CN115212880A - Preparation method of Cu @ g-PAN + PANI/STO photocatalyst - Google Patents

Preparation method of Cu @ g-PAN + PANI/STO photocatalyst Download PDF

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CN115212880A
CN115212880A CN202111643905.7A CN202111643905A CN115212880A CN 115212880 A CN115212880 A CN 115212880A CN 202111643905 A CN202111643905 A CN 202111643905A CN 115212880 A CN115212880 A CN 115212880A
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pan
pani
photocatalyst
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谭红琳
孙楠
李馨茹
白耀宁
欧阳滔远
闫昱玮
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Kunming University of Science and Technology
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Abstract

The invention discloses a preparation method of Cu @ g-PAN + PANI/STO photocatalyst, wherein PAN and PANI are dissolved in N, N-dimethylformamide and doped with a proper amount of CuCl 2 ·2H 2 And (3) reacting the O with the L-ascorbic acid solution to prepare a Cu dispersion, and dispersing the Cu dispersion in strontium titanate in ethanol. Firstly, through hydrothermal reaction and then low-temperature sintering, the Cu @ g-PAN + PANI (CI)/STO photocatalyst with extremely stable chemical property is obtained. The CI layer can protect Cu nanoparticles from being oxidized, and the CI layer promotes charge separation and shows a quasi-promoter effect. The photocatalytic hydrogen production proves the high-efficiency photocatalytic reducibility; the degradation of 4-nitrophenol shows its excellent photocatalytic oxidation. The method realizes the aim of simply and easily preparing the high-efficiency and high-stability photocatalyst, and proves that the photocatalyst has good application prospect in the aspect of solving the problems of energy and environmental pollution under the irradiation of sunlight.

Description

Preparation method of Cu @ g-PAN + PANI/STO photocatalyst
Technical Field
The invention relates to the field of photocatalytic materials, in particular to a preparation method of a Cu @ g-PAN + PANI/STO photocatalyst.
Background
The research of high-efficiency photocatalysts is the key point of improving energy utilization efficiency and relieving environmental pollution, in recent years, the Local Surface Plasmon Resonance (LSPR) effect of metal nano materials is more and more concerned, and the LSPR can be used for improving various photocatalytic efficiencies. Copper nanoparticles, which are inexpensive and easily available as compared with noble metals such as gold and silver, are being widely studied. Copper, as an abundant, inexpensive metal on earth, is receiving increasing attention due to its attractive photocatalytic properties, copper nanoparticles have relatively low interband transition thresholds (2.1 eV for Cu, 2.4 eV for au, 3.8 eV for ag) and relatively long wavelength LSPR absorption. However, the copper nanoparticles are very easily oxidized in the air, so that the photocatalytic effect is greatly reduced. Therefore, the copper-based photocatalyst with stable and efficient chemical properties obtained by using a simple, easy, convenient and generalizable manufacturing technology is an attractive exploration field in the aspect of solar energy utilization.
The precious metal-based photocatalyst prepared based on the LSPR effect reported at present has high cost, and the stability of chemical properties is required to be improved, so that the invention aims at finding a stable copper-based photocatalyst preparation technology with low cost and feasible method, and shows the prospect of reasonably designing the copper-based photocatalyst with high stability and efficiency.
Disclosure of Invention
The invention aims to provide a stable copper-based photocatalyst: the preparation method of Cu @ g-PAN + PANI/STO aims at solving the problems of unstable chemical property, high production cost and the like of the existing copper nanoparticles and achieves the aim of low-cost and high-efficiency photocatalytic hydrogen production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a Cu @ g-PAN + PANI/STO photocatalyst comprises the following specific steps:
(1) Mixing CuCl under magnetic stirring 2 ·2H 2 O solution and L-ascorbic acid solution;
(2) Centrifugally washing the dispersion liquid containing the copper nanoparticles obtained by mixing in the step (1) to reserve the copper nanoparticles at the bottom, and dispersing the copper nanoparticles in an ethanol solution;
(3) Dissolving polyacrylonitrile and polyaniline in N, N-dimethylformamide solution;
(4) Dispersing strontium titanate in ethanol solution;
(5) Mixing the dispersion liquid obtained in the steps (2) and (4) with the solution obtained in the step (3) and then uniformly stirring;
(6) Carrying out hydrothermal treatment on the dispersion liquid obtained in the step (5) and then centrifuging;
(7) And (4) putting the solution obtained in the step (6) into a tube furnace to sinter to obtain a product.
Step (1) CuCl 2 ·2H 2 The concentration of O is 2.85mmol/L, the concentration of L-ascorbic acid is 0.8 mol/L, and the mixing and stirring time is 16 h.
In the step (3), 0.1g of polyacrylonitrile, 0.005g of polyaniline and 26ml of N, N-dimethylformamide are required to be added.
In the step (4), 0.1g of strontium titanate and 80ml of ethanol are required to be added.
In the mixing process of the step (5), the addition amount of the solution in the step (3) is 60ml,10ml and 4ml.
The hydrothermal reaction in the step (6) needs to be carried out for 6h at 90 ℃.
The sintering atmosphere of the sample in the step (7) sintering process needs to be controlled to Ar (80%) and H 2 (20%) air flow.
The sintering process of the step (7) needs to be annealed for 2.5 hours at 650 ℃.
The invention has the beneficial effects that:
the Cu NPs wrapped in g-PAN + PANI (CI) are successfully synthesized by using the Cu NPs as precursors through hydrothermal treatment. Due to the excellent LSPR effect of the Cu NPs, the ultrathin Cu @ CI/STO shows extremely high photocatalytic hydrogen evolution rate under the irradiation of visible light. PANI doped g-PAN not only acts as an encapsulant to protect Cu from oxygen attack, but also improves the efficiency of electron-hole separation. The photocatalytic hydrogen production proves the high photocatalytic efficiency, the catalytic reaction of the 4-nitrophenol shows that the prepared catalyst has excellent thermal catalysis application, and the high-efficiency degradation of the 4-nitrophenol in the sun proves the practical value of the catalyst. The method ensures the further application of the copper in photocatalysis and thermocatalysis, opens up a way for utilizing cheap and abundant copper in catalysis, and has wide application prospect in the fields of wastewater treatment, new energy hydrogen production, composite materials, batteries, utilization of non-rare and noble metals and the like.
Drawings
FIG. 1 is a schematic diagram of the synthesis of Cu @ CI/STO in the process of the present invention.
FIG. 2a is a TEM image of Cu @ CI/STO structure in example 1 of the present invention; b and c are HRTEM images of a Cu @ CI/STO structure; d is the relation between the thickness of the carbon layer, the surface carbon content and the addition amount of the solution; e is an XRD spectrum; f is Raman spectrum; g is infrared spectrum; h is XPS spectrum of Cu 2p after 1 month of standing in air (Cu @ CI/STO and Cu/STO); i is XPS spectrum of N1 s (Cu @ CI/STO).
FIG. 3a, b are SEM images of a Cu @ CI/STO-60ml structure; c is TEM with Cu @ CI/STO-60ml structure (inset is Cu NPs particle size distribution diagram); c-i are the corresponding element distributions.
FIG. 4a is a TEM image of Cu @ CI/STO-10ml structure; b is an HRTEM image of a Cu @ CI/STO-10ml structure.
FIG. 5a is the photocatalytic hydrogen evolution rates for Cu @ CI/STO, cu @ g-PAN/STO and Cu/STO; b is Cu @ CI/STO-4ml,10ml and 60ml photocatalytic hydrogen evolution rate; c is a cyclic test of the performance stability of Cu @ CI/STO-4ml photocatalytic hydrogen evolution.
FIG. 6a is an XPS spectrum of Cu 2p after photocatalytic reaction (Cu @ CI/STO) and the corresponding Auger electron spectrum; b is ultraviolet visible absorption spectrum; c is photoluminescence spectrum. d is the electrochemical impedance plot.
FIG. 7a is a UV-visible absorption spectrum during the reduction of 4-nitrophenol in the presence of Cu @ CI/STO; b is an ultraviolet-visible absorption spectrum in the reduction process of 4-nitrophenol in the presence of Cu/STO; c is when NaBH 4 The thermal effect of SPR excitation enhances the schematic of the catalytic reduction of Cu @ CI/STO with 4-nitrophenol when used as an electron donor.
FIG. 8a is the UV-visible absorption spectrum of Cu @ CI/STO during the reduction of 4-nitrophenol in sunlight; b is the temperature change with time under sunlight with or without Cu @ CI/STO at different time; and c is a degradation image of 4-nitrophenol under sunlight at different times.
Detailed Description
The present invention is further illustrated by the following examples, wherein the details are not set forth in any detail as part of the common general knowledge or the technical skill in the art.
Example 1
A preparation method of a Cu @ CI/STO photocatalyst comprises the following specific steps:
(1) 50ml 2.85mmol/L CuCl is stirred under magnetic stirring (800 r/min) 2 ·2H 2 Mixing the O solution and 50ml of 0.8 mol/L L-ascorbic acid solution for 16 hours;
(2) Centrifuging the solution containing the copper nanoparticles mixed in the step (1) three times, washing with ethanol, retaining the copper nanoparticles (about 3 mg) at the bottom, and dispersing the copper nanoparticles in 5ml of ethanol solution;
(3) Dissolving 0.1g of polyacrylonitrile and 0.005g of polyaniline in an N, N-dimethylformamide solution;
(4) Dispersing 0.1g of strontium titanate in 80ml of ethanol solution;
(5) Mixing the dispersion liquid obtained in the steps (2) and (4) with 4ml of the solution obtained in the step (3) and then uniformly stirring;
(6) Carrying out hydrothermal treatment on the dispersion liquid obtained in the step (5) at 90 ℃ for 6h, and then washing and centrifuging for 5 times by using ethanol;
(7) Obtained in step (6)The solution of (2) was sintered in a tube furnace, controlled to Ar (80%) and H 2 (20%) gas flow, annealing temperature 650 deg.C, annealing time 2.5h, thus obtaining Cu @ CI/STO-4ml photocatalyst. In the photocatalytic hydrogen production, 74.2 mu mol of 50mg of photocatalyst is subjected to photocatalytic hydrogen production for 4 hours under the irradiation of visible light with the wavelength of more than 420nm, and the hydrogen production is not reduced after 3 times of circulation. In the photocatalytic degradation of 4-nitrophenol, 10 mg of photocatalyst is used for degrading 4-nitrophenol into 4-aminophenol after 15min under the irradiation of visible light with the wavelength of more than 420nm, and the extremely high degradation rate is also reflected under the irradiation of sunlight.
Example 2
A preparation method of a Cu @ CI/STO photocatalyst comprises the following specific steps:
(1) 50ml 2.85mmol/L CuCl is stirred under magnetic stirring (800 r/min) 2 ·2H 2 Mixing the O solution and 50ml of 0.8 mol/L L-ascorbic acid solution for 16 hours;
(2) Centrifuging the solution containing the copper nanoparticles mixed in the step (1) three times, washing with ethanol, retaining the copper nanoparticles (about 3 mg) at the bottom, and dispersing the copper nanoparticles in 5ml of ethanol solution;
(3) Dissolving 0.1g of polyacrylonitrile and 0.005g of polyaniline in an N, N-dimethylformamide solution;
(4) Dispersing 0.1g of strontium titanate in 80ml of ethanol solution;
(5) Mixing the dispersion liquid obtained in the steps (2) and (4) with 10ml of the solution obtained in the step (3) and then uniformly stirring;
(6) Carrying out hydrothermal treatment on the dispersion liquid obtained in the step (5) at 90 ℃ for 6h, and then washing and centrifuging for 5 times by using ethanol;
(7) Putting the solution obtained in the step (6) into a tube furnace for sintering, wherein Ar (80%) and H are controlled 2 (20%) gas flow, annealing temperature 650 ℃ and annealing time 2.5h, thus obtaining Cu @ CI/STO-10ml photocatalyst. In the photocatalytic hydrogen production, 58.6 mu mol of 50mg of photocatalyst is used for producing hydrogen through photocatalysis for 4 hours under the irradiation of visible light with the wavelength of more than 420 nm.
Example 3
A preparation method of a Cu @ CI/STO photocatalyst comprises the following specific steps:
(1) 50ml 2.85mmol/L CuCl is added under magnetic stirring (800 r/min) 2 ·2H 2 Mixing the O solution and 50ml of 0.8 mol/L-ascorbic acid solution for 16 hours;
(2) Centrifuging the solution containing copper nanoparticles mixed in step (1) three times, washing with ethanol, retaining the bottom copper nanoparticles (about 3 mg), and dispersing them in 5ml of ethanol solution;
(3) Dissolving 0.1g of polyacrylonitrile and 0.005g of polyaniline in an N, N-dimethylformamide solution;
(4) Dispersing 0.1g of strontium titanate in 80ml of ethanol solution;
(5) Mixing the dispersion liquid obtained in the steps (2) and (4) with 60ml of the solution obtained in the step (3) and then uniformly stirring;
(6) Carrying out hydrothermal treatment on the dispersion liquid obtained in the step (5) at 90 ℃ for 6h, and then washing and centrifuging for 5 times by using ethanol;
(7) Putting the solution obtained in the step (6) into a tube furnace for sintering, wherein Ar (80%) and H are controlled 2 (20%) gas flow, annealing temperature 650 deg.C, annealing time 2.5h, thus obtaining Cu @ CI/STO-60ml photocatalyst. In the hydrogen production by photocatalysis, 34.5 mu mol of 50mg of photocatalyst is used for producing hydrogen by photocatalysis for 4 hours under the irradiation of visible light with the wavelength of more than 420 nm.
Example 4
A preparation method of a Cu @ g-PAN/STO photocatalyst comprises the following specific steps:
(1) 50ml 2.85mmol/L CuCl is stirred under magnetic stirring (800 r/min) 2 ·2H 2 Mixing the O solution and 50ml of 0.8 mol/L L-ascorbic acid solution for 16 hours;
(2) Centrifuging the solution containing copper nanoparticles mixed in step (1) three times, washing with ethanol, retaining the bottom copper nanoparticles (about 3 mg), and dispersing them in 5ml of ethanol solution;
(3) 0.1g of polyacrylonitrile was dissolved in an N, N-dimethylformamide solution;
(4) Dispersing 0.1g of strontium titanate in 80ml of ethanol solution;
(5) Mixing the dispersion liquid obtained in the steps (2) and (4) with 4ml of the solution obtained in the step (3) and then uniformly stirring;
(6) Carrying out hydrothermal treatment on the dispersion liquid obtained in the step (5) at 90 ℃ for 6h, and then washing and centrifuging for 5 times by using ethanol;
(7) Putting the solution obtained in the step (6) into a tube furnace for sintering, wherein Ar (80%) and H are controlled 2 (20%) gas flow, annealing temperature 650 deg.C, annealing time 2.5h, thus obtaining Cu @ g-PAN/STO photocatalyst. In the photocatalytic hydrogen production, 53.1 mu mol of 50mg of photocatalyst is used for photocatalytic hydrogen production for 4 hours under the irradiation of visible light with the wavelength of more than 420 nm.
Example 5
A preparation method of a Cu/STO photocatalyst comprises the following specific steps:
(1) 50ml 2.85mmol/L CuCl is stirred under magnetic stirring (800 r/min) 2 ·2H 2 Mixing the O solution and 50ml of 0.8 mol/L L-ascorbic acid solution for 16 hours;
(2) Centrifuging the solution containing the copper nanoparticles mixed in the step (1) three times, washing with ethanol, retaining the copper nanoparticles (about 3 mg) at the bottom, and dispersing the copper nanoparticles in 5ml of ethanol solution;
(3) Dispersing 0.1g of strontium titanate in 80ml of ethanol solution;
(4) Mixing the dispersion liquid obtained in the step (2) with the solution obtained in the step (3) and then uniformly stirring;
(5) Carrying out hydrothermal treatment on the dispersion liquid obtained in the step (4) at 90 ℃ for 6h, and then washing and centrifuging the dispersion liquid for 5 times by using ethanol;
(6) Putting the solution obtained in the step (5) into a tube furnace for sintering, wherein Ar (80%) and H are controlled 2 (20%) gas flow, annealing temperature 650 deg.C, annealing time 2.5h, thus obtaining Cu/STO photocatalyst. In the photocatalytic hydrogen production, 50mg of photocatalyst is used for producing 4.1 mu mol of hydrogen through 4h of photocatalysis under the irradiation of visible light with the wavelength of more than 420 nm. In the photocatalytic degradation of 4-nitrophenol, 10 mg of photocatalyst degrades 4-nitrophenol into 4-aminophenol after 75min under the irradiation of visible light with the wavelength of more than 420 nm.
In conclusion, the preparation method of the Cu @ CI/STO photocatalyst provided by the invention utilizes the hot electrons generated by the local surface plasmons and the carrier separation effect attached to the hot electrons, so that the photocatalytic effect of the material is improved. When the g-PAN/PANI wraps the Cu nano particles, photo-generated electrons generated by the Cu nano particles tend to be transferred to a g-PAN/PANI shell structure, so that charge separation is caused, the separated charges further enter a conduction band of the STO, the photocatalytic hydrogen production performance is improved, and the service life of carriers is effectively prolonged by introducing the PANI. In addition, the good stability of the catalyst is attributed to the existence of a g-PAN/PANI carbon layer, and the Cu nano particles can be protected from being oxidized by the carbon layer package. The catalytic reaction of the 4-nitrophenol shows that the prepared catalyst has excellent thermal catalysis application, and the practical value is proved by high-efficiency degradation in the sun. The invention can open up new opportunities for designing new copper-based materials and catalysts, and has wide application prospects in the fields of wastewater treatment, new energy hydrogen production, composite materials, batteries, utilization of non-rare and precious metals and the like.

Claims (8)

1. A preparation method of a Cu @ g-PAN + PANI/STO photocatalyst is characterized by comprising the following specific steps:
(1) Mixing CuCl under magnetic stirring 2 ·2H 2 O solution and L-ascorbic acid solution;
(2) Centrifugally washing the dispersion liquid containing the copper nanoparticles obtained by mixing in the step (1) to reserve the copper nanoparticles at the bottom, and dispersing the copper nanoparticles in an ethanol solution;
(3) Dissolving polyacrylonitrile and polyaniline in N, N-dimethylformamide solution;
(4) Dispersing strontium titanate in ethanol solution;
(5) Mixing the dispersion liquid obtained in the steps (2) and (4) with the solution obtained in the step (3) and then uniformly stirring;
(6) Carrying out hydrothermal treatment on the dispersion liquid obtained in the step (5) and then centrifuging;
(7) And (4) putting the solution obtained in the step (6) into a tube furnace to sinter to obtain a product.
2. According to claimThe preparation method of the Cu @ g-PAN + PANI/STO photocatalyst as claimed in claim 1, which is characterized in that the step (1) of CuCl 2 ·2H 2 The concentration of O is 2.85mmol/L, the concentration of L-ascorbic acid is 0.8 mol/L, and the mixing and stirring time is 16 h.
3. The method for preparing the Cu @ g-PAN + PANI/STO photocatalyst according to claim 1, wherein 0.1g polyacrylonitrile, 0.005g polyaniline and 26ml N, N-dimethylformamide are added in the step (3).
4. The method for preparing the Cu @ g-PAN + PANI/STO photocatalyst according to claim 1, wherein 0.1g of strontium titanate and 80ml of ethanol are required to be added in the step (4).
5. The method for preparing a Cu @ g-PAN + PANI/STO photocatalyst according to claim 1, wherein the amount of the solution added in step (3) is 60ml,10ml and 4ml in the mixing process in step (5).
6. The method for preparing the Cu @ g-PAN + PANI/STO photocatalyst according to claim 1, wherein the hydrothermal reaction in the step (6) needs to be carried out at 90 ℃ for 6h.
7. The method for preparing the Cu @ g-PAN + PANI/STO photocatalyst according to claim 1, wherein the sintering atmosphere of the sample in the sintering process in the step (7) needs to be controlled to Ar (80%) and H 2 (20%) air flow.
8. The method for preparing the Cu @ g-PAN + PANI/STO photocatalyst according to claim 1, wherein the sintering process in the step (7) requires annealing at 650 ℃ for 2.5h.
CN202111643905.7A 2021-12-29 2021-12-29 Preparation method of Cu @ g-PAN + PANI/STO photocatalyst Pending CN115212880A (en)

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Citations (4)

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