CN114887661A - Preparation method and application of Ti-based porphyrin material - Google Patents

Preparation method and application of Ti-based porphyrin material Download PDF

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CN114887661A
CN114887661A CN202210241859.6A CN202210241859A CN114887661A CN 114887661 A CN114887661 A CN 114887661A CN 202210241859 A CN202210241859 A CN 202210241859A CN 114887661 A CN114887661 A CN 114887661A
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porphyrin
photocatalytic
based copper
photocatalytic material
copper porphyrin
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贾朝刚
刘兴燕
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Chongqing Technology and Business University
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    • 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
    • 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
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
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Abstract

The invention discloses a Ti-based copper porphyrin photocatalytic material. According to the Ti-based copper porphyrin photocatalytic material, active site Cu is provided by adding porphyrin organic ligand Cu, and Cu introduced into the center of porphyrin is a non-noble metal, so that the cost is low, the operation process is simple and easy to control, the reaction conditions are not harsh, the catalytic effect of the obtained copper porphyrin photocatalytic material is 17.5 times that of a pure porphyrin MOF material, and the Ti-based copper porphyrin photocatalytic material is suitable for industrial production.

Description

Preparation method and application of Ti-based porphyrin material
Technical Field
The invention relates to the technical field of photocatalytic hydrogen evolution, in particular to a Ti-based porphyrin photocatalytic material and a preparation method and application thereof.
Background
With the rapid development of human economy and civilization, the demand for energy is also increasing. However, over-exploitation of traditional fossil fuels has resulted in a serious set of environmental pollution. Therefore, it is very important and urgent to replace the conventional fossil energy with pollution-free renewable energy, especially hydrogen energy. Efficient conversion of inexhaustible solar energy to hydrogen energy by photocatalytic water splitting is the most promising strategy. However, most of the reported semiconductors do not have a significant improvement in photocatalytic performance due to low separation efficiency of photogenerated carriers and slow electron transfer rate. Therefore, it is necessary to search for a more suitable and efficient photocatalyst for obtaining hydrogen energy.
Metal-organic frameworks (MOFs) have become popular materials for photocatalytic hydrogen evolution due to a series of excellent characteristics, such as high specific surface area, porosity and structural diversity. The porphyrin is used as a natural photosynthetic center and has the feasibility of implanting transition metal in the center of the unit. However, due to the inherent properties of the metal clusters and the organic connectors, the photo-generated electrons are generally transferred from the organic connectors to the metal clusters through a conventional ligand-metal charge transfer (LMCT) transition route, which consumes a large amount of time while consuming a relatively low carrier separation efficiency. This limits the application of conventional MOFs materials to hydrogen production.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a Ti-based copper porphyrin material to solve the problems of low carrier separation efficiency and poor charge transfer in the prior art.
The invention also provides a preparation method of the Ti-based copper porphyrin photocatalytic material, and the Ti-based copper porphyrin photocatalytic material can be prepared by the method.
The invention also provides an application of the Ti-based copper porphyrin photocatalytic material, and the Ti-based copper porphyrin photocatalytic material prepared by the preparation method is suitable for photocatalytic hydrogen evolution reaction.
In order to solve the technical problems, the invention adopts the following technical scheme:
a Ti-based copper porphyrin photocatalytic material is Ti-based copper porphyrin MOF.
The preparation method of the Ti-based copper porphyrin photocatalytic material comprises the following steps:
step 1) Ti (on-board) 4 and tetracarboxyphenyl porphyrin copper are used as raw materials, and Ti-based copper porphyrin MOF is prepared by a hydrothermal method.
The Ti-based copper porphyrin photocatalytic material prepared by the preparation method is suitable for photocatalytic hydrogen evolution reaction.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a novel Ti-based copper porphyrin MOF material, which can transfer electrons from LUMO of porphyrin to copper center instead of Ti-oxo cluster, thus effectively improving carrier separation efficiency; furthermore, protons can be directly reduced to hydrogen at the active Cu sites through transient CuII/CuI centers without the need for expensive platinum co-catalysts.
2. The preparation method of the Ti-based porphyrin photocatalytic material has simple and easily-controlled operation process and non-harsh reaction conditions.
3. Compared with a Ti-based pure porphyrin photocatalyst, the hydrogen yield of the Ti-based copper porphyrin photocatalyst material prepared by the invention is improved by 17.5 times.
Drawings
FIG. 1 is an SEM photograph of Cu-PTM prepared in example 1.
FIG. 2 is an SEM image of Co-PTM prepared in comparative example 1.
FIG. 3 is an SEM photograph of Ni-PTM prepared in comparative example 2.
FIG. 4 is an SEM photograph of 2H-PTM prepared in comparative example 3.
Fig. 5 is a graph of photocatalytic hydrogen evolution for all samples.
Fig. 6 is an XRD pattern of all samples.
Fig. 7 is a FTIR plot for all samples.
Detailed Description
The present invention will be further described with reference to the following examples and accompanying drawings.
Example (b):
the preparation method of the Ti-based copper porphyrin photocatalytic material comprises the following steps:
ti (OBu)4 (157.5. mu.L), CuTCPP (75mg), benzoic acid (4.05g) were added to 10ml of DEF, thoroughly stirred, charged into a reaction vessel, and reacted at 150 ℃ for 5 days. And after the reaction is cooled, centrifuging to obtain a solid, washing for a plurality of times by using acetone, and finally drying to obtain the Cu-PTM.
The prepared Ti-based copper porphyrin MOF material is used for photocatalytic hydrogen evolution, and the specific steps are as follows:
(1) preparing a hydrogen production system: 10mg of photocatalyst was dispersed in 17mL of deionized water, 3mL of Triethanolamine (TEOA) as sacrificial reagent, and red as photosensitizer, and air was removed by bubbling nitrogen for 15 min.
(2) Photocatalytic hydrogen evolution test: photocatalytic hydrogen production experiments were performed in a 100mL light reaction vessel using a 300W Xe lamp equipped with a UV filter (. lamda. gtoreq.420 nm). The gas product was detected and analyzed using a GC gas chromatograph equipped with a thermal conductivity detector (beijing, GC7920) and a high purity N2 carrier gas. The cycling stability test was performed at a duration of 5h per cycle.
Fig. 5 is a graph showing the results of photocatalytic hydrogen evolution of all materials, and it can be found that Ti-based copper porphyrin MOF materials exhibit excellent photocatalytic hydrogen evolution effects.
Comparative example 1:
the preparation method of the Ti-based cobalt porphyrin photocatalytic material comprises the following steps:
ti (OBu)4 (157.5. mu.L), CoTCPP (75mg), benzoic acid (4.05g) were added to 10mL DEF, stirred well, charged to the reaction vessel, and reacted at 150 ℃ for 5 days. After the reaction is cooled, the solid is obtained by centrifugation, washed for a plurality of times by acetone, and finally dried to obtain the Co-PTM.
The structure of the prepared Ti-based cobalt porphyrin photocatalytic material can be seen from FIG. 2.
The prepared Ti-based cobalt porphyrin material is used for photocatalytic hydrogen evolution, and the specific steps are as follows:
(1) preparing a hydrogen production system: 10mg of photocatalyst was dispersed in 17mL of deionized water, 3mL of Triethanolamine (TEOA) as sacrificial reagent, and red as photosensitizer, and air was removed by bubbling nitrogen for 15 min.
(2) Photocatalytic hydrogen evolution test: photocatalytic hydrogen production experiments were performed in a 100mL light reaction vessel using a 300W Xe lamp equipped with a UV filter (. lamda. gtoreq.420 nm). The gas product was detected and analyzed using a GC gas chromatograph equipped with a thermal conductivity detector (beijing, GC7920) and a high purity N2 carrier gas. The cycling stability test was performed at a duration of 5h per cycle.
As can be seen from FIG. 5, the catalytic effect of the Ti-based cobalt porphyrin photocatalytic material is obviously weaker than that of the Ti-based copper porphyrin photocatalytic material.
Comparative example 2:
the preparation method of the Ti-based nickel porphyrin photocatalytic material comprises the following steps:
ti (OBu)4 (157.5. mu.L), NiTCPP (75mg), benzoic acid (4.05g) were added to 10mL DEF, stirred well, charged to the reaction vessel, and reacted at 150 ℃ for 5 days. After the reaction is cooled, the solid is obtained by centrifugation, washed for a plurality of times by acetone, and finally dried to obtain the Ni-PTM.
The structure of the Ti-based nickel porphyrin photocatalytic material can be seen from FIG. 3.
The prepared Ti-based nickel porphyrin material is used for photocatalytic hydrogen evolution, and the specific steps are as follows:
(1) preparing a hydrogen production system: 10mg of photocatalyst was dispersed in 17mL of deionized water, 3mL of Triethanolamine (TEOA) as sacrificial reagent, and red as photosensitizer, and air was removed by bubbling nitrogen for 15 min.
(2) Photocatalytic hydrogen evolution test: photocatalytic hydrogen production experiments were performed in a 100mL light reaction vessel using a 300W Xe lamp equipped with a UV filter (. lamda. gtoreq.420 nm). The gas product was detected and analyzed using a GC gas chromatograph equipped with a thermal conductivity detector (beijing, GC7920) and a high purity N2 carrier gas. The cycling stability test was performed at a duration of 5h per cycle.
As can be seen from FIG. 5, the catalytic effect of the Ti-based nickel porphyrin photocatalytic material is obviously weaker than that of the Ti-based copper porphyrin photocatalytic material.
Comparative example 3:
the preparation method of the Ti-based porphyrin photocatalytic material comprises the following steps:
ti (OBu)4 (157.5. mu.L), TCPP (75mg), benzoic acid (4.05g) were added to 10mL DEF, stirred well, charged to the reaction vessel, and reacted at 150 ℃ for 5 days. After the reaction is cooled, the solid is obtained by centrifugation, washed for a plurality of times by acetone, and finally dried to obtain the 2H-PTM.
The structure of the prepared Ti-based porphyrin photocatalytic material can be seen from the SEM image of FIG. 4, and the crystal form of the prepared sample can also be seen from FIG. 6.
The prepared Ti-based porphyrin material is used for photocatalytic hydrogen evolution, and the specific steps are as follows:
(1) preparing a hydrogen production system: 10mg of photocatalyst was dispersed in 17mL of deionized water, 3mL of Triethanolamine (TEOA) as sacrificial reagent, and red as photosensitizer, and air was removed by bubbling nitrogen for 15 min.
(2) Photocatalytic hydrogen evolution test: photocatalytic hydrogen production experiments were performed in a 100mL light reaction vessel using a 300W Xe lamp equipped with a UV filter (. lamda. gtoreq.420 nm). The gas product was detected and analyzed using a GC gas chromatograph equipped with a thermal conductivity detector (beijing, GC7920) and a high purity N2 carrier gas. The cycling stability test was performed at a duration of 5h per cycle.
Through intensive research on the existing Ti-based porphyrin MOF material, Cu, Co and Ni are respectively introduced into porphyrin centers and compared with pure porphyrin, the finding that after non-noble metal is introduced into the porphyrin centers, electrons can be most transferred from LUMO of the porphyrin to the non-noble metal centers instead of Ti-oxo clusters, and thus, the carrier separation efficiency can be effectively improved. Thereby greatly improving the hydrogen production rate. Meanwhile, compared with noble metals such as Pt and Pd, the introduction of non-noble metals undoubtedly reduces the production cost. Therefore, it is necessary to explore the introduction of non-noble metals into porphyrin center for improving the photocatalytic hydrogen production efficiency.
In the photocatalysts synthesized by us, electrons can be transferred from LUMO of porphyrin to copper center instead of Ti-oxo cluster, which can effectively improve carrier separation efficiency. Furthermore, protons can be directly reduced to hydrogen at the active Cu sites via transient CuII/CuI centers without the need for expensive platinum co-catalysts, suggesting that low cost Cu may be an ideal replacement for noble metal platinum as a co-catalyst.
According to the invention, after the catalytic effects of the products of the examples and comparative examples 1-3 are studied, the hydrogen production rate of the metal added into the center of porphyrin is higher than that of pure porphyrin. When the porphyrin center metal is Cu, the hydrogen production rate is 3457.61 mu mol g -1 ·h -1 17.5 times that of the pure MOF material. It has been found through extensive research that, in the synthesized Ti-based copper porphyrin material, electrons can be transferred from LUMO of porphyrin to copper center rather than Ti-oxo cluster, and at the same time, protons can be directly reduced to hydrogen at active Cu sites through transient CuII/CuI centers without the need of expensive platinum co-catalyst. Since copper is a non-noble metal, it is less costly to apply it to practical production. Therefore, the invention can improve the photocatalytic hydrogen production efficiency by using the low-cost Cu synthetic photocatalyst, and is beneficial to industrial application.
The invention provides a Ti-based copper porphyrin photocatalytic material, which introduces metal copper as an active site in the center of porphyrin, and photogenerated electrons can pass through a novel ligand-connector metal charge transfer (LLMCT) way, in which the photogenerated electrons can be transferred to the copper center instead of Ti-oxo clusters, thus effectively improving the carrier separation efficiency and further improving the photocatalytic hydrogen production efficiency. The Ti-based copper porphyrin photocatalytic material prepared by the invention has excellent hydrogen production efficiency.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.

Claims (4)

1. A Ti-based copper porphyrin photocatalytic material is characterized by comprising the following steps:
step 1), Ti (OBu)4, copper tetracarboxyphenylporphyrin and benzoic acid are used as raw materials, and a Ti-based copper porphyrin MOF material is prepared by a hydrothermal method;
and 2) centrifugally washing the sample obtained in the step 1) by using acetone, and drying the obtained solid at 60 ℃ for 6 hours in vacuum to obtain the Ti-based copper porphyrin photocatalyst.
2. The method for preparing a Ti-based copper porphyrin photocatalytic material as recited in claim 1, wherein in step 1), the mass ratio of CuTCPP to benzoic acid is 1: 54.
3. The method for preparing a Ti-based copper porphyrin photocatalytic material as recited in claim 1, wherein in step 1), the raw material is added into an organic solvent, and after the raw material is sufficiently dissolved, the raw material is put into a reaction kettle to react for 5 days at 150 ℃.
4. An application of the Ti-based copper porphyrin photocatalytic material is characterized in that the Ti-based copper porphyrin photocatalytic material prepared by the preparation method of any one of claims 2-4 is suitable for photocatalytic hydrogen evolution reaction.
CN202210241859.6A 2022-03-11 2022-03-11 Preparation method and application of Ti-based porphyrin material Pending CN114887661A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117427691A (en) * 2023-10-10 2024-01-23 广东工业大学 Cu modified Ti-based MOF material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117427691A (en) * 2023-10-10 2024-01-23 广东工业大学 Cu modified Ti-based MOF material and preparation method and application thereof

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