Derivatives containing fused ring units with asymmetric sulfonyl groups, uses thereof, hydrogen production devices, and photovoltaic modules

Abstract

The present application provides a derivative containing an asymmetric sulfonyl-containing fused ring unit, which has a structure as shown in formula (I), wherein each symbol is defined in the description. Thus, the derivative containing an asymmetric sulfonyl-containing fused ring unit of the present application has photocatalytic activity, can be used as a photocatalyst, and can be applied to a hydrogen production device.

Description

TECHNICAL FIELD

[0001] The present application relates to an organic conjugated molecule, its use, a hydrogen production device, and a photoelectric assembly, and in particular to a derivative containing an asymmetric sulfonyl-containing fused ring unit, its use, a hydrogen production device, and a photoelectric assembly. BACKGROUND

[0002] With the rapid development of social economy and the increase of population, traditional non-renewable resources such as oil, natural gas and coal are being consumed at an extremely fast rate, and resource shortage has become one of the major problems in the world today. Therefore, it is very important to develop and utilize green and sustainable new energy. Common methods for producing hydrogen include hydrolysis, water gas method, oil cracking and water splitting, etc. Among them, the method of producing hydrogen by splitting water using solar energy has the advantages of low cost and no secondary pollution, and is a recyclable hydrogen production technology. In addition, there are also solar cells that convert electrical energy into chemical energy, which use solar cells as a source of electrical energy to carry out photoelectric conversion reactions to produce hydrogen.

[0003] In recent years, organic conjugated molecules as photocatalysts have been developed more and more rapidly, because they have potential advantages such as tunable optical and electronic properties, low-cost manufacturing and flexible molecular structure, however, the efficiency of the materials on the market still cannot reach the level of industrialization.

[0004] Therefore, how to synthesize high-efficiency materials that have good hydrogen production efficiency as photocatalysts to reach the level of industrialization has become the goal of relevant scholars and practitioners. SUMMARY

[0005] One object of the present application is to provide a derivative containing an asymmetric sulfonyl-containing fused ring unit, which introduces a sulfonyl structure and is modified asymmetrically, and has better thermal stability and hydrogen production effect.

[0006] Another object of the present application is to provide a use of a derivative containing an asymmetric sulfonyl-containing fused ring unit and a hydrogen production device. The derivative containing an asymmetric sulfonyl-containing fused ring unit has excellent photocatalytic activity, can be used as a photocatalyst and applied to a hydrogen production device, and is beneficial to improving the efficiency of the hydrogen production device.

[0007] Still another object of the present application is to provide a photoelectric assembly comprising the aforementioned derivative containing an asymmetric sulfonyl-containing fused ring unit, which has excellent photocatalytic activity and can be widely used in various photoelectric assemblies.

[0008] One embodiment of the present application is to provide a derivative containing an asymmetric sulfonyl-containing fused ring unit, which has a structure as shown in Formula (I-1), Formula (I-2), Formula (I-3), Formula (I-4), Formula (I-5), or Formula (I-6):

[0009]

[0010] wherein R is 2-ethylhexyl, and n is an integer from 1 to 100.

[0011] Another embodiment of the present application is to provide a use of the aforementioned derivative containing an asymmetric sulfonyl-containing fused ring unit as a photocatalyst.

[0012] Yet another embodiment of the present application is to provide a hydrogen production device, which comprises a solution system containing the aforementioned derivative containing an asymmetric sulfonyl-containing fused ring unit and water, and the solution system can further comprise an additive.

[0013] Still another embodiment of the present application is to provide a photoelectric component, which comprises the aforementioned derivative containing an asymmetric sulfonyl-containing fused ring unit, and the photoelectric component can be an organic solar cell, an organic light-emitting diode, an organic transistor, an organic photodetector, or a biological imaging.

[0014] Thus, the present application synthesizes a derivative containing an asymmetric sulfonyl-containing fused ring unit, which can improve wettability and increase electron output points by introducing a sulfonyl structure, so as to improve the photocatalytic hydrogen production effect, and can be widely applied to related industries. BRIEF DESCRIPTION OF DRAWINGS

[0015] In order to make the above and other objects, features, advantages and embodiments of the present application more comprehensible, the following will briefly describe the attached drawings:

[0016] FIG. 1 is a C-NMR mass spectrum of Example 1 to Example 3 and Comparative Example 1; 13 C-NMR mass spectrum;

[0017] FIG. 2 is an XPS analysis diagram of Example 1 to Example 3 and Comparative Example 1;

[0018] FIG. 3 is a TGA analysis diagram of Example 1 to Example 3 and Comparative Example 1;

[0019] FIG. 4 is an ultraviolet-visible diffuse reflectance spectrogram of Example 1 to Example 3 and Comparative Example 1;

[0020] FIG. 5 is a photoelectron spectrogram of Example 1 to Example 3 and Comparative Example 1;

[0021] FIG. 6 is a graph showing the results of photocatalytic water splitting for hydrogen production for system A, system B, and system C;

[0022] FIG. 7 is a graph showing the results of photocatalytic water splitting for hydrogen production for examples 7-9 and comparative example 2;

[0023] FIG. 8 is a graph showing the results of photocatalytic water splitting for hydrogen production for example 7 and comparative examples 3-4;

[0024] FIG. 9 is a histogram showing the results of photocatalytic water splitting for hydrogen production for example 7 and comparative examples 5-6;

[0025] FIG. 10 is a graph showing the results of apparent quantum efficiency for example 7 at different wavelengths;

[0026] FIG. 11 is a graph showing the fluorescence images for examples 1-3 and comparative example 1;

[0027] FIG. 12 is a graph showing the contact angle images for examples 1-3 and comparative example 1 with water;

[0028] FIG. 13 is a graph showing the UV-Vis transmission spectra for examples 7-9 and comparative example 2; and

[0029] FIG. 14 is a graph showing the time-resolved transient photoluminescence spectra for examples 7-9 and comparative example 2. DETAILED DESCRIPTION

[0030] The following will discuss the embodiments of the present application in more detail. However, the embodiments can be applications of various inventive concepts and can be embodied in various different specific ranges. The specific embodiments are only for the purpose of illustration and are not limited to the disclosed ranges.

[0031] In the present application, the structure of a compound is sometimes represented by a skeleton formula, which can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. If a functional group is explicitly drawn in the structural formula, the drawn one is used.

[0032] In the present application, if a group is not specifically indicated as being substituted or unsubstituted, the group can represent a substituted or unsubstituted group. For example, "alkyl" can represent a substituted or unsubstituted alkyl group.

[0033] <Derivative containing a fused ring unit having a non-symmetrical sulfonyl group>

[0034] The present application provides a derivative containing a fused ring unit having a non-symmetrical sulfonyl group, which has a structure represented by formula (I):

[0035]

[0036] wherein each wavy line independently represents a connection to a monomer unit, and the monomer units are connected by a metal catalyzed coupling, Ar is an aromatic ring compound, and n is an integer from 1 to 100.

[0037] In detail, the donor-acceptor type (D-A) conjugated polymers previously studied have achieved excellent photocatalytic hydrogen production effects, and the push-pull system generated thereby can reduce the energy gap of the polymer to enhance the collection of solar energy and effectively separate photoinduced excitons, however, this type of conjugated polymer limits the number of electron-withdrawing groups, such as sulfonyl groups, resulting in more than 50% of the units in the conjugated polymer not being electron-output sites.

[0038] Therefore, the present application synthesizes derivatives containing non-symmetrical fused ring units with sulfonyl groups having a structure as shown in formula (I), which can be used as a conjugated polymer of a double acceptor type (A1-A2), by incorporating a sulfonyl-containing acceptor unit into the main chain of the polymer, the wettability of the conjugated polymer can be enhanced by the interaction of the OH group in the chain and water, and the sulfonyl group also has abundant electron-output sites, which can transfer electrons to the cocatalyst, and by modifying the asymmetric structure, the conjugated polymer has better thermal stability and hydrogen production effect.

[0039] Specifically, the aforementioned Ar can be, but is not limited to, a structure represented by formula (i-1), formula (i-2), formula (i-3), or formula (i-4):

[0040]

[0041] wherein each X is independently a substituted or unsubstituted organic ring or a linear, branched, or cyclic alkyl group having a carbon number of 1 to 30.

[0042] In addition, the aforementioned metal-catalyzed coupling can be a Suzuki-Miyaura coupling, a Stille coupling, or a Direct arylation coupling, and the aforementioned monomer unit can have one of the structures represented by Formula (ii-1), Formula (ii-2), Formula (ii-3), Formula (ii-4), Formula (ii-5), Formula (ii-6), Formula (ii-7), Formula (ii-8), Formula (ii-9), Formula (ii-10), Formula (ii-11), Formula (ii-12), Formula (ii-13), Formula (ii-14), Formula (ii-15), Formula (ii-16), Formula (ii-17), Formula (ii-18), Formula (ii-19), Formula (ii-20), Formula (ii-21), Formula (ii-22), Formula (ii-23), Formula (ii-24), Formula (ii-25), Formula (ii-26), Formula (ii-27), Formula (ii-28), Formula (ii-29), Formula (ii-30), Formula (ii-31), or Formula (ii-32):

[0043]

[0044]

[0045]

[0046] wherein each X is independently a substituted or unsubstituted organic ring or a linear, branched, or cyclic alkyl group having a carbon number of 1 to 30.

[0047] The aforementioned substituted organic ring means that at least one hydrogen atom of the organic ring can be substituted with a substituent such as a tritium atom, a halogen atom, or a monovalent group, wherein the monovalent group can be, but is not limited to, a hydroxyl group, a nitrile group, a nitro group, an amine group, an amide group, a hydrazine group, a hydrazone group, an acetate group or a salt thereof, a sulfonate group or a salt thereof, a phosphate group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C3-C10 cycloalkenyl group, a C3-C10 heterocycloalkyl group, a C3-C10 heterocycloalkenyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, a C6-C30 arylthio group, a C2-C30 heteroaryl group, an aldehyde group, or a silyl group, and in addition, when at least two hydrogen atoms are substituted, the types of substituents can be the same or different. Common substituents can be, but are not limited to, a C1-C60 alkyl group, a C6-C30 aryl group, or a C2-C30 heteroaryl group.

[0048] The organic ring can be, but is not limited to, benzene, pentalene, indene, naphtalene, azulene, heptalene, indacene, acenaphthylene, fluorene, spiro-fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, thiophene, pyrrole, imidazole, pyrazole, triazole, thiazole, oxazole, isothiazole, isoxazole, benzothiazole, benzimidazole, benzoxazole, pyridine, pyrazine, pyrimidine, pyridazine, isoindole, indole, indazole, purine, isoquinoline, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, phenanthridine, acridine, phenoxazine, or phenothiazine.

[0049] For example, the derivative of the present application containing the asymmetrically sulfonated fused ring unit can have a structure as shown in Formula (I-1), Formula (I-2), Formula (I-3), Formula (I-4), Formula (I-5), or Formula (I-6):

[0050]

[0051]

[0052] wherein R is 2-ethylhexyl, and n is an integer from 1 to 100.

[0053] The monomer units in the aforementioned derivative containing the asymmetrically sulfonated fused ring unit shown in Formula (I-1), Formula (I-2), and Formula (I-3) are coupled by Suzuki-Miyaura coupling, which is an organic coupling reaction in which aryl or alkenyl boronic acids or esters cross-couple with chloro, bromo, iodo arenes or alkenes under metal catalysis.

[0054] The monomer units in the aforementioned derivative containing the asymmetrically sulfonated fused ring unit shown in Formula (I-4) are coupled by Stille coupling, which is an organic coupling reaction in which organotin compounds cross-couple with chloro, bromo, iodo arenes or alkenes under metal catalysis.

[0055] ​The monomer units in the derivatives containing non-symmetrical fused ring units with sulfonyl groups represented by the aforementioned formula (I-5) and formula (I-6) are coupled by direct arylation coupling, which is an organic coupling reaction in which a C-H bond-containing organic molecule is cross-coupled with a chloro, bromo, iodo, or alkenyl aromatic or olefin under metal catalysis.

[0056] <Use of derivatives containing non-symmetrical fused ring units with sulfonyl groups>

[0057] The present application provides a use of the aforementioned derivatives containing non-symmetrical fused ring units with sulfonyl groups as a photocatalyst, which can improve the hydrogen production efficiency when applied to a hydrogen production device.

[0058] <Hydrogen production device>

[0059] The present application provides a hydrogen production device comprising a solution system, and the solution system comprises the aforementioned derivatives containing non-symmetrical fused ring units with sulfonyl groups and water, and other additives such as sacrificial agents can be added. Specifically, when the solution system is irradiated by a light source, the hydrogen production device can carry out photocatalytic hydrolysis to produce hydrogen, and since the derivatives containing non-symmetrical fused ring units with sulfonyl groups of the present application have photocatalytic activity, it is beneficial to improve the efficiency of the hydrogen production device.

[0060] <Photoelectric component>

[0061] The present application provides a photoelectric component comprising the aforementioned derivatives containing non-symmetrical fused ring units with sulfonyl groups, and the photoelectric component can be, but is not limited to, an organic solar cell, an organic light-emitting diode, an organic transistor, an organic photodetector, or a biological imaging. Organic solar cells, organic light-emitting diodes, organic transistors, organic photodetectors, and biological imaging are all prior art and will not be described here.

[0062] The following specific examples are further used to demonstrate the present application, which can be used by those skilled in the art without excessive interpretation to fully utilize and practice the present application, and these examples should not be considered as limiting the scope of the present application, but as a material and method for illustrating how to implement the present application.

[0063] <Synthesis example>

[0064] The preparation of Synthesis Example 1 to Synthesis Example 3 of the present application is to put 2,6-dibromo-4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (BDTTBr), meta-chloroperoxybenzoic acid (m-CPBA) and dichloromethane (DCM) into a flask and react at different temperatures, then wash with sodium bicarbonate (NaHCO3) to obtain an organic layer, then extract with water and dichloromethane, then remove water in the organic layer with anhydrous magnesium sulfate (MgSO4), and purify by column chromatography, and finally further purify by ethanol until precipitation to obtain the products of Synthesis Example 1 to Synthesis Example 3. The content of each component of Synthesis Example 1 to Synthesis Example 3, the reaction temperature and the yield are listed in Table 1 below.

[0065]

[0066]

[0067] Synthesis Example 1 to Synthesis Example 3 of the present application respectively have a structure as shown in Formula (A), Formula (B) and Formula (C):

[0068]

[0069] wherein R is 2-ethylhexyl.

[0070] <Example / Comparative Example>

[0071] The preparation of Example 1 to Example 3 of the present application is to mix the monomer of the synthesis example, sodium carbonate (Na2CO3), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), tetra-n-butylammonium bromide (TBAB), water, toluene and 3,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]thiophene 5,5-dioxide (BSO) monomer into a reaction mixture, then vacuum and nitrogen degassing for 30 minutes, then reflux for 72 hours, then pour the reaction mixture into methanol, and wash with methanol, hexane, chloroform and water to remove the reactants and by-products, and finally collect the polymer and vacuum dry to obtain the derivatives containing non-symmetrical sulfonyl-containing fused ring units of Example 1 to Example 3. The content of each component of Example 1 to Example 3 and the type of synthesis example are listed in Table 2 below.

[0072]

[0073]

[0074] In addition, the preparation method of Comparative Example 1 of the present application is to mix 736 mg of BDTTBr monomer, 2544 mg of sodium carbonate, 55 mg of tetrakis(triphenylphosphine)palladium, 13 mg of tetra-n-butylammonium bromide, 10 mL of water, 40 mL of toluene, and 468 mg of BSO monomer into a reaction mixture, and the remaining steps are the same as those of Examples 1 to 3, to obtain the product of Comparative Example 1.

[0075] Examples 1 to 3 and Comparative Example 1 of the present application are coupled by Suzuki-Miyaura coupling. Taking Example 1 as an example, the reaction equation is shown in Table 3 below.

[0076]

[0077] The preparation of Example 4 of the present application is to add 0.215 g of Synthesis Example 1, 0.253 g of 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-bis(trimethylstannane) monomer, 0.004 g of tris(dibenzylideneacetone)dipalladium, 0.014 g of tri-o-tolylphosphine, and 25 mL of anhydrous dimethylformamide (DMF) into a round-bottom flask, then use nitrogen to ventilate for 20 minutes, react at 150°C for 48 hours. After the reaction is completed, wash with methanol and hexane to remove the reactants and by-products, and finally dissolve the polymer in chloroform at high temperature and pour it into methanol to precipitate the precipitate, to obtain the derivative containing the asymmetric sulfonyl-containing fused ring unit of Example 4.

[0078] Example 4 of the present application is coupled by Stille coupling. The reaction equation is shown in Table 4 below.

[0079]

[0080] The preparation of Example 5 of the present application is to add 0.54 g of Synthesis Example 1, 0.28 g of 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene monomer, 0.24 g of potassium carbonate, 0.021 g of trimethylacetic acid, 0.0157 g of palladium (II) acetate and 7.056 mL of dimethylformamide into a round-bottom flask, then use nitrogen to ventilate for 20 minutes, react at 80°C for 20 hours, and the rest of the steps are the same as Example 4 to obtain the derivative containing the non-symmetrical sulfonyl-containing fused ring unit of Example 5.

[0081] Example 5 of the present application is coupled by Direct arylation coupling, and the reaction equation is shown in Table Five.

[0082]

[0083]

[0084] The preparation of Example 6 of the present application is to add 0.85 g of Synthesis Example 1, 0.326 g of 4-(2-ethylhexyl)-4H-dithieno[3,2-b:2',3'-d]pyrrole monomer, 0.38 g of potassium carbonate, 0.034 g of trimethylacetic acid, 0.025 g of palladium (II) acetate and 11.088 mL of dimethylformamide into a round-bottom flask, then use nitrogen to ventilate for 20 minutes, react at 80°C for 20 hours, and the rest of the steps are the same as Example 4 to obtain the derivative containing the non-symmetrical sulfonyl-containing fused ring unit of Example 6.

[0085] Example 6 of the present application is coupled by Direct arylation coupling, and the reaction equation is shown in Table Six.

[0086]

[0087] Specifically, Examples 1 to 6 and Comparative Example 1 of the present application each have a structure as shown in Formula (I-1), Formula (I-2), Formula (I-3), Formula (I-4), Formula (I-5), Formula (I-6) and Formula (I-7):

[0088]

[0089]

[0090] wherein R is 2-ethylhexyl.

[0091] <Physical property measurement of examples / comparative examples>

[0092] Referring to FIG. 1, the XPS analysis graphs of Examples 1 to 3 and Comparative Example 1 are shown to represent different chemical bonding states of sulfur. As shown in FIG. 2, the characteristic peaks of R-S-R are between 162 eV and 166 eV, and the characteristic peaks of R-SO2-R are between 167 eV and 170 eV. The theoretical ratios of R-SO2-R to R-S-R of Examples 1 to 3 and Comparative Example 1 are 2:3, 3:2, 4:1 and 1:4, respectively, which are consistent with the results of FIG. 2. 13 C-NMR mass spectrum to determine the structure of the derivative containing the asymmetric sulfonyl-containing fused ring unit. As shown in the results of FIG. 1, the characteristic peaks of the side chain alkyl are mainly between 10 ppm and 50 ppm, and the characteristic peaks of the aromatic carbon are mainly between 120 ppm and 160 ppm. Specifically, the characteristic peaks of the carbon atoms adjacent to the thiophene and the thiophene 1,1-dioxide in the side chain are at 42 ppm and 37 ppm, respectively. Therefore, the intensity of the characteristic peak gradually decreases at 42 ppm as the thiophene in the side chain is oxidized to thiophene 1,1-dioxide.

[0093] Referring to FIG. 2, the XPS analysis graphs of Examples 1 to 3 and Comparative Example 1 are shown to represent different chemical bonding states of sulfur. As shown in FIG. 2, the characteristic peaks of R-S-R are between 162 eV and 166 eV, and the characteristic peaks of R-SO2-R are between 167 eV and 170 eV. The theoretical ratios of R-SO2-R to R-S-R of Examples 1 to 3 and Comparative Example 1 are 2:3, 3:2, 4:1 and 1:4, respectively, which are consistent with the results of FIG. 2.

[0094] Referring to FIG. 3, the TGA analysis graphs of Examples 1 to 3 and Comparative Example 1 are shown to determine the thermal stability of the derivative containing the asymmetric sulfonyl-containing fused ring unit by using a thermogravimetric analyzer (model TA Q600) to measure the thermal cracking temperature (Td) under the conditions of a temperature range of 30°C to 800°C and nitrogen. The results are recorded in Table 7 below. As shown in the above results, Example 1 has thermal stability under a nitrogen atmosphere, and Examples 2 to 3 have lower thermal stability, which is attributed to the poor solubility and large steric hindrance of the monomers in polymerization.

[0095]

[0096] <Photophysical property measurement of examples / comparative examples>

[0097] Referring to FIG. 4, UV-Vis DRS spectra of Examples 1-3 and Comparative Example 1 were measured using a spectrophotometer (Hitachi U-3300) to determine the light absorption properties of the derivatives containing the fused ring unit with an asymmetric sulfonyl group, and the optical bandgap (Eg) was calculated using a Tauc-Plot, and the results are recorded in Table 8 below.

[0098] Referring to FIG. 5, photoelectron spectra of Examples 1-3 and Comparative Example 1 were measured using a photoelectron spectrometer (AC-II) to determine the HOMO energy level, and the LUMO energy level was calculated by subtracting the optical bandgap (Eg) from the HOMO energy level, and the results are recorded in Table 8 below.

[0099]

[0100] As can be seen from the results in Table 8, the HOMO and LUMO energy levels of Examples 1-3 are lower than those of Comparative Example 1 due to the intramolecular charge transfer and the introduction of electron-withdrawing functional groups.

[0101] <Photocatalytic activity of the examples / comparative example>

[0102] The photocatalytic water splitting hydrogen production effects of the following three systems were observed: System A is a system in which the derivative containing the fused ring unit with an asymmetric sulfonyl group of Example 1 is added to water, System B is a system in which only water is present, and System C is a system in which only the derivative containing the fused ring unit with an asymmetric sulfonyl group of Example 1 is present, and the above systems were subjected to photocatalytic water splitting hydrogen production under light irradiation. Referring to FIG. 6, a graph of the photocatalytic water splitting hydrogen production results of Systems A, B, and C is shown. As can be seen from the results in FIG. 6, the hydrogen production of Systems B and C was 0, i.e., only water or only the derivative containing the fused ring unit with an asymmetric sulfonyl group of Example 1 cannot provide catalytic activity for photocatalytic water splitting hydrogen production, whereas System A, which contains both water and the derivative containing the fused ring unit with an asymmetric sulfonyl group of Example 1, showed an increase in hydrogen production under light irradiation, indicating that the derivative containing the fused ring unit with an asymmetric sulfonyl group of Example 1 can act as a photocatalyst, and that it is essential to have water.

[0103] In addition, the photocatalytic hydrogen evolution experiments were performed for Examples 1 to 3 and Comparative Example 1. First, 2 mg of Examples 1 to 3 and Comparative Example 1 and 1 mL of NMP solvent were loaded into a reactor for ultrasonic treatment for 10 minutes, followed by adding 9 mL of water, 3 wt% of a cocatalyst H2PtCl6, and a sacrificial agent, and using potassium hydroxide to adjust different pH values to form a solution system, wherein the sacrificial agent can be ascorbic acid (AA), triethylamine (TEA), or triethanolamine (TEOA). The examples / comparative examples, the types and concentrations of the sacrificial agent, and the pH values of the solution system in each solution system are listed in Table Nine below.

[0104]

[0105] Subsequently, the solution systems of Examples 7 to 9 and Comparative Examples 2 to 6 were degassed using argon gas and kept under negative pressure, and irradiated with a 350-watt xenon lamp as a light source, and the relationship between the hydrogen production rate (HER) and time was measured by gas chromatography (GC), and the results are listed in Table Ten below.

[0106] Referring to FIGS. 7, 8, and 9, FIG. 7 shows the photocatalytic hydrogen evolution results of Examples 7 to 9 and Comparative Example 2, FIG. 8 shows the photocatalytic hydrogen evolution results of Examples 7 and Comparative Examples 3 to 4, and FIG. 9 shows the photocatalytic hydrogen evolution histogram of Examples 7 and Comparative Examples 5 to 6. As can be seen from the results of FIG. 7, as the content of the sulfonyl group increases, the HER shows a downward trend, however, Example 7 has a better hydrogen production efficiency than Comparative Example 2, indicating that the derivative of Example 1 containing the asymmetric sulfonyl-containing fused ring unit has a better photocatalytic hydrogen evolution effect than Comparative Example 1, which can prove that the A1-A2 type conjugated polymer has great potential in photocatalysis. In addition, as can be seen from the results of FIGS. 8 and 9, different types and concentrations of the sacrificial agent and the pH value of the solution system will affect the photocatalytic hydrogen evolution effect, and the preferred type of sacrificial agent is AA, and the pH value of the solution system is preferably 4.0.

[0107]

[0108] Please refer to Figure 10, which illustrates the apparent quantum yield results of Example 7 at different wavelengths. Specifically, apparent quantum yield (AQY) is defined as the ratio of the number of electrons that react to the number of incident photons at a given wavelength. In Example 7, monochromatic light at 420 nm, 460 nm, 500 nm, and 550 nm was used, with an irradiation area and irradiation time of 6 cm². 2 The light intensity at each wavelength and the amount of hydrogen gas in Example 7 at each wavelength were measured over a period of 3600 seconds and substituted into the formula to obtain the AQY. The results are listed in Table 11 below. The formulas related to AQY are well known in the art and will not be elaborated here. Currently, most polymeric photocatalysts exhibit high AQY at wavelengths between 400 nm and 500 nm, but the AQY drops sharply at wavelengths greater than 500 nm. However, the maximum radiant intensity of the solar spectrum occurs between wavelengths of 500 nm and 600 nm, so AQY in the above wavelength range is very important. As can be seen from the results in Figure 10, Example 7 still has excellent AQY at 500 nm and 550 nm, which is a breakthrough in the AQY of the derivative of the present invention containing an asymmetric sulfonyl fused ring unit in the relevant field.

[0109]

[0110] <Particle Aggregation Measurement in Examples / Comparative Examples>

[0111] Please refer to Figures 11, 12, and 13. Figure 11 shows fluorescence microscopy (FM) images of Examples 1 to 3 and Comparative Example 1; Figure 12 shows contact angle images of Examples 1 to 3 and Comparative Example 1 with water; and Figure 13 shows ultraviolet-visible transmission spectra of Examples 7 to 9 and Comparative Example 2. As can be seen from the results in Figure 11, Examples 1 to 3 and Comparative Example 1 can all aggregate into micron-sized particles, while the particles aggregated in Example 1 are larger, with a particle size ranging from 20 μm to 50 μm.

[0112] Furthermore, as can be seen from the results in Figures 12 and 13, the contact angles of Examples 2 to 3 with water are smaller than those in Example 1. This indicates that the introduction of sulfonyl groups into the side chains increases the affinity for the water surface, leading to a low degree of particle aggregation. Therefore, when prepared as a solution system, the transmittance of Example 7 is lower than that of Examples 8 to 9. This is because the solution system of Example 7 has a strong multiple scattering effect and light absorption capacity, which indicates that a certain degree of aggregation is beneficial to improving its photocatalytic activity.

[0113] Referring to FIG. 14, time-resolved transient photoluminescence decay spectra (TRPL) of Examples 7 to 9 and Comparative Example 2 are shown to estimate the lifetime of the derivatives containing the asymmetric sulfonyl-containing fused ring unit, and the results are recorded in Table 12 below. From the above results, it can be seen that Example 7 has a longer lifetime, which indicates that the derivative of Example 1 containing the asymmetric sulfonyl-containing fused ring unit exhibits a slow electron-hole recombination rate, which is beneficial to improve the photocatalytic activity.

[0114]

[0115] In summary, the derivative containing the asymmetric sulfonyl-containing fused ring unit of the present application can be an asymmetric donor-acceptor conjugated polymer, which contains acylsulfone groups that can provide high wettability and increase the electron output point, and has better solar energy collection capability. Therefore, when used as a photocatalyst in a hydrogen production device, it can produce excellent hydrogen production efficiency. More importantly, the apparent quantum efficiency of the derivative containing the asymmetric sulfonyl-containing fused ring unit of the present application at a wavelength of 500 nm breaks the current research record, so it can be widely used in related devices for solar energy conversion or the field of organic electronics.

[0116] Although the present application has been disclosed with embodiments as above, it is not intended to limit the present application, and those skilled in the art can make various modifications and improvements without departing from the spirit and scope of the present application. Therefore, the scope of protection of the present application shall be subject to the scope defined by the following appended patent claims.

Claims

1. A derivative containing a non-symmetrically sulfonyl-bearing fused ring unit, characterized by, having one of the structures of Formula (I-1), Formula (I-2), Formula (I-3), Formula (I-4), Formula (I-5), or Formula (I-6): wherein R is 2-ethylhexyl and n is an integer from 1 to 100.

2. Use of the derivative according to claim 1 containing a non-symmetric condensed ring unit with sulfonyl groups, characterized in that, The derivative containing the unsymmetrical fused ring unit having a sulfonyl group is used as a photocatalyst.

3. A hydrogen production apparatus characterized by comprising: A solution system comprising the derivative containing the unsymmetrical fused ring unit having a sulfonyl group and water.

4. The hydrogen generation apparatus according to claim 3, wherein The solution system further comprises an additive.

5. An optoelectronic assembly, comprising: The derivative containing the unsymmetrical fused ring unit having a sulfonyl group.

6. The optoelectronic assembly of claim 5, wherein, The optoelectronic component is an organic solar cell, an organic light emitting diode, an organic transistor, an organic photodetector, or a bioimaging.

Images