CN115739163A - Sulfide-nitride heterojunction composite photocatalyst and preparation method and application thereof - Google Patents
Sulfide-nitride heterojunction composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 claims description 22
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- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 20
- 235000019254 sodium formate Nutrition 0.000 claims description 20
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention discloses a sulfide-nitride heterojunction composite photocatalyst and a preparation method and application thereof, wherein a two-dimensional layered W is used 2 N 3 Dispersing the nanosheets into ethylenediamine, adding cadmium acetate after uniform dispersion, adding an ethylenediamine solution containing l-cysteine, and then carrying out solvothermal reaction. The invention successfully constructs the heterojunction of cadmium sulfide and tungsten nitride for the first time, and the prepared composite material of the one-dimensional cadmium sulfide and the two-dimensional tungsten nitride heterojunction has good photoresponse, can catalyze and reform formic acid to generate hydrogen or synthesis gas under the irradiation of simulated sunlight, and shows good photocatalytic activity and controllability of reaction selectivity. The method is simple to operate and good in repeatability.
Description
Technical Field
The invention belongs to the field of hydrogen energy preparation, relates to a photocatalytic clean preparation technology of hydrogen energy, and particularly relates to a sulfide-nitride heterojunction composite photocatalyst as well as a preparation method and application thereof.
Background
Formic acid (HCOOH, FA) as a biomass contains a high content of hydrogen (H) 2 4.4 wt.%) and carbon monoxide (CO, 60 wt.%in the total weight of the catalyst mixture) It is an ideal energy storage material. Formic acid is renewable and can be produced from biomass or by direct hydrogenation or electrochemical reduction of carbon dioxide (CO) 2 ) Regeneration is carried out. In the past decades, photocatalysis has received great attention as a green solar energy conversion technology and has been used for formic acid reforming. Initially, a large number of noble metal-based catalysts were used for hydrogen production by photocatalytic reforming of formic acid, due to the excellent catalytic performance of noble metal promoters. However, due to the rarity and high cost of noble metals, noble metal-free photocatalyst systems have received more attention in recent years, but there is still room for great improvements in efficiency. On the other hand, the photocatalytic reforming of formic acid to produce CO, which is a valuable chemical feedstock in the chemical industry. For example, synthesis gas (a mixture of carbon monoxide and hydrogen) can be used to generate high value chemicals via the fischer-tropsch process. Therefore, it is of great significance to develop a photocatalytic system with high efficiency, low cost and controllable selectivity for formic acid reforming.
The principle of preparing hydrogen by photocatalytic reforming of formic acid is as follows: under the irradiation of certain energy light, the semiconductor photocatalyst is excited by light to generate electron and hole pairs, then the electrons migrate to the surface of the catalyst to reduce protons in a reaction system into hydrogen, and the holes migrate to the surface of the catalyst to perform oxidation reaction with formate. Generally, there are two reaction paths for photocatalytic reforming of formic acid, namely dehydrogenation reaction in which products are hydrogen and carbon dioxide and dehydration reaction in which products are carbon monoxide and water, and the two reactions are in a competitive relationship in a catalytic system, which often results in low selectivity for photocatalytic reforming of formic acid to produce hydrogen or carbon monoxide. In addition, the fixed proportion of the generated hydrogen and carbon monoxide for the synthesis gas is not beneficial to the flexible application of the photocatalytic reforming formic acid system.
Disclosure of Invention
The invention aims to provide a sulfide-nitride heterojunction composite photocatalyst as well as a preparation method and application thereof, so as to realize the efficient photocatalytic preparation of solar fuel by the photocatalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a sulfide-nitride heterojunction composite photocatalyst comprises the following steps:
two-dimensional layered W 2 N 3 Dispersing the nanosheets into ethylenediamine, adding cadmium acetate after uniform dispersion, adding an ethylenediamine solution containing l-cysteine, and then carrying out solvothermal reaction to obtain the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
Further, two-dimensional layered W 2 N 3 The dosage ratio of the nano sheets to the ethylenediamine is 10-100 mg:30mL.
Further, two-dimensional layered W 2 N 3 The dosage ratio of the nano sheets to the cadmium acetate is 10-100 mg:2mmol.
Further, two-dimensional layered W 2 N 3 The dosage ratio of the nano-sheets to the l-cysteine is 10mg-100mg:4mmol of the total weight of the solution.
Further, an ethylenediamine solution containing l-cysteine was prepared by adding l-cysteine to ethylenediamine, wherein the amount ratio of l-cysteine to ethylenediamine was 4mmol:20mL.
Furthermore, the temperature of the solvothermal reaction is 175-185 ℃ and the time is 24-48 hours.
Further, two-dimensional layered W 2 N 3 The nanosheet is prepared by the following process: WO (International patent application) 3 Powder and Na 2 WO 4 ·2H 2 Mixing O powder uniformly, and keeping the temperature at 730-750 ℃ for 5-6 hours under the protective atmosphere to obtain two-dimensional layered W 2 N 3 Nanosheets.
Further, WO 3 Powder and Na 2 WO 4 ·2H 2 The molar ratio of O powder is 1-5;
the protective atmosphere is a mixed gas of argon and ammonia gas or ammonia gas;
at a rate of 1-3 deg.C/min -1 The rate of temperature rise is from 25 ℃ to 730-750 ℃.
A sulfide-nitride heterojunction composite photocatalyst prepared by the method.
A sulfide-nitride heterojunction composite photocatalyst is applied to preparing hydrogen or synthesis gas by photocatalytic reforming formic acid.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material for the first time, the composite material utilizes the capability of the one-dimensional cadmium sulfide to generate a photon-generated carrier and the special reaction active site of the two-dimensional tungsten nitride, has excellent performance of photocatalytic reforming formic acid, and can realize the conversion of products in the photocatalytic reforming formic acid reaction through the concentration of formic acid or the concentration of sodium formate in a reaction system. The raw materials of the invention are cheap and easy to obtain, the operation is simple, and the repeatability of the preparation method is good.
Furthermore, the reaction time in the invention is not less than 24 hours, which is to satisfy the nucleation growth of the one-dimensional cadmium sulfide in the solvothermal reaction process, and if the reaction time is too short, cadmium sulfide which is not in a one-dimensional structure exists in the obtained composite material, the efficiency of the photocatalytic reforming of formic acid is reduced.
Further, the temperature requirement of 730-750 ℃ in the present invention is because Na is contained when the temperature is higher than 730 ℃ 2 WO 4 Can be melted into two-dimensional tungsten nitride (W) 2 N 3 ) The growth reaction of (2) provides an environment of molten salt, and other types of tungsten nitride can be obtained at the temperature higher than 750 ℃, so that the adjustment of the selectivity of the photocatalytic reformed formic acid cannot be realized.
The one-dimensional cadmium sulfide in the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material prepared by the invention has excellent capability of generating photon-generated carriers, and provides a basis for efficiently carrying out photocatalytic reforming on formic acid. The two-dimensional tungsten nitride has similar metallicity, and the work function of the two-dimensional tungsten nitride is higher than that of the one-dimensional cadmium sulfide, so that a built-in electric field is formed between the one-dimensional cadmium sulfide and the two-dimensional tungsten nitride when the two-dimensional tungsten nitride and the one-dimensional cadmium sulfide are constructed into the heterojunction composite material, thereby promoting the separation of electrons and holes in a photon-generated carrier generated by the one-dimensional cadmium sulfide, and avoiding the carrierThe efficiency of photocatalysis is further improved by the sub-compounding. The two-dimensional tungsten nitride provides a (110) crystal face suitable for hydrogen evolution reaction and a nitrogen vacancy suitable for carbon monoxide evolution reaction, and the two reactions are influenced by proton concentration and formate concentration, so that the selectivity of the photocatalytic reformed formic acid can be regulated by adjusting the concentration of formic acid or sodium formate. The composite material has good photoresponse, can catalytically reform formic acid to generate hydrogen or synthesis gas under the irradiation of simulated sunlight, shows good photocatalytic activity and controllability of reaction selectivity, and has the photocatalytic hydrogen production rate of 1109.64 +/-30.31 mu mol h -1 The hydrogen production quantum efficiency at 420nm is 61.00%, the quantum efficiency of the synthesis gas can reach 76.84%, and the synthesis gas has good stability.
Drawings
FIG. 1 shows one-dimensional cadmium sulfide (CdS) and two-dimensional tungsten nitride (W) 2 N 3 ) And one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material (CdS/W) 2 N 3 ) X-ray diffraction (XRD) pattern of (a).
FIG. 2 is a Transmission Electron Micrograph (TEM) of a one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite.
Fig. 3 is an enlarged view of fig. 2 at block.
FIG. 4 is a graph of photocatalytic hydrogen production rate under simulated sunlight under a one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
FIG. 5 is a test chart of the photocatalytic stability of the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
FIG. 6 is a test chart of the activity and selectivity of the photocatalytic reforming formic acid of the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material under different sodium formate concentrations.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments in conjunction with the accompanying drawings.
The invention relates to a technology for preparing hydrogen energy at low cost by simulating and utilizing solar energy to realize photocatalytic reforming of formic acid, and provides a one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material which can realize photocatalytic reforming of formic acid to prepare hydrogen and selectively prepare synthesis gas and is beneficial to industrial application of photocatalytic reforming formic acid.
A preparation method of a sulfide-nitride heterojunction composite photocatalyst comprises the following steps:
the method comprises the following steps: first, 0.01mol of WO 3 Powder and 0.01mol of Na 2 WO 4 ·2H 2 O powder (molar ratio 1-5) was ball milled at 400rpm for 60min for mixing. Then, 100mg of the resulting mixture was uniformly placed in a magnetic boat. In the mixed gas of argon and ammonia (the volume percentage of ammonia is 5%) or ammonia atmosphere, the prepared precursor is heated at 1-3 deg.C/min -1 The temperature is raised from 25 ℃ to 730-750 ℃ at the temperature raising rate, kept at 730-750 ℃ for 5-6 hours and then naturally cooled to room temperature. Finally, the product was ultrasonically cleaned in deionized water for 30 minutes to dissolve Na 2 WO 4 Then filtering, washing and freeze-drying to obtain two-dimensional layered W 2 N 3 A nanosheet.
Step two: 10mg-100mg of the two-dimensional layered W obtained in the first step 2 N 3 The nanosheets were dispersed into 30mL of ethylenediamine using an ultrasonic sonicator and sonicated for 20 minutes. Then, the mixture was stirred at room temperature for 12 hours, and 2mmol of cadmium acetate was added to the above mixed suspension. Subsequently, 20mL of an ethylenediamine solution containing 4mmol l-cysteine was slowly dropped into the above mixed suspension while stirring for 2 hours. Thereafter, the mixture was transferred to a 100mL Teflon liner and sealed with a stainless steel autoclave and reacted at 175-185 ℃ for 24-48 hours. And cooling to room temperature, collecting precipitates by a centrifugal method, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying for 12 hours in vacuum at 80 ℃ to obtain the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
Different masses (10 mg-100mg, preferably 10mg, 30mg, 50mg, 70mg and 100 mg) of W 2 N 3 Different one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite materials (CdS/W) are prepared by using the nano sheets 2 N 3 ) Designated CW-1, CW-3, CW-5, CW-7 and CW-10, respectively.
Step three: and (3) adding the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material prepared in the second step into a formic acid aqueous solution to perform a photocatalytic reforming formic acid test. The method comprises the following specific steps:
1) Adding 4mg of one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction photocatalyst into a reactor with the volume of 105mL, and adding 80mL of formic acid aqueous solution with the total volume;
2) Introducing argon into the reactor for purging for 15min before illumination to remove air in the system;
3) And turning on a magnetic stirrer and turning on a xenon lamp power supply.
A sulfide-nitride heterojunction composite photocatalyst is applied to preparing hydrogen or synthesis gas by photocatalytic reforming formic acid.
Example 1
The method comprises the following steps: first, 0.01mol of WO 3 Powder and 0.01mol of Na 2 WO 4 ·2H 2 O powder (molar ratio 1. Then, 100mg of the resulting mixture was uniformly placed in a magnetic boat. At NH 3 Under the atmosphere, the prepared precursor is heated at 1 ℃/min -1 At a heating rate of 25 ℃ to 750 ℃ and kept at 750 ℃ for 5 hours, and then naturally cooled to room temperature. Finally, the product was ultrasonically cleaned in deionized water for 30 minutes to dissolve Na 2 WO 4 Then filtering, washing and freeze-drying to obtain the two-dimensional layered W 2 N 3 Nanosheets.
Step two: the two-dimensional layered W obtained in the step one 2 N 3 The nanosheets were dispersed into 30mL of ethylenediamine using an ultrasonic sonicator and sonicated for 20 minutes. Then, the mixture was stirred at room temperature for 12 hours, and 2mmol of cadmium acetate was added to the above mixed suspension. Subsequently, 20mL of an ethylenediamine solution containing 4mmol of l-cysteine was slowly dropped into the above mixed suspension while stirring for 2 hours. Thereafter, the mixture was transferred to a 100mL Teflon liner and sealed with a stainless steel autoclave and reacted at 180 ℃ for 24 hours.After cooling to room temperature, the precipitate was collected by centrifugation, washed 3 times with deionized water and absolute ethanol, respectively, and vacuum-dried at 80 ℃ for 12 hours. Different masses (10 mg, 30mg, 50mg, 70mg and 100 mg) of W 2 N 3 Different one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite materials (CdS/W) are prepared by using the nano sheets 2 N 3 ) Designated CW-1, CW-3, CW-5, CW-7 and CW-10, respectively.
Step three: and (3) adding the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material prepared in the second step into 4M formic acid aqueous solution to perform a photocatalytic reforming formic acid test. The method comprises the following specific steps:
1) Adding 4mg of one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction photocatalyst into a reactor with the volume of 105mL, and adding 4mol/L formic acid aqueous solution with the total volume of 80 mL;
2) Introducing argon into the reactor for purging for 15min before illumination to remove air in the system;
3) Turning on a magnetic stirrer and a xenon lamp power supply;
example 2
The method comprises the following steps: first, 0.01mol of WO 3 Powder and 0.01mol of Na 2 WO 4 ·2H 2 O powder (molar ratio 1) was ball milled at 400rpm for 60min for mixing. Then, 100mg of the resulting mixture was uniformly placed in a magnetic boat. At NH 3 Under the atmosphere, the prepared precursor is heated at 1 ℃/min -1 Is raised from 25 ℃ to 750 ℃ at the temperature raising rate, is kept at 750 ℃ for 5 hours, and is naturally cooled to room temperature. Finally, the product was ultrasonically cleaned in deionized water for 30 minutes to dissolve Na 2 WO 4 Then filtering, washing and freeze-drying to obtain two-dimensional layered W 2 N 3 A nanosheet.
Step two: the two-dimensional layer W obtained in the step one 2 N 3 The nanosheets were dispersed into 30mL of ethylenediamine using an ultrasonic sonicator and sonicated for 20 minutes. Then, the mixture was stirred at room temperature for 12 hours, and 2mmol of cadmium acetate was added to the above mixed suspension. Subsequently, 20mL of an ethylenediamine solution containing 4mmol of l-cysteine was slowly dropped into the mixed suspension while stirring for 2 hoursIn the suspension. Thereafter, the mixture was transferred to a 100mL Teflon liner and sealed with a stainless steel autoclave and reacted at 180 ℃ for 24 hours. After cooling to room temperature, the precipitate was collected by centrifugation, washed 3 times with deionized water and absolute ethanol, respectively, and vacuum-dried at 80 ℃ for 12 hours. 50mg W 2 N 3 One-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material (CdS/W) prepared by using nano sheets 2 N 3 ) Named CW-5.
Step three: and (3) adding the CW-5 prepared in the step (II) into 8M formic acid aqueous solution with sodium formate of different concentrations to perform a photocatalytic reforming formic acid test. The method comprises the following specific steps:
1) Adding 4mg of one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction photocatalyst (CW-5) into a reactor with the volume of 105mL, and adding 8mol/L formic acid aqueous solution with different sodium formate concentrations (0 mol/L, 0.5mol/L, 1mol/L, 2mol/L, 4mol/L and 6 mol/L) with the total volume of 80 mL;
2) Introducing argon into the reactor for purging for 15min before illumination to remove air in the system;
3) And turning on the magnetic stirrer and turning on the xenon lamp power supply.
FIG. 1 shows one-dimensional cadmium sulfide (CdS) and two-dimensional tungsten nitride (W) 2 N 3 ) And one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material (CdS/W) 2 N 3 ) The obtained composite material has one-dimensional cadmium sulfide (CdS) and two-dimensional tungsten nitride (W) simultaneously 2 N 3 ) Characteristic peak of (2). The XRD results indicate that the composite material is composed of one-dimensional cadmium sulfide and two-dimensional tungsten nitride.
Fig. 2 and 3 are Transmission Electron Micrographs (TEM) of one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite materials. The obtained composite material is further proved to be composed of one-dimensional cadmium sulfide and two-dimensional tungsten nitride, and the two materials are in contact with each other to form a heterojunction.
FIG. 4 is a graph showing the photocatalytic hydrogen production rate under simulated sunlight under a one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material, and the photocatalytic reforming formic acid hydrogen production rate of a sample CW-5 reaches 408.90 +/-48.46 mu mol h -1 Apparent quantum efficiency measured at 420nmThe rate is 61.00 percent (the calculation formula of the apparent quantum efficiency AQY (%) of the photocatalytic hydrogen production reaction is
FIG. 5 is a photo-catalytic stability test chart of the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material, which shows that the catalyst has good stability.
FIG. 6 is a graph showing the activity and selectivity of the photocatalytic reforming formic acid of the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material under different sodium formate concentrations, and in 8mol/L formic acid aqueous solution, when the concentration of sodium formate in the system is increased from 0mol/L to 6mol/L, H is added 2 The selectivity of the composite material is gradually adjusted from 91% to 32%, which proves that the selectivity of the photocatalytic reformed formic acid can be adjusted and controlled by adjusting the concentration of sodium formate in the photocatalytic reformed formic acid system of the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
Example 3
The method comprises the following steps: first, 0.01mol of WO 3 Powder and Na 2 WO 4 ·2H 2 O powder (molar ratio 1. Then, 100mg of the mixture was uniformly placed in a magnetic boat. In the atmosphere of the mixed gas of argon and ammonia (the volume percentage of ammonia is 5 percent), at the temperature of 2 ℃/min -1 At a heating rate of 25 ℃ to 750 ℃ for 5 hours, and then naturally cooling to room temperature. Finally, the product was ultrasonically cleaned in deionized water for 30 minutes to dissolve Na 2 WO 4 Then filtering, washing and freeze-drying to obtain the two-dimensional layered W 2 N 3 Nanosheets.
Step two: 10mg of the two-dimensional layer W obtained in the first step 2 N 3 The nanosheets were dispersed into 30mL of ethylenediamine using an ultrasonic sonicator and sonicated for 20 minutes. Then, the mixture was stirred at room temperature for 12 hours, and 2mmol of cadmium acetate was added to the above mixed suspension. Subsequently, 20mL of an ethylenediamine solution containing 4mmol of l-cysteine was slowly dropped into the above mixed suspension while stirring for 2 hours. Thereafter, the mixture was transferred to a 100mL polytetrafluoroethylene liner and usedThe steel autoclave was sealed and reacted at 175 ℃ for 28 hours. And cooling to room temperature, collecting precipitates by a centrifugal method, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and performing vacuum drying for 12 hours at 80 ℃ to prepare the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
Example 4
The method comprises the following steps: first, 0.01mol of WO 3 Powder and Na 2 WO 4 ·2H 2 O powder (molar ratio 1. Then, 100mg of the mixture was uniformly placed in a magnetic boat. In the atmosphere of the mixed gas of argon and ammonia (the volume percentage of ammonia is 5 percent), at the temperature of 3 ℃/min -1 The temperature is raised from 25 ℃ to 730 ℃ at the temperature raising rate, and the temperature is naturally cooled to room temperature after the temperature is kept for 6 hours. Finally, the product was ultrasonically cleaned in deionized water for 30 minutes to dissolve Na 2 WO 4 Then filtering, washing and freeze-drying to obtain the two-dimensional layered W 2 N 3 Nanosheets.
Step two: 15mg of the two-dimensional layer W obtained in the first step 2 N 3 The nanosheets were dispersed into 30mL of ethylenediamine using an ultrasonic sonicator and sonicated for 20 minutes. Then, the mixture was stirred at room temperature for 12 hours, and 2mmol of cadmium acetate was added to the above mixed suspension. Subsequently, 20mL of an ethylenediamine solution containing 4mmol of l-cysteine was slowly dropped into the above mixed suspension while stirring for 2 hours. Thereafter, the mixture was transferred to a 100mL Teflon liner and sealed with a stainless steel autoclave and reacted at 185 ℃ for 24 hours. And cooling to room temperature, collecting precipitates by a centrifugal method, washing the precipitates respectively for 3 times by using deionized water and absolute ethyl alcohol, and performing vacuum drying at 80 ℃ for 12 hours to prepare the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
Example 5
The method comprises the following steps: first, 0.01mol of WO 3 Powder and Na 2 WO 4 ·2H 2 O powder (molar ratio 1. Then, 100mg of the mixture was uniformly placed in a magnetic boat. In an ammonia atmosphere at 3 deg.C/min -1 The temperature is raised from 25 ℃ to 740 ℃ at the temperature raising rate of (2) and kept for 5 hours, and then the temperature is naturally cooled to room temperature. Finally, the product was ultrasonically cleaned in deionized water for 30 minutes to dissolve Na 2 WO 4 Then filtering, washing and freeze-drying to obtain two-dimensional layered W 2 N 3 Nanosheets.
Step two: 20mg of the two-dimensional layer W obtained in the first step 2 N 3 The nanosheets were dispersed into 30mL of ethylenediamine using an ultrasonic sonicator and sonicated for 20 minutes. Then, the mixture was stirred at room temperature for 12 hours, and 2mmol of cadmium acetate was added to the above mixed suspension. Subsequently, 20mL of an ethylenediamine solution containing 4mmol l-cysteine was slowly dropped into the above mixed suspension while stirring for 2 hours. Thereafter, the mixture was transferred to a 100mL Teflon liner and sealed with a stainless steel autoclave and reacted at 178 ℃ for 26 hours. And cooling to room temperature, collecting precipitates by a centrifugal method, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and performing vacuum drying for 12 hours at 80 ℃ to prepare the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
Example 6
The method comprises the following steps: first, 0.01mol of WO 3 Powder and Na 2 WO 4 ·2H 2 O powder (molar ratio 1. Then, 100mg of the mixture was uniformly placed in a magnetic boat. In the atmosphere of the mixed gas of argon and ammonia (the volume percentage of ammonia is 5 percent), at the temperature of 2 ℃/min -1 The temperature is raised from 25 ℃ to 750 ℃ at the temperature raising rate of (2) and kept for 6 hours, and then the temperature is naturally cooled to room temperature. Finally, the product was ultrasonically cleaned in deionized water for 30 minutes to dissolve Na 2 WO 4 Then filtering, washing and freeze-drying to obtain the two-dimensional layered W 2 N 3 Nanosheets.
Step two: 80mg of the two-dimensional layered W obtained in the first step 2 N 3 The nanosheets were dispersed into 30mL of ethylenediamine using an ultrasonic sonicator and sonicated for 20 minutes. Then, the mixture was stirred at room temperature for 12 hours, and 2mmol of cadmium acetate was added to the above mixed suspension. Subsequently, 20 hours of stirring were carried outA mL of an ethylenediamine solution containing 4mmol of l-cysteine was slowly dropped into the mixed suspension. Thereafter, the mixture was transferred to a 100mL Teflon liner and sealed with a stainless steel autoclave and reacted at 185 ℃ for 25 hours. And cooling to room temperature, collecting precipitates by a centrifugal method, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and performing vacuum drying for 12 hours at 80 ℃ to prepare the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
Example 7
CW-5 prepared in example 2 was added to a mixed aqueous solution of formic acid and sodium formate having a sodium formate concentration and a formic acid concentration added to 8mol/L to perform a photocatalytic reforming formic acid test. The method comprises the following specific steps:
1) Adding 4mg of one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction photocatalyst (CW-5) into a reactor with the volume of 105mL, and adding a mixed aqueous solution containing 0mol/L of sodium formate and 8mol/L of formic acid, 1mol/L of sodium formate and 7mol/L of formic acid, 2mol/L of sodium formate and 6mol/L of formic acid, 4mol/L of sodium formate and 4mol/L of formic acid, 6mol/L of sodium formate and 2mol/L of formic acid, 7mol/L of sodium formate and 1mol/L of formic acid and 8mol/L of sodium formate and 0mol/L of formic acid into the reactor with the total volume of 80 mL;
2) Introducing argon into the reactor for purging for 15min before illumination to remove air in the system;
3) And turning on the magnetic stirrer and turning on the xenon lamp power supply.
In example 7, the photocatalytic hydrogen production rate reaches 1109.64 +/-30.31 mu mol h -1 。
Example 8
CW-5 prepared in example 2 was added to a 7mol/L aqueous formic acid solution containing 1mol/L sodium formate to conduct a photocatalytic reforming formic acid test. The method comprises the following specific steps:
1) Adding 12mg of one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction photocatalyst (CW-5) into a reactor with the volume of 105mL, and adding 7mol/L formic acid aqueous solution containing 1mol/L sodium formate with the total volume of 80 mL;
2) Introducing argon into the reactor for purging for 15min before illumination to remove air in the system;
3) The magnetic stirrer was started and the xenon lamp power supply with the 420nm bandpass filter was turned on.
In example 8, the quantum efficiency of hydrogen production at 420nm is 61.00%, and the quantum efficiency of synthesis gas production can reach 76.84%, and the synthesis gas has good stability.
The invention discloses a photocatalytic water splitting system with spatially separated active sites, which is characterized in that hydrogen and carbon monoxide of photocatalytic reforming formic acid are respectively generated at active sites at different positions on a catalyst, the activity of different active sites is regulated and controlled by regulating and controlling the concentration of protons and formate radicals in a reaction system to realize the selective regulation and control of the reaction system, and the flexible preparation of hydrogen and synthesis gas with different proportions by photocatalytic reforming formic acid is realized.
The invention successfully constructs the heterojunction of cadmium sulfide and tungsten nitride for the first time, and the prepared composite material of the one-dimensional cadmium sulfide and the two-dimensional tungsten nitride heterojunction has good photoresponse, can catalyze and reform formic acid to generate hydrogen or synthesis gas under the irradiation of simulated sunlight, and shows good photocatalytic activity and controllability of reaction selectivity.
The method is simple to operate and good in repeatability, and provides a reliable scheme for improving the development and application of a novel photocatalyst for photocatalytic reforming of formic acid.
Claims (10)
1. The preparation method of the sulfide-nitride heterojunction composite photocatalyst is characterized by comprising the following steps of:
two-dimensional layered W 2 N 3 Dispersing the nanosheets into ethylenediamine, adding cadmium acetate after uniform dispersion, adding an ethylenediamine solution containing l-cysteine, and then carrying out solvothermal reaction to obtain the one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction composite material.
2. The method for preparing a sulfide-nitride heterojunction composite photocatalyst as claimed in claim 1, wherein the two-dimensional layered W is 2 N 3 The dosage ratio of the nano-sheets to the ethylenediamine is10mg-100mg：30mL。
3. The method for preparing a sulfide-nitride heterojunction composite photocatalyst as claimed in claim 1, wherein the two-dimensional layered W is 2 N 3 The dosage ratio of the nano sheets to the cadmium acetate is 10-100 mg:2mmol of the resulting solution.
4. The method for preparing a sulfide-nitride heterojunction composite photocatalyst as claimed in claim 1, wherein the two-dimensional layered W is 2 N 3 The dosage ratio of the nano-sheets to the l-cysteine is 10mg-100mg:4mmol.
5. The method for preparing the sulfide-nitride heterojunction composite photocatalyst as claimed in claim 1, wherein the l-cysteine-containing ethylenediamine solution is prepared by adding l-cysteine to ethylenediamine, wherein the dosage ratio of l-cysteine to ethylenediamine is 4mmol:20mL.
6. The method for preparing the sulfide-nitride heterojunction composite photocatalyst as claimed in claim 1, wherein the temperature of the solvothermal reaction is 175-185 ℃ and the time is 24-48 hours.
7. The method for preparing the sulfide-nitride heterojunction composite photocatalyst as claimed in claim 1, wherein the two-dimensional layered W is 2 N 3 The nanosheet is prepared by the following process: mixing WO 3 Powder and Na 2 WO 4 ·2H 2 Mixing O powder, and keeping the temperature at 730-750 ℃ for 5-6 hours in a protective atmosphere to obtain two-dimensional layered W 2 N 3 A nanosheet.
8. The method for preparing a sulfide-nitride heterojunction composite photocatalyst as claimed in claim 7, wherein WO is 3 Powder and Na 2 WO 4 ·2H 2 The molar ratio of O powder is 1-5;
the protective atmosphere is a mixed gas of argon and ammonia gas or ammonia gas;
at a rate of 1-3 deg.C/min -1 The rate of temperature rise is from 25 ℃ to 730-750 ℃.
9. A sulfide-nitride heterojunction composite photocatalyst prepared according to the method of any one of claims 1 to 8.
10. The application of the sulfide-nitride heterojunction composite photocatalyst in preparing hydrogen or synthesis gas by photocatalytic reforming formic acid is characterized in that one-dimensional cadmium sulfide and two-dimensional tungsten nitride heterojunction photocatalyst are added into a reactor, then formic acid aqueous solution or formic acid aqueous solution containing sodium formate is added, argon is introduced for purging, and the hydrogen or synthesis gas is prepared by stirring and illuminating.
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