Ce / TCPP co-doped photocatalysts and their application in CO2 bioactivation
By co-doping UiO-66-NH2 photocatalyst with Ce/TCPP, the problems of small photoresponse range and low charge transfer efficiency of traditional MOF-based photocatalysts were solved, achieving efficient NADH regeneration and CO2 activation into high-value compounds.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- INSTITUTE OF PROCESS ENGINEERING CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2023-02-01
- Publication Date
- 2026-06-30
AI Technical Summary
Traditional MOF-based photocatalysts suffer from low NADH regeneration efficiency due to their small visible light response range and low charge transfer efficiency, which hinders their application in the process of CO2 activation into high-value compounds.
A Ce/TCPP-UiO-66-NH2 photocatalyst was prepared by co-doping UiO-66-NH2 with rare earth element Ce and organic ligand porphyrin (TCPP), which broadened the light absorption range and improved the charge transfer rate.
The regeneration efficiency of NADH reached 95%, and the yield of CO2 converted into high-value compounds such as formic acid/methanol was significantly increased.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of photocatalysis, specifically relating to a method for preparing and applying a photocatalyst for the cyclic regeneration of NADH hydrogen donors activated by CO2. Background Technology
[0002] In the process of converting CO2 into high-value compounds such as formic acid, formaldehyde, and methanol by activating key formate dehydrogenases (FDH), formaldehyde dehydrogenase (FaldDH), and alcohol dehydrogenase (ADH), the coenzyme NADH is required as a hydrogen proton to catalyze the reaction. However, the high price of NADH hinders its industrial application. Considering cost issues, photocatalysis is used to convert NADDH... + In-situ reduction to NADH is an effective method. Currently, photocatalysts used for photocatalytic NADH regeneration include metal semiconductors, inorganic semiconductors, organic dyes, and metal-organic frameworks (MOFs). Among these, MOF materials have attracted widespread attention in the field of photocatalysis due to their large specific surface area, abundant active sites, and tunable structure. However, traditional MOF-based photocatalysts suffer from low NADH regeneration efficiency due to their small visible light response range and low charge transfer efficiency. Therefore, designing and synthesizing novel MOF-based photocatalysts with high light utilization and fast charge transfer rates holds great promise. Summary of the Invention
[0003] In view of the problems existing in the prior art, the primary objective of this invention is to overcome the shortcomings of low photocatalytic activity of traditional MOF material UiO-66-NH2, and to prepare a Ce / TCPP co-doped photocatalyst Ce / TCPP-UiO-66-NH2 with simple synthesis method, low cost and high NADH regeneration efficiency, and to use it to construct a CO2 bioactivation to formic acid / methanol system.
[0004] To prepare a photocatalyst with high NADH regeneration efficiency based on UIO-66-NH2, the first aspect of the present invention provides a photocatalyst Ce / TCPP-UiO-66-NH2 based on UiO-66-NH2 co-doped with rare earth element (Ce) and organic ligand porphyrin (TCPP) and its application; preferably, the co-doped photocatalyst is used for the NADH recycling regeneration of CO2 bio-activated hydrogen donor.
[0005] A second aspect of the present invention provides a method for preparing a co-doped photocatalyst Ce / TCPP-UiO-66-NH2, comprising:
[0006] (1) Dissolve zirconium chloride (ZrCl4), 2-aminoterephthalic acid (NH2-BDC), benzoic acid (BA), medium-tetra-4-carboxyphenylporphyrin (TCPP), and CeCl3·7H2O in DMF, and stir and sonicate for 30 min each.
[0007] (2) Place the mixed solution from (1) into a 50 mL reaction vessel and heat at 120 °C. o The reaction was carried out at C for 24 h.
[0008] (3) After the reaction is complete, the mixed solution is centrifuged, washed and vacuum dried to obtain Ce / TCPP-UiO-66-NH2.
[0009] According to the present invention, the molar ratio of ZrCl4 to NH2-BDC in step (1) is (1.2~2.5):1, and / or the molar ratio of CeCl3·7H2O to NH2-BDC in step (1) is (1.2~3.8):1, and / or the molar ratio of TCPP to NH2-BDC in step (1) is (0.1~0.35):1, and / or the molar ratio of BA to NH2-BDC in step (1) is 16:1.
[0010] In some embodiments of the present invention, the required volume of DMF in step (1) is 20-25 mL.
[0011] In some embodiments of the present invention, the washing of the precipitate in step (3) is performed by alternating washing with DMF and acetone until the filtrate is colorless; the vacuum drying temperature is 80 °C and the time is 8 h.
[0012] A third aspect of the present invention provides a method for utilizing a co-doped photocatalyst Ce / TCPP-UiO-66-NH2 to convert NAD+ + The construction of the NADH system includes: an electron donor, a co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared by the preparation method described in the second aspect of this invention, an electron medium, and NAD. + The mixture was placed in phosphate buffer solution and irradiated with a xenon lamp under an argon atmosphere. The OD was then measured using a multi-functional microplate reader. 340 Calculate the amount of NADH generated; preferably, the electron donor is TEOA or EDTA.
[0013] In some embodiments of the present invention, the amount of co-doped photocatalyst Ce / TCPP-UiO-66-NH2 is 20~25mg.
[0014] The fourth aspect of this invention provides a photoenzymatic coupling activation system for CO2 to formic acid / methanol based on a co-doped photocatalyst Ce / TCPP-UiO-66-NH2, comprising:
[0015] (1) The co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared by the preparation method described in the second aspect of the present invention;
[0016] (2) Under illumination of the co-doped photocatalyst Ce / TCPP-UiO-66-NH2, NAD3 is continuously transferred. + Catalytic reduction to NADH;
[0017] (3) CO2 is activated into high-value compounds using a formate dehydrogenase or formate / formaldehyde / methanol dehydrogenase cascade reaction with NADH as a coenzyme; preferably, the high-value compounds include formate / methanol. The regenerated NADH as described in claim 6 can be further applied to the activation of CO2 into formate / methanol.
[0018] The fifth aspect of this invention provides the application of a co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared by the preparation method according to the second aspect of this invention in CO2 bioactivation, comprising: [the following is a list of components: an electron donor, the co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared by the preparation method according to the second aspect of this invention, an electron medium, and NAD2]. + In a system where CO2 is continuously introduced into the key enzyme activated by CO2, and the mixture is stirred at a constant speed under light irradiation, the co-doped photocatalyst Ce / TCPP-UiO-66-NH2 first activates NAD+. + The CO2 is reduced to NADH, and then the CO2 activation key enzyme uses the generated NADH to activate CO2 into a high-value compound; preferably, the CO2 activation key enzyme includes formate dehydrogenase or formate / formaldehyde / methanol dehydrogenase; preferably, the high-value compound includes formate / methanol.
[0019] Compared with the prior art, the present invention has at least the following beneficial effects:
[0020] (1) The co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared in this invention broadens the light absorption range of UiO-66-NH2 by doping rare earth elements Ce and TCPP, while reducing the photogenerated electron-hole recombination rate and increasing the charge transfer rate.
[0021] (2) The co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared in this invention achieves a NADH regeneration efficiency of 95% after 3 h of illumination.
[0022] (3) The co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared in this invention was applied to the CO2 bioactivation to formic acid system to obtain 3.1 mM formic acid, which has great potential in the conversion of CO2 into high-value compounds (formic acid / formaldehyde / methanol). Attached Figure Description
[0023] Figure 1 FTIR spectrum of co-doped photocatalyst Ce / TCPP-UiO-66-NH2.
[0024] Figure 2 XRD pattern of co-doped photocatalyst Ce / TCPP-UiO-66-NH2.
[0025] Figure 3 The regeneration efficiency of NADH by co-doped photocatalyst Ce / TCPP-UiO-66-NH2.
[0026] Figure 4 The photoenzymatic coupling activation of CO2 to formic acid production is based on the co-doped photocatalyst Ce / TCPP-UiO-66-NH2. Detailed Implementation
[0027] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. Those skilled in the art should understand that the following embodiments are merely simple examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be determined by the claims.
[0028] Example 1: Preparation of electronic dielectric [Cp*Rh(bpy)Cl2]COOH
[0029] First, 0.1 mM red powder [Cp*RhCl2]2 was suspended in anhydrous methanol. Then, 0.2 mM 2,2'-bipyridine-5,5'-dicarboxylic acid was added. After the suspension became clear and formed a pale yellow solution, anhydrous diethyl ether was added dropwise to the solution at 4 °C until an orange-yellow granular precipitate appeared. Finally, the obtained precipitate was dried in a vacuum drying oven at 80 °C for 2 h to obtain the electronic medium [Cp*Rh(bpy)Cl2]COOH.
[0030] Example 2: Preparation of UiO-66-NH2 and photocatalytic regeneration of NADH
[0031] (1) Preparation of UiO-66-NH2: 1 mM ZrCl4, 0.4 mM NH2-BDC and 16 mM BA were dissolved in 20 mL DMF. The mixed solution was then stirred and sonicated for 30 min each. Finally, the solution was placed in a hydrothermal reactor and reacted in an oven at 120 ℃ for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The solution was centrifuged to obtain a precipitate. The precipitate was washed with DMF and acetone until the filtrate was colorless. Finally, the precipitate was placed in an oven at 80 ℃ and vacuum dried for 8 h to obtain UiO-66-NH2.
[0032] (2) NADH regeneration: 25 mg UiO-66-NH2 and 5 mM [Cp*Rh(bpy)Cl2]COOH were placed in a 50 mL centrifuge tube and sonicated for 5 min, followed by the addition of 1 mM NAD. + Mix with 5 mM TEOA, place in a photocatalytic reactor, and incubate at 25°C. o NADH regeneration experiments were conducted under argon atmosphere and illumination. After 3 hours of illumination, the regeneration efficiency of NADH by UiO-66-NH2 was 45%.
[0033] Example 3: Preparation of 1-Ce / TCPP-UiO-66-NH2 and photocatalytic regeneration of NADH
[0034] (1) Preparation of 1-Ce / TCPP-UiO-66-NH2: 1 mM ZrCl4, 0.4 mM NH2-BDC, 16 mM BA, 0.05 mM TCPP, and 0.7 mM CeCl3·7H2O were dissolved in 25 mL DMF. The mixture was then stirred and sonicated for 30 min each. Finally, the solution was placed in a hydrothermal reactor and reacted in an oven at 120 ℃ for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The solution was then centrifuged to obtain a precipitate. The precipitate was washed with DMF and acetone until the filtrate was colorless. Finally, the precipitate was placed in an oven at 80 ℃ and vacuum dried for 8 h to obtain the co-doped photocatalyst 1-Ce / TCPP-UiO-66-NH2.
[0035] (2) NADH regeneration: 25 mg 1-Ce / TCPP-UiO-66-NH2 and 5 mM [Cp*Rh(bpy)Cl2]COOH were placed in a 50 mL centrifuge tube and sonicated for 5 min, followed by the addition of 1 mM NAD. + Mix with 5 mM TEOA, place in a photocatalytic reactor, and incubate at 25°C. oNADH regeneration experiments were conducted under argon atmosphere and illumination. After 3 hours of illumination, the regeneration efficiency of NADH by the co-doped photocatalyst 1-Ce / TCPP-UiO-66-NH2 was 86%.
[0036] Example 4: Preparation of 2-Ce / TCPP-UiO-66-NH2 and photocatalytic regeneration of NADH
[0037] (1) Preparation of 2-Ce / TCPP-UiO-66-NH2: 0.85 mM ZrCl4, 0.4 mM NH2-BDC, 16 mM BA, 0.1 mM TCPP, and 1.5 mM CeCl3·7H2O were dissolved in 25 mL DMF. The mixture was then stirred and sonicated for 30 min each. Finally, the solution was placed in a hydrothermal reactor and reacted in an oven at 120 ℃ for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The solution was then centrifuged to obtain a precipitate. The precipitate was washed with DMF and acetone until the filtrate was colorless. Finally, the precipitate was placed in an oven at 80 ℃ and vacuum dried for 8 h to obtain the co-doped photocatalyst 2-Ce / TCPP-UiO-66-NH2.
[0038] (2) NADH regeneration: 25 mg 2-Ce / TCPP-UiO-66-NH2 and 5 mM [Cp*Rh(bpy)Cl2]COOH were placed in a 50 mL centrifuge tube and sonicated for 5 min, followed by the addition of 1 mM NAD. + Mix with 5 mM TEOA, place in a photocatalytic reactor, and incubate at 25°C. o NADH regeneration experiments were conducted under argon atmosphere and illumination. After 3 hours of illumination, the regeneration efficiency of NADH by the co-doped photocatalyst 2-Ce / TCPP-UiO-66-NH2 was 95%.
[0039] Example 5: Preparation of 3-Ce / TCPP-UiO-66-NH2 and photocatalytic regeneration of NADH
[0040] (1) Preparation of 3-Ce / TCPP-UiO-66-NH2: 0.48 mM ZrCl4, 0.4 mM NH2-BDC, 16 mM BA, 0.1 mM TCPP, and 0.5 mM CeCl3·7H2O were dissolved in 25 mL DMF. The mixture was then stirred and sonicated for 30 min each. Finally, the solution was placed in a hydrothermal reactor and reacted in an oven at 120 ℃ for 24 h. After the reaction was completed, the reactor was allowed to cool naturally to room temperature. The solution was then centrifuged to obtain a precipitate. The precipitate was washed with DMF and acetone until the filtrate was colorless. Finally, the precipitate was placed in an oven at 80 ℃ and vacuum dried for 8 h to obtain the co-doped photocatalyst 3-Ce / TCPP-UiO-66-NH2.
[0041] (2) NADH regeneration: 25 mg 3-Ce / TCPP-UiO-66-NH2 and 5 mM [Cp*Rh(bpy)Cl2]COOH were placed in a 50 mL centrifuge tube and sonicated for 5 min, followed by the addition of 1 mM NAD. + Mix with 5 mM TEOA, place in a photocatalytic reactor, and incubate at 25°C. o NADH regeneration experiments were conducted under argon atmosphere and illumination. After 3 hours of illumination, the regeneration efficiency of the co-doped photocatalyst 3-Ce / TCPP-UiO-66-NH2 for NADH was 81%.
[0042] Example 6: Photoenzymatic activation of CO2 to formic acid based on 2-Ce / TCPP-UiO-66-NH2
[0043] 25 mg of co-doped photocatalyst 2-Ce / TCPP-UiO-66-NH2 and 5 mM [Cp*Rh(bpy)Cl2]COOH were placed in a 50 mL centrifuge tube and sonicated for 5 min. Then 1 mM NAD was added. + Mix with 5 mM TEOA, place in a photocatalytic reactor containing membrane-immobilized formate dehydrogenase, and incubate at 25°C. o Under light irradiation (C), CO2 was continuously introduced for the reaction. After 3 hours of irradiation, 3.1 mM formic acid was obtained.
[0044] In summary, the co-doped photocatalyst Ce / TCPP-UiO-66-NH2 provided by this invention has the characteristics of wide light absorption range, small band gap and fast photogenerated carrier transfer rate. After 3 h of irradiation, the NADH regeneration efficiency can reach 95% and the formic acid yield can reach 3.1 mM.
[0045] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.
Claims
1. A rare earth element and organic ligand porphyrin co-doped photocatalyst based on UiO-66-NH2, characterized in that, The photocatalyst is Ce / TCPP-UiO-66-NH2, and the preparation method of the co-doped photocatalyst Ce / TCPP-UiO-66-NH2 includes the following steps: (1) Dissolve zirconium chloride (ZrCl4), 2-aminoterephthalic acid (NH2-BDC), benzoic acid (BA), medium-tetra-4-carboxyphenylporphyrin (TCPP), and CeCl3·7H2O in DMF, and stir and sonicate for 30 min each. (2) The mixed solution in (1) was placed in a 50 mL reaction kettle and reacted for 24 h under the condition of 120 o C (3) After the reaction is complete, the mixed solution is centrifuged, washed and vacuum dried to obtain Ce / TCPP-UiO-66-NH2.
2. The method for preparing the co-doped photocatalyst Ce / TCPP-UiO-66-NH2 according to claim 1, characterized in that, The molar ratio of ZrCl4 to NH2-BDC in step (1) is (1.2~2.5):1, and / or the molar ratio of CeCl3·7H2O to NH2-BDC in step (1) is (1.2~3.8):1, and / or the molar ratio of TCPP to NH2-BDC in step (1) is (0.1~0.35):1, and / or the molar ratio of BA to NH2-BDC in step (1) is 16:
1.
3. The method for preparing the co-doped photocatalyst Ce / TCPP-UiO-66-NH2 according to claim 1, characterized in that, The required volume of DMF in step (1) is 20~25 mL.
4. The method for preparing the co-doped photocatalyst Ce / TCPP-UiO-66-NH2 according to claim 1, characterized in that, The washing in step (3) involves alternating washing with DMF and acetone until the filtrate is colorless; the vacuum drying temperature is 80 °C and the time is 8 h.
5. A method for utilizing co-doped photocatalyst Ce / TCPP-UiO-66-NH2 to convert NAD+ + Methods for reverting to NADH include: An electron donor, a co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared by the preparation method of claim 1, an electron medium, and NAD + The mixed solution was irradiated by a xenon lamp light source under an argon atmosphere in a phosphate buffer solution, and the OD was measured using a multifunctional microplate detector 340 The amount of NADH generated was calculated.
6. A method for photoenzymatic activation of CO2 to formic acid and / or methanol based on the co-doped photocatalyst Ce / TCPP-UiO-66-NH2, comprising: (1) The co-doped photocatalyst Ce / TCPP-UiO-66-NH2 prepared by the preparation method described in claim 1; (2) Under illumination of the co-doped photocatalyst Ce / TCPP-UiO-66-NH2, NAD3 is continuously transferred. + Catalytic reduction to NADH; (3) CO2 is activated into formic acid and / or methanol by using formic acid dehydrogenase or formic acid / formaldehyde / methanol dehydrogenase cascade reaction with NADH as coenzyme.
7. The method according to claim 6, characterized in that, The photocatalyst Ce / TCPP-UiO-66-NH2 prepared by the method described in claim 1, containing an electron donor, an electron medium, and NAD, is used. + In a system where CO2 is continuously introduced into the key enzyme activated by CO2, and the mixture is stirred at a constant speed under light irradiation, the co-doped photocatalyst Ce / TCPP-UiO-66-NH2 first activates NAD+. + The CO2 is reduced to NADH, and then the key enzyme for CO2 activation uses the generated NADH to activate CO2 into high-value compounds; the key enzyme for CO2 activation includes formate dehydrogenase or formate / formaldehyde / methanol dehydrogenase; the high-value compounds include formic acid and / or methanol.