEM) of CMPDTT-1. (b) Image taken using transmission electron microscopy (TEM) of CMPDTT-1. (c) Magnification of the previous one. (d) Image taken using an ambient scanning electron microscope (ESEM) of the TiO2 @ CMPDTT-1 sample (15% by weight of CMPDTT-1). (e) TEM image of the TiO2 @ CMPDTT-1 sample (10% by weight of CMPDTT-1). (f) Magnification of the previous one that shows in the inserted figure an elementary analysis using X-ray energy dispersion (EDX). Figure 3. A) 77 K nitrogen adsorption isotherms of TiO2 @ CMPDTT-1 hybrid materials with a microporous polymer content of 1% (line 3, triangles), 5% (line 4, circles) and 15% ( line 5, squares) by weight respectively (adsorption with full symbols and desorption with empty symbols). B) X-ray diffraction characterization of the TiO2 @ CMPDTT-1 hybrid material (with a microporous polymer content of 1% (line 3), 5% (line 4) and 10% (line 5) by weight). C) UV-Vis diffuse reflectance spectra of TiO2 (line 1), CMPDTT1 polymer (line 2) and TiO2 @ CMPDTT-1 hybrid materials with a microporous polymer content of 1% (line 3), 5% (line 4) and 10% (line 5) by weight. D) Fluorescence spectra of TiO2 (line 1), CMPDTT-1 polymer (line 2) and TiO2 @ CMPDTT-1 hybrid materials with a microporous polymer content of 1% (line 3), 5% (line 4 ), 10% (line 5) and 15% (line 6) by weight. Figure 4. Diagram showing the production of hydrogen from water when the reaction is photocatalyzed by TiO2, by CMPDTT-1 polymer, or by TiO2 @ CMPDTT-1 hybrid material with a porous polymer content of 1%, 5 %, 10% and 15%. Figure 5. Graph showing the cumulative production of different products in a process of artificial photosynthesis by CO2 photoreduction in 15 hours of reaction: hydrogen (black bar), CO (striped bar), and CH4 (dotted bar);


    using the different catalysts: TiO2, CMPDTT-1 and the TiO2 @ CMPDTT-1 hybrid catalysts with a porous polymer content of 1%, 5%, 10% and 15%. EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the products of the invention.
    Example 1
    Obtaining the porous conjugated polymers CMPDTT-1 and CMPDTT-2
    10 Table 1: Starting materials and resulting polymer:
    Monomer comprising at least one aryl group Halogenated monomerPolymer
    CMPDTT-1
    CMPDTT-2


    For the preparation of porous conjugated polymers, represented above and named as CMPDTT-1 and CMPDTT-2, 2,6-dibromoditiene [3,2-b: 2´, 3´-d] thiophene are added under an inert atmosphere (2 , 6-Br-DTT, 1 mmol, 5 0.352 g, Sigma Aldrich), and 1,3,5-trietinylbenzene (1 mmol, 0.15 g, Sigma Aldrich) to prepare CMPDTT-1 or 4, 4 '' - dietinyl-5 '- (4-ethynylphenyl) -1,1': 3 ', 1' '- terphenyl (1 mmol, 0.25g) (synthesized using the method described in Angew. Chemie, Int. Ed., 54, (2015) 12748-12752) to prepare CMPDTT-2, (Pd- [PPh3] 4 (0.04 mmol, 50 mg, Sigma Aldrich), CuI (0.08 mmol, 15 mg, Sigma Aldrich) to a Schlenk flask 50 mL containing 2 mL of triethylamine and 2 mL of dimethylformamide (DMF) The suspension is degassed by bubbling argon at 100 qC for 20 min.The reaction mixture is stirred at 100 qC for 3 days under argon. filter using polyamide microfilters (0.45Pm, Sartorius) and wash with a large excess of clean DMF, chloroform, toluene and ace tonitrile The solid formed is suspended in
    15 a mixture of acetonitrile / water (1: 1 v / v) with an excess of sodium cyanide in order to remove the remains of Pd (0) from the sample. It is filtered again and washed several times with water and acetonitrile. It is dried under vacuum and the polymers are characterized.
    In Scheme 1 the reactions for the preparation of CMPDTT-1 and CMPDTT-2 polymers are presented schematically.


    Example 2
    Obtaining the porous conjugated polymers CMPBOPHY-1 and CMPBOPHY-2
    Table 2: Starting materials and resulting polymer:


    Monomer comprising at least one aryl group Halogenated monomerPolymer
    CMPBOPHY-1
    CMPBOPHY-2

    The compound BOPHY (halogenated monomer) (120 mg, 0.203 mmol) (previously synthesized following the method described in J. Am Chem. Soc, 136, (2014), 5623) is introduced into a 10 mL microwave reaction tube. 1,3,5trietinylbenzene (30 mg, 0.203 mmol, Sigma Aldrich) or 4, 4 '' - dietinyl-5 '- (4-ethynylphenyl)


    1,1 ': 3', 1 '' - terphenyl (61 mg, 0.203 mmol) (synthesized following the procedure described in Angew. Chem. Int. Ed. 54, (2015) 12748-12752) in a DMF / Et3N solution (2: 1.5 mL). The reaction mixture is degassed by bubbling a stream of argon for 10 minutes. The reaction is carried out under radiation
    5 microwaves for 15 min at 800 rpm and 120 qC. The reaction crude is filtered and washed with ethyl acetate (AcOEt), dichloromethane (DCM), tetrahydrofuran (THF) and ether. The solid obtained is dispersed in 20 mL of a solution of NaCN (200 mg) in H2O / THF (1: 1 v / v). The dispersion is stirred overnight. The polymer is then filtered again and washed with
    Abundant H2O and CH3CN (acetonitrile). Finally, CMPBOPHY-1 (88%) or CMPBOPHY-2 (90%) compounds are obtained as dark red solids.
    In Scheme 2 the reactions for the preparation of CMPBOPHY-1 and CMPBOPHY-2 polymers are presented schematically. fifteen

    Scheme 2
    The general experimental methods used in the characterization and analysis of CMPDTT-1 and CMPDTT-2 polymers are described below: Microanalysis
    The elementary analysis was carried out using a Thermo Fisher Flash 2000 model.
    10 Carbon magnetic resonance of solids carbon. The 13 nuclear spectra of solid nuclear magnetic resonance (13CRMN) were recorded with a Bruker spectrometer model AV400 (Larmor frequencies of 400, 100 and 161 MHZ for 13C and 1H, respectively) using a MAS probe (acronym for magical English) angle spinning) of 4 mm at a speed
    15 kHz The measurements were taken using a contact time of 2.75 ms and a relaxation time of 4 s. The number of scanned was 1024. Fourier transform infrared spectroscopy (FTIR)
    The FTIR spectra were recorded on a Nicolet 6700 Thermo Scientific 20 model spectrometer in wave number or absorption frequency (cm-1).
    N2 adsorption-desorption isotherms


    The nitrogen adsorption-desorption isotherms at -196 ° C were carried out using a Quantachrome Quadrasorb model. Before measuring the samples were previously degassed for 12 h at 100qC. The surface area was determined using the BET (Brunauer-Emmett-Teller) theory and the pore size using the DFT method. Thermogravimetric analysis (TGA)
    For the experiments, a TA Instruments model TA-STD-Q600 was used. The experiments were carried out in an inert atmosphere of 40 qC at 800 qC with a heating ramp of 10 qC · min-1 in high resolution mode.
    The result of the elementary analysis is indicated below:
    Elemental analysis of CMPDTT-1:% C (% Ctheo) = 66.67 ± 0.06 (65.45); % H (% Htheo) = 2.61 ± 0.02 (1.8); % S (% Stheo) = 23.97 ± 0.37 (32.72); Elemental analysis of CMPDTT-2:% C (% Ctheo) = 74.9 ± 0.49 (75.45); % H
    (% Htheo) = 3.1 ± 0.06 (2.9); % S (% Stheo) = 15.58 ± 0.29 (21.5).
    The nuclear magnetic resonance spectra of carbon solids of the CMPDTT-1 and CMPDTT-2 polymers are shown in Figure 1D. The presence of functional groups in CMPDTT-1 and CMPDTT-2 polymers is
    determined by FTIR being evident the presence of triple bonds in the material
    (band at 2187 cm-1) (Figure 1B). Figure 1C represents the isothermal curves. The result is a surface area of 350 m2g-1 and 413 m2g-1, for CMPDTT-1 and CMDTT-2, respectively. The pore distribution analyzed by density functional theory (DFT) methods (Figure 4C, internal) shows in both cases micropores (ca. 1.5 nm) and in the case of CMPDTT-1, mesopores at 2.5 and 3.7 nm.
    The results of thermogravimetric analysis of polymers CMPDTT1 and CMPDTT-2 are shown in Figure 1D. Thus, it is observed that under an inert atmosphere the thermal decomposition produces a decrease in weight of about 2025% at 800ºC in both cases, while under air, an almost total thermal decomposition is observed at a temperature of around 345ºC for CMPDTT-1 and 365 ° C for CMPDTT-2.


    Example 3 Obtaining the TiO2 @ CMPDTT-1 and TiO2 @ CMPDTT-2 hybrid materials. General method: once the nature of the porous conjugate polymer to be used (CMPDTT-1 or CMPDTT-2) and its proportion in the hybrid material, as well as the nature of the inorganic semiconductor are selected, both the polymer and the inorganic semiconductor are weighed. The inorganic semiconductor TiO2 (PC500, Crystal Active) is calcined at 400 ° C for 4 h at a heating rate of 10 ° C min-1 in order to stabilize the sample. Both materials, inorganic semiconductor and polymer, are dispersed in a mixture of solvents. In the case of TiO2-based hybrids, the solvent mixture will be water / acetonitrile (1: 1, volumetric ratio), previously soaking the mixture of solid materials in the acetonitrile and then adding the water. The dispersion is stirred at room temperature for half an hour or until homogenization, the use of ultrasound is not recommended. Then, the solvent is removed under reduced pressure using a rotary evaporator. The solid material obtained is crushed in an agate mortar to complete homogenization. If necessary, the process of dissolution, evaporation and crushing is repeated until a homogeneous material is achieved. As an example, the amounts used to obtain 1 g of the TiO2 @ CMPDTT-1 15% hybrid were 150 mg of CMPDTT-1 polymer and 850 mg of TiO2. Hybrid materials were routinely characterized by all conventional techniques. The experimental methods and materials used in the characterization and analysis of the TiO2 @ CMPDTT-1 and TiO2 @ CMPDTT-2 hybrid materials (1, 5, 10 or 15%) are described below: Scanning electron microscopy
    High-resolution scanning electron microscopy, SEM (acronym in English Scanning Electron Microscope) were obtained with a Nova Nano microscope model SEM230 (FEG-SEM). The scanning electron microscopy (ESEM) images were taken with a Philips model XL 30 ESEM device. Samples were prepared directly by dispersing the powder on a polished aluminum surface. Transmission electron microscopy.


    Transmission electron microscopy, TEM (acronym for Transmission Electron Microscopy), was used to perform the microstructure characterization of the materials. For this, a Philips microscope model FEI TECNAI20 was used, working at an acceleration voltage of 200 kV. The samples were analyzed in powder after depositing on Cu mesh microscopes of 200 meshes with a conductive carbon sheet. For this, the powder samples were previously ground in agate mortar and dispersed in water for approx. 5 minutes. Subsequently, a couple of drops of the dispersion were added to the grids and allowed to dry at room temperature. The TEM microscope is equipped with an XEDS module (X-ray dispersive energy microanalysis) with a PV9760 / 54 detection unit (resolution 138/10 eV; active area 300 mm2), which allows a semi-quantitative estimation of the elements present in the sample, or detect areas that contain atoms of S, C, Ti and O. X-ray powder diffraction (DRX)
    An EMPYREAN model Panalytical diffractometer is used for this, using the copper emission kD (O = 1.54178 Å) as the irradiation source at a scan rate of 0.2 q s-1. UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS)
    Powder samples without prior treatment were used to carry out the measurements. A Perkin Elmer model Lambda 1050 UV / Vis / NIR spectrophotometer was used. Fluorescence spectroscopy
    Fluorescence measurements of the solid state samples were carried out in front-face mode using a Perkin Elmer fluorometer model LS 55 and using an excitation wavelength of 280 nm with a cut filter at 350 nm. Adsorption-desorption measures
    The adsorption-desorption isotherms of the hybrid materials were obtained following the same procedure as that indicated to obtain the isotherms of the PCPs.


    The morphological characterization of the materials is carried out by electron microscopy. Using TEM and SEM, the degree of compatibility between the organic and inorganic components of the hybrid samples can be seen. By way of example, in Figure 2A depicting images of the CMPDTT-1 polymer taken by SEM, the porous nature of the polymer as well as the micrometric size of the particles are observed. Both observations are confirmed by TEM Figure 2B and Figure 2C. However, in the samples of the 10% TiO2 @ CMPDTT-1 hybrid, these polymeric macroparticles are surrounded by 10 TiO2 nanoparticles, bright white nanoparticles in the ESEM image shown in Figure 2D. Figure 2E and its magnification Figure 2F show the same but seen by TEM. Figure 2F is a magnification of an edge of the hybrid microparticle shown in Figure 2E where both polymeric and hybrid materials coexist. To demonstrate this point, an analysis was carried out by
    15 dispersion of X-ray energy (EDX acronym in English) that allows an elementary analysis of the sample. In said analysis, shown as an inserted image of Figure 2F, in addition to the presence of carbon, the characteristic sulfur of CMPDTT polymers can be seen. On the other hand, the characterization by X-ray diffraction of the materials
    20 shows that the incorporation of the polymer into the hybrid materials does not affect the crystalline structure of the semiconductor, in this case TiO2 (Figure 3B). The characterization of the adsorption properties allows concluding that the hybrids show a surface area proportional to the original porosity of the inorganic semiconductor and the polymer (Figure 3A).
    25 In the study of the light absorption capacity of the hybrid materials, it is carried out by UV / vis absorption spectroscopy in the diffuse reflectance mode, and a displacement of the absorption in the visible is observed as the proportion of polymer in the hybrid (Figure 3C). The fluorescence emission capacity of the starting inorganic semiconductor, in
    In this case TiO2, it is deactivated as conjugated polymer is incorporated (Figure 3D).
    Example 4 Evaluation as heterogeneous photocatalysts of organic-inorganic hybrid materials in hydrogen production 25


    The evaluation of the new hybrid materials described in the present invention is carried out in a heterogeneous phase (solid photocatalyst dispersed in a liquid medium) using a conventional photochemical reactor. The reactor consists of a flat bottom cylindrical flask equipped with three mouths, made of borosilicate and with an effective volume of 1 L. 5-500 mg of photocatalyst is added to 750 mL of an aqueous solution containing 10% by volume of methanol . After adding the photocatalyst, the solution under stirring is irradiated with a 150 W medium pressure mercury ultraviolet lamp for at least 6 hours. As an inert carrier gas, argon was used with a flow rate of 60 mL min1. The reactor is tightly closed and maintained at atmospheric pressure and temperature of 15qC by cooling with a running water circuit. After 30 min of purging with argon, irradiation is started and the evolution of the generated hydrogen is measured by any analytical method that allows its quantification. In the present example, gas chromatography with a molecular sieve column and a thermal conductivity undetector (TCD, acronym for Thermal Conductivity Detector) was used. The hybrid materials described herein have higher hydrogen production values than those obtained independently using both the inorganic reference semiconductor and the porous conjugate polymer. As an example, Figure 4 shows the hydrogen production kinetics for TiO2 @ CMPDTT-1 hybrids at different amounts of polymer charge (1%, 5%, 10% and 15%) compared to TiO2 and CMPDTT-1 polymer. In the case of these hybrids based on CMPDTT-1 the best result is achieved with 10% load. In addition, it has been proven in our laboratories that such production is prolonged during long irradiation times (up to 72 h) without loss of activity.
    Example 5
    Evaluation as heterogeneous photocatalysts of organic-inorganic hybrid materials in CO2 photoreduction
    The CO2 photoreduction experiments were carried out in a continuous reactor. The gas phase photoreactor has an effective volume of 190 mL and is


    made of steel and provided with a borosilicate glass window to carry out the irradiation. The catalyst (3-500 mg) is deposited on a glass microfiber filter, used as a support, and placed inside the reactor. It is illuminated using 4 6 W fluorescent tubes whose emission is focused on a wavelength of 365 nm. CO2 (99.9999%) and water (Milli-Q) are passed through an evaporation and mixing controller (EMC for its English acronym Controlled Evaporation and Mixing) that maintains a 7: 1 molar ratio (CO2: H2O ). The reaction conditions were set at 25-3000 ° C temperature and 1-50 bar pressure. The reaction mixture is analyzed over 15 hours of illumination by gas chromatography to detect H2, CH4, CO, CH3OH, C2H4 and C2H6 among others. Hybrid materials show a higher production of H2, CO and CH4 than TiO2 and the conjugated polymer used as reference. As an example, Figure 5 shows how the production of H2, CO and CH4 is much higher in the case of using the TiO2 hybrid with a 10% polymer load CMPDTT-1. In addition, a change in the selectivity of the reaction is observed, observing a greater
    methane ratio

    权利要求:
    Claims (23)
    [1]
    1. A porous conjugated polymer characterized by comprising repeated units comprising:
    - a core comprising at least one aryl group and
    - branches, where each branch comprises a structure of formula I or a structure of formula II:
    where R1 and R2 each independently represent H, C1-C4 alkyl, -Ph, PhOCH3, -SO3, -COOR7, -PO3, -NO2, -NH2, -C {CH, -SH, -SCOCH3;R7 is selected from H and C1-C4 alkyl,and where R1 and R2 are placed in positions 2 and 4 or 1 and 4 or 2 and 3 respectively inthe structure (I),
    Where R1 ', R2', R3 ', R4', R5 'and R6' each independently represents H, C1-C4 alkyl, -Ph, -PhOCH3, -SO3, -COOR7 ', -PO3, -NO2, - NH2, -C {CH, -SH, -SCOCH3; R7 ’is selected from H and C1-C4 alkyl. and where the core is attached to at least three branches through single bonds -C-C- or triple bonds -C {C- between the aryl group or aryls of the core and the
    Structure of formula I or structure of formula II and where each branch is linked to two nuclei.

    [2]
    2. The polymer according to claim 1, wherein R1 and R2 in formula (I) are in positions 2 and 3 respectively.
    [3]
    3. The polymer according to any of the preceding claims, characterized in that it has a specific surface area greater than 10 m2 · g-1.
    [4]
    4. The polymer according to claim 3, characterized in that it has a specific surface area greater than 100 m2 · g-1.
    The polymer according to any of the preceding claims, wherein each core is attached to three branches.
    [6]
    6. The polymer according to claim 5, wherein the nuclei comprising at least one aryl group are selected from the following:
    [7]
    7. The polymer according to claim 6, characterized in that it has a structure selected from the following:

    [8]
    8. The polymer according to claim 6, characterized in that it has a structure selected from the following:

    [9]
    9. The polymer according to any of claims 1 to 4, wherein each core is attached to four branches.

    [10]
    10. The polymer according to claim 9, wherein the nuclei comprising at least one aryl group are selected from the following:
    5 Where R8 can be H, methyl or halogen selected from fluorine, chlorine, bromine or iodine.
    [11]
    11.- Hybrid material comprising a porous conjugated polymer such as
    10 defined in any of the preceding claims and at least one inorganic semiconductor.
    [12]
    12. Hybrid material according to claim 11 wherein the porous conjugate polymer is in a proportion between 0.1-99.9% by weight with respect to the hybrid material.
    13. Hybrid material according to claim 12 wherein the porous conjugate polymer is in a proportion of 1%, 5%, 10% or 15% by weight with respect to the hybrid material.
    14. Hybrid material according to any of claims 11 to 13 characterized in that the semiconductor is selected from TiO2, TiSi, ZnO, NaTaO3, NaNbO3, SnO2, In2O3, Fe2O3, WO3, InP, C3N4, GaN, BN, ZnS, CdS , ZnSe, CdSe, CdTe, BiWO6, BiVO4.
    15. Hybrid material according to any of claims 11 to 14 characterized in that the inorganic semiconductor is doped or additive with at least one metallic and / or non-metallic element.

    [16]
    16. Method of preparing a porous conjugated polymer as defined in any of claims 1-10, characterized in that it comprises coupling in the presence of Pd (0) or Pd (II) of:
    -  a halogenated monomer of formula I ’:
    where R1 and R4 or R1 and R2 or R3 and R4 are halogens selected from fluorine, chlorine bromine or iodine and the rest of the substituents R3 and R2, R3 and R4 or R1 and R2 are independently H, C1-C4 alkyl, -Ph, -PhOCH3, -SO3, -COOR7, -PO3, -NO2, NH2, -C {CH, -SH, -SCOCH3; R7 is selected from H and C1-C4 alkyl,
    or, of a halogenated monomer of formula II ’:
    where R1 ’, R2’, R3 ’, R4’, R5 ’and R6’ each independently represent H, alkylC1-C4, -Ph, -PhOCH3, -SO3, -COOR7 ’, -PO3, -NO2, -NH2, -C {CH, -SH, -SCOCH3;R7 ’is selected from H and C1-C4 alkyl,
    20 X is a halogen selected from fluorine, chlorine bromine or iodine,
    -  with a second monomer comprising at least one aryl group and further comprising:
    -  at least three terminal alkyne substituents, or
    -  at least three substituents derived from boronic acid (-B (OH) 2) or ester
    Boronic (-B (ORaRb)), where Ra and Rb each independently represent a C1-C4 alkyl or Ra and Rb can form a C3-C7 carbocycle optionally substituted with C1-C4 alkyl groups.

    [17]
    17. Method according to claim 16 characterized in that the monomer comprising at least one aryl group is selected from the following:
    iodine and where Y is selected from:
    18. Method according to claim 16, wherein the second monomer comprises at least three terminal alkyne substituents and the reaction takes place in the presence of a copper cocatalyst and a base.
    [19]
    19. Method according to claim 18 characterized in that the catalyst of Pd (0) is
    15 (triphenylphosphine) palladium and the copper cocatalyst is copper iodide (CuI) and the base is triethylamine.
    [20]
    20. Method according to claim 16, wherein the second monomer comprises at least three substituents derived from boronic acid or boronic ester and the reaction
    20 takes place in the presence of a base.
    [21]
    21. Method according to claim 20, wherein the catalyst is selected from tetrakis- (triphenylphosphine) palladium and palladium diacetate and the base is selected from K2CO3, NaOtBu, Cs2CO3 and K3PO4.

    [22]
    22. Method of preparing the hybrid material as defined in any of claims 11-15 characterized in that it comprises:
    - mixture of a porous conjugate polymer described in any one of claims 1 to 10 with at least one inorganic semiconductor in an organic solvent, mixtures of organic solvents or mixture of water and an organic solvent,
    -  remove the solvent.
    [23]
    23. Method of preparation of the hybrid material according to claim 22 wherein the solvent is selected from acetonitrile, methanol and acetonitrile / water mixture.
    [24]
    24. Method of preparing the hybrid material according to claim 22 or 23, characterized in that the mixture of the porous conjugate polymer and at least one inorganic semiconductor is carried out by stirring for a time between 1 min and 300 min.
    [25]
    25. Method of preparing the hybrid material according to any of claims 22 to 24, characterized in that it comprises a step of crushing the mixture in a mortar once the solvent has been removed.
    [26]
    26.- Method of preparing the hybrid material according to any of claims 22 to 25 characterized in that the inorganic semiconductor is subjected to a heat treatment between 100 ° C and 1000 ° C in times between 2 h and 5 days prior to the mixing of the porous conjugate polymer and inorganic semiconductor.
    [27]
    27.- Use of the polymer described in any of claims 1-10 or of the hybrid material described in any of claims 11-15 as a photocatalyst.
    [28]
    28.- Use according to claim 27 as a photocatalyst in a process of photoproduction of hydrogen from water.

    29- Use according to claim 27 as a photocatalyst in a CO2 photoreduction process.

    DRAWINGS
    FIGURE 1A
     FIGURE 1B 

    Weight (%)
    FIGURE 1C
    100
    80
    60
    40  CMPDTT-1 / air
     CMPDTT-1 / N2
    twenty  CMPDTT-2 / air CMPDTT-2 / N2
    0
    100 200300400500600700800
    Temperature (0C)
    FIGURE 1D


    FIGURE 3

    FIGURE 4
    FIGURE 5
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20130263925A1|2012-04-05|2013-10-10|Merck Patent Gmbh|Hole Carrier Layer For Organic Photovoltaic Device|
    WO2015077427A1|2013-11-20|2015-05-28|The University Of Akron|Highly Fluorescent Pyrrole-BF2 Chromophores|
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