CN113680356A - Zn for photocatalytic decomposition of pure water1-xCdxS/D-ZnS（en）0.5/Pi/NiaPreparation method of Pi type catalyst - Google Patents
Zn for photocatalytic decomposition of pure water1-xCdxS/D-ZnS（en）0.5/Pi/NiaPreparation method of Pi type catalyst Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 80
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
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- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 13
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- 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
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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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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Abstract
The application firstly utilizes a solvothermal method to prepare Zn1‑xCdxS/D‑ZnS(en)0.5A heterojunction material. And further carrying out two-step photochemical synthesis modification on the phosphorus oxide (Pi) protective layer and NiaPi promoter is synthesized and loaded on the surface of the material. NiaThe Pi material can further capture photo-generated electrons and holes generated by the catalyst to generate Ni in situIP and NiIIIPi(2MPi→MIP+MIIIPi) co-catalystOxidizing agents and respectively with NiIP and NiIIIPi cocatalyst as reaction site for producing hydrogen and H2O2And (4) reacting. In addition, the catalyst material is protected from photo-corrosion by Pi, so that Zn1‑ xCdxS/D‑ZnS(en)0.5/Pi/NiaThe Pi material further realizes an excellent hydrogen production process by photocatalytic decomposition of pure water. The two-step photochemical synthesis provided by the application for preparing Zn1‑xCdxS/D‑ZnS(en)0.5/Pi/NiaThe method of Pi catalyst can be used for constructing more efficient and stable Zn1‑xCdxThe S decomposition pure water catalytic system has higher innovativeness and practicability.
Description
Technical Field
The invention relates to a method for producing hydrogen by photocatalytic water, in particular to a photochemical modification method for serial application of photocatalytic partially decomposed water and photocatalytic decomposed pure water.
Background
The hydrogen energy is used as a secondary energy, has the advantages of high combustion heat value (the energy density is 143kJ/g), large reserve (water can be used as a hydrogen source), reproducibility (a combustion product is water, and the water can be reduced into the hydrogen again), convenience in storage and transportation and the like, and can be used for relieving the problems of the existing energy crisis and environmental pollution. Compared with the existing hydrogen production method by fossil fuel, the photocatalytic water splitting hydrogen production method with simple operation and low cost has great technical potential, but the preparation of the photocatalyst with high activity and high stability is still a long-term and difficult challenge. Among the photocatalytic materials, ZnxCd1-xThe S-based catalyst is considered to be one of the most potential photocatalytic materials due to the advantages of controllable energy band structure, high efficiency of photocatalytic partial water decomposition (PPWS) hydrogen production and the like. However, in the application of photocatalytic pure water decomposition, due to the defects of poor stability and low hydrogen production efficiency caused by lack of sacrificial reagent for capturing photoproduction cavities, Zn is restrictedxCd1-xResearch and development of S-based catalysts have been advanced.
The process of photocatalytic decomposition of pure water can be divided into: photocatalytic total decomposition of water (2H)2O→2H2+O2POWS) and photocatalytic intermediate stage decomposition of water (2H)2O→H2+H2O2PIWS). Unlike the photocatalytic partial water splitting reaction (PPWS), the photohole reaction pathways are numerous due to the lack of capture of sacrificial reagents. Except that four electrons (O) are generated2) Transfer of the product and possible formation of a single electron·OH), two electrons (H)2O2) Transfer of by-products, wherein H2O2Will oxidize S2-Cause to causeCatalyst poisoning (CdS + 4H)2O2→Cd2++SO4 2-+4H2O). Furthermore, ZnxCd1-xThe S-based catalyst can generate the photo-corrosion phenomenon (oxygen-free photo-corrosion: CdS +2 h)+→Cd2++ S; aerobic photo etching: CdS +4h++2H2O+O2→ Cd2++SO4 2-+4H+) This allows the water oxidation process to act as a kinetic-determining step for the reaction of decomposing pure water, directly affecting the stability of the catalyst and the efficiency of decomposing pure water.
Given that stability is an important indicator of catalyst application, Zn is improvedxCd1-xThe problem of photo-corrosion of S-based catalysts is imperative. Through a large amount of literature research, the following findings are obtained: since the phosphide has metalloid and high stability characteristics, Zn is transformed intoxCd1-xAfter the phosphide cocatalyst is introduced into the S-based catalyst, the problem of photo-corrosion can be effectively relieved. In 2018, the group of problems of the Lugong boiler uses combustible and explosive white phosphorus as a phosphorus source and adopts a hydrothermal method to produce ZnxCd1-xOuter layer of S-based catalyst to prepare Ni2The P shell material realizes the process of photocatalytic total water decomposition (POWS), and makes AG/Ni dissolved in an artificial cheek (AG) high-efficiency separation system2The P/CdS catalytic system shows higher hydrogen production rate (0.838 mmol.h) for decomposing pure water-1·g-1). In 2020, Chenyubin task group utilized high temperature pyrolysis NaH2PO2The generated virulent PH3 is used as a phosphorus source to prepare RP @ CoP/Cd0.9Zn0.1An S-type Z-scheme system capable of decomposing pure water in a photocatalytic intermediate-stage water decomposition (PIWS) route, achieving an apparent quantum efficiency of 6.4% at 420 nm. By contrast, it is easy to find that: although the catalyst system is loaded with the phosphide promoter, the performance of the catalyst system in photocatalytic decomposition of pure water to produce hydrogen is far different from the traditional performance of photocatalytic partial decomposition of water to produce hydrogen. And the modification process with high toxicity and high energy consumption also limits the application space of phosphide. From the perspective of green, safety and energy saving, the rapid and convenient photochemical synthesis method for preparing phosphide has great advantages.
As is well known, phosphorusThe compound preparation process is mixed with a large amount of phosphate compounds, and the effect of the phosphate is often neglected. Recently, the group of zhengshihui topics assembled NiCoPi modified CdS catalytic systems, which found: NiCoPi can capture photogenerated electrons and holes of CdS catalyst, thereby generating NiICoP and NiCoIIIPi, and taking the catalytic site as a catalytic site to carry out photocatalytic hydrogen production and oxidation sacrificial reagent reaction. The phosphate promoter can be used as a hydrogen production promoter and a water oxidation promoter at the same time, and the dual-functional characteristic enables the phosphate promoter to have extremely high application value in the field of photocatalytic pure water. Although the transition metal phosphate catalyst has been widely applied to the fields of electrocatalysis and photoelectrocatalysis decomposition of pure water, the transition metal phosphate catalyst is used as a cocatalyst to modify ZnxCd1-xThe research on the process of photocatalytic decomposition of pure water by using an S-based catalyst is rarely reported.
Disclosure of Invention
In view of the above circumstances, the present inventors have conducted intensive studies and have found a catalyst for photocatalytic decomposition of pure water and a method for producing the same.
The invention aims to provide a preparation method of a catalyst for photocatalytic decomposition of pure water, which comprises the following steps:
(1) zn is added1-xCdxS/D-ZnS(en)0.5The quasi-II type heterojunction catalyst material is dispersed in H2PO2 -In the solution, carrying out ultrasonic treatment under the protection of inert gas;
(2) then transferring the suspension into a photocatalytic reactor, sealing the container, vacuumizing the whole reaction system by using a vacuum pump, irradiating the reactor by using a visible light source, and keeping the temperature at room temperature while stirring continuously;
(3) after the reaction is finished, opening the reactor, removing supernatant, centrifugally recovering precipitate, drying in an oven and recovering to obtain phosphate radical modified Zn1-xCdxS/D-ZnS(en)0.5Marked as Zn1-xCdxS/D-ZnS(en)0.5/Pi。
Further, the preparation method also comprises the step of adding Zn1-xCdxS/D-ZnS(en)0.5The step of further modifying the/Pi specifically comprises the following steps:
taking Zn1-xCdxS/D-ZnS(en)0.5Pi samples, dispersed to contain Ni2 +H of (A) to (B)2PO2 -In the water solution, the suspension is subjected to ultrasonic treatment under the protection of inert gas, then the suspension is transferred to a photocatalytic reactor, after the container is sealed, the whole reaction system is vacuumized by a vacuum pump, a visible light source is utilized to irradiate the reactor, the room temperature is kept, the reactor is continuously stirred, after the reaction is finished, the reactor is opened, the supernatant is removed, the precipitate is centrifugally recovered, and after the precipitate is dried in an oven, the Zn loaded with transition metal phosphate is recovered1-xCdxS/D-ZnS(en)0.5Pi, marked Zn1-xCdxS/D-ZnS(en)0.5/Pi/NiaPi。
The invention also provides the photocatalytic decomposition pure water catalyst prepared by the method.
The invention also provides Zn1-xCdxS/D-ZnS(en)0.5The photochemical modification method comprises the following steps:
(1) zn is added1-xCdxS/D-ZnS(en)0.5The quasi-II type heterojunction catalyst material is dispersed in H2PO2 -In the solution, carrying out ultrasonic treatment under the protection of inert gas;
(2) then transferring the suspension into a photocatalytic reactor, sealing the container, vacuumizing the whole reaction system by using a vacuum pump, irradiating the reactor by using a visible light source, and keeping the temperature at room temperature while stirring continuously;
(3) after the reaction is finished, opening the reactor, removing supernatant, centrifugally recovering precipitate, drying in an oven and recovering to obtain phosphate radical modified Zn1-xCdxS/D-ZnS(en)0.5Marked as Zn1-xCdxS/D-ZnS(en)0.5/Pi。
Further, the photochemical modification method also comprises the step of adding Zn1-xCdxS/D-ZnS(en)0.5The step of further modifying the/Pi specifically comprises the following steps:
taking Zn1-xCdxS/D-ZnS(en)0.5Pi samples, dispersed to contain Ni2+H of (A) to (B)2PO2 -In the water solution, the suspension is subjected to ultrasonic treatment under the protection of inert gas, then the suspension is transferred to a photocatalytic reactor, after the container is sealed, the whole reaction system is vacuumized by a vacuum pump, a visible light source is utilized to irradiate the reactor, the room temperature is kept, the reactor is continuously stirred, after the reaction is finished, the reactor is opened, the supernatant is removed, the precipitate is centrifugally recovered, and after the precipitate is dried in an oven, the Zn loaded with transition metal phosphate is recovered1-xCdxS/D-ZnS(en)0.5Pi, marked Zn1-xCdxS/D-ZnS(en)0.5/Pi/NiaPi。
The invention also provides a method for producing hydrogen by connecting photocatalytic partial decomposition water and photocatalytic decomposition pure water in series, which comprises the following steps:
(1) zn is added1-xCdxS/D-ZnS(en)0.5Sample, dispersed in H2PO2 -In the solution, carrying out ultrasonic treatment under the protection of inert gas; then transferring the suspension into a photocatalytic reactor, sealing the container, vacuumizing the whole reaction system by using a vacuum pump, irradiating the reactor by using a visible light source, keeping the temperature and continuously stirring, carrying out quantitative analysis on gas generated by the system through chromatography, opening the reactor after the reaction is finished, removing supernatant, centrifugally recovering precipitate, drying in an oven, and recovering to obtain phosphate radical modified Zn1-xCdxS/D-ZnS(en)0.5Marked as Zn1-xCdxS/D-ZnS(en)0.5/Pi；
(2) Zn is added1-xCdxS/D-ZnS(en)0.5Pi samples, dispersed to contain Ni2 +H of (A) to (B)2PO2 -In the water solution, the suspension is treated by ultrasonic treatment under the protection of inertia, then the suspension is transferred to a photocatalytic reactor, after the container is sealed, the whole reaction system is vacuumized by a vacuum pump, a visible light source is utilized to irradiate the reactor, and the room temperature is kept and the reactor is continuously stirredThe gas generated in the system was quantitatively analyzed by chromatography.
In each of the above-mentioned technical solutions of the present invention,
preferably, Zn1-xCdxS/D-ZnS(en)0.5Is Zn0.21Cd0.79S/D-ZnS(en)0.5The product obtained after phosphate radical modification is Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi；
Preferably, the inert other is nitrogen, argon or helium;
preferably, said H2PO2 -The solution is NaH2PO2、KH2PO2One of (1);
preferably, the ultrasonic treatment time is 20-60 min;
preferably, the vacuum treatment time is 10-30 min;
preferably, the visible light source is one of sunlight, a xenon lamp, a mercury lamp, an incandescent lamp, a light-emitting diode lamp and the like, and the processing time is 2-5 h;
preferably, the drying temperature of the oven is 50-70 ℃, and the drying time is 10-15 h;
preferably, Zn is generated in the first step of photocatalytic partial decomposition of water to produce hydrogen0.21Cd0.79S/D-ZnS(en)0.5The feed is 100-400mg, and is dispersed into 80mL of NaH with the concentration of 0.15625-0.625mol/L2PO2An aqueous solution;
preferably, Zn is generated by partially decomposing water through photocatalysis in the second step0.21Cd0.79S/D-ZnS(en)0.5The dosage of the/Pi is 80-100mg, and the NaH with the concentration of 0.42-1.12mmol/L is dispersed into 80mL2PO2And NiSO with concentration of 0.015-0.040mmol/L4An aqueous solution;
preferably, Zn is generated by photocatalytic decomposition of pure water0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi was charged at 25-35mg and dispersed in 80mL of pure water.
The invention also provides Zn1-xCdxS/D-ZnS(en)0.5The preparation method of the heterojunction material is characterized in that zinc acetate, cadmium acetate and L-cysteine are mixed and dissolved in an ethylenediamine/ultrapure water mixed solvent, after ultrasonic stirring, the uniformly stirred suspension is transferred into a reaction kettle and reacts for 24 hours at 180 ℃, then the precipitate is centrifuged and cleaned, and after drying in an oven, a yellow sample is recovered and marked as Zn1-xCdxS/D-ZnS(en)0.5。
Further, the preparation method comprises the steps of mixing and dissolving 0.5mmol of zinc acetate, 0.5mmol of cadmium acetate and 2mmol of L-cysteine in a mixed solvent of ethylenediamine, 31.5ml of ultrapure water and 1.5ml of L-cysteine, ultrasonically stirring for 30min, transferring the uniformly stirred suspension into a reaction kettle, reacting for 24h at 180 ℃, centrifuging, cleaning precipitate, drying in an oven at 60 ℃ for 12h, recovering a yellow sample marked as Zn0.21Cd0.79S/D-ZnS(en)0.5。
Compared with the prior art, the invention has the beneficial effects that:
the work firstly utilizes a solvothermal method to prepare Zn1-xCdxS/D-ZnS(en)0.5A heterojunction material. And further carrying out two-step photochemical synthesis modification on the phosphorus oxide (Pi) protective layer and NiaPi promoter is synthesized and loaded on the surface of the material. NiaThe Pi material can further capture photo-generated electrons and holes generated by the catalyst to generate Ni in situIP and NiIIIPi(2MPi→MIP+MIIIPi) a cocatalyst, and NiIP and NiIIIPi cocatalyst as reaction site for producing hydrogen and H2O2And (4) reacting. In addition, the catalyst material is protected from photo-corrosion by Pi, so that Zn1-xCdxS/D-ZnS(en)0.5/Pi/NiaThe Pi material further realizes an excellent hydrogen production process by photocatalytic decomposition of pure water. The two-step photochemical synthesis proposed by this work for the preparation of Zn1-xCdxS/D-ZnS(en)0.5/Pi/NiaThe method of Pi catalyst can be used for constructing more efficient and stable Zn1- xCdxThe S decomposition pure water catalytic system has higher innovationThe performance and certain practicability.
Drawings
FIG. 1 different Zn1-xCdxS/D-ZnS(en)0.5An XRD pattern (A) of the sample; lattice parameter and Zn1-xCdxS linear relation graph (B) between Cd contents (x) in solid solution material
FIG. 2 Zn1-xCdxS/D-ZnS(en)0.5Photocatalytic hydrogen production property test in first-step photochemical synthesis process
FIG. 3 Zn0.21Cd0.79S/D-ZnS(en)0.5NiSO with Pi at different concentrations4·6H2O and NaH2PO2Zn prepared in a charge combination0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPhotocatalytic decomposition pure water hydrogen production test of Pi (1-5) sample
FIG. 4 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaCarrying out photocatalytic decomposition on pure water and apparent quantum efficiency (420nm) test (A) on a Pi sample under irradiation of different light intensities; zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi and the recovered sample (Zn) after the photocatalytic decomposition pure water test as described above0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi-PIWS test recycled) at 0.25M Na2SO3/0.35M Na2Photocatalytic hydrogen production in S sacrificial agent solution and apparent quantum efficiency (420nm) test (B), where hydrogen production rate units: mmol h-1 g-1
FIG. 5D-ZnS (en)0.5、Zn0.21Cd0.79S/D-ZnS(en)0.5、Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi、Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaXRD patterns of Pi and CdS. Powder diffraction cards with histograms of CdS (No.41-1049) and ZnS (No.05-0566)
FIG. 6 Zn0.21Cd0.79S/D-ZnS(en)0.5(A，D)、Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi(B，E)、Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaSEM image of Pi (C, F) sample
FIG. 7 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi samples were tested for H at 1.5V vs. rhe test voltage2O2The resulting I-t test curve (A) and the I-t test curve (B) of the Rotating Ring Disk Electrode (RRDE), where IdiskRepresentative of dial current, IringRepresenting the loop current
FIG. 8 different Zn1-xCdxS/D-ZnS(en)0.5Ultraviolet-visible diffuse reflectance spectrum (A) and band conversion spectrum (B) of the material
FIG. 9D-ZnS (en)0.5Mott-Schottky dot plot of materials
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
EXAMPLE 1 Zn at different feed ratios1-xCdxS/D-ZnS(en)0.5Preparation of
The experiment selects different Zn/Cd molar charge ratios for preparing Zn1-xCdxS/D-ZnS(en)0.5Raw material, and Zn in a Zn/Cd molar ratio of 1: 11-xCdxS/D-ZnS(en)0.5Solid solution materials were the starting study. According to Vegard's law (FIG. 1), we prepared Zn/Cd ratios1-xCdxS/D-ZnS(en)0.5Converting Zn/Cd theoretical ratio of solid solution, and finding that: when the Zn/Cd molar ratio is 1: 1, Zn is prepared1-xCdxS/D-ZnS(en)0.5The theoretical composition of a solid solution is Zn0.21Cd0.79S/D-ZnS(en)0.5。
Respectively mixing zinc acetate and cadmium acetate (1mmol of zinc acetate +0mmol of cadmium acetate, 0.6mmol of zinc acetate + 0.4mmol of cadmium acetate, 0.4mmol of zinc acetate +0.6mmol of cadmium acetate, 0.3mmol of zinc acetate +0.7mmol of cadmium acetate and 0mmol of zinc acetate +1mmol of cadmium acetate) and 2mmol of L-cysteine in a mixed solvent of ethylenediamine, ultrapure water and 31.5ml to 1.5ml, ultrasonically stirring for 30min, transferring the uniformly stirred suspension into a reaction kettle, and reacting at 180 ℃ for 24 h. Then centrifuging and cleaningThe precipitated material was dried in an oven at 60 ℃ for 12h and recovered to give final samples, labeled D-ZnS (en)0.5、Zn0.29Cd0.71S/D-ZnS(en)0.5、 Zn0.14Cd0.86S/D-ZnS(en)0.5、Zn0.11Cd0.89S/D-ZnS(en)0.5、CdS。
Example 2 Zn1-xCdxS/D-ZnS(en)0.5Preparation of/Pi and comparison of hydrogen production performance
With Zn0.21Cd0.79S/D-ZnS(en)0.5By way of example, Zn1-xCdxS/D-ZnS(en)0.5Preparation of/Pi.
Weighing 160mg of Zn0.21Cd0.79S/D-ZnS(en)0.5Sample, NaH dispersed in 80ml of 0.28125M2PO2And (4) carrying out ultrasonic treatment on the mixture in the aqueous solution for 30min under the protection of argon. Then the suspension was transferred to a photocatalytic reactor, and after the vessel was sealed, the entire reaction system was vacuumed with a vacuum pump for 15 min. Irradiating the reactor with visible light source (300W xenon lamp with 420nm front cut-off filter) for 3h, maintaining room temperature, stirring, passing gas generated by the system through chromatogram (Tianmei GC7900, TCD, Ar as carrier gas,
molecular sieve column), and the hydrogen production test results of different samples are shown in fig. 2 and table 1. After the reaction is finished, opening the reactor, removing supernatant, centrifugally recovering precipitate, drying in an oven at 60 ℃ for 12h, and recovering to obtain a yellow sample, wherein the yellow sample is marked as Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi。
TABLE 1 Zn1-xCdxS/D-ZnS(en)0.5Testing data of photocatalytic hydrogen production property in the first step photochemical synthesis process, wherein the hydrogen production rate unit is as follows: mmol h-1 g-1
Example 3 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPreparation of Pi
Weighing 82mg of Zn0.21Cd0.79S/D-ZnS(en)0.5Pi samples, dispersed in 80ml of NiSO of different concentrations4·6H2O and NaH2PO2In the aqueous solution, the specific feeding combination is as follows:
①NiSO4·6H2o (0.076mM) and NaH2PO2(0.532mM)；
②NiSO4·6H2O (0.114mM) and NaH2PO2(0.798mM)；
③NiSO4·6H2O (0.152mM) and NaH2PO2(1.064mM)；
④NiSO4·6H2O (0.190mM) and NaH2PO2(1.330mM)；
⑤NiSO4·6H2O (0.228mM) and NaH2PO2(1.596mM)。
And (4) carrying out ultrasonic treatment on the suspension for 30min under the protection of argon. Then the suspension was transferred to a photocatalytic reactor, and after the vessel was sealed, the entire reaction system was vacuumed with a vacuum pump for 15 min. Irradiating the reactor with visible light source (300W xenon lamp with 420nm front cut-off filter) for 2h, maintaining room temperature, stirring, passing gas generated by the system through chromatogram (Tianmei GC7900, TCD, Ar as carrier gas,
molecular sieve column), quantitative analysis was performed. After the reaction is finished, opening the reactor, removing supernatant, centrifugally recovering precipitate, drying in an oven at 60 ℃ for 12h, and recovering to obtain yellow samples which are respectively marked as Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi(1～5)。
TABLE 2 Zn0.21Cd0.79S/D-ZnS(en)0.5Pi at different concentrationsNiSO4·6H2O and NaH2PO2Zn prepared in a charge combination0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaAnd (3) photocatalytic decomposition pure water hydrogen production property test data of a Pi (1-5) sample, wherein the hydrogen production rate unit is as follows: mmol h-1 g-1
By the pair of Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaAnd (3) carrying out photocatalytic decomposition pure water hydrogen production test on the Pi (1-5) sample, and finding that: zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe Pi (4) sample has the highest photocatalytic hydrogen production performance, and the hydrogen production rate can reach 1.793mmol h under the condition of visible light irradiation-1 g-1Under the irradiation of ultraviolet-visible light, the hydrogen production rate can reach 5.135mmol h-1 g-1(FIG. 3 and Table 2). To our knowledge, this is the highest hydrogen production rate value reported so far, significantly higher than other Zn1-xCdxThe values of the hydrogen production rate of pure water by photocatalytic decomposition of S-based catalytic system (Table 3) show that Zn prepared by us0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe Pi catalytic system is very competitive.
TABLE 3 Zn reported in the literature so far1-xCdxTest parameter value for hydrogen production by photocatalytic decomposition of pure water of S-based catalytic system
Example 4 photocatalytic decomposition of pure Water to Hydrogen test
Weighing 30mg of Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi (4) sample, dispersed in 80ml of ultrapure water, was sonicated for 30min under argon blanket. Then the suspension was transferred to a photocatalytic reactor, and after the vessel was sealed, the entire reaction system was vacuumed with a vacuum pump for 15 min. Irradiating the reactor with visible light source (300W xenon lamp with 420nm front cut-off filter), stirring at room temperature, passing the gas generated by the system through chromatography (Tianmei GC7900, TCD, Ar as carrier gas,
molecular sieve column), quantitative analysis was performed.
Example 5 photocatalytic decomposition of pure Water under illumination of varying light intensities and apparent Quantum efficiency (420nm) test data
We studied Zn in detail0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe test process of photocatalytic decomposition of pure water of Pi sample is carried out under different illumination conditions, and Zn is added0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe performance of the Pi samples all decayed significantly after 1.5 hours, and then the hydrogen production rates tended to stabilize (fig. 4A and table 4). To explore the reason for performance degradation, we will explore Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi and Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi (recovered sample after photocatalytic decomposition pure water test) is subjected to photocatalytic hydrogen production test under the condition of sacrificial reagent, and research finds that Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi samples at 0.35M NA2S/0.25M NA2SO3In the sacrificial agent solution, 37.203mmol h is shown-1 g-1Hydrogen production rate of, and Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi (recovered sample after photocatalytic decomposition pure water test) exhibited 22.224mmol h-1 g-1Hydrogen production rate (FIG. 4B and Table 4), albeit in comparison with Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe performance of the Pi material is attenuated by 1.67 times, and a higher photocatalytic hydrogen production rate is still displayed, which indicates that the performance attenuation is probably due to Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi materials are caused by the shedding of the complexed ethylenediamine (en) reagent, which acts as a quasi-sacrificial reagent. Although the ethylenediamine reagent continuously drops in the process of photocatalytic decomposition of pure water, Zn is not caused0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPhoto-corrosion of Pi material, so that Zn is added0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi (recovered sample after photocatalytic decomposition pure water test) still maintains higher photocatalytic hydrogen production performance in the sacrificial agent solution.
TABLE 4 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi samples photocatalytically decomposed pure water and apparent quantum efficiency (420nm) under different light intensity irradiation
Testing data; zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi and the recovered sample (Zn) after the photocatalytic decomposition pure water test as described above0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi (sample recovered after photocatalytic decomposition pure water test)) was 0.25M Na2SO3/0.35M Na2Photocatalytic hydrogen production in S sacrificial agent solution and apparent quantum efficiency (420nm) test data, where hydrogen production rate units: mmol h-1 g-1
Example 6 catalyst sample characterization
For the prepared Zn0.21Cd0.79S/D-ZnS(en)0.5、Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi、 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi, etc., and Zn is shown in FIG. 50.21Cd0.79S/D-ZnS(en)0.5、 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi、Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe XRD patterns of the Pi, etc. samples were located between CdS (No.41-1049) and ZnS (No.05-0566) powder diffraction cards, indicating that Zn was formed in both of the above materials0.21Cd0.79S solid solution material instead of a mixture of ZnS and CdS formed. In addition to D-ZnS (en)0.5Material comparison, Zn0.21Cd0.79S/D-ZnS(en)0.5、 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi、Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi et al sample D-ZnS (en)0.5The XRD diffraction peak of the component gradually disappears, which shows that D-ZnS (en) is modified by photochemical synthesis0.5The components are gradually peeled off. Furthermore, Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi、 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaNo characteristic peak of phosphorus oxide was observed in XRD diffraction spectrum of samples such as Pi, etc., and various phosphorus oxides (Pi and Ni) in the above materialsaPi) are all amorphous structures; and with Zn0.21Cd0.79S/D-ZnS(en)0.5In contrast, Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi、 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe diffraction intensity of the (002) crystal face in the Pi sample is higher than that of the (101) crystal face, which shows that Zn is modified by photochemical synthesis0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe dominant growth direction of the sulfide component in Pi material is from [101 ]]Is converted to [002]And (4) direction.
TABLE 5 Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaEnergy Dispersive Spectroscopy (EDS) experimental data for Pi samples
As can be seen from FIG. 6, Zn0.21Cd0.79S/D-ZnS(en)0.5The heterojunction material contains two different morphologies, namely sea urchin micron sphere Zn0.21Cd0.79S material and micro-sheet type D-ZnS (en)0.5A material. After the first step of photochemical synthesis modification, Zn0.21Cd0.79S/D-ZnS(en)0.5The shape of the/Pi material slightly changes, wherein sea urchin micron spherical Zn0.21Cd0.79The small pricks on the surface layer of the S material are gradually shortened to generate a nano rod material, and a layer of phosphorus oxide covers the surface layer; micro-sheet type D-ZnS (en)0.5The thickness of the material becomes significantly thinner due to D-ZnS (en)0.5The ethylenediamine complexing agent within the material gradually comes off, resulting in D-ZnS (en)0.5A partial peeling effect of the material occurs. Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe morphology of the Pi material is further changed, wherein the micron spherical Zn0.21Cd0.79The S material surface layer has obvious nano-particle material load, and the nano-particles should be NiaPi nanometer material; micro-sheet type D-ZnS (en)0.5Further thinning of the thickness of the material, D-ZnS (en)0.5The material is exfoliated into smaller nanoplatelets.
We further address Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaMicrometer spherical Zn in Pi material0.21Cd0.79Energy Dispersive Spectroscopy (EDS) analysis of S material (Table 5) we found the presence of Zn, Cd, S, N, O, P, C, Fe, Co, Ni, Mn, etc., and the presence of N in the material, indicating that although XRD did not detect Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaD-ZnS (en) in Pi material0.5The characteristic peak of the component, but a trace amount of ethylenediamine complexing reagent is coordinated in Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe surface layer of Pi material, these complexing reagents can act as quasi-sacrificial reagents to assist the catalyst in the photocatalytic decomposition of pure water.
EXAMPLE 7 electrocatalytic detection of H2O2Testing
According to the above experimentKnown as Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi material can carry out photocatalytic decomposition pure water hydrogen production reaction, and in order to further explore the oxidation water product of the catalyst, we carry out electrocatalysis detection on H2O2Testing and finding out that: adding MnO to a reaction solution of photocatalytic decomposition and pure water2After the catalyst, the current value of the system sharply decreases (FIG. 7A), which shows that the photo-generated holes of the catalyst oxidize water to generate H during the photocatalytic reaction2O2Which is then MnO-free2Decomposition into O2. We further performed an electron transfer number test experiment (FIG. 7B), and the optical current was measured by rotating the ring plate electrode, and it was found that Zn was converted0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaThe number of electron transfers (n) in the photocatalytic decomposition of pure water by the Pi material was 2.04. The results of these studies demonstrate that: zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPhotocatalytic intermediate-stage water (2H) decomposition process adopted in photocatalytic water decomposition process of Pi material2O→H2+H2O2PIWS) path.
Example 8 Mott-Schottky test
As can be seen from FIG. 8, Zn0.21Cd0.79S/D-ZnS(en)0.5The band gap (Eg) of the material was 2.46eV, and further, it was found that Zn was obtained by a literature conversion method0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaIn the Pi material, Zn0.21Cd0.79The Conduction Band (CB) and Valence Band (VB) energy levels of the S component are-0.41V and +2.05V (vs NHE), respectively. We further tested D-ZnS (en)0.5Mott-Schottky testing of the material (fig. 9), study found: D-ZnS (en)0.5Conduction band energy level (CB) and p-type defect donor energy level (E) in a materialFp) respectively-1.12V and +0.87V (vs NHE), indicating Zn0.21Cd0.79S and D-ZnS (en)0.5A quasi-II heterojunction structure is formed among the components, photoproduction electrons and holes generated by light excitation in the transfer catalyst can be efficiently separated, the photoproduction holes are further transferred into an ethylenediamine complexing reagent on the surface layer, and then the photoproduction electrons and the holes are further formed by the surface layerLoaded NiaPi traps and in situ generates NiIP and NiIIIPi(2MPi→MIP+MIIIPi) a cocatalyst, and NiIP and NiIIIPi cocatalyst as reaction site for producing hydrogen and H2O2And (4) reacting.
Claims (10)
1. A preparation method of a catalyst for decomposing pure water by photocatalysis is characterized by comprising the following steps:
(1) zn is added1-xCdxS/D-ZnS(en)0.5The quasi-II type heterojunction catalyst material is dispersed in H2PO2 -In the solution, carrying out ultrasonic treatment under the protection of inert gas;
(2) then transferring the suspension into a photocatalytic reactor, sealing the container, vacuumizing the whole reaction system by using a vacuum pump, irradiating the reactor by using a visible light source, and keeping the temperature at room temperature while stirring continuously;
(3) after the reaction is finished, opening the reactor, removing supernatant, centrifugally recovering precipitate, drying in an oven and recovering to obtain phosphate radical modified Zn1-xCdxS/D-ZnS(en)0.5Marked as Zn1-xCdxS/D-ZnS(en)0.5/Pi。
2. The method of claim 1, further comprising adding Zn1-xCdxS/D-ZnS(en)0.5The step of further modifying the/Pi specifically comprises the following steps:
taking Zn1-xCdxS/D-ZnS(en)0.5Pi samples, dispersed to contain Ni2+H of (A) to (B)2PO2 -In the water solution, the suspension is treated by ultrasonic under the protection of inert gas, then the suspension is transferred to a photocatalytic reactor, after the container is sealed, the whole reaction system is vacuumized by a vacuum pump, a visible light source is used for irradiating the reactor, the room temperature is kept, the reactor is continuously stirred, after the reaction is finished, the reactor is opened, the supernatant is removed, the precipitate is centrifugally recovered, and after the precipitate is dried in an oven, the negative load is recoveredZn loaded with transition metal phosphate1-xCdxS/D-ZnS(en)0.5Pi, marked Zn1-xCdxS/D-ZnS(en)0.5/Pi/NiaPi。
3. The production method according to claim 1 or 2, characterized in that Zn1-xCdxS/D-ZnS(en)0.5Is Zn0.21Cd0.79S/D-ZnS(en)0.5The product obtained after phosphate radical modification is Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi；
The inert gas is nitrogen, argon or helium;
said H2PO2 -The solution is NaH2PO2、KH2PO2One of (1);
the ultrasonic treatment time is 20-60 min;
the vacuum treatment time is 10-30 min;
the visible light source is one of sunlight, a xenon lamp, a mercury lamp, an incandescent lamp, a light-emitting diode lamp and the like, and the processing time is 2-5 h;
the drying temperature of the drying oven is 50-70 ℃, and the drying time is 10-15 h;
Zn0.21Cd0.79S/D-ZnS(en)0.5in the preparation of/Pi, Zn0.21Cd0.79S/D-ZnS(en)0.5The feed is 100-400mg, and is dispersed into 80mL of NaH with the concentration of 0.15625-0.625mol/L2PO2An aqueous solution.
4. A catalyst for photocatalytic decomposition of pure water prepared by the method as claimed in any one of claims 1 to 3.
5. Zn1-xCdxS/D-ZnS(en)0.5The photochemical modification method comprises the following steps:
(1) zn is added1-xCdxS/D-ZnS(en)0.5The quasi-II type heterojunction catalyst material is dispersed in H2PO2 -In solution, under inert gasCarrying out ultrasonic treatment under protection;
(2) then transferring the suspension into a photocatalytic reactor, sealing the container, vacuumizing the whole reaction system by using a vacuum pump, irradiating the reactor by using a visible light source, and keeping the temperature at room temperature while stirring continuously;
(3) after the reaction is finished, opening the reactor, removing supernatant, centrifugally recovering precipitate, drying in an oven and recovering to obtain phosphate radical modified Zn1-xCdxS/D-ZnS(en)0.5Marked as Zn1-xCdxS/D-ZnS(en)0.5/Pi。
6. The photochemical modification method according to claim 5, further comprising reacting Zn1-xCdxS/D-ZnS(en)0.5The step of further modifying the/Pi specifically comprises the following steps:
taking Zn1-xCdxS/D-ZnS(en)0.5Pi samples, dispersed to contain Ni2+H of (A) to (B)2PO2 -In the water solution, the suspension is subjected to ultrasonic treatment under the protection of inert gas, then the suspension is transferred to a photocatalytic reactor, after the container is sealed, the whole reaction system is vacuumized by a vacuum pump, a visible light source is utilized to irradiate the reactor, the room temperature is kept, the reactor is continuously stirred, after the reaction is finished, the reactor is opened, the supernatant is removed, the precipitate is centrifugally recovered, and after the precipitate is dried in an oven, the Zn loaded with transition metal phosphate is recovered1-xCdxS/D-ZnS(en)0.5Pi, marked Zn1-xCdxS/D-ZnS(en)0.5/Pi/NiaPi；
Preferably, Zn1-xCdxS/D-ZnS(en)0.5Is Zn0.21Cd0.79S/D-ZnS(en)0.5The product obtained after phosphate radical modification is Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi；
Preferably, the inert other is nitrogen, argon or helium;
preferably, said H2PO2 -The solution is NaH2PO2、KH2PO2One of (1);
preferably, the ultrasonic treatment time is 20-60 min;
preferably, the vacuum treatment time is 10-30 min;
preferably, the visible light source is one of sunlight, a xenon lamp, a mercury lamp, an incandescent lamp, a light-emitting diode lamp and the like, and the processing time is 2-5 h;
preferably, the drying temperature of the oven is 50-70 ℃, and the drying time is 10-15 h;
preferably, Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaIn the process of Pi preparation, Zn0.21Cd0.79S/D-ZnS(en)0.5The dosage of the/Pi is 80-100mg, and the NaH with the concentration of 0.42-1.12mmol/L is dispersed into 80mL2PO2And NiSO with concentration of 0.015-0.040mmol/L4An aqueous solution.
7. A method for producing hydrogen by photocatalytic partial decomposition of water and photocatalytic decomposition of pure water in series comprises the following steps:
(1) zn is added1-xCdxS/D-ZnS(en)0.5Sample, dispersed in H2PO2 -In the solution, carrying out ultrasonic treatment under the protection of inert gas; then transferring the suspension into a photocatalytic reactor, sealing the container, vacuumizing the whole reaction system by using a vacuum pump, irradiating the reactor by using a visible light source, keeping the temperature and continuously stirring, carrying out quantitative analysis on gas generated by the system through chromatography, opening the reactor after the reaction is finished, removing supernatant, centrifugally recovering precipitate, drying in an oven, and recovering to obtain phosphate radical modified Zn1-xCdxS/D-ZnS(en)0.5Marked as Zn1-xCdxS/D-ZnS(en)0.5/Pi；
(2) Zn is added1-xCdxS/D-ZnS(en)0.5Pi samples, dispersed to contain Ni2+H of (A) to (B)2PO2 -In the water solution, the suspension is treated by ultrasonic treatment under the protection of inertia, and then the suspension is transferred to the photocatalysis reactionIn the reactor, after the container is sealed, the whole reaction system is vacuumized by a vacuum pump, a visible light source is used for irradiating the reactor, the temperature is kept at room temperature, the reactor is continuously stirred, and the gas generated by the system is subjected to quantitative analysis through chromatography.
8. Method for the tandem production of hydrogen by the photocatalytic partial decomposition of water and by the photocatalytic decomposition of pure water according to claim 7, characterized in that preferably Zn1-xCdxS/D-ZnS(en)0.5Is Zn0.21Cd0.79S/D-ZnS(en)0.5The product obtained after phosphate radical modification is Zn0.21Cd0.79S/D-ZnS(en)0.5/Pi；
Preferably, the inert other is nitrogen, argon or helium;
preferably, said H2PO2 -The solution is NaH2PO2、KH2PO2One of (1);
preferably, the ultrasonic treatment time is 20-60 min;
preferably, the vacuum treatment time is 10-30 min;
preferably, the visible light source is one of sunlight, a xenon lamp, a mercury lamp, an incandescent lamp, a light-emitting diode lamp and the like, and the processing time is 2-5 h;
preferably, the drying temperature of the oven is 50-70 ℃, and the drying time is 10-15 h;
preferably, Zn is generated in the first step of photocatalytic partial decomposition of water to produce hydrogen0.21Cd0.79S/D-ZnS(en)0.5The feed is 100-400mg, and is dispersed into 80mL of NaH with the concentration of 0.15625-0.625mol/L2PO2An aqueous solution;
preferably, Zn is generated by partially decomposing water through photocatalysis in the second step0.21Cd0.79S/D-ZnS(en)0.5The dosage of the/Pi is 80-100mg, and the NaH with the concentration of 0.42-1.12mmol/L is dispersed into 80mL2PO2And NiSO with concentration of 0.015-0.040mmol/L4An aqueous solution;
preferably, Zn is generated by photocatalytic decomposition of pure water0.21Cd0.79S/D-ZnS(en)0.5/Pi/NiaPi was charged at 25-35mg and dispersed in 80mL of pure water.
9. Zn1-xCdxS/D-ZnS(en)0.5The preparation method of the heterojunction material is characterized in that zinc acetate, cadmium acetate and L-cysteine are mixed and dissolved in an ethylenediamine/ultrapure water mixed solvent, after ultrasonic stirring, the uniformly stirred suspension is transferred into a reaction kettle and reacts for 24 hours at 180 ℃, then the precipitate is centrifuged and cleaned, and after drying in an oven, a yellow sample is recovered and marked as Zn1-xCdxS/D-ZnS(en)0.5。
10. The preparation method according to claim 9, characterized in that 0.5mmol of zinc acetate, 0.5mmol of cadmium acetate and 2mmol of L-cysteine are mixed and dissolved in a mixed solvent of ethylenediamine and ultrapure water (31.5 ml: 1.5 ml), after ultrasonic stirring for 30min, the uniformly stirred suspension is transferred to a reaction kettle and reacted at 180 ℃ for 24h, then centrifuged, the precipitated material is washed, dried in an oven at 60 ℃ for 12h, and then a yellow sample is recovered, which is marked as Zn0.21Cd0.79S/D-ZnS(en)0.5。
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