CN114832834A - L-CNSx/MCS composite photocatalyst and preparation method and application thereof - Google Patents

L-CNSx/MCS composite photocatalyst and preparation method and application thereof Download PDF

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CN114832834A
CN114832834A CN202210549774.4A CN202210549774A CN114832834A CN 114832834 A CN114832834 A CN 114832834A CN 202210549774 A CN202210549774 A CN 202210549774A CN 114832834 A CN114832834 A CN 114832834A
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cnsx
mcs
composite photocatalyst
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CN114832834B (en
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冯胜
周赟
戴晓军
范鲁芳
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Changzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
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    • C—CHEMISTRY; METALLURGY
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention belongs to the technical field of photocatalyst and environmental material preparation, and particularly relates to an L-CNSx/MCS composite photocatalyst, and a preparation method and application thereof. The invention utilizes L-CNSx and MCS to construct L-CNSx/MCSS-Scheme heterojunction as an effective and powerful system for enhancing and stabilizing visible light driven HER. On the one hand, the effective L-CNSx/MCS heterojunction enhances the stability of the MCS photocatalyst. On the other hand, the strong internal electric field greatly facilitates the spatial separation of the redox sites in the heterojunction. With the addition of L-cysteine, not only the sulfur source is provided, but also the blocking effect is achieved to improve the stability.

Description

L-CNSx/MCS composite photocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalyst and environmental material preparation, and particularly relates to an L-CNSx/MCS composite photocatalyst, and a preparation method and application thereof.
Background
The widespread use of fossil fuels has created environmental pollution and energy shortages, and the development of clean and renewable energy sources has become an increasingly important step in achieving environmental sustainability. At present, renewable energy sources such as solar energy, wind energy, hydroenergy, biomass, geothermal energy and the like have attracted much attention. But renewable energy generally has the characteristics of regionality, unsustainability, inconvenience in storage and transportation and the like. In contrast, hydrogen energy is considered one of the most promising energy sources for its high efficiency, cleanliness, ease of storage and transportation.
Among the various hydrogen production processes, photocatalytic water splitting is considered a promising technology for converting solar energy into chemical energy. The photocatalytic water splitting hydrogen production is cleaner, more economic and more energy-saving, can promote the energy revolution, realizes sustainable development, has great promotion effect on the construction of low-carbon society, and shows wide development prospect.
Many semiconductor materials are used for photocatalytic hydrogen production, where metal sulfides have been the focus of research in recent years due to their suitable band structures. The Mn-Cd-S solid solution further improves the photocatalytic hydrogen evolution performance of the original single metal sulfide (CdS, MnS), well improves the potential position of a conductive band and enhances the redox capability. However, in the process of photocatalysis, sulfide ions are oxidized into sulfur or sulfate, which causes severe photo-corrosion of MCS, limits its photocatalytic performance, and its stability and activity still face great challenges. The construction of a heterojunction of sulfide catalyst is one of the most effective measures to improve the space charge separation of MCS and to suppress its photo-corrosion. Of the many catalysts, cobalt-based catalysts are cheaper and more durable, particularly CoNiSx (CNSx) with sulfur octahedral vacancies centered on the face center, and Ni 2+ And Co 2+ And tetrahedral vacancies are all vacancies. These empty tetrahedral sites provide 3D paths for electron transitions and electrolyte ions, but when used alone, suffer from limited hydrogen production efficiency and poor stability.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an L-CNSx/MCS composite photocatalyst and a preparation method and application thereof. Firstly, synthesizing CNSx, then loading MCS on the surface of the CNSx by a solvothermal method, and sealing the end by using L-cysteine to prepare an L-CNSx/MCS composite photocatalyst; the L-CNSx/MCS composite photocatalyst is used for producing hydrogen by photocatalytic water decomposition.
The invention firstly provides an L-CNSx/MCS composite photocatalyst which is of a three-dimensional structure, wherein the composite photocatalyst is formed by growing MCS with an irregular nanoparticle structure on the surface of a cube CNSx in an in-situ growth mode, and the composite material L-CNSx/MCS is more stable in circulation by using an L-cysteine end sealing.
The invention also provides a preparation method of the L-CNSx/MCS composite photocatalyst, which comprises the following steps:
(1) dissolving cobalt salt and nickel salt in a methanol solution, adding a methanol solution of 2-methylimidazole, fully stirring, standing, collecting precipitate, washing, and dispersing in an ethanol solution to obtain the CNSx precursor dispersion liquid.
(2) And (2) adding the CNSx precursor dispersion liquid in the step (1) into an L-cysteine solution, adjusting the pH value to be alkaline, performing ultrasonic treatment, and stirring to obtain an L-CNSx precursor solution.
(3) And (3) dissolving soluble manganese salt, chromium salt and thioacetamide in deionized water, adding the L-CNSx precursor solution prepared in the step (2), uniformly mixing, moving into a reaction kettle, and carrying out solvothermal reaction to obtain the L-CNSx/MCS composite photocatalyst.
Further preferably, the mass ratio of the manganese salt to the chromium salt to thioacetamide in step (3) is 0.25:0.27: 0.48. And/or the manganese salt and the chromium salt are each Mn (CH) 3 COO) 2 ·4H 2 O、Cd(CH 3 COO) 2 ·2H 2 O。
Further, in the step (3), the conditions of the solvothermal reaction are as follows: the reaction was carried out at 180 ℃ for 24h.
And/or, washing and drying steps are also included after the reaction is finished, and the drying temperature is 60 ℃.
Further, the molar ratio of the manganese salt, the chromium salt, the cobalt salt, the nickel salt, the dimethyl imidazole and the L-cysteine is 3400:3100:5-15:1-3:16-48:5-15, and the molar ratio of the cobalt salt to the L-cysteine is 1: 1.
The invention also provides application of the L-CNSx/MCS composite photocatalyst in photocatalytic hydrogen production.
Further, the application comprises the following steps:
irradiating with xenon lamp, dispersing L-CNSx/MCS composite photocatalyst in reaction solution (0.35M Na) 2 S and 0.25M Na 2 SO 3 ) Is added into a photoreactor in vacuum N 2 And reacting under a gas atmosphere.
Furthermore, the dosage of the reaction solution and the photocatalyst is 20mg of the L-CNSx/MCS composite photocatalyst added into each 100mL of the reaction solution.
The invention also provides the preparation of the following materials:
the preparation method of the MnS photocatalyst specifically comprises the following steps: mn (CH) 3 COO) 2 ·4H 2 Dissolving O and thioacetamide in deionized water, stirring until the O and thioacetamide are completely dissolved, carrying out solvothermal reaction, cooling after the reaction is finished, centrifuging, washing with ethanol and deionized water, and drying. More specifically, Mn (CH) 3 COO) 2 ·4H 2 The mass ratio of O to thioacetamide is 0.25: 0.48.
The preparation method of the CdS photocatalyst specifically comprises the following steps: cd (CH) 3 COO) 2 ·2H 2 Dissolving O and thioacetamide in deionized water, stirring until the O and thioacetamide are completely dissolved, carrying out solvothermal reaction, cooling after the reaction is finished, centrifuging, washing with ethanol and deionized water, and drying. More specifically, Cd (CH) 3 COO) 2 ·2H 2 The mass ratio of O to thioacetamide is 0.27: 0.48.
The preparation method of the MCS solid solution photocatalyst specifically comprises the following steps: mn (CH) 3 COO) 2 ·4H 2 O、 Cd(CH 3 COO) 2 ·2H 2 Dissolving O and thioacetamide in deionized water, stirring for dissolving completely, thermally reacting, cooling, centrifuging, and removing ions with ethanolWashing with water and drying.
Compared with the prior art, the invention has the following beneficial effects: the invention utilizes rich redox chemical reaction of Ni-Co sulfide, optimal synergistic effect and better stability. The invention utilizes L-CNSx and MCS to construct L-CNSx/MCSS-Scheme heterojunction which is used as an effective and powerful system for enhancing and stabilizing HER driven by visible light. On the one hand, the effective L-CNSx/MCS heterojunction enhances the stability of the MCS photocatalyst. On the other hand, the strong internal electric field greatly promotes the spatial separation of the redox sites in the heterojunction. With the addition of L-cysteine, not only is a sulfur source provided, but also the effect of blocking and improving stability is achieved.
The invention realizes the aim of producing hydrogen by taking L-CNSx/MCS as a composite photocatalyst through photocatalysis. Under the irradiation of simulated sunlight, the photocatalytic hydrogen production is realized through the separation and transfer of photoproduction electron-hole pairs, the preparation method of the catalyst is simple, and the catalyst adopts nontoxic and cheap raw materials, thereby being an environment-friendly energy conversion technology.
Drawings
FIG. 1 is an XRD spectrum of CNSx, MnS, CdS and MCS prepared in the examples.
Figure 2 is an XRD spectrum of the composite photocatalyst prepared in examples 1 to 4.
FIG. 3 is an SEM photograph of L-CNSx/MCS in example 2.
FIG. 4 is a graph of the catalytic hydrogen production rate of the light embodiment.
FIG. 5 is a diagram of a cycle test of the example.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
In the following examples, photocatalytic activity was evaluated using the following procedure: in a photoreactor, xenon lamp irradiation, the reaction solution (0.35M Na) 2 S and 0.25M Na 2 SO 3 ) Added to the reactor, followed by 20mg of photocatalytic material, N being sustained 2 And vacuumizing after purging, closing the gas outlet to enable the inside of the reactor to reach certain pressure, sealing the reactor, opening a xenon lamp light source, and sampling and analyzing at intervals of 0.5 h.
Example 1: preparation of CNSx/MCS composite photocatalytic material
(1) Preparing an L-CNSx precursor:
3mmol of Co (NO) 3 ) 2 ·6H 2 O、0.6mmol Ni(NO 3 ) 2 ·6H 2 O is weighed into 60ml of methanol respectively and stirred for 0.5h to be fully dissolved. The solution is poured into 60ml of methanol solution containing 9.65mmol of 2-methylimidazole, stirred and dissolved, then kept stand for 12 hours, centrifuged to obtain a precipitate, washed with methanol for 4 times, and finally the collected CNSx is placed into ethanol solution for standby. Adding 3mmol L-cysteine into the ethanol solution, performing ultrasonic treatment for 0.5h, and stirring for 1h to obtain an L-CNSx precursor solution with the concentration of 0.2g/L and without pH adjustment.
(2) Preparation of uncapped CNSx/MCS:
0.25g of Mn (CH) 3 COO) 2 ·4H 2 O、0.27g Cd(CH 3 COO) 2 ·2H 2 O and 0.48g thioacetamide are dissolved in 35mL deionized water, 10mL of L-CNS solution without pH adjustment is added, the mixture is stirred for 0.5h and then transferred into a 50mL reaction kettle, and the reaction is continuously carried out for 24h at 180 ℃. The centrifugal product is washed by ethanol and deionized water for a plurality of times and dried for 12h at the temperature of 60 ℃.
Example 2: preparation of L-CNSx/MCS-1 composite photocatalytic material
(1) Preparing an L-CNSx precursor:
3mmol of Co (NO) 3 ) 2 ·6H 2 O、0.6mmol Ni(NO 3 ) 2 ·6H 2 O is weighed into 60ml of methanol respectively and stirred for 0.5h to be fully dissolved. The solution was poured into a solution of 9.65mmol 2-methylimidazole in 60ml methanol and dissolved with stirringAfter decomposition, standing for 12h, centrifuging to obtain precipitate, washing with methanol for 4 times, and finally placing the collected CNSx in ethanol solution for standby. Adding 3mmol L-cysteine into the ethanol solution, adjusting the pH value to 9, carrying out ultrasonic treatment for 0.5h, and stirring for 1h to obtain an L-CNSx precursor solution with the concentration of 0.2 g/L.
(2) Preparation of L-CNSx/MCS-1:
0.25g of Mn (CH) 3 COO) 2 ·4H 2 O、0.27g Cd(CH 3 COO) 2 ·2H 2 O and 0.48g thioacetamide are dissolved in 35mL deionized water, 5mL L-CNS solution is added, stirred for 0.5h and then transferred into a 50mL reaction kettle, and the reaction is continuously carried out for 24h at 180 ℃. The centrifugal product is washed by ethanol and deionized water for a plurality of times and dried for 12h at the temperature of 60 ℃.
Example 3: preparation of L-CNSx/MCS-2 composite photocatalytic material
(1) Preparing an L-CNSx precursor:
3mmol of Co (NO3) 2.6H 2O and 0.6mmol of Ni (NO3) 2.6H 2O are weighed into 60ml of methanol respectively, and stirred for 0.5H to be fully dissolved. The solution is poured into 60ml of methanol solution containing 9.65mmol of 2-methylimidazole, stirred and dissolved, then kept stand for 12 hours, centrifuged to obtain a precipitate, washed with methanol for 4 times, and finally the collected CNSx is placed into ethanol solution for standby. Adding 3mmol L-cysteine into the ethanol solution, adjusting the pH value to 9, carrying out ultrasonic treatment for 0.5h, and stirring for 1h to obtain an L-CNSx precursor solution with the concentration of 0.2 g/L.
(2) Preparation of L-CNSx/MCS-2:
0.25g of Mn (CH) 3 COO) 2 ·4H 2 O、0.27g Cd(CH 3 COO) 2 ·2H 2 O and 0.48g thioacetamide are dissolved in 35mL deionized water, 10mL L-CNS solution is added, stirred for 0.5h and then transferred into a 50mL reaction kettle, and the reaction is continuously carried out for 24h at 180 ℃. The centrifugal product is washed by ethanol and deionized water for a plurality of times and dried for 12h at the temperature of 60 ℃.
Example 4: preparation of L-CNSx/MCS-3 composite photocatalytic material
(1) Preparing a L-CNSx precursor:
3mmol of Co (NO3) 2.6H 2O and 0.6mmol of Ni (NO3) 2.6H 2O are weighed into 60ml of methanol respectively, and stirred for 0.5H to be fully dissolved. The solution is poured into 60ml of methanol solution containing 9.65mmol of 2-methylimidazole, stirred and dissolved, then kept stand for 12 hours, centrifuged to obtain a precipitate, washed with methanol for 4 times, and finally the collected CNSx is placed into ethanol solution for standby. Adding 3mmol L-cysteine into the ethanol solution, adjusting pH to 9, performing ultrasonic treatment for 0.5h, and stirring for 1h to obtain L-CNSx precursor solution with the concentration of 0.2 g/L.
(2) Preparation of L-CNSx/MCS-3:
0.25g of Mn (CH) 3 COO) 2 ·4H 2 O、0.27g Cd(CH 3 COO) 2 ·2H 2 O and 0.48g thioacetamide are dissolved in 35mL deionized water, 15mL L-CNS solution is added, stirred for 0.5h and then transferred into a 50mL reaction kettle, and the reaction is continuously carried out for 24h at 180 ℃. The centrifugal product is washed by ethanol and deionized water for a plurality of times and dried for 12h at the temperature of 60 ℃.
Example 5: preparation of MnS, CdS and MCS solid solution photocatalytic material
(1) Preparing MnS:
0.25g of Mn (CH) 3 COO) 2 ·4H 2 O and 0.48g thioacetamide are dissolved in 35ml deionized water, stirred for 0.5h and then transferred into a 50ml reaction kettle, and the reaction is continuously carried out for 24h at 180 ℃. The centrifugal product is washed by ethanol and deionized water for a plurality of times and dried for 12h at the temperature of 60 ℃.
(2) Preparing CdS:
0.25g of Cd (CH) 3 COO) 2 ·2H 2 O and 0.48g thioacetamide are dissolved in 35ml deionized water, stirred for 0.5h and then transferred into a 50ml reaction kettle for continuous reaction for 24h at 180 ℃. The centrifugal product is washed by ethanol and deionized water for a plurality of times and dried for 12h at the temperature of 60 ℃.
(3) Preparation of MCS solid solutions:
0.25g of Mn (CH) 3 COO) 2 ·4H 2 O、Cd(CH 3 COO) 2 ·2H 2 O and 0.48g thioacetamide are dissolved in 35ml deionized water, stirred for 0.5h and then transferred into a 50ml reaction kettle for continuous reaction for 24h at 180 ℃. The centrifugal product is washed by ethanol and deionized water for a plurality of times and dried for 12h at the temperature of 60 ℃.
Comparative example: preparation of L-CNSx/MCS-2 composite photocatalytic material
(1) Preparation of L-CNSx powder:
3mmol of Co (NO) 3 ) 2 ·6H 2 O、0.6mmol Ni(NO 3 ) 2 ·6H 2 O is weighed into 60ml of methanol respectively and stirred for 0.5h to be fully dissolved. The solution is poured into 60ml of methanol solution containing 9.65mmol of 2-methylimidazole, stirred and dissolved, then kept stand for 12 hours, centrifuged to obtain a precipitate, washed with methanol for 4 times, and finally the collected CNSx is placed into ethanol solution for standby. Adding 3mmol L-cysteine into ethanol solution, performing ultrasonic treatment for 0.5h, stirring for 1h, adjusting pH to 9, transferring into a 100ml reaction kettle, and continuously reacting at 180 deg.C for 24h. Washing the centrifugal product with ethanol and deionized water for many times, and drying at 60 ℃ for 12h to obtain L-CNSx powder.
(2) Preparation of L-CNSx/MCS-2 (comparative):
0.25g of Mn (CH) 3 COO) 2 ·4H 2 O、0.27g Cd(CH 3 COO) 2 ·2H 2 Dissolving O and 0.48g thioacetamide in 35ml deionized water, stirring for 0.5h, dispersing 2mg of L-CNSx powder in 35ml deionized water, stirring for 0.5h, mixing the two solutions, stirring again for 0.5h, transferring into a 100ml reaction kettle, and continuously reacting for 24h at 180 ℃. The centrifugal product is washed by ethanol and deionized water for a plurality of times and dried for 12h at the temperature of 60 ℃.
The experimental results are as follows:
FIGS. 1 and 2 are XRD spectra of MnS, CdS, CNSx, uncapped CNSx/MCS, L-CNSx/MCS photocatalysts; the XRD pattern of the L-CNSx/MCS is clearly shown in the figure, and the characteristic peaks of the CNSx and the MCS are contained, so that the successful synthesis of the L-CNSx/MCS composite photocatalyst is illustrated.
FIG. 3 is an SEM image of the L-CNSx/MCS-2 composite photocatalyst; from the figure, it can be seen that L-CNSx/MCS-2 is a three-dimensional cube shape.
FIG. 4 is a hydrogen production rate diagram of uncapped CNSx/MCS, L-CNSx/MCS-y (y is 1,2,3), MnS, CdS, and MCS prepared in examples 1 to 8, and it can be seen from the diagram that MCS has better photocatalytic hydrogen production performance compared with MnS and CdS; compared with L-CNSx and MCS, the L-CNSx/MCS prepared by the invention has better photocatalytic hydrogen production performance. Compared with uncapped CNSx/MCS, the L-CNSx/MCS-2 has better hydrogen production performance.
FIG. 5 is a stability experiment chart, and through a continuous test of 25h, the L-CNSx/MCS-2 photocatalytic hydrogen production amount is still kept more than 87 mmol.h -1 ·g -1 The above. The L-CNSx/MCS-2 composite material has higher hydrogen production stability, and the L-CNSx/MCS-2 is more stable than uncapped CNSx/MCS.
The method for preparing the L-CNSx/MCS by firstly preparing the L-CNSx powder is compared with the method for preparing the L-CNSx precursor to prepare the L-CNSx/MCS, and the experimental result shows that the method for preparing the precursor and then preparing the composite material in the experiment has higher hydrogen production amount (92.1 mmol. h) -1 ·g -1 ) The hydrogen production amount (81.3 mmol. multidot.h) was higher than that of comparative example -1 ·g -1 )。
In the scheme of the invention, the L-cysteine-terminated CNSx and MCS are adopted to construct an L-CNSx/MCS S-type heterojunction which is used as an effective and powerful system for enhancing and stabilizing visible light-driven water decomposition hydrogen production, and the L-CNSx/MCS terminated by L-cysteine is more stable than the non-terminated CNSx/MCS.
The L-CNSx/MCSS-Scheme junction enhances the stability of the MCS photocatalyst on one hand, and in addition, the strong internal electric field greatly promotes the spatial separation of the redox sites in the heterojunction. Compared with other samples, the maximum hydrogen production efficiency of the optimized L-CNSx/MCS-2S-Scheme heterojunction under visible light irradiation is 91.2 mmol.h -1 ·g -1 The apparent quantum yield is as high as 25.5% (lambda. 420 nm). The work provides an effective method for obtaining a stable photocatalytic hydrogen production system.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.

Claims (7)

1. An L-CNSx/MCS composite photocatalyst is characterized in that: the L-CNSx/MCS composite photocatalyst is of a three-dimensional structure, and is formed by growing MCS with an irregular nanoparticle structure on the surface of a cube CNSx in an in-situ growth mode and simultaneously sealing an end by using L-cysteine.
2. The method for preparing the L-CNSx/MCS composite photocatalyst as claimed in claim 1, wherein: the method comprises the following steps:
(1) dissolving cobalt salt and nickel salt in a methanol solution, adding a methanol solution of 2-methylimidazole, fully stirring, standing, collecting precipitate, washing, and dispersing in an ethanol solution to obtain a CNSx precursor dispersion solution;
(2) adding the CNSx precursor dispersion liquid in the step (1) into an L-cysteine solution, adjusting the pH value to be alkaline, performing ultrasonic treatment, and stirring to obtain an L-CNSx precursor solution;
(3) and (3) dissolving soluble manganese salt, chromium salt and thioacetamide in deionized water, adding the L-CNSx precursor solution prepared in the step (2), uniformly mixing, moving into a reaction kettle, and carrying out solvothermal reaction to obtain the L-CNSx/MCS composite photocatalyst.
3. The method for preparing the L-CNSx/MCS composite photocatalyst according to claim 2, wherein: in the step (3), the mass ratio of the manganese salt to the chromium salt to the thioacetamide is 0.25:0.27: 0.48;
and/or the manganese salt and the chromium salt are each Mn (CH) 3 COO) 2 ·4H 2 O、Cd(CH 3 COO) 2 ·2H 2 O。
4. The method for preparing the L-CNSx/MCS composite photocatalyst according to claim 2, wherein: in the step (3), the conditions of the solvothermal reaction are as follows: reacting for 24 hours at 180 ℃;
and/or, the reaction also comprises the steps of washing and drying after the reaction is finished, wherein the drying temperature is 60 ℃.
5. The method for preparing the L-CNSx/MCS composite photocatalyst according to claim 2, wherein: the molar ratio of the manganese salt, the chromium salt, the cobalt salt, the nickel salt, the dimethyl imidazole and the L-cysteine is 3400:3100:5-15:1-3:16-48:5-15, and the molar ratio of the cobalt salt to the L-cysteine is 1: 1.
6. The application of the L-CNSx/MCS composite photocatalyst in photocatalytic hydrogen production, as claimed in claim 1.
7. The application of the L-CNSx/MCS composite photocatalyst in photocatalytic hydrogen production, which is disclosed by claim 6, is characterized in that: the method comprises the following steps:
irradiating with xenon lamp, dispersing L-CNSx/MCS composite photocatalyst in reaction solution, wherein the composite photocatalyst contains 0.35M Na 2 S and 0.25M Na 2 SO 3 Then the whole is added into a photoreactor in vacuum N 2 Reacting in a gas atmosphere; the dosage of the reaction solution and the photocatalyst is 20mg of L-CNSx/MCS composite photocatalyst added into each 100mL of the reaction solution.
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