CN115611952B - Catalyst, preparation method thereof, catalyst system and application - Google Patents

Catalyst, preparation method thereof, catalyst system and application Download PDF

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CN115611952B
CN115611952B CN202211258500.6A CN202211258500A CN115611952B CN 115611952 B CN115611952 B CN 115611952B CN 202211258500 A CN202211258500 A CN 202211258500A CN 115611952 B CN115611952 B CN 115611952B
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catalyst
formula
catalyst system
ligand
obtaining
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CN115611952A (en
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徐聪
陈琪
孙猛
孔超
金向华
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Jinhong Gas Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C07F15/004—Iridium compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst, a preparation method, a catalyst system and application thereof, wherein the catalyst is selected from substances shown as a formula (I) and/or a formula (II); wherein M is selected from Ru and/or Ir; r is selected from H, NH 2 and CH 3. The catalyst of the invention has high efficiency of photocatalytic hydrogen production by adopting a novel ligand and M-tpy-Cl 3. Meanwhile, 1 ligand can coordinate with two M-tpy-Cl 3, so that the catalyst has a bimetallic center, and the photocatalytic hydrogen production efficiency of the catalyst is further improved.

Description

Catalyst, preparation method thereof, catalyst system and application
Technical Field
The invention relates to the field of photocatalytic hydrogen production, in particular to a catalyst, a preparation method thereof, a catalyst system and application thereof.
Background
Hydrogen is one of the green clean energy sources currently considered to be better. Hydrogen, as an energy carrier, has become a key to solving these increasing world energy demand problems because of its energy density (122 kJ/g) higher than gasoline (40 kJ/g), and pollution-free reaction products. The current main way to obtain hydrogen is still to convert fossil fuels (such as petroleum, coal, natural gas, etc.) to obtain hydrogen, which is the most main method to obtain hydrogen at present. However, this approach is still used with conventional fossil fuels, and these resources are calculated from the worldwide consumption rate and are available for human use for up to 220 years. Thus, a method for producing hydrogen by photocatalytic decomposition of water or other substances has been found, in which a catalyst is used, but the catalytic efficiency of the existing catalyst is low, resulting in low hydrogen production efficiency.
Disclosure of Invention
The invention aims to provide a catalyst which can realize high-efficiency photocatalytic hydrogen production.
Another object of the invention is to provide a method for preparing the catalyst, a catalyst system and use thereof.
To achieve the above object, embodiments of the present invention provide a catalyst selected from the group consisting of substances represented by formula (i) and/or formula (ii);
Wherein M is selected from Ru and/or Ir; r is selected from H, NH 2 and CH 3.
The embodiment of the invention provides a preparation method of the catalyst, which comprises the following steps:
obtaining a ligand represented by formula (III);
carrying out coordination reaction on the ligand and M-tpy-Cl 3 shown in the formula (IV) to obtain a catalyst;
Formula (III) formula (IV)
Wherein M is selected from Ru and/or Ir; r is selected from H, NH 2 and CH 3.
In one or more embodiments of the invention, the step of obtaining a ligand of formula (iii) comprises:
Obtaining an intermediate of formula (v);
Reacting the intermediate with a first reactant under alkaline conditions to obtain a ligand shown in a formula (III);
wherein the first reactant is selected from guanidine, formamidine, acetamidine.
In one or more embodiments of the invention, the step of obtaining an intermediate as shown in formula (v) comprises:
Mixing 2-aldehyde pyridine with 2-acetyl pyridine under alkaline condition to obtain the intermediate.
Embodiments of the present invention also provide a catalyst system comprising a solvent and a catalyst as described above.
In one or more embodiments of the present invention, the catalyst system further comprises a support on which the catalyst is supported.
In one or more embodiments of the present invention, the support is at least one of an alumina support, an activated carbon support, and a zeolite.
In one or more embodiments of the invention, the catalyst system further comprises a photosensitizer;
In one or more embodiments of the invention, the photosensitizer is Ru (bpy) 3(ClO4)2.
Embodiments of the present invention provide for the use of a catalyst or catalyst system as described above in photocatalytic hydrogen production.
Compared with the prior art, the catalyst obtained by adopting the novel ligand and M-tpy-Cl 3 has high photocatalytic hydrogen production efficiency. Meanwhile, 1 ligand can coordinate with two M-tpy-Cl 3, so that the catalyst has a bimetallic center, and the photocatalytic hydrogen production efficiency of the catalyst is further improved.
Drawings
FIG. 1 is a flow chart of a method of preparing a catalyst according to an embodiment of the invention;
Fig. 2 is a data graph of catalyst hydrogen production according to an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
The catalyst system according to the preferred embodiment of the present invention comprises a solvent and a catalyst.
In particular, the catalyst system may also include a photosensitizer. Thereby improving the photocatalytic efficiency. Preferably, the photosensitizer may be Ru (bpy) 3(ClO4)2.
Preferably, the catalyst system may be a support on which the catalyst may be supported. The catalyst is selected from substances shown in a formula (I) and/or a formula (II). Wherein M is selected from Ru (ruthenium) and Ir (iridium); r is selected from H, NH 2 and CH 3.
The two M's in the formula (II) may be different or the same.
Specifically, the carrier may be at least one of an alumina carrier, an activated carbon carrier, and zeolite.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a catalyst, including the steps of:
S1, obtaining the ligand shown in the formula (III). Wherein R is selected from H, NH 2 and CH 3.
The ligand represented by formula (III) may be the following compound:
Specifically, the step of obtaining a ligand represented by formula (III) comprises:
s11, obtaining an intermediate shown as a formula (V).
Specifically, the step of obtaining an intermediate represented by formula (v) comprises:
and mixing 2-aldehyde pyridine with 2-acetyl pyridine under alkaline condition to react, thus obtaining the intermediate shown in the formula (V).
S12, reacting the intermediate with a first reactant under alkaline conditions to obtain the ligand shown in the formula (III). Wherein the first reactant is selected from guanidine, formamidine, acetamidine.
S2, carrying out coordination reaction on the ligand and M-tpy-Cl 3 shown in the formula (IV) to obtain the catalyst. Wherein M is selected from ruthenium and iridium.
Embodiments of the present invention provide for the use of a catalyst or catalyst system in photocatalytic hydrogen production.
Specifically, the method for preparing hydrogen by using the catalyst or the catalyst system comprises the following steps:
In a first step, a catalyst system is obtained.
In particular, the step of obtaining a catalyst system may comprise:
the catalyst, solvent and photosensitizer are mixed to obtain a catalyst system.
Wherein the solvent may be selected from methanol and TEA (triethanolamine).
And secondly, mixing the catalyst system with the reactant, and reacting under the condition of illumination to obtain the hydrogen.
Wherein the reactants may be selected from methanol and water.
The catalyst of the present invention and the method for preparing the same will be described in detail with reference to specific examples.
Example 1
To a 250mL Erlenmeyer flask containing 150mL of distilled water, 0.72g (18 mmol) of NaOH was added, and after dissolution by stirring, 5mL of 2-aldehyde pyridine was added and the mixture was placed in an ice bath system so as not to exceed 10 ℃. 4mL of 2-acetylpyridine was added dropwise, and the reaction was stirred for 30min. After a large amount of pale yellow precipitate appears in the system, the solution is filtered by suction and washed with a large amount of water. Drying under reduced pressure at room temperature to obtain a pale yellow product, namely the intermediate shown in the formula (V).
Example 2
10Mmol of formamidine acetate was weighed and added to 100mL of absolute ethyl alcohol, followed by stirring. 11mmol of granular NaOH was weighed into the solution, so that acetic acid was completely reacted, and the solution became opaque milky flocculent. A solution of 9mmol of the intermediate (formula (V)) in 40mL of ethanol was slowly added dropwise over 1 hour. Reflux reaction for 6h, after the reaction was completed, cool to room temperature. 20mL of saturated NH 4 Cl solution was added to bring the pH to approximately 7. Ethanol was dried by spin-evaporation, 40mL of water was added to dissolve the precipitated NH 4 Cl, and the resulting yellow precipitate was suction filtered to give the ligand of formula (III-1).
Example 3
20Mmol of acetamidine hydrochloride is weighed and added into 200mL of absolute ethyl alcohol, and the mixture is stirred. 22mmol of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. 30mL of ethanol solution in which 19mmol of the intermediate (formula (V)) was dissolved was slowly added dropwise over 1 hour. After 3h of reflux reaction, the reaction mixture was cooled to room temperature and 30mL of saturated NH 4 Cl solution was added to bring the pH to approximately 7. Ethanol is spun out, 60mL of water is added to dissolve the precipitated NH 4 Cl, and after cooling with ice water, the precipitated white precipitate is filtered out with suction to obtain the ligand shown as the formula (III-2).
Example 4
Under ice bath conditions, 20mmol of sodium metal is added into 30mL of absolute ethyl alcohol, and the solution is stirred to be completely dissolved, so as to obtain sodium ethoxide solution. The ice bath was removed, 15mmol of guanidine nitrate was added, and the reaction was stirred for 30min to allow the nitric acid to react completely. 30mL of ethanol solution in which 10mmol of the intermediate (formula (V)) was dissolved was slowly added dropwise over 1 hour. After reflux reaction for 8 hours, the mixture is placed into ice water for cooling, white flocculent precipitate is separated out, suction filtration is carried out, and a small amount of ethanol is used for washing, so that the ligand shown as the formula (III-3) is obtained.
Example 5
0.5Mmol of the ligand of formula (III-1) (represented by L) and 0.25mmol of Ru-tpy-Cl 3 were weighed into a 100mL round-bottomed flask, 50mg of ascorbic acid, 20mg of anhydrous LiCl, and ethanol were added: h2o=4:1 in 40mL, reflux reaction for 6H under argon. After the reaction is completed, cooling to room temperature, removing insoluble substances by suction filtration, purifying filtrate by a neutral alumina column, wherein the developing agent proportion is methylene dichloride: methanol=30:1, and collecting the mauve band, namely the catalyst (shown as a formula (I) in which R=H and M=Ru) in the invention.
Example 6
0.4Mmol of the ligand represented by formula (III-1) (represented by L) and 0.9mmol of Ru-tpy-Cl 3 were weighed into a 100mL round-bottomed flask, 50mg of ascorbic acid, 20mg of anhydrous LiCl, and ethanol were added: h2o=4:1 in 40mL, reflux reaction for 6H under argon. After the reaction is completed, cooling to room temperature, removing insoluble substances by suction filtration, purifying filtrate by a neutral alumina column, wherein the developing agent proportion is methylene dichloride: methanol=4:1, and collecting the blue-violet band, namely the catalyst (shown as a formula (II) in which R=H and M=Ru).
Comparative example 1
A catalyst of the following formula is commonly used in the market, and is called Ru-tpy-bpy for short.
The catalysts of examples 5 and 6 and the catalyst of comparative example 1 were subjected to the following hydrogen production test.
The catalyst amount was 2X 10 -7 mol, and the selected solvent was a mixed solvent (6:1) system of methanol solution and TEA as sacrificial agent. The sample was charged with the photosensitizer Ru (bpy) 3(ClO4)2, 8mg (11. Mu. Mol), 500. Mu.L of water, and the total volume of the solution was 4.2mL. The total volume of the branched test tube with the air suction head used was 27.2mL, and each measurement was performed by extracting 100. Mu.L of the upper gas by using a precision airtight sample injection needle of Hamilton company, and adding the gas chromatography, and the obtained result was calibrated by a hydrogen standard curve. The results obtained are shown in FIG. 2.
According to the figure 2, the binuclear Ru complex has better catalytic performance than that of a mononuclear Ru complex and is better than that of a common catalyst Ru-tpy-bpy, and the catalytic performance is better improved. Furthermore, we have found that the three-component photocatalytic system constructed is indispensable, lacks proton-transfer solvents, photosensitizers, sacrificial agents, catalysts and conditions without illumination (the data for the above conditions are relatively similar in FIG. 2, resulting in partial coincidence of the data folding lines in the figure), and that no hydrogen or only very small amounts of hydrogen are produced in the system, which indicates that these components are indispensable. Thus, it is considered that hydrogen is hardly produced in the absence of a catalyst, a photosensitizer, methanol or water in the catalyst system, and hydrogen production is low in the absence of TEA or water in the catalyst system. In addition, we also observed that the system began to slow down the hydrogen production rate by 5 hours, and continued to have hydrogen evolved with light, but at a low rate.
In summary, the catalyst of the embodiments of the present invention achieves a catalyst with high photocatalytic hydrogen production efficiency by employing a novel ligand with M-tpy-Cl 3. Meanwhile, 1 ligand can coordinate with two M-tpy-Cl 3, so that the catalyst has a bimetallic center, and the photocatalytic hydrogen production efficiency of the catalyst is further improved.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. A catalyst, characterized in that the catalyst is selected from the group consisting of substances represented by formula (i) and/or formula (ii);
Wherein M is selected from Ru; r is selected from H.
2. A method for preparing the catalyst according to claim 1, comprising the steps of:
obtaining a ligand represented by formula (III);
carrying out coordination reaction on the ligand and M-tpy-Cl 3 shown in the formula (IV) to obtain a catalyst;
Wherein M is selected from Ru; r is selected from H.
3. The method for preparing a catalyst according to claim 2, wherein the step of obtaining the ligand represented by formula (iii) comprises:
Obtaining an intermediate of formula (v);
Reacting the intermediate with a first reactant under alkaline conditions to obtain a ligand shown in a formula (III);
wherein the first reactant is selected from guanidine, formamidine, acetamidine.
4. A process for preparing a catalyst according to claim 3, wherein the step of obtaining an intermediate of formula (v) comprises:
Mixing 2-aldehyde pyridine with 2-acetyl pyridine under alkaline condition to obtain the intermediate.
5. A catalyst system comprising a solvent and the catalyst of claim 1.
6. The catalyst system of claim 5, further comprising a support on which the catalyst is supported.
7. The catalyst system of claim 6, wherein the support is at least one of an alumina support, an activated carbon support, and a zeolite.
8. The catalyst system of claim 5, wherein the catalyst system further comprises a photosensitizer.
9. The catalyst system of claim 8, wherein the photosensitizer is Ru (bpy) 3(ClO4)2.
10. Use of a catalyst according to any one of claims 1 or a catalyst system according to claim 8 or 9 for photocatalytic hydrogen production.
CN202211258500.6A 2022-10-13 2022-10-13 Catalyst, preparation method thereof, catalyst system and application Active CN115611952B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111848688A (en) * 2020-08-11 2020-10-30 中国科学院长春应用化学研究所 Cationic metal iridium complex, preparation method thereof and photocatalytic hydrolysis method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111848688A (en) * 2020-08-11 2020-10-30 中国科学院长春应用化学研究所 Cationic metal iridium complex, preparation method thereof and photocatalytic hydrolysis method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Component Analysis of Dyads Designed for Light-Driven Water Oxidation;Lars Kohler等;《 Inorg. Chem. 》;第53卷;第912-921页 *
Coordination Arrays: Synthesis and Characterisation of Rack-Type Dinuclear Complexes;Garry S. Hanan等;《Chem. Eur. J.》;第2卷;第1292-1302页 *
Darren Brown等.Di-[1,10]-phenanthrolinyl Diazines: A New Family of Bis-tridentate Chelators.《Org. Lett.》.2002,第4卷第1253-1256页. *

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