CN112774694B - Preparation method and application of functional carbon quantum dot modified Ag-In-Zn-S quantum dot - Google Patents

Preparation method and application of functional carbon quantum dot modified Ag-In-Zn-S quantum dot Download PDF

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CN112774694B
CN112774694B CN202110013431.1A CN202110013431A CN112774694B CN 112774694 B CN112774694 B CN 112774694B CN 202110013431 A CN202110013431 A CN 202110013431A CN 112774694 B CN112774694 B CN 112774694B
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fca
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李丰华
邓邦亚
毛宝东
李丽霞
薛奕钦
曹金东
刘艳红
张栋琪
董维旋
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Jiangsu University
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Abstract

The invention belongs to the technical field of photocatalytic hydrogen production, and relates to a preparation method of Ag-In-Zn-S quantum dots modified by functional carbon quantum dots, which comprises the following steps: mixing CDs with 1M ferrocenecarboxylic acid solution taking dimethyl sulfoxide as a solvent, fixing the volume to 20mL by using distilled water, and carrying out hydrothermal reaction at 110-140 ℃ for 2-4 h to obtain a precursor of CDs-FcA; mixing silver nitrate, indium nitrate, zinc acetate and L-cysteine to obtain an aqueous solution, adjusting the pH value of the solution to 8.5 by using 1M NaOH, adding a CDs-FcA precursor and thioacetamide, uniformly stirring by using ultrasonic waves, carrying out hydrothermal reaction at 110 ℃ for 2-4 h, and carrying out centrifugal washing after the reaction is finished. According to the invention, the higher visible light response capability of the Ag-In-Zn-S quantum dot is utilized, and the photogenerated holes In the quantum dot can be rapidly extracted through the two-stage lower HOMO energy level orbitals, so that the recombination efficiency of photogenerated charges is greatly reduced, and the hydrogen production efficiency by photolysis of water is more efficient. The invention has simple process, low price and easy obtaining, is convenient for batch production, is nontoxic and harmless and meets the environment-friendly requirement.

Description

Preparation method and application of functional carbon quantum dot modified Ag-In-Zn-S quantum dot
Technical Field
The invention belongs to the technical field of photocatalytic hydrogen production, and relates to a preparation method and application of functional carbon quantum dot modified Ag-In-Zn-S quantum dots.
Background
Photocatalytic water splitting is considered to be one of the most desirable methods for producing hydrogen directly from continuous solar energy and water. However, visible light accounts for approximately 43% of sunlight, and utilization is far below expectations, which plays a key role in better utilization of solar energy. Quantum Dots (QDs) are considered to be the most promising visible light active photocatalyst candidate particles due to their unique Quantum confinement effects, desirable optical properties and large specific surface area. Compared with the traditional II-VI quantum dots, the cadmium-free I-III-VI quantum dots attract wide attention in the field of photocatalysis due to the adjustable forbidden bandwidth and low toxicity of the components, and are the most promising visible light activity candidate quantum dots.
In photocatalytic research, a promoter plays an important role in charge separation. Carbon quantum dots (CDs) have been widely studied as a nanocarbon material having unique photoelectric properties, good water solubility, and high stability. Because of their unique optoelectronic properties, CDs are used in photocatalysts in a variety of functional components, such as photosensitizers, electron acceptors, and electron storage. It is worth mentioning that in photocatalysis, CDs mainly function as electron acceptors and charge storage media. However, there are few reports of CDs as hole acceptors, and the role of CDs as a highly efficient hole transfer agent has not been clearly demonstrated. In consideration of the multiple energy levels of CDs and the key role of energy band arrangement in photocatalyst design, CDs are expected to be a hole transport material with tunable Highest Occupied Molecular Orbital (HOMO) energy level to achieve efficient hole transfer.
In view of the analysis, the invention firstly connects ferrocenecarboxylic acid (FcA) with CDs, then constructs the AIZS-CDs-FcA three-component composite photocatalyst by In-situ synthesis and Ag-In-Zn-S (AIZS) quantum dot composition, and is applied to the field of photocatalytic hydrogen production.
Disclosure of Invention
Aiming at the defects In the prior art, the invention aims to disclose a preparation method of a functional carbon quantum dot modified Ag-In-Zn-S quantum dot.
Technical scheme
A preparation method of functional carbon quantum dot modified Ag-In-Zn-S quantum dots comprises the following steps:
A. mixing CDs with 1M ferrocenecarboxylic acid solution with dimethyl sulfoxide as a solvent, fixing the volume to 20mL by using distilled water, and carrying out hydrothermal reaction at 110-140 ℃ for 2-4 h, preferably at 140 ℃ for 4h to obtain a CDs-FcA precursor, wherein the mass fraction ratio of the CDs-FcA is 3-15%: 4-22%;
B. mixing silver nitrate, indium nitrate, zinc acetate and L-cysteine to obtain a water solution, adjusting the pH value of the solution to 8.5 by using 1M NaOH, adding a CDs-FcA precursor and thioacetamide, uniformly stirring by ultrasonic, carrying out hydrothermal reaction at 110 ℃ for 2-4 h, preferably carrying out hydrothermal reaction at 110 ℃ for 4h, and after the reaction is finished, carrying out centrifugal washing to obtain a functional carbon quantum dot modified Ag-In-Zn-S quantum dot (AIZS-CDs-FcA composite photocatalyst), wherein the silver nitrate: indium nitrate: zinc acetate: l-cysteine: CDs-FcA precursor: thioacetamide: the mass ratio of water is 0.0288-0.0864: 0.649: 0.186: 0.6058: 0.003-0.018: 0.244:50.
The preparation method of the CDs comprises the following steps: two high-purity graphite rods (6.15 mm in diameter and 15cm in length) were used as an anode and a cathode, respectively, and inserted into an electrolytic cell (18.2 M.OMEGA.cm) containing ultrapure water-11000mL), applying 30V direct current voltage by a direct current power supply to carry out electrolysis until colorless electrolyte turns into dark brown; the solution was filtered through slow quantitative filter paper and the resulting solution was centrifuged for 30min at 8000rpm in a high speed centrifuge to remove graphite oxide precipitates and large particles of graphite, lyophilized to obtain dry powders of CDs for use.
Ag-In-Zn-S quantum dots, the preparation method thereof is specified In G.Gong, Y.h.Liu, B.d.Mao, L.l.Tan, Y.l.Yang, W.d.Shi, Ag docking of Zn-In-S quality dots for photo-catalytic hydrogenation, simple and basic quantum association, applied.Catal.B, environ, 216(2017) 11-19.
The functional carbon quantum dot prepared by the invention modifies the Ag-In-Zn-S quantum dot, the morphology is a structure that 0D-0D is loaded In an amorphous porous organic matter, FcA is an amorphous porous structure, and the Ag-In-Zn-S quantum dot and CDs are uniformly loaded on FcA to fix the quantum dot and effectively increase the specific surface area of hole consumption.
Another purpose of the invention is to apply the prepared AIZS-CDs-FcA composite photocatalyst to photocatalytic hydrogen production.
Photocatalytic activity evaluation of the photocatalyst prepared in the present invention: under visible light conditions, 0.02g of catalyst and 0.528g L-ascorbic acid were added to a photoreactor, and N was passed through at a large flow rate2After the gas in the bottle is completely discharged, opening a customized xenon lamp for irradiation under the condition of magnetic stirring, sampling and analyzing once every 1H, and obtaining H through calculation2The amount of (c).
The invention realizes the research of improving the hole transfer rate and efficiently producing hydrogen by photocatalysis by taking CDs as hole conductors for the first time. Under the excitation of visible light, the photoproduction holes are quickly transferred to FcA through the carbon quantum dots, so that the recombination is greatly reduced, more electrons are used for hydrogen production reaction, and the photocatalytic performance is greatly improved.
Advantageous effects
According to the invention, the Ag-In-Zn-S quantum dot has higher visible light response capability, and the CDs-FcA hole promoter plays a role In quickly conducting holes, so that the photogenerated holes In the quantum dot can be quickly extracted through the two-stage lower HOMO energy level orbitals, the recombination efficiency of photogenerated charges is greatly reduced, and the more efficient hydrogen production efficiency by photolysis of water is realized. The invention has simple process, low price, easy obtainment, convenient batch production, no toxicity and no harm, and meets the environment-friendly requirement.
Drawings
FIG. 1 XRD diffraction patterns of AIZS-CDs-FcA, AIZS-FcA and AIZS photocatalyst;
FIG. 2 is (a) a photoluminescence spectrum and (b) UV-visible absorption spectra of AIZS-CDs-FcA, AIZS-FcA and AIZS photocatalyst;
FIG. 3 is a projection view of AIZS-CDs-FcA;
FIG. 4 shows (a) photocatalytic hydrogen production curves for AIZS-CDs-FcA, AIZS-FcA, and AIZS (b) hydrogen production rates;
FIG. 5 is a graph of electrochemical impedance of AIZS-CDs-FcA, AIZS-FcA, and AIZS.
Detailed Description
The present invention will be described in detail below with reference to examples to provide those skilled in the art with a better understanding of the present invention, but the present invention is not limited to the following examples.
Example 1
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 0.48mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 140 ℃ for 4h, and cooling the solution for later use.
(2) Preparation of AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the solution is added with the CDs-FcA obtained in the step (1) and 0.244g of thioacetamide, ultrasonic stirring is carried out, hydrothermal reaction is carried out for 4 hours in an autoclave at the temperature of 110 ℃, and centrifugal washing is carried out after the hydrothermal reaction is finished, so that the AIZS-CDs-FcA composite photocatalyst is obtained.
Taking 0.02g of catalyst and 0.528g L-ascorbic acid of the sample in (2), adding the catalyst and the ascorbic acid into a photoreactor, and introducing N at a large flow rate2After the gas in the bottle is exhausted, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analyzing are carried out once every 1h, and the hydrogen production rate is calculated to be 0.6 mmol/g/h.
Example 2
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 1.2mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 140 ℃ for 4h, and cooling for later use.
(2) Preparing an AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the solution is added with the CDs-FcA obtained in the step (1) and 0.244g of thioacetamide, ultrasonic stirring is carried out, hydrothermal reaction is carried out for 4 hours in an autoclave at the temperature of 110 ℃, and centrifugal washing is carried out after the hydrothermal reaction is finished, so that the AIZS-CDs-FcA composite photocatalyst is obtained.
Taking 0.02g of catalyst and 0.528g L-ascorbic acid of the sample in (2), adding the catalyst and the ascorbic acid into a photoreactor, and introducing N at a large flow rate2After the gas in the bottle is exhausted, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analyzing are carried out once every 1h, and the hydrogen production rate is calculated to be 1.25 mmol/g/h.
Example 3
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 1.92mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 140 ℃ for 4h, and cooling the solution for later use.
(2) Preparing an AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the CDs-FcA and 0.244g of thioacetamide in the step (1) are added, the mixture is stirred ultrasonically, the hydrothermal reaction is carried out in an autoclave at the temperature of 110 ℃ for 4 hours, and after the reaction is finished, the composite photocatalyst AIZS-CDs-FcA is obtained through centrifugal washing.
Taking 0.02g of catalyst and 0.528g L-ascorbic acid of the sample in (2), adding the catalyst and the ascorbic acid into a photoreactor, and introducing N at a large flow rate2After the gas in the bottle is exhausted, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analyzing are carried out once every 1h, and the hydrogen production rate is calculated to be 2.3 mmol/g/h.
Example 4
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 2.64mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 140 ℃ for 4h, and cooling the solution for later use.
(2) Preparing an AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the solution is added with the CDs-FcA obtained in the step (1) and 0.244g of thioacetamide, ultrasonic stirring is carried out, hydrothermal reaction is carried out for 2 hours in an autoclave at the temperature of 110 ℃, and centrifugal washing is carried out after the hydrothermal reaction is finished, so that the AIZS-CDs-FcA composite photocatalyst is obtained.
Taking 0.02g of the catalyst and 0.528g L-ascorbic acid as samples in (2), adding into the photoreactor, and introducing N at a large flow rate2After the gas in the bottle is completely discharged, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analysis are carried out once at intervals of 1h, and the hydrogen production rate is calculated to be 1.58 mmol/g/h.
Example 5
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 1.92mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 110 ℃ for 4h, and cooling for later use.
(2) Preparation of AIZS-CDs-FcA composite photocatalyst:
weighing 0.0288g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine, mixing and dissolving in 50g of water, mixing the solutions, adjusting the pH value of the solution to 8.5 by using 1M NaOH, adding the CDs-FcA and 0.244g of thioacetamide in the step (1), carrying out ultrasonic stirring, carrying out hydrothermal reaction in an autoclave at the temperature of 110 ℃ for 3 hours, and carrying out centrifugal washing after the reaction is finished to obtain the AIZS-CDs-FcA composite photocatalyst.
Taking 0.02g of the catalyst and 0.528g L-ascorbic acid as samples in (2), adding into the photoreactor, and introducing N at a large flow rate2After the gas in the bottle is exhausted, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analyzing are carried out once every 1h, and the hydrogen production rate is calculated to be 1.5 mmol/g/h.
Example 6
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 0.48mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 120 ℃ for 4h, and cooling the solution for later use.
(2) Preparing an AIZS-CDs-FcA composite photocatalyst:
0.0864g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed and mixed to be dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the solution is added into the CDs-FcA and 0.244g of thioacetamide in the step (1), ultrasonic stirring is carried out, hydrothermal reaction is carried out for 4 hours in a high-pressure kettle at the temperature of 110 ℃, and centrifugal washing is carried out after the hydrothermal reaction is finished, so that the AIZS-CDs-FcA composite photocatalyst is obtained.
Taking 0.02g of the catalyst and 0.528g L-ascorbic acid as samples in (2), adding into the photoreactor, and introducing N at a large flow rate2After the gas in the bottle is exhausted, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analyzing are carried out once every 1h, and the hydrogen production rate is calculated to be 2.0 mmol/g/h.
Example 7
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 1.92mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 110 ℃ for 4h, and cooling the solution for later use.
(2) Preparing an AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the solution is added with the CDs-FcA obtained in the step (1) and 0.244g of thioacetamide, ultrasonic stirring is carried out, hydrothermal reaction is carried out for 2 hours in an autoclave at the temperature of 110 ℃, and centrifugal washing is carried out after the hydrothermal reaction is finished, so that the AIZS-CDs-FcA composite photocatalyst is obtained.
Taking 0.02g of the catalyst and 0.528g L-ascorbic acid as samples in (2), adding into the photoreactor, and introducing N at a large flow rate2After the gas in the bottle is exhausted, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analyzing are carried out once every 1h, and the hydrogen production rate is calculated to be 2.1 mmol/g/h.
Example 8
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 1.92mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 110 ℃ for 4h, and cooling for later use.
(2) Preparation of AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the CDs-FcA and 0.244g of thioacetamide in the step (1) are added, the mixture is stirred ultrasonically, the hydrothermal reaction is carried out in an autoclave at the temperature of 110 ℃ for 2 hours, and after the reaction is finished, the composite photocatalyst AIZS-CDs-FcA is obtained through centrifugal washing.
Taking 0.02g of the catalyst and 0.528g L-ascorbic acid as samples in (2), adding into the photoreactor, and introducing N at a large flow rate2After the gas in the bottle is completely discharged,and (3) turning on a customized xenon lamp for irradiation under the condition of magnetic stirring, sampling and analyzing once at intervals of 1h, and calculating to obtain the hydrogen production rate of 1.5 mmol/g/h.
Example 9
(1) Preparation of CDs-FcA precursor:
transferring 12mg of CDs and 1.92mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 130 ℃ for 2h, and cooling the solution for later use.
(2) Preparation of AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the CDs-FcA and 0.244g of thioacetamide in the step (1) are added, the mixture is stirred ultrasonically, the hydrothermal reaction is carried out in an autoclave at the temperature of 110 ℃ for 3 hours, and after the reaction is finished, the composite photocatalyst AIZS-CDs-FcA is obtained through centrifugal washing.
Taking 0.02g of catalyst and 0.528g L-ascorbic acid of the sample in (2), adding the catalyst and the ascorbic acid into a photoreactor, and introducing N at a large flow rate2After the gas in the bottle is exhausted, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analyzing are carried out once every 1h, and the hydrogen production rate is calculated to be 1.8 mmol/g/h.
Example 10
(1) Preparation of CDs-FcA precursor:
transferring 3mg of CDs and 0.48mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 140 ℃ for 4h, and cooling the solution for later use.
(2) Preparing an AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the solution is added with the CDs-FcA obtained in the step (1) and 0.244g of thioacetamide, ultrasonic stirring is carried out, hydrothermal reaction is carried out for 4 hours in an autoclave at the temperature of 110 ℃, and centrifugal washing is carried out after the hydrothermal reaction is finished, so that the AIZS-CDs-FcA composite photocatalyst is obtained.
Taking the middle sample in (2)0.02g of catalyst and 0.528g L-ascorbic acid were added to the photoreactor and N was passed through at a large flow rate2After the gas in the bottle is completely discharged, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analysis are carried out once at intervals of 1h, and the hydrogen production rate is calculated to be 0.58 mmol/g/h.
Example 11
(1) Preparation of CDs-FcA precursor:
and transferring 6mg of CDs and 0.96mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 110 ℃ for 4h, and cooling the solution for later use.
(2) Preparation of AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the solution is added with the CDs-FcA obtained in the step (1) and 0.244g of thioacetamide, ultrasonic stirring is carried out, hydrothermal reaction is carried out for 2 hours in an autoclave at the temperature of 110 ℃, and centrifugal washing is carried out after the hydrothermal reaction is finished, so that the AIZS-CDs-FcA composite photocatalyst is obtained.
Taking 0.02g of catalyst and 0.528g L-ascorbic acid of the sample in (2), adding the catalyst and the ascorbic acid into a photoreactor, and introducing N at a large flow rate2After the gas in the bottle is completely discharged, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analysis are carried out once at intervals of 1h, and the hydrogen production rate is calculated to be 0.7 mmol/g/h.
Example 12
(1) Preparation of CDs-FcA precursor:
and transferring 9mg of CDs and 1.44mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 130 ℃ for 4h, and cooling for later use.
(2) Preparation of AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the solution is added with the CDs-FcA obtained in the step (1) and 0.244g of thioacetamide, ultrasonic stirring is carried out, hydrothermal reaction is carried out for 3 hours in an autoclave at the temperature of 110 ℃, and centrifugal washing is carried out after the hydrothermal reaction is finished, so that the AIZS-CDs-FcA composite photocatalyst is obtained.
Taking 0.02g of the catalyst and 0.528g L-ascorbic acid as samples in (2), adding into the photoreactor, and introducing N at a large flow rate2After the gas in the bottle is completely discharged, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analysis are carried out once at intervals of 1h, and the hydrogen production rate is calculated to be 0.76 mmol/g/h.
Example 13
(1) Preparation of CDs-FcA precursor:
and transferring 15mg of CDs and 2.4mg of ferrocenecarboxylic acid solution into a transparent glass bottle, metering the volume to 20mL of solution, transferring the solution into an autoclave for hydrothermal reaction at 140 ℃ for 4h, and cooling for later use.
(2) Preparing an AIZS-CDs-FcA composite photocatalyst:
0.0576g of silver nitrate, 0.649g of indium nitrate, 0.186g of zinc acetate dihydrate and 0.6058g L-cysteine are weighed, mixed and dissolved in 50g of water, the solution is mixed, the pH value of the solution is adjusted to 8.5 by using 1M NaOH, the CDs-FcA and 0.244g of thioacetamide in the step (1) are added, the mixture is stirred ultrasonically, the hydrothermal reaction is carried out in an autoclave at the temperature of 110 ℃ for 4 hours, and after the reaction is finished, the composite photocatalyst AIZS-CDs-FcA is obtained through centrifugal washing.
Taking 0.02g of catalyst and 0.528g L-ascorbic acid of the sample in (2), adding the catalyst and the ascorbic acid into a photoreactor, and introducing N at a large flow rate2After the gas in the bottle is exhausted, a customized xenon lamp is turned on under the condition of magnetic stirring for irradiation, sampling and analyzing are carried out once every 1h, and the hydrogen production rate is calculated to be 0.73 mmol/g/h.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications, equivalents, flow charts, and other related technical fields that are made by the present invention will be included in the scope of the present invention.

Claims (6)

1.A preparation method of a functional carbon quantum dot modified Ag-In-Zn-S quantum dot is characterized by comprising the following steps:
A. mixing carbon quantum dots (CDs) with 1M ferrocenecarboxylic acid (FcA) solution taking dimethyl sulfoxide as a solvent, fixing the volume to 20mL by using distilled water, and carrying out hydrothermal reaction at 110-140 ℃ for 2-4 h to obtain a CDs-FcA precursor, wherein the mass fraction ratio of the CDs-FcA is 3-15%: 4-22%;
B. mixing silver nitrate, indium nitrate, zinc acetate and L-cysteine to obtain an aqueous solution, adjusting the pH value of the solution to 8.5 by using 1M NaOH, adding a CDs-FcA precursor and thioacetamide, ultrasonically stirring uniformly, carrying out hydrothermal reaction at 110 ℃ for 2-4 h, and carrying out centrifugal washing after the reaction is finished to obtain the functional carbon quantum dot modified Ag-In-Zn-S quantum dot, wherein the silver nitrate: indium nitrate: zinc acetate: l-cysteine: CDs-FcA precursor: thioacetamide: the mass ratio of water is 0.0288-0.0864: 0.649: 0.186: 0.6058: 0.003-0.018: 0.244:50.
2. The preparation method of the functional carbon quantum dot modified Ag-In-Zn-S quantum dot according to claim 1, wherein the preparation method comprises the following steps: and step A, mixing CDs with 1M ferrocenecarboxylic acid solution taking dimethyl sulfoxide as a solvent, metering the volume to 20mL by using distilled water, and carrying out hydrothermal reaction at 140 ℃ for 4 hours.
3. The preparation method of the functional carbon quantum dot modified Ag-In-Zn-S quantum dot according to claim 1, wherein the preparation method comprises the following steps: and B, carrying out hydrothermal reaction at 110 ℃ for 4 h.
4. The Ag-In-Zn-S quantum dot modified by the functional carbon quantum dot prepared by the method of any one of claims 1 to 3.
5. The functional carbon quantum dot modified Ag-In-Zn-S quantum dot of claim 4, wherein: the morphology is a structure of loading 0D-0D In an amorphous porous organic matter, FcA is an amorphous porous structure, and Ag-In-Zn-S quantum dots and CDs are uniformly loaded on FcA to fix the quantum dots and effectively increase the specific surface area of hole consumption.
6. The use of the functional carbon quantum dot as claimed In claim 4 or 5 to modify Ag-In-Zn-S quantum dots, wherein: the method is applied to photocatalytic hydrogen production.
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