CN107983371B - Photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2And preparation method and application thereof - Google Patents
Photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2And preparation method and application thereof Download PDFInfo
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- 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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Abstract
The invention discloses a photocatalytic material Cu2‑xS/Mn0.5Cd0.5S/MoS2And a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) preparation of substrate Mn0.5Cd0.5S solid solution; 2) mixing Mn prepared in the step 1)0.5Cd0.5Ultrasonically dispersing S solid solution in water, adding soluble copper salt and Na2S and Na2SO3Stirring for reaction to obtain in-situ loaded Cu2‑xS/Mn0.5Cd0.5S; 3) adding (NH) into the solution after the reaction in the step 2)4)2MoS4The MoS is directionally loaded by adopting a loading method of visible light photoreduction2Formation of Cu2‑xS/Mn0.5Cd0.5S/MoS2. Cu of the invention2‑xS/Mn0.5Cd0.5S/MoS2The preparation and synthesis method of the composite photocatalytic material has the advantages of simple conditions, no pollution, good stability and higher commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of new energy and photocatalytic materials, and particularly relates to a photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2The photocatalyst can be used for hydrogen production by photocatalytic water splitting and treatment of photocatalytic sulfide pollutants.
Background
Due to the continuous improvement of human energy demand, the excessive use of fossil fuels and the like, serious energy crisis and environmental pollution problems are brought, and the development of human beings is seriously influenced. The hydrogen energy is also called as future petroleum, is used as a clean, pollution-free, renewable and high-combustion-value secondary energy source, replaces non-renewable energy sources such as fossil fuel and the like, and has profound significance for solving the energy problem. At present, the main hydrogen production means comprise hydrogen production by cracking fossil fuel, hydrogen production by electrically decomposing water, biological hydrogen production, photocatalytic hydrogen production and the like. More than 90% of commercial hydrogen sources are obtained from fossil fuels such as coal, petroleum and natural gas, however, the reserves of the fossil fuels are limited, and the hydrogen production process generates greenhouse effect and environmental pollution. Among them, 4% of hydrogen is obtained by electrolyzing water, but the energy consumption of hydrogen production by electrolyzing water is too large, so that the cost of hydrogen production by electrolyzing water in industry is high. Biological hydrogen production is a new hydrogen production mode, hydrogen is produced through photosynthesis of green algae bacteria, oxygen is generated while algae produce hydrogen, the oxygen is a catalase activity inhibitor, the hydrogen generation efficiency is reduced, and meanwhile, many other gases are generated in the biological hydrogen production process, so that the hydrogen is difficult to separate.
The emerging hydrogen production by water splitting through catalytic photolysis utilizes the photovoltaic characteristic of a semiconductor, and photo-generated electrons are generated for hydrogen production by water splitting through continuous irradiation of sunlight, so that hydrogen production without energy consumption and pollution can be realized, and the gas product is single, thereby being beneficial to subsequent separation. Therefore, the deep theoretical combined experimental research on the method has very important strategic and practical significance. However, the catalytic photolysis of water for hydrogen production has the following technical problems: 1. the sunlight utilization rate is low; 2. the light quantum yield is low (about 4%); 3. Energy level mismatch; 4. the reverse reaction carriers recombine. These technical difficulties result in inefficient catalytic photolysis of water to produce hydrogen. Although the existing CdS semiconductor catalyst is relatively matched with the energy gap of a solar spectrum, the problems of low hydrogen production efficiency caused by photo-corrosion and catalytic photolysis of water exist. Cd prepared by doping and modifying CdSxMn1-xAlthough the S solid solution photocatalyst improves the efficiency of catalyzing and photolyzing water to produce hydrogen, the S solid solution photocatalyst improves the efficiency of catalyzing and photolyzing water to produce hydrogenThe problem of low hydrogen production efficiency still exists.
In conclusion, the problem of low efficiency of hydrogen production by catalytic photolysis of water in the prior art is still lack of an effective solution.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2The preparation method and the application thereof, and the catalyst has relatively excellent photocatalytic performance.
In order to solve the technical problems, the technical scheme of the invention is as follows:
photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2The preparation method comprises the following steps:
1) preparation of substrate Mn0.5Cd0.5S solid solution;
2) mixing Mn prepared in the step 1)0.5Cd0.5Ultrasonically dispersing S solid solution in water, adding soluble copper salt and Na2S and Na2SO3Stirring for reaction to obtain in-situ loaded Cu2-xS/Mn0.5Cd0.5S；
3) Adding (NH) into the solution after the reaction in the step 2)4)2MoS4The MoS is directionally loaded by adopting a loading method of visible light photoreduction2Formation of Cu2-xS/Mn0.5Cd0.5S/MoS2。
Preferably, in step 1), the substrate Mn0.5Cd0.5The preparation method of the S solid solution comprises the following steps:
dissolving soluble manganese salt and soluble cadmium salt with equal molar weight in water, and recording as A solution; dissolving L-cystine in alkaline aqueous solution to obtain solution B, slowly adding the solution A into the solution B, and carrying out hydrothermal reaction to obtain the L-cystine. The L-cystine used in the invention is taken as a sulfur source, because the L-cystine is beneficial to the purification of products, and the speed of releasing the sulfur source is relatively slow, thus being beneficial to the generation of solid solution.
Further preferably, the soluble manganese saltIs Mn (CH)3COO)2·4H2O、MnCl2、MnSO4Or Mn (NO)3)3。
Further preferably, the soluble cadmium salt is Cd (CH)3COO)2·2H2O、CdCl2、CdSO4Or Cd (NO)3)3。
Further preferably, the pH of the solution B is 10.5.
Further preferably, the molar ratio of the soluble manganese salt, the soluble cadmium salt and the L-cystine is 1:1: 6.
More preferably, the solution A is slowly added into the solution B and then stirred for 20-40 min. Is beneficial to the formation of the precursor, and then carries out hydrothermal reaction.
Further preferably, the temperature of the hydrothermal reaction is 125-135 ℃, and the time of the hydrothermal reaction is 9-11 h.
Further preferably, in step 2), the obtained Cu is prepared2-xS/Mn0.5Cd0.5In S, Cu/(Mn + Cd) was 0.015 by mol.
Cu prepared by the preparation method2-xS/Mn0.5Cd0.5S/MoS2The composite photocatalytic material is characterized in that Cu/(Mn + Cd) is 0.015 by molar amount.
Preferably, the Cu2-xS/Mn0.5Cd0.5S/MoS2In the composite photocatalytic material, MoS2Is 3.0 wt%.
Cu as described above2-xS/Mn0.5Cd0.5S/MoS2The composite photocatalytic material is applied to the hydrogen production and sulfide treatment by photocatalytic water decomposition.
The process of photocatalytic water splitting to produce hydrogen is carried out in solution of sodium sulfide and sodium sulfite, and can be used as sacrificial agent in catalytic process to facilitate photocatalytic reaction and consume sodium sulfide pollutant.
The invention has the beneficial effects that:
(1) cu prepared by the invention2-xS/Mn0.5Cd0.5S/MoS2The composite photocatalytic material shows excellent hydrogen production activity for photocatalytic decomposition of water, and the hydrogen production rate reaches 13752.4 mu mol/h/g. Experimental research shows that Cu2-xS/Mn0.5Cd0.5S/MoS2The photocatalyst shows good photocatalytic performance, the hydrogen production rate under visible light reaches 13752.4 mu mol/h/g, and the photocatalyst is monomer Mn0.5Cd0.522 times of S is MoS2/Mn0.5Cd0.53.48 times of S is Cu2-xS/Mn0.5Cd0.51.7 times of S. MoS alone2The load carrying property is pure Mn0.5Cd0.56.32 times S, Cu alone2-xS load property is pure Mn0.5Cd0.512.95 times of S, and the two are loaded together. The performance is further improved through the synergistic effect of the Mn and the Mn, and the performance is monomer Mn0.5Cd0.522 times of S.
(2) Cu of the invention2-xS/Mn0.5Cd0.5S/MoS2The preparation and synthesis method of the composite photocatalytic material has the advantages of simple conditions, no pollution, good stability and higher commercial application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is an X-ray powder diffraction pattern of a sample prepared in example 1 of the present invention and a standard card corresponding to each sample;
FIG. 2 is a light absorption spectrum of a sample prepared in example 1 of the present invention;
FIG. 3 is SEM and TEM (scanning electron microscope and transmission electron microscope) spectra of a sample prepared in example 1 of the present invention;
FIG. 4 is an XPS (X-ray photoelectron spectroscopy) spectrum of a sample obtained in example 1 of the present invention;
FIG. 5 shows a sample prepared in example 1 of the present invention and Mn alone0.5Cd0.5S，Cu2-xS/Mn0.5Cd0.5S， MoS2/Mn0.5Cd0.5S and different Cu2-xS，MoS2And (4) comparing the photocatalytic hydrogen production performance by the loading sequence.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, due to the shortage of energy and a series of environmental pollution caused by burning energy, extensive research on preparing novel high-efficiency pollution-free hydrogen energy by people is carried out, and photocatalytic high-efficiency hydrogen production is an important hotspot.
Based on the Cu, the invention provides Cu modified by double promoters2-xS/Mn0.5Cd0.5S/MoS2A composite photocatalytic material, a preparation method thereof and application in photocatalytic hydrogen production and sulfide treatment.
In one embodiment of the present application, there is provided a Cu2-xS/Mn0.5Cd0.5S/MoS2The preparation method of the composite photocatalytic material comprises the following steps:
firstly, synthetic Mn is prepared0.5Cd0.5S solid solution base material, then ingeniously utilizing different solubilities to obtain Cu by in-situ loading2-xS-modified Mn0.5Cd0.5S solid solution, which constructs a nano-scale local P-N junction. The construction of the P-N junction can effectively promote the separation of carriers, and the photogenerated holes flow to Cu2-xS, photo-generated electron flow to the substrate materialMn0.5Cd0.5And (3) S solid solution. The electrons and holes are effectively separated and then are reduced by light (NH)4)2MoS4Method of (2) Directional Loading of MoS2In Mn0.5Cd0.5S solid solution substrate, thereby realizing spatially separated dual-promoter modified Mn0.5Cd0.5And S is respectively used as an active site for oxidation and reduction, so that the separation of a photon-generated carrier is greatly promoted, and the performance of photocatalytic hydrogen production under visible light is improved.
As a preferable scheme, the preparation method comprises the following steps:
(1) first, a substrate Mn was synthesized0.5Cd0.5S solid solution, 1mmol of Mn (CH)3COO)2·4H2O and 1mmol of Cd (CH)3COO)2·2H2O was dissolved in 35mL of deionized water and labeled A. 6mmol of L-cystine was dissolved in 35mL of water outside the forest, adjusted to pH 10.5 with 6mol/L NaOH and labeled B. Slowly adding the solution A into the solution B, continuously stirring for 30min, transferring the solution into a stainless steel reaction kettle, and heating for 10h at 130 ℃;
(2) mn to be synthesized0.5Cd0.5S ultrasonic dispersing in 100mL water, and adding a certain amount of Cu (NO)3)2Adding the solution dropwise to the solution for ion exchange, and adding Na2S and Na2SO3Respectively leading the concentration to reach 0.35mol/L and 0.25mol/L, stirring for half an hour to obtain Cu loaded in situ2-xS/Mn0.5Cd0.5S, wherein the molar ratio Cu/(Mn + Cd) is 0.015;
(3) the obtained Cu2-xS/Mn0.5Cd0.5S and Na2S and Na2SO3Adding a certain amount of (NH) into the solution4)2MoS4The MoS is directionally loaded through a loading method of visible light photoreduction2Generation of Cu2-xS/Mn0.5Cd0.5S/MoS2。
Through experimental research, Cu2-xS/Mn0.5Cd0.5S/MoS2The photocatalyst shows a very good photocatalytic performance,the hydrogen production rate under visible light reaches 13752.4 mu mol/h/g, which is monomer Mn0.5Cd0.522 times of S is MoS2/Mn0.5Cd0.53.48 times of S is Cu2-xS/Mn0.5Cd0.51.7 times of S. MoS alone2The load carrying property is pure Mn0.5Cd0.56.32 times S, Cu alone2-xS load property is pure Mn0.5Cd0.512.95 times of S, and the two are loaded together. The performance is further improved through the synergistic effect of the Mn and the Mn, and the performance is monomer Mn0.5Cd0.522 times of S.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
Example 1: cu2-xS/Mn0.5Cd0.5S/MoS2Preparation of composite photocatalytic material
The method comprises the following specific steps:
(1) preparation of Mn by hydrothermal method0.5Cd0.5S solid solution:
1mmol of Mn (CH)3COO)2·4H2O and 1mmol of Cd (CH)3COO)2·2H2O was dissolved in 35mL of deionized water and labeled A. 6mmol of L-cystine was dissolved in 35mL of water outside the forest, adjusted to pH 10.5 with 6mol/L NaOH and labeled B. Slowly adding the solution A into the solution B, continuously stirring for 30min, transferring the solution into a stainless steel reaction kettle, and heating at 130 ℃ for 10 h.
(2) Preparation of Cu by means of in situ ion exchange2-xS/Mn0.5Cd0.5S：
Mn to be synthesized0.5Cd0.5S ultrasonic dispersing in 100mL water, and adding a certain amount of Cu (NO)3)2Adding the solution dropwise to the solution for ion exchange, and adding Na2S and Na2SO3To make it reach the concentration0.35mol/L and 0.25mol/L, stirring for half an hour, and obtaining Cu loaded in situ2-xS/Mn0.5Cd0.5And S, wherein the molar ratio Cu/(Mn + Cd) is 0.015.
(3) Preparation of Cu by photoreduction2-xS/Mn0.5Cd0.5S/MoS2The composite photocatalytic material is as follows:
the obtained Cu2-xS/Mn0.5Cd0.5S and Na2S and Na2SO3Adding a certain amount of (NH) into the solution4)2MoS4The MoS is directionally loaded through a loading method of visible light photoreduction2Formation of Cu2-xS/Mn0.5Cd0.5S/MoS2Wherein MoS2Is 3.0 wt%.
Mn prepared as described above0.5Cd0.5S，Cu2-xS/Mn0.5Cd0.5S/MoS2And Cu2-xS/Mn0.5Cd0.5S， MoS2/Mn0.5Cd0.5The X-ray diffraction pattern of S is shown in FIG. 1, and the diffraction peaks are all in accordance with the matrix Mn0.5Cd0.5S one-to-one correspondence, surface loaded MoS2And Cu2-xThe absence of diffraction peaks for S is due to their low content and high degree of dispersion.
Cu prepared by the above method2-xS/Mn0.5Cd0.5S/MoS2The ultraviolet-visible diffuse reflection absorption spectrum of the compound is shown in figure 2, after the cocatalyst is loaded, the absorption of the band edge of the energy band is not obviously changed, but the absorption after 500nm is obviously changed, and the sulfide of the transition metal is indirectly proved to be loaded on the surface.
Cu prepared by the above method2-xS/Mn0.5Cd0.5S/MoS2The SEM and TEM images are shown in FIG. 3, the morphology obtained after hydrothermal treatment is composed of small particles of tens of nanometers, and MoS cannot be observed on the surface2And Cu2-xThe presence of S. Further observation of TEM and HRTEM images revealed spatially separated MoS2And Cu2-xS tightly attached to Mn0.5Cd0.5Of SThe surface, and the active sites for oxidation and reduction reactions, respectively, electrons and holes can be effectively separated.
Cu prepared by the above method2-xS/Mn0.5Cd0.5S/MoS2The XPS graph of (1) as shown in FIG. 4 shows that, from X-ray photoelectron spectroscopy, Mn, Cd, S, Cu and Mo elements can be detected, and the detection of tetravalent Mo is basically consistent with that reported in the prior literature, which fully indicates that MoS is generated by the loading2At the surface of the substrate, the main body in the energy spectrum of Cu is Cu+Meanwhile, due to the existence of satellite peaks, the Cu part is also shown2+The existence of (A) proves that we load Cu2-xS is on the material.
Application example 1: photocatalytic activity test
1. The experimental method comprises the following steps:
the photocatalytic hydrogen production activity test is carried out in a closed glass reactor connected with circulating cooling water (15 ℃), and before the photocatalytic reaction is started, argon is blown for 30min to remove oxygen. A300W xenon lamp (a simulated solar light lamp) is selected as a light source for top irradiation, and the catalytic activity is evaluated through the hydrogen production amount.
0.05g of a sample (photocatalytic material prepared in example 1) was ultrasonically uniformly dispersed in 0.35mol/L of Na2S and 0.25mol/L of Na2SO3In the solution, oxygen in the solution was removed by bubbling high-purity argon gas for half an hour before irradiation, irradiation was performed, and 50 μ l was manually sampled every 30min and injected into a hydrogen-producing chromatograph for testing.
1. The experimental results are as follows:
example 1 Mn synthesized0.5Cd0.5S，Cu2-xS/Mn0.5Cd0.5S/MoS2And Cu2-xS/Mn0.5Cd0.5S， MoS2/Mn0.5Cd0.5The schematic diagram of the S photocatalytic material in sulfide treatment and hydrogen production is shown in FIG. 5, and as can be seen from FIG. 5, MoS is loaded independently2Can greatly improve the photocatalytic hydrogen production activity, and the optimal load is 3.0 wt% MoS2Hydrogen production comparable to Mn alone0.5Cd0.5S activityThe sexual activity is improved by 6.32 times. Meanwhile, the optimal molar ratio of Cu/(Mn + Cd) is 0.015, and Cu2-xS/Mn0.5Cd0.5S/MoS2Hydrogen production comparable to Mn alone0.5Cd0.5The S activity is improved by 12.94 times. We combine the two, and simultaneously utilize our skillfully loading method to load Cu firstly2-xS/Mn0.5Cd0.5S constructs a p-n junction, and utilizes the p-n junction to effectively and directionally load MoS2Thus realizing the simultaneous loading of the oxidation promoter Cu2-xS and reduction promoter MoS2And the effective space separation of the hydrogen production catalyst and the hydrogen production catalyst can be realized, so that the hydrogen production activity can be further improved. Experimental research shows that Cu2-xS/Mn0.5Cd0.5S/MoS2The photocatalyst shows good photocatalytic performance, the hydrogen production rate under visible light reaches 13752.4 mu mol/h/g, and the photocatalyst is monomer Mn0.5Cd0.522 times of S is MoS2/Mn0.5Cd0.53.48 times of S is Cu2-xS/Mn0.5Cd0.51.7 times of S. MoS alone2The load carrying property is pure Mn0.5Cd0.56.32 times S, Cu alone2-xS load property is pure Mn0.5Cd0.512.95 times of S, and the two are loaded together. The performance is further improved through the synergistic effect of the Mn and the Mn, and the performance is monomer Mn0.5Cd0.522 times of S.
To further verify the smart loading scheme we used, we performed experiments simultaneously changing the order of loading of the two promoters. Firstly, loading 3.0 wt% MoS2Loading Cu on the material in situ2-xS, which relieves us of a problem of selectivity when forming p-n junctions. As a result, the hydrogen production result of the load mode and Cu made by us are found2-xS/Mn0.5Cd0.5S/MoS2The catalytic properties of the materials vary widely, indicating such a disordered MoS2And Cu2-xThe synergistic effect between S is not very good, and only in the load mode, the oxidation promoter Cu with space separation can be realized2-xS and reduction promoter MoS2Better promoting the photocatalytic hydrogen productionIs carried out.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (9)
1. Photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2The preparation method is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of substrate Mn0.5Cd0.5S solid solution;
2) mixing Mn prepared in the step 1)0.5Cd0.5Ultrasonically dispersing S solid solution in water, adding soluble copper salt and Na2S and Na2SO3Stirring for reaction to obtain in-situ loaded Cu2-xS/Mn0.5Cd0.5S; preparation of the obtained Cu2-xS/Mn0.5Cd0.5In S, Cu/(Mn + Cd) is 0.015 by molar amount;
3) adding (NH) into the solution after the reaction in the step 2)4)2MoS4The MoS is directionally loaded by adopting a loading method of visible light photoreduction2Formation of Cu2-xS/Mn0.5Cd0.5S/MoS2；MoS2Is 3.0 wt%.
2. The method of claim 1, wherein: in step 1), substrate Mn0.5Cd0.5The preparation method of the S solid solution comprises the following steps:
dissolving soluble manganese salt and soluble cadmium salt with equal molar weight in water, and recording as A solution; dissolving L-cystine in alkaline aqueous solution to obtain solution B, slowly adding the solution A into the solution B, and carrying out hydrothermal reaction to obtain the L-cystine.
3. The method of claim 2The preparation method is characterized by comprising the following steps: the soluble manganese is Mn (CH)3COO)2·4H2O、MnCl2、MnSO4Or Mn (NO)3)2The soluble cadmium salt is Cd (CH)3COO)2·2H2O、CdCl2、CdSO4Or Cd (NO)3)2。
4. The method of claim 2, wherein: the pH value of the solution B is 10.6.
5. The method of claim 2, wherein: the mol ratio of the soluble manganese salt to the soluble cadmium salt to the L-cystine is 1:1: 6.
6. The method of claim 2, wherein: slowly adding the solution A into the solution B, stirring for 20-40min, and then carrying out hydrothermal reaction.
7. The method of claim 6, wherein: the temperature of the hydrothermal reaction is 125-135 ℃, and the time of the hydrothermal reaction is 9-11 h.
8. Cu produced by the production method according to any one of claims 1 to 72-xS/Mn0.5Cd0.5S/MoS2A composite photocatalytic material.
9. Cu as claimed in claim 82-xS/Mn0.5Cd0.5S/MoS2The composite photocatalytic material is applied to the hydrogen production and sulfide treatment by photocatalytic water decomposition.
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