CN113559881A - Composite photocatalyst, preparation method and application thereof in hydrogen production by decomposing water - Google Patents

Composite photocatalyst, preparation method and application thereof in hydrogen production by decomposing water Download PDF

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CN113559881A
CN113559881A CN202110922495.3A CN202110922495A CN113559881A CN 113559881 A CN113559881 A CN 113559881A CN 202110922495 A CN202110922495 A CN 202110922495A CN 113559881 A CN113559881 A CN 113559881A
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cds
cop
zif
composite photocatalyst
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陈哲
陈�峰
赵子铭
刘风磊
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Jilin Institute of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B01J35/33—
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

A composite photocatalyst compounded by CdS and CoP, a preparation method and application thereof in hydrogen production by catalytic decomposition of water under the irradiation of visible light belong to the technical field of photocatalysts. The composite photocatalyst is prepared by calcining and compounding CdS and CoP, wherein the mass dosage ratio (load) of the CoP to the CdS is 5-20: 100. the method comprises the steps of CdS precursor preparation, CdS @ ZIF-67 preparation, catalyst preparation and the like. Since CoP is a non-noble metal promoter, loading it on cadmium sulfide greatly reduces the cost of photocatalysis. The preparation method is simple and feasible, and is convenient for large-scale production. The CoP/CdS composite photocatalyst has higher activity of hydrogen production by photocatalytic decomposition of water, and when the load is optimal, the photocatalytic activity of the composite photocatalyst is more than 82 times of that of pure CdS, so that the electrochemical effect of the composite photocatalyst is greatly superior to that of CdS.

Description

Composite photocatalyst, preparation method and application thereof in hydrogen production by decomposing water
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a CdS and CoP compounded composite photocatalyst, a preparation method and application thereof in hydrogen production by catalytic decomposition of water under visible light irradiation.
Background
In this century, the human society faces two major problems: energy crisis and environmental pollution, the two major problems are caused by serious dependence on non-renewable energy sources such as petroleum, coal, natural gas and the like. In order to solve these problems, scientists have studied new materials and urgently needed to develop new renewable energy sources, and found that hydrogen energy is considered as an ideal substitute, and photocatalytic decomposition of water under visible light irradiation can well solve the problems. The cocatalyst has no catalytic performance, but the catalytic performance of the main catalyst can be obviously improved by adding a small amount of the cocatalyst. When the cocatalyst is transition metal phosphide, the photocatalyst has the advantages of low price, abundant reserves, capability of promoting light absorption, capability of improving the separation and transfer efficiency of a photoproduction electron hole pair by reducing the overpotential and the interface resistance of the material, forming a heterojunction to form energy band bending, forming a Schottky junction and serving as an electron bridge through the metal property, and capability of providing an active site for a photocatalytic reaction and promoting the generation of a surface reaction. The cobalt phosphide is one of transition metal phosphide, has excellent catalytic activity, can effectively improve the photocatalytic hydrogen production capacity by using the cobalt phosphide as a cocatalyst, and has low cost.
Disclosure of Invention
The invention aims to provide a composite photocatalyst compounded by CdS and CoP, a preparation method and application thereof in hydrogen production by photocatalytic decomposition of water under visible light irradiation, wherein the CdS is used as a main catalyst, and the CoP is used as a cocatalyst.
The composite photocatalyst is prepared by calcining and compounding CdS and CoP, wherein the mass dosage ratio (load) of the CoP to the CdS is 5-20: 100. the preparation method of the composite photocatalyst comprises the following steps:
(1) preparing a CdS precursor: weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 80-120 mL of deionized water, stirring for 1-3H, centrifuging and drying; then adding the two dry products into 30-50 mL of ethylenediamine together, and carrying out water-soluble reaction for 20-30 h at 170-190 ℃ to obtain a solid CdS precursor;
(2) preparation of CdS @ ZIF-67: dispersing 100mg of the CdS precursor obtained in the step (1) in 15-30 mL of methanol, carrying out ultrasonic treatment for 20-40 minutes, and then adding 25-100 mg of Co (NO 3). 6H2O to obtain a solution A; additionally weighing 25-150 mg of dimethyl imidazole, 20-40 mg of PVP and 10-20 mL of methanol solution, and reacting at room temperature for 4-10 hours to prepare a ZIF solution; quickly pouring the ZIF solution into the solution A, strongly stirring for 3-5 minutes at room temperature, standing the obtained mixture for 1.5-3.0 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell;
(3) carrying out phosphorization and calcination reaction on the CdS @ ZIF-67 obtained in the step (2) and sodium hypophosphite: the CdS @ ZIF and the sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 340-360 ℃ at the speed of 3-5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and calcined for 1.5-3.0 h, and finally the CdS and CoP composite photocatalyst is obtained in the porcelain boats containing the CdS @ ZIF.
And performing electrochemical measurement on the prepared composite photocatalyst by using an electrochemical workstation, wherein a three-electrode system is adopted, and Na2SO4 aqueous solution is used as electrolyte. Weighing 20mg of composite photocatalyst, dispersing the composite photocatalyst in 2-3 mL of ethanol, grinding for 8-10 min until the composite photocatalyst is a viscous suspension, transferring the viscous suspension to a 1.5 x 2cm2 Fluorine Tin Oxide (FTO) conductive glass sheet by using a spin coating method, and drying for 20-30 h at room temperature to obtain a working electrode, wherein the other two electrodes respectively use a platinum electrode as a counter electrode and a silver chloride electrode as a reference electrode. And when the transient photocurrent is measured, starting a 300w xenon lamp to irradiate the working electrode, and performing irradiation and non-irradiation treatment on the working electrode at the same time interval within the operation time of 0-600 s, wherein the test interval of switching the lamp each time is a period, and the period is cycled for multiple periods, so that the response curve (i-t) of the photocurrent of the working electrode along with the change of time is obtained. Under illumination, under the conditions that the scanning range is-1.4 to-0.6V and the sampling interval is 0.001V, the linear scanning volt-ampere characteristic curve (LSV) of the working electrode is measured. And measuring the Electrochemical Impedance Spectroscopy (EIS) of the working electrode in the environment with the frequency range of 0.01-100Hz and the voltage of 0-0.7V. The mott-schottky (MS) curve measurements of the working electrode were recorded at a frequency of 1000 Hz and a potential in the range of-1.5 to 0.6v (vs rhe).
Testing the hydrogen production performance: preparing a sulfide sacrificial agent solution by using 7-9 mL of sodium sulfide nonahydrate, 2-4 mL of anhydrous sodium sulfite and 100mL of distilled water, and adding the composite photocatalyst (the mass ratio of the composite photocatalyst to the volume of the sulfide sacrificial agent solution is 1 mg: 1-2 mL); and then, under the irradiation of visible light, selecting optical filters with the wavelength of 420nm to respectively perform hydrogen production tests on the solutions with different composite photocatalyst contents.
The invention has the beneficial effects that:
according to the composite photocatalyst compounded by CdS and CoP, CoP is a non-noble metal cocatalyst, so that the cost of photocatalysis is greatly reduced by loading the CoP on cadmium sulfide. The preparation method is simple and easy to implement, does not need expensive and complicated equipment, and is convenient for large-scale production. The CoP/CdS composite photocatalyst has higher activity of preparing hydrogen by decomposing water through photocatalysis. Wherein, when the load is optimal, the photocatalytic activity of the composite photocatalyst is more than 82 times of that of pure CdS, and the electrochemical effect of the composite photocatalyst is greatly superior to that of CdS.
Drawings
FIG. 1 is an SEM image of a 15% CoP/CdS nanowire catalyst.
FIG. 2 is an XRD pattern of the prepared CdS and 15% CoP/CdS composite photocatalyst.
FIG. 3 is a graph of photocatalytic hydrogen production for composite photocatalysts with different CoP loadings (5%, 10%, 15%, 20% correspond to the products of examples 2, 3, 1, 4, respectively).
FIG. 4 is an electrochemical LSV plot of CdS, CoP, and 15% CoP/CdS.
FIG. 5 is an electrochemical IT plot of CdS, CoP, and 15% CoP/CdS.
FIG. 6 is the electrochemical Mott-Schottky plot of CdS, CoP.
FIG. 7 is an electrochemical impedance plot of CdS, CoP, and 15% CoP/CdS.
As can be seen in FIG. 1, the 15% CoP/CdS composite is a well-defined one-dimensional nanofiber with a diameter of about 300 nanometers.
As can be seen in fig. 2, the XRD pattern of 15% CoP/CdS is essentially identical to that of CdS, where no diffraction peak of CoP is visible due to low loading and good dispersion of CoP.
As can be seen in FIG. 3, the prepared 15% CoP/CdS has excellent performance of hydrogen production by photocatalytic water decomposition under the irradiation of visible light, and the hydrogen production performance is as high as 4729.38 mu molg-1 h-1.
As can be seen in fig. 4, the CoP/CdS electrode with 15% by weight shows a lower breakthrough point compared to pure CdS, CoP, indicating that 15% CoP/CdS can promote the catalytic reduction of hydrogen ions to hydrogen by lowering the overpotential as a promoter.
As can be seen in fig. 5, the 15% CoP/CdS nanocomposite electrode has a significantly higher photocurrent density due to the rapid separation of electron-hole pairs at the electrode and electrolyte interface of 15% CoP/CdS.
As can be seen in fig. 6, CdS, CoP is shown to have a positive slope, indicating its n-type semiconductor properties.
As can be seen in fig. 7, the 15% wt CoP/CdS showed smaller arcs compared to pure CdS, CoP, indicating that the 15% CoP/CdS has faster interfacial charge transport and more efficient carrier separation capability.
Detailed Description
Example 1
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor was weighed, dispersed in 20mL of methanol, and sonicated for 30 minutes, followed by addition of 75mg of Co (NO 3). 6H2O to obtain solution A. Preparing ZIF from another beaker, weighing 150mg of dimethylimidazole, 40mg of PVP and 10mL of methanol solution, and reacting at room temperature for 8 hours to prepare a ZIF solution; and quickly pouring the ZIF solution into the solution A, violently stirring for 5 minutes at room temperature, standing the mixture for 2 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 15% CoP/CdS composite photocatalyst compounded by CdS and CoP is obtained in the porcelain boats containing the CdS @ ZIF, wherein the mass of the product is 115 mg. 50mg of the composite photocatalyst is added into 60mL of sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite and 100mL of distilled water, a 300W xenon lamp (a cut-off filter with the wavelength of 420nm is added to filter light below 420 nm) is used as a light source, the illumination time is 1 hour (the illumination intensity influences visible light catalysis, the stronger the light is, the more photons are, the more electrons are excited in unit time and area, the more electron-holes are, and the stronger the oxidizing power is), and a photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 4729.38 mu molg-1 h-1.
Example 2
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor was weighed, dispersed in 20mL of methanol, sonicated for 30 minutes, and then 25mg of Co (NO 3). 6H2O was added to obtain solution A. Preparing ZIF from another beaker, weighing 150mg of dimethylimidazole, 40mg of PVP and 10mL of methanol solution, and reacting at room temperature for 8 hours to prepare a ZIF solution; and quickly pouring the ZIF solution into the solution A, violently stirring for 5 minutes at room temperature, standing the mixture for 2 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 5% CoP/CdS composite photocatalyst compounded by CdS and CoP (the product mass is 105 mg) is obtained in the porcelain boats containing the CdS @ ZIF. 50mg of the composite photocatalyst is added into 60mL of sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite and 100mL of distilled water, a 300W xenon lamp (a cut-off filter with the wavelength of 420nm is added to filter light below 420 nm) is used as a light source, the illumination time is 1 hour (the illumination intensity influences visible light catalysis, the stronger the light is, the more photons are, the more electrons are excited in unit time and area, the more electron-holes are, and the stronger the oxidizing power is), and a photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 315.898 mu molg-1 h-1.
Example 3
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor is weighed, dispersed in 20mL of methanol, and subjected to ultrasonic treatment for 30 minutes, and then 50mg of Co (NO 3). 6H2O is added to obtain a solution A. Preparing ZIF from another beaker, weighing 150mg of dimethylimidazole, 40mg of PVP and 10mL of methanol solution, and reacting at room temperature for 8 hours to prepare a ZIF solution; and quickly pouring the ZIF solution into the solution A, violently stirring for 5 minutes at room temperature, standing the mixture for 2 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 10% CoP/CdS composite photocatalyst compounded by CdS and CoP (the product mass is 110 mg) is obtained in the porcelain boats containing the CdS @ ZIF. 50mg of the composite photocatalyst is added into 60mL of sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite and 100mL of distilled water, a 300W xenon lamp (a cut-off filter with the wavelength of 420nm is added to filter light below 420 nm) is used as a light source, the illumination time is 1 hour (the illumination intensity influences visible light catalysis, the stronger the light is, the more photons are, the more electrons are excited in unit time and area, the more electron-holes are, and the stronger the oxidizing power is), and a photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 1868.2993 mu molg-1 h-1.
Example 4
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor is weighed, dispersed in 20mL of methanol, and subjected to ultrasonic treatment for 30 minutes, and then 100mg of Co (NO 3). 6H2O is added to obtain a solution A. Preparing ZIF from another beaker, weighing 150mg of dimethylimidazole, 40mg of PVP and 10mL of methanol solution, and reacting at room temperature for 8 hours to prepare a ZIF solution; and quickly pouring the ZIF solution into the solution A, violently stirring for 5 minutes at room temperature, standing the mixture for 2 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 20% CoP/CdS composite photocatalyst compounded by CdS and CoP (the product mass is 120 mg) is obtained in the porcelain boats containing the CdS @ ZIF. 50mg of the composite photocatalyst was added to 60mL of a sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite, and 100mL of distilled water, and a 300W xenon lamp (with a 420nm cut-off filter added to filter light below 420 nm) was used as a light source, and the light irradiation time was 1 hour. (the light intensity influences the visible light catalysis, the stronger the light, the more photons, the more electrons are excited in unit time and area, the more electron-holes are, the stronger the oxidizing power is), and the photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 402.413 mu molg-1 h-1.
Example 5
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor is weighed, dispersed in 20mL of methanol, and subjected to ultrasonic treatment for 30 minutes, and then 0mg of Co (NO 3). 6H2O is added to obtain a solution A. Preparing ZIF from another beaker, weighing 150mg of dimethylimidazole, 40mg of PVP and 10mL of methanol solution, and reacting at room temperature for 8 hours to prepare a ZIF solution; and quickly pouring the ZIF solution into the solution A, violently stirring for 5 minutes at room temperature, standing the mixture for 2 hours, and centrifuging to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 0% CoP/CdS composite photocatalyst compounded by CdS and CoP (the product mass is 100 mg) is obtained in the porcelain boats containing the CdS @ ZIF. 50mg of the composite photocatalyst is added into 60mL of sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite and 100mL of distilled water, a 300W xenon lamp (a cut-off filter with the wavelength of 420nm is added to filter light below 420 nm) is used as a light source, the illumination time is 1 hour (the illumination intensity influences visible light catalysis, the stronger the light is, the more photons are, the more electrons are excited in unit time and area, the more electron-holes are, and the stronger the oxidizing power is), and a photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 67.425 mu molg-1 h-1.
Example 6
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor was weighed, dispersed in 20mL of methanol, and sonicated for 30 minutes, followed by addition of 75mg of Co (NO 3). 6H2O to obtain solution A. Preparing ZIF from another beaker, weighing 100mg of dimethylimidazole, 40mg of PVP and 10mL of methanol solution, and reacting at room temperature for 8 hours to prepare a ZIF solution; and quickly pouring the ZIF solution into the solution A, violently stirring for 5 minutes at room temperature, standing the mixture for 2 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 15% CoP/CdS composite photocatalyst compounded by CdS and CoP (the product quality is 114 mg) is obtained in the porcelain boats containing the CdS @ ZIF. 50mg of the composite photocatalyst is added into 60mL of sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite and 100mL of distilled water, a 300W xenon lamp (a cut-off filter with the wavelength of 420nm is added to filter light below 420 nm) is used as a light source, the illumination time is 1 hour (the illumination intensity influences visible light catalysis, the stronger the light is, the more photons are, the more electrons are excited in unit time and area, the more electron-holes are, and the stronger the oxidizing power is), and a photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 3213.725 mu molg-1 h-1.
Example 7
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor was weighed, dispersed in 20mL of methanol, and sonicated for 30 minutes, followed by addition of 75mg of Co (NO 3). 6H2O to obtain solution A. Preparing ZIF from another beaker, weighing 50mg of dimethylimidazole, 40mg of PVP and 10mL of methanol solution, and reacting at room temperature for 8 hours to prepare a ZIF solution; and quickly pouring the ZIF solution into the solution A, violently stirring for 5 minutes at room temperature, standing the mixture for 2 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 15% CoP/CdS composite photocatalyst compounded by CdS and CoP (the product mass is 112 mg) is obtained in the porcelain boats containing the CdS @ ZIF. 50mg of the composite photocatalyst is added into 60mL of sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite and 100mL of distilled water, a 300W xenon lamp (a cut-off filter with the wavelength of 420nm is added to filter light below 420 nm) is used as a light source, the illumination time is 1 hour (the illumination intensity influences visible light catalysis, the stronger the light is, the more photons are, the more electrons are excited in unit time and area, the more electron-holes are, and the stronger the oxidizing power is), and a photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 2985.6452 mu molg-1 h-1.
Example 8
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor was weighed, dispersed in 20mL of methanol, and sonicated for 30 minutes, followed by addition of 75mg of Co (NO 3). 6H2O to obtain solution A. Preparing ZIF from another beaker, weighing 25mg of dimethylimidazole, 40mg of PVP and 10mL of methanol solution, and reacting at room temperature for 8 hours to prepare a ZIF solution; and quickly pouring the ZIF solution into the solution A, violently stirring for 5 minutes at room temperature, standing the mixture for 2 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 15% CoP/CdS composite photocatalyst compounded by CdS and CoP (the product quality is 110 mg) is obtained in the porcelain boats containing the CdS @ ZIF. 50mg of the composite photocatalyst was added to 60mL of a sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite, and 100mL of distilled water, and a 300W xenon lamp (with a 420nm cut-off filter added to filter light below 420 nm) was used as a light source, and the light irradiation time was 1 hour. (the light intensity influences the visible light catalysis, the stronger the light, the more photons, the more electrons are excited in unit time and area, the more electron-holes are, the stronger the oxidizing power is), and the photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 2370.529 mu molg-1 h-1.
Example 9
Respectively weighing 3mmol of CdCl2 and 6mmol of C5H10NNaS2, respectively adding into 100mL of deionized water, stirring for 1H, centrifuging and drying; and then adding the two dry products into 40mL of ethylenediamine together, and carrying out water bath reaction at 180 ℃ for 24h to obtain a solid CdS precursor. 100mg of the precursor was weighed, dispersed in 20mL of methanol, and sonicated for 30 minutes, followed by addition of 75mg of Co (NO 3). 6H2O to obtain solution A. Preparing ZIF from another beaker, weighing 150mg of dimethylimidazole, 20mg of PVP and adding 10mL of methanol solution, quickly pouring ZIF into the solution A, violently stirring at room temperature, standing the mixture for 2h, centrifuging and drying to obtain CdS @ ZIF-67 with CdS as a core and ZIF as a shell. The CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 350 ℃ at the speed of 5 ℃/min in the hydrogen-argon atmosphere (the flow ratio of hydrogen to argon is 1: 20) and is calcined for 2 hours, and finally, a 15% CoP/CdS composite photocatalyst compounded by CdS and CoP (the product mass is 113 mg) is obtained in the porcelain boats containing the CdS @ ZIF. 50mg of the composite photocatalyst was added to 60mL of a sulfide sacrificial agent consisting of 8.43mL of sodium sulfide nonahydrate, 3.16mL of anhydrous sodium sulfite, and 100mL of distilled water, and a 300W xenon lamp (with a 420nm cut-off filter added to filter light below 420 nm) was used as a light source, and the light irradiation time was 1 hour. (the light intensity influences the visible light catalysis, the stronger the light, the more photons, the more electrons are excited in unit time and area, the more electron-holes are, the stronger the oxidizing power is), and the photocatalytic water hydrogen production experiment is carried out. The hydrogen production performance data is 4630.53 mu molg-1 h-1.
Example 10
Selecting the CoP/CdS composite photocatalyst with the highest hydrogen production performance in example 1, weighing 20mg of sample, dispersing the sample in 2mL of ethanol, grinding for 9min until the sample becomes viscous suspension, transferring the sample suspension onto a tin fluoride oxide (FTO) conductive glass sheet with the thickness of 1.5 multiplied by 2cm2 by using a spin coating method, and drying for 24h at room temperature to obtain the working electrode. And when the transient photocurrent is measured, starting a 300w xenon lamp to irradiate the working electrode, and performing irradiation and non-irradiation treatment on the working electrode at the same time interval within the operation time of 0-600 s, wherein the test interval of switching the lamp each time is a period, and the period is cycled for multiple periods, so that the response curve (i-t) of the photocurrent changing along with the time is obtained. Under illumination, under the conditions that the scanning range is-1.4 to-0.6V and the sampling interval is 0.001V, the linear scanning volt-ampere characteristic curve (LSV) of the working electrode is measured. The Electrochemical Impedance Spectroscopy (EIS) of the working electrode was measured in the frequency range of 0.01-100Hz and the voltage range of 0-0.7V. The mott-schottky (MS) curve measurements of the working electrode were recorded at a frequency of 1000 Hz and a potential in the range of-1.5 to 0.6v (vs rhe).

Claims (6)

1. A preparation method of a CdS and CoP composite photocatalyst comprises the following steps:
(1) preparing a CdS precursor: 3mmol of CdCl are weighed2And 6mmol C5H10NNaS2Respectively adding the mixture into 80-120 mL of deionized water, stirring for 1-3 h, centrifuging and drying; then adding the two dry products into 30-50 mL of ethylenediamine together, and carrying out water-soluble reaction for 20-30 h at 170-190 ℃ to obtain a solid CdS precursor;
(2) preparation of CdS @ ZIF-67: dispersing 100mg of CdS precursor obtained in the step (1) in 15-30 mL of methanol, carrying out ultrasonic treatment for 20-40 minutes, and then adding 25-100 mg of Co (NO)3)·6H2O, obtaining a solution A; additionally weighing 25-150 mg of dimethyl imidazole, 20-40 mg of PVP and 10-20 mL of methanol solution, and reacting at room temperature for 4-10 hours to prepare a ZIF solution; quickly pouring the ZIF solution into the solution A, strongly stirring for 3-5 minutes at room temperature, standing the obtained mixture for 1.5-3.0 hours, centrifuging and drying to obtain CdS @ ZIF-67 taking CdS as a core and ZIF as a shell;
(3) carrying out phosphorization and calcination reaction on the CdS @ ZIF-67 obtained in the step (2) and sodium hypophosphite: the CdS @ ZIF and sodium hypophosphite are respectively placed in two porcelain boats in a tubular furnace, the porcelain boats containing the sodium hypophosphite are placed close to the direction of blown gas, the tubular furnace is heated to 340-360 ℃ at the speed of 3-5 ℃/min under the atmosphere of hydrogen and argon and calcined for 1.5-3.0 hours, and finally the composite photocatalyst compounded by CdS and CoP is obtained in the porcelain boats containing the CdS @ ZIF, wherein the flow ratio of hydrogen to argon is 1: 20.
2. a composite photocatalyst compounded by CdS and CoP is characterized in that: is prepared by the method of claim 1.
3. The CdS @ CoP nanowire of CoP compounded CdS is characterized in that the length of the CdS and CoP compounded nanowire prepared by the preparation method in claim 1 is 300-800nm, and the dispersibility is good.
4. The CdS @ CoP nanowire of CoP composite CdS is characterized in that the nanowire prepared by the preparation method of claim 1 can clearly see that CoP nanoparticles are well attached to the CdS nanowire.
5. The use of the composite photocatalyst of CdS and CoP as defined in claim 2 in photocatalytic decomposition of water under irradiation of visible light to produce hydrogen.
6. The application of the CdS and CoP compounded composite photocatalyst as defined in claim 3 in hydrogen production by photocatalytic decomposition of water under the irradiation of visible light, wherein the CdS and CoP compounded composite photocatalyst is characterized in that: preparing a sulfide sacrificial agent solution by using 7-9 mL of sodium sulfide nonahydrate, 2-4 mL of anhydrous sodium sulfite and 100mL of distilled water, and adding the composite photocatalyst of claim 2, wherein the mass ratio of the composite photocatalyst to the sulfide sacrificial agent solution is 1 mg: 1-2 mL; and finally, under the irradiation of visible light, selecting an optical filter with the wavelength of 420nm to carry out photocatalytic hydrogen production.
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