CN114100692A - Porphyrin-based multifunctional photocatalytic MOFs (metal-organic frameworks) material - Google Patents
Porphyrin-based multifunctional photocatalytic MOFs (metal-organic frameworks) material Download PDFInfo
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- 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]
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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Abstract
The invention discloses a porphyrin-based multifunctional photocatalytic MOFs material, which is a Zr-Ni PMOFs visible light absorption semiconductor material synthesized by a solvothermal method, can simultaneously carry out benzyl alcohol conversion and reduction hydrogen production, and can simultaneously carry out benzyl alcohol conversion and CO conversion2And (4) reducing. The invention reports a Zr-Ni MOFs multifunctional photocatalytic oxidation-reduction coupling system for the first time, and provides a basis for the MOFs material to fully utilize electrons and holes in the photocatalytic system through a coupling strategy; the bifunctional coupling reaction can be realized by using para-substituted aromatic alcohol, and the reaction is proved to have universality.
Description
Technical Field
The invention relates to a porphyrin-based multifunctional photocatalytic MOFs material, belonging to the technical field of photocatalysis.
Background
Photocatalysis is considered to be an effective way to deal with energy crisis and environmental pollution. The photocatalyst generates holes and electrons under the illumination condition, so that the photocatalyst has redox capability under the illumination condition, can convert solar energy into energy substances, and can degrade or synthesize substances. Although the application of inorganic semiconductors and organic polymers in the field of photocatalysis has made great progress and development, the application of inorganic semiconductors and organic polymers in the field of photocatalysis has certain limitations due to the inherent defects and deficiencies of the two materials. Therefore, the development of new materials to improve catalytic performance remains the current direction of effort.
The metal-organic framework complexes (MOFs) are ordered framework structure materials constructed by metal ions and organic ligands, have the dual advantages of inorganic materials and organic materials, can be reasonably designed on the molecular level, and provide an ideal platform for the research of a photocatalytic mechanism due to the detailed structure. Among the MOFs, MOFs based on porphyrin derivatives are one of the hot spots in research because porphyrin-based MOFs (abbreviated as PMOFs) have excellent light absorption properties, long excited state lifetime, and excellent light stability and chemical stability.
To date, there have been some reports of porphyrin-based MOFs in photocatalytic applications, but most of them are studied on single photocatalytic hydrogen production, organic synthesis or CO2Reducing, and most PMOFs mainly rely on a post-treatment process to introduce noble metals (Ir, Pt, Ru, Au, Pd) into the PMOFs to improve the photocatalytic efficiency, which not only easily causes the problems of unstable structure or low selectivity, but also severely limits the practical application thereof; in addition, to promote photocatalytic reduction of H2The rate of the reaction is usually controlled by adding some sacrificial agent, such as methanol (CH)3OH), ethanol (CH)3CH2OH), lactic acid (CH)3CH (OH) COOH), triethanolamine (N (CH)2CH2OH)3) Etc. to trap holes, the presence of the sacrificial agent not only wastes the energy of the photogenerated holes, but also causes unnecessary oxidationThe product increases the cost of the system, so that researches and developments of MOFs multifunctional photocatalytic materials which are constructed by low-toxicity metal ions and fully utilize electron holes are imperative.
Disclosure of Invention
Aiming at the problems, the invention researches and provides a porphyrin-based multifunctional photocatalytic MOFs material.
In order to achieve the above purpose, the invention provides the following technical scheme: a porphyrin-based multifunctional photocatalytic MOFs material is a Zr-Ni PMOFs visible light absorption semiconductor material synthesized by a solvothermal method, can simultaneously carry out benzyl alcohol conversion and reduction hydrogen production, and can simultaneously carry out benzyl alcohol conversion and CO2And (4) reducing.
Furthermore, the Zr-Ni PMOFs visible light absorption semiconductor material is not only suitable for coupling reaction in which benzyl alcohol participates, but also can realize the above-mentioned bifunctional coupling reaction by using para-substituted aromatic alcohol.
Further, the Zr-Ni PMOFs synthesized by the solvothermal method refer to the following components: reacting ZrCl4Ultrasonically dissolving benzoic acid and Ni-TCPP in DMF, transferring the solution to a reaction kettle, heating for reaction, centrifugally separating Zr-Ni PMOFs, washing, and drying in vacuum to obtain purple powdery crystals.
Further, the ZrCl4: benzoic acid: the Ni-TCPP was heated at a weight ratio of 4:50:3 in a muffle furnace at 120 ℃ for 72 hours, centrifuged at 12000rpm for 5 min, washed three times with ethanol, and dried at 70 ℃ in a vacuum environment for 12 hours at a yield of 53%.
Further, the conduction band potential of the Zr-Ni PMOFs is-1.22V, and enough H is available+A reducing driving force; the valence band potential is + 1.12V, which provides sufficient oxidizing power for the selective oxidation of benzyl alcohol.
Further, the Zr-Ni PMOFs have strong absorption in a wave band of 200-800 nm, and the band gap width is 2.34 eV.
The beneficial technical effects of the invention are as follows: the Zr-Ni MOFs multifunctional photocatalytic oxidation-reduction coupling system is reported for the first time, and a basis is provided for the MOFs material to fully utilize electrons and holes in the photocatalytic system through a coupling strategy; the bifunctional coupling reaction can be realized by using para-substituted aromatic alcohol, and the reaction is proved to have universality.
Drawings
In order to more clearly illustrate the embodiments of the present application or technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained by those skilled in the art according to the drawings.
In FIG. 1, (a), (b) are SEM images of Zr-Ni PMOFs at different multiples, (c) are TEM images, (d) and (e) are EDX mapping images of Zr-Ni PMOFs;
FIG. 2 shows (a) the UV-vis DRS spectrum of Zr-Ni PMOFs and (b) the band diagram;
FIG. 3 is a Mott-Schottky plot of Zr-Ni PMOFs;
FIG. 4 (a) Zr-Ni PMOFs photocatalyst for PhCH2Photocatalytic decomposition of OH to release H2And PhCHO, (b) is generated by photocatalytic oxidation reduction under the action of Zr-Ni PMOFs under different visible light irradiation time2The amount of photogenerated electrons relative to the utilization of holes;
FIG. 5 is a graph showing the photocatalytic conversion of benzyl alcohol to benzaldehyde and H using different trapping agents on Zr-Ni PMOFs samples under light irradiation for 8 hours2Control experimental graphs of (1);
FIG. 6 shows the photocatalytic decomposition of different aromatic alcohols (RPhCH) by Zr-Ni PMOFs under visible light irradiation2OH, R = -OMe, -Me, -OH, -Cl and-NO2) A comparison chart of hydrogen production reaction for 8 h;
FIG. 7 is a schematic representation of a process for coupling benzyl alcohol oxidation and CO2The mechanism of the reductive bifunctional coupling is shown schematically.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Zr-Ni PMOFs synthesized by solvothermal method, ZrCl4Ultrasonically dissolving benzoic acid and Ni-TCPP in DMF, transferring the solution into a reaction kettle, heating for 72 h in a muffle furnace at 120 ℃, centrifuging for 5 min at 12000rpm after heating reaction, centrifugally separating Zr-Ni PMOFs, washing with ethanol for three times, and drying for 12 h in a vacuum environment at 70 ℃ to obtain purple powdery crystals with the yield of 53%. Said ZrCl4: benzoic acid: the weight ratio of Ni-TCPP is 4:50: 3.
When Zr-Ni PMOFs were dispersed in deionized water at a concentration of 0.05 wt%, as shown in the SEM of Zr-Ni PMOFs of FIG. 1 (a), a significant Tyndall phenomenon was observed, indicating that the catalyst had good dispersibility in water. The structure of the catalyst can be clearly observed from an image of a Scanning Electron Microscope (SEM). FIGS. 1 (a) and (b) show the microstructure of Zr-Ni PMOFs at different multiples, with lamellar structures stacked together to form a cube-like structure. At the same time, the scanning electron microscope (TEM) image also further confirmed the 3D morphology of Zr — Ni PMOFs, and the structure of the layered stack is evident from fig. 1 (c). The EDX mapping images of Zr-Ni PMOFs in FIGS. 1 (d) and (e) show the elemental contents and distributions of Zr-Ni PMOFs.
The optical properties were evaluated using the UV-vis absorption spectrum FIG. 2, and the sample showed broad and strong absorption in the 200-800 nm region due to the characteristics of the porphyrin ligand. The UV-visible absorption spectrum of the Zr-Ni PMOFs has only a Q band at 625 nm, which dominates due to the highly symmetrical structure of the sample, and has an absorption band (. lamda.abs) edge at 529 nm, corresponding to an optical bandgap (Eg) of 2.34 e V.
FIG. 3 examines the flat band potential (Efb) of Zr-Ni PMOFs using Mott-Schottky. The CB for Zr-Ni PMOFs was about-1.2V compared to Normal Hydrogen Electrode (NHE). CB of Zr-Ni PMOFs is far more than H+/H2(0V) the redox potential is more negative, which means that the excited electrons in the conduction band have a stronger reducing power, driving thermodynamicallyHydrogen is more easily released during operation. From the obtained band gap values, the Valence Band (VB) of the Zr-Ni PMOFs was calculated to be 1.12V (FIG. 2).
The photocatalysis aromatic alcohol is converted into aromatic aldehyde and the hydrogen production coupling reaction system comprises:
the visible light driven HER test was performed on a commercial reaction apparatus (LabSolar II, Perfect light Co) connected to an online gas chromatograph (GC 7900, forri, Ar as carrier gas, TCD as detector). A300W Xe lamp equipped with an optical filter (PLS-300, lambda. gtoreq.400 nm) as the light source recorded by a PL-MW2000 spectrometer (Perfect light Co.) with an average visible light intensity of about 100 mW/cm2. The photocatalytic cracking of the benzyl alcohol is carried out in a Pyrex top irradiation reaction vessel connected with a glass closed gas circulation system. In a typical experiment, 20 mg of photocatalyst and 30 μ L H were mixed2PtCl6The solution was added to 50 mL of acetonitrile containing 0.1M aromatic alcohol. The reaction suspension was then degassed using a mechanical pump and stirred in the dark for 30 minutes to reach the adsorption-desorption equilibrium. The temperature of the suspension is controlled to be about 10 ℃ by a water cooling system. After the reaction was completed, H produced from the reaction system was measured using an on-line gas chromatograph (GC 2014, Shimadzu)2Amount of the compound (A). At the same time, the suspension was centrifuged to obtain a clear solution. The clear solution was analyzed using gas chromatography and gas chromatography-mass spectrometer (GC-MS, agilent 7890A).
Photocatalytic conversion of aromatic alcohol into aromatic aldehyde and hydrogen production coupled reaction:
the control group (light and dark response) was first tested and the results showed no PhCHO and no H in the absence of light2Under visible light irradiation, as shown in FIG. 4a, when Zr-Ni PMOF was used as a catalyst, the amount of PhCHO produced and H2The generation amount can reach 19.9 and 20.7 mu mol h-1. By H2Molar ratio to PhCHO further investigated the utilization of photo-generated electrons relative to holes (Ru) as shown in FIG. 4b, H on Zr-Ni PMOF catalyst2And PhCHO, first increased with increasing time of illumination and then reached a plateau. At the beginning of the photocatalytic cracking of benzyl alcohol (1H), H2（10μmol) is much lower than that of PhCHO (20.7. mu. mol), Ru is only 48.3, while Ru increases rapidly with increasing reaction time (1-3 h), a change in this phase possibly being subjected to [ PtCl ]6]2-Conversion to Pt0The influence of (c). The photocatalytic reaction gradually slows after 3 h until Ru reaches 96% (approaching 1) at the 8 th h, which shows that the stoichiometric synergetic photo-oxidation-reduction reaction can be realized by increasing the reaction time, and the photo-generated electrons and holes in the same reaction system are effectively utilized, so that the adverse effect of adding a sacrificial agent is avoided. FIG. 4 Zr-Ni PMOF photocatalyst for PhCH2Photocatalytic oxidation of OH to PhCHO and release of H2Under the irradiation of visible light, the coupling reaction effect (b) is H2And the molar ratio of PhCHO and the electron-hole utilization ratio (Ru).
A series of control experiments are carried out to research the photocatalytic conversion of photo-generated electrons and holes to the benzyl alcohol into benzaldehyde and H2Using triethanolamine and AgNO3Respectively as a hole (h)+) And electron (e)-) Sacrificial agent, as shown in FIG. 5a, when 17 mg AgNO was added to the reaction system3When the mixture is illuminated for 8 hours, benzyl alcohol and H2The yields of (a) were 199.1 and 39.1. mu. mol, respectively, and the yield of benzaldehyde was much greater than that of H2The main reason is that the photo-generated electrons generated in the reaction process are AgNO3Therefore, the hydrogen evolution reaction is greatly inhibited. At the same time, the photogenerated holes accelerate the conversion of benzyl alcohol to benzaldehyde. However, when 1 ml triethanolamine was added to the reaction, we can observe from FIG. 5b that benzaldehyde and H were generated after 8H of light irradiation2Yields of (5) were 27.1 and 9.9. mu. mol, respectively. This is probably because the added triethanolamine consumed the photogenerated holes, inhibiting the efficiency of the photocatalytic conversion of benzyl alcohol to benzaldehyde and H+While further limiting the photo-generated electrons from coupling H to the electron beam+Conversion to H2. The test results show that in the photocatalysis hydrogen production and aromatic alcohol oxidation coupling system, the oxidation of the benzyl alcohol is carried out by utilizing the hole effect generated by the light excitation for carrying out the photocatalysis conversion, and the generation of the hydrogen is generated by utilizing the conversion of the benzyl alcoholH+Reducing under the action of electrons.
In order to further verify the universal applicability of the Zr-Ni PMOF catalyst to the double-function coupling action of the aromatic alcohol selective oxidation and hydrogen production, the Zr-Ni PMOF catalyst is applied to a series of aromatic alcohols RPhCH with different substituents2OH ( R = -NO2and-OH, -H, -Cl, -Me and-OMe) were tested. As can be seen from FIG. 6, Zr-Ni PMOF has a certain photocatalytic conversion activity on aromatic alcohols (p-nitrobenzyl alcohol, p-chlorobenzyl alcohol, p-hydroxybenzyl alcohol, p-toluyl alcohol and p-methoxybenzyl alcohol). The aldehyde hydrogen yield ratio is close to 1: 1. the order of activity of the different primary alcohols is: para methoxy benzyl alcohol>P-methyl phenethyl alcohol>Para hydroxy benzyl alcohol>P-chlorobenzyl alcohol>P-nitrobenzyl alcohol. These substances all have selectivity for RPhCHO of more than 80%.
Photocatalytic conversion of benzyl alcohol to benzaldehyde and CO2Reduction coupling reaction system:
in 10 mL of acetonitrile (CH) containing 0.2M benzyl alcohol3CN) was added 20 mg of Zr-Ni PMOF powder and 30 μ L H2Pt Cl6And (3) solution. The reaction system is degassed by a mechanical pump and then high-purity CO2Pumping to 0.3 atm. A300W xenon lamp provided with a 400nm cut-off filter (lambda is more than or equal to 400nm) is used as a visible light source. The suspension temperature is controlled to be about 10 ℃ by adopting a water cooling system. After the reaction was completed, PhCHO, CO and H generated in the reaction system were measured by Shimadzu 2014 GC and Agilent 7890B GC, respectively2The amount of (c).
Photocatalytic conversion of benzyl alcohol to benzaldehyde and CO2Reduction coupling reaction:
in conventional photocatalysis of CO2In reduction, photo-generated electrons are used to reduce CO2Various organic matters are generated, and the problem of photogenerated hole waste caused by adding a hole sacrificial agent exists. We extended the bifunctional photocatalytic redox system to photocatalytic CO2Reduction, i.e. light-driving of CO in the same reaction system2The reduction and the selective oxidation of the alcohol are carried out, and the results are shown in FIG. 7, and the same reaction system can realize CO under the irradiation of visible light2Reduction and alcohol oxidation in PhCH2CH of OH3In CN solution, PhCHO, CO and H2In a yield ofRespectively 230, 110, 35. mu. mol g-1。
Comparative examples
Synthesis of Zr PMOFs: reacting ZrCl4And the benzoic acid and the TCPP are ultrasonically dissolved in a DMF solution, then the solution is transferred into an autoclave and heated for 72 hours in a muffle furnace at 120 ℃, after heating reaction, Zr PMOF12000rpm is centrifuged for 5 min for separation, washed for 3 times by ethanol, and dried for 12 hours in vacuum at 70 ℃ to obtain purple powdery crystals with the yield of 47 percent. Said ZrCl4: benzoic acid: the weight ratio of TCPP was 4:50: 3.
Synthesis of Ni-Ni PMOFs: separately sonicating Ni (NO) in DMF3) 2·6H2O, benzoic acid and TCPP, then transferring the solution into an autoclave, heating the autoclave in a muffle furnace at 120 ℃ for 72 h, after heating reaction, centrifuging Ni-Ni PMOFs at 12000rpm for 5 min for separation, washing the crystals with ethanol for 3 times, and drying the crystals in vacuum at 70 ℃ for 12 h to obtain purple powdery crystals with the yield of 55%.
The 4Q bands of the comparative Ni TCPP, Zr PMOFs and Ni-Ni PMOFs all maintain the visible light response characteristic of the porphyrin structure, but the slight blue shift of the soret band is caused by the transfer of electrons from the porphyrin macrocycle to metal ions, while the ultraviolet-visible absorption spectrum of the Zr-Ni PMOFs has only one Q band at 625 nm. The peak at 625 nm is dominated in the Q band by the highly symmetric structure of the four samples, with Ni TCPP, Zr PMOF, Ni-Ni PMOF and Zr-Ni PMOF having absorption band (. lamda.abs) edges at 429, 440 and 529 nm corresponding to optical bandgaps (Eg) of 2.89, 2.82 and 2.34 e V, respectively. The bimetallic porphyrin-based MOF (Zr-Ni PMOF) has wider light absorption range and is more beneficial to photocatalytic reaction.
From the obtained band gap values, the Valence Bands (VB) of Ni TCPP, Zr PMOFs, Ni-Ni PMOFs and Zr-Ni PMOFs were calculated to be 2.53, 2.32, 2.22 and 1.12V, respectively. The CB's of Ni TCPP, Zr PMOFs, Ni-Ni PMOFs and Zr-Ni PMOFs were about-0.26, -0.40, -0.50V and-1.2V, respectively, as compared to the Normal Hydrogen Electrode (NHE).
Description of the drawings: CB of Zr-Ni PMOFs is much higher than H+/H2(0V) redox potential, which means that excited electrons in the conduction band have a stronger reducing power and are more susceptible to hydrogen evolution when thermodynamically driven。
Ni-TCPP and Zr PMOFs showed lower PhCHO production (0.15 and 0.32. mu. mol h)-1) And H2Production amounts (0.1 and 0.3. mu. mol h)-1) For Ni-Ni PMOFs, the catalytic activity is slightly improved, and the PhCHO generation amount and H of the Ni-Ni PMOFs are increased2The amounts of formation were 1.1 and 1.2. mu. mol h, respectively-1. PhCHO yield and H when Zr-Ni PMOF was used as catalyst2The generation amount can reach 19.9 and 20.7 mu mol h-1。
Description of the drawings: bimetallic porphyrin-based mofs (zrnpmof) have further advantages in the coupling reaction of selective oxidation of benzyl alcohol and hydrogen production.
General theory: compared with the prior art, the Zr-Ni MOFs multifunctional photocatalytic oxidation reduction coupling system provided by the invention provides a basis for the MOFs material to fully utilize electrons and holes in the photocatalytic system through a coupling strategy; the bifunctional coupling reaction can be realized by using para-substituted aromatic alcohol, and the reaction is proved to have universality.
Through the tests, the characteristics of the application are verified, the research and development requirements are met, the problems in the prior art can be well solved, and the research is supported and subsidized by the natural science foundation committee (KJ 2020A 0022) of the education hall of Anhui province and high-quality and elegant youth talent culture plan (gxyq 2020101) of Anhui province.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (6)
1. A porphyrin-based multifunctional photocatalytic MOFs material is characterized in that: the material is a Zr-Ni PMOFs visible light absorption semiconductor material synthesized by adopting a solvothermal method, can simultaneously carry out benzyl alcohol conversion and reduction hydrogen production, and can simultaneously carry out benzyl alcohol conversion and CO2And (4) reducing.
2. The porphyrin-based multifunctional photocatalytic MOFs material according to claim 1, wherein: the Zr-Ni PMOFs visible light absorption semiconductor material is not only suitable for coupling reaction with benzyl alcohol, but also can realize the above difunctional coupling reaction by using para-substituted aromatic alcohol.
3. The porphyrin-based multifunctional photocatalytic MOFs material according to claim 1, wherein: the Zr-Ni PMOFs synthesized by the solvothermal method refer to the following components: reacting ZrCl4Ultrasonically dissolving benzoic acid and Ni-TCPP in DMF, transferring the solution to a reaction kettle, heating for reaction, centrifugally separating Zr-Ni PMOFs, washing, and drying in vacuum to obtain purple powdery crystals.
4. The porphyrin-based multifunctional photocatalytic MOFs material according to claim 3, wherein: said ZrCl4: benzoic acid: the Ni-TCPP was heated at a weight ratio of 4:50:3 in a muffle furnace at 120 ℃ for 72 hours, centrifuged at 12000rpm for 5 min, washed three times with ethanol, and dried at 70 ℃ in a vacuum environment for 12 hours at a yield of 53%.
5. The porphyrin-based multifunctional photocatalytic MOFs material according to claim 1, wherein: the conduction band potential of the Zr-Ni PMOFs is-1.22V, and enough H is available+A reducing driving force; the valence band potential is + 1.12V, which provides sufficient oxidizing power for the selective oxidation of benzyl alcohol.
6. The porphyrin-based multifunctional photocatalytic MOFs material according to claim 1, wherein: the Zr-Ni PMOFs have strong absorption in a wave band of 200-800 nm, and the band gap width is 2.34 eV.
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