CN113578348B - Two-dimensional in-plane heterogeneous CuS/CuO, and preparation method and application thereof - Google Patents
Two-dimensional in-plane heterogeneous CuS/CuO, and preparation method and application thereof Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/159—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with reducing agents other than hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a two-dimensional in-plane heterogeneous CuS/CuO. The invention discloses a preparation method of the two-dimensional in-plane heterogeneous CuS/CuO, and a simple partial vulcanization method is utilized to successfully synthesize the two-dimensional ultrathin heterojunction material of CuO and CuS. The particle size of the two-dimensional in-plane heterogeneous CuS/CuO obtained by the method is 100nm multiplied by 50nm, a large amount of synthesis can be realized by amplifying the raw material consumption, and meanwhile, the two-dimensional in-plane heterogeneous CuS/CuO has better light absorption capacity and conductivity than CuO, can improve the separation capacity of photo-generated electrons and holes, and further can improve the photocatalytic reduction of CO 2 The effect of the capacity. Two-dimensional in-plane heterogeneous CuS/CuO photocatalytic reduction of CO 2 The ethanol preparation shows excellent catalytic activity and stability, the yield can reach 270 mu mol/(g.h), and the yield can be stably maintained to be 250 mu mol/(g.h) for a long time under the full spectrum.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a two-dimensional in-plane heterogeneous CuS/CuO, and a preparation method and application thereof.
Background
Today, fossil energy is in increasing shortage, and it will be a necessary trend to explore new clean energy and methods for preparing the same. CO 2 Not only is the main gas causing the greenhouse effect, but also is an important resource for reuse.
In recent years, numerous scientific studies have shown that: CO 2 Can be converted into valuable products which can be used as fuel, such as methanol, ethylene, ethanol, carbon monoxide, methane and the like. CO is processed by 2 The catalytic reduction is a clean energy source, so that the problem of energy shortage can be relieved, and the greenhouse effect which is harmful to the ecological environment of the earth can be relieved. Thus, the catalytic reduction of CO 2 Has profound significance in the research of (2).
Light energy is of great interest as a clean and renewable resource, and therefore photocatalytic reduction of CO 2 Is a promising method, but also has the problems of low catalytic efficiency, high catalyst preparation cost and the like. At present, CO is reduced by photocatalysis 2 In the field, semiconductor photocatalysts are widely studied due to their special band structure and low cost.
CuO photocatalyst has good absorption performance in visible light region and CO absorption performance due to low price 2 Reduction ofThe multi-selectivity of the product has received much attention and is considered one of the potential photocatalysts. However, a single CuO catalyst has limited application in this field because it has low separation efficiency for photo-generated electrons and holes and cannot effectively use the photo-generated electrons and holes. So various copper oxide composite photocatalytic materials (CuO-metal, cuO-semiconductor, cuO-MOFs) and the like gradually enter the field of view of researchers, but most of the preparation methods of the composite photocatalysts are complex, cannot realize a large amount of synthesis, do not achieve great breakthrough in performance, and are limited in production cost, environmental friendliness and the like.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a two-dimensional in-plane heterogeneous CuS/CuO, a preparation method and application thereof, wherein the obtained two-dimensional in-plane heterogeneous CuS/CuO is used as a catalyst for carrying out photocatalytic reduction on carbon dioxide, and the carbon dioxide can be reduced into ethanol with high added value in a wide spectrum range with high yield of 270 mu mol/(g.h), so that the performance (50 mu mol/(g.h)) of reducing the carbon dioxide into the ethanol by the current CuO composite material photocatalyst is greatly improved.
The preparation method of the two-dimensional in-plane heterogeneous CuS/CuO comprises the following steps:
and 2, adding the precursor into water to uniformly disperse, then dripping a vulcanizing agent, and stirring and reacting for 10-200s at 25-35 ℃ to obtain the two-dimensional in-plane heterogeneous CuS/CuO.
The invention prepares the precursor CuO nanosheets by a reflux method, and then prepares the two-dimensional in-plane heterogeneous CuS/CuO photocatalytic material by vulcanizing the precursor by a simple partial vulcanization method. Compared with a CuO precursor, the light absorption range of the two-dimensional in-plane heterogeneous CuS/CuO obtained by partial vulcanization is widened to the infrared region, and meanwhile, a built-in electric field can be constructed to promote the separation of photo-generated electron holes, so that the photocatalytic performance is greatly improved. The catalyst is applied to photocatalytic reduction of CO 2 Can convert CO in a wide spectrum 2 Reduction to high value added product C 2 H 5 OH。
Preferably, the specific operation of step 1 is as follows: stirring ethylene glycol, dissolving copper acetate in water, dropwise adding the water into the ethylene glycol for stirring, dropwise adding n-propylamine for stirring reaction for 25-35min, adding potassium carbonate-potassium bicarbonate buffer solution for stirring, and maintaining the system temperature at 25-35 ℃; then the temperature of the system is raised to 100-150 ℃ and stirred for reaction for 5-10h, and then the precursor is obtained by washing and drying.
Preferably, the mass ratio of the n-propylamine to the copper acetate is 0.8-1.2:0.8-1.2.
Preferably, the sum of the masses of n-propylamine, ethylene glycol, water and potassium carbonate-potassium bicarbonate buffer is a, and the mass of copper acetate is b, then a: b=1: 2.
preferably, the specific operation of step 2 is as follows: dispersing the precursor obtained in the step 1 in water, then dripping a vulcanizing agent, stirring and reacting for 10-200s at 25-35 ℃, centrifugally washing, and drying to obtain the two-dimensional in-plane heterogeneous CuS/CuO.
Preferably, the vulcanizing agent is at least one of ammonium sulfide, sodium sulfide and carbon disulfide, and preferably ammonium sulfide.
Preferably, the volume to mass ratio of vulcanizing agent to precursor (μl: mg) is 0.8-1.2:0.8-1.2.
The two-dimensional in-plane heterogeneous CuS/CuO is prepared by adopting the preparation method of the two-dimensional in-plane heterogeneous CuS/CuO.
The two-dimensional in-plane heterogeneous CuS/CuO is used as a catalyst for catalyzing carbon dioxide to prepare ethanol.
The two-dimensional in-plane heterogeneous CuS/CuO catalysis method comprises the following steps: the two-dimensional in-plane heterogeneous CuS/CuO is coated on the surface of a glass plate, dried and placed in a photocatalysis reaction tank, water is added into the reaction tank, circulating condensed water is opened after sealing, the system pressure is reduced to 0.5-1.5KPa through vacuum pump filtration to remove impurity gases such as oxygen, nitrogen and the like in a catalytic system, carbon dioxide is introduced to the system pressure of 75-85KPa, then vacuumizing is carried out again, the process is repeated for 3 times, finally, the carbon dioxide is introduced to the system pressure of 75-85KPa, and illumination is carried out through a xenon lamp.
The product is detected by using nuclear magnetism, and the non-impurity introduction of the produced ethanol is determined by comparison with a blank experiment of introducing Ar, and the photocatalytic performance of the two-dimensional in-plane heterogeneous CuS/CuO obtained by the invention is compared with that of a pure-phase CuO nano-plate catalyst, so that the obvious improvement of the heterogeneous structure on the photocatalytic performance is shown.
Preferably, the condensed water temperature is 5 ℃.
Preferably, the deuterating agent used for nuclear magnetic resonance detection is heavy water (D 2 O), the reference sample is DMSO.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for preparing the two-dimensional in-plane heterogeneous CuS/CuO by adopting the method of refluxing and then partially vulcanizing at normal temperature has the advantages of low energy consumption, realization of large-scale synthesis and good industrial application prospect.
2. According to the invention, cuS is introduced into two-dimensional CuO by a partial vulcanization method, and the light absorption range of the CuO is expanded to the infrared region, so that the CO is reduced by the photocatalysis of the catalyst 2 The performance is greatly improved, and the problem that the existing photocatalyst has weak light absorption and utilization capacity is solved to a certain extent.
3. The two-dimensional in-plane heterogeneous CuS/CuO obtained by the invention can be used as a catalyst to efficiently carry out CO 2 Reduction to C with high added value 2 H 5 OH, and the product has high selectivity and easy separation, and has certain industrial application prospect.
4. The two-dimensional in-plane heterogeneous CuS/CuO obtained by the invention is used as a catalyst for photocatalytic reduction of CO 2 Preparation C 2 H 5 The productivity of OH can reach 270 mu mol/(g.h), which is improved by more than 18 times than that of the pure CuO two-dimensional nano-sheet catalyst; the light utilization range is wide, the activity is high, the stability is good, and the yield can be stably maintained to be 250 mu mol/(g.h) for a long time under the full spectrum.
Drawings
FIG. 1 is an optical photograph of a two-dimensional in-plane heterogeneous CuS/CuO obtained by the present invention, which can realize a large amount of synthesis.
FIG. 2 is an X-ray diffraction (XRD) pattern of a two-dimensional in-plane heterogeneous CuS/CuO and CuO catalyst obtained in accordance with the present invention.
FIG. 3 is a Raman spectrum of a two-dimensional in-plane heterogeneous CuS/CuO and CuO catalyst obtained by the invention.
Fig. 4 is a Transmission Electron Microscope (TEM) photograph of the two-dimensional in-plane heterogeneous CuS/CuO and CuO catalyst obtained in the present invention, wherein fig. 4a is a TEM photograph of the CuO catalyst, and fig. 4b is a TEM photograph of the two-dimensional in-plane heterogeneous CuS/CuO obtained in the present invention.
FIG. 5 is a photograph of an HRTEM of a two-dimensional in-plane heterogeneous CuS/CuO obtained according to the present invention.
FIG. 6 is a graph of the ultraviolet visible absorption spectra (UV-vis) of the resulting two-dimensional in-plane heterogeneous CuS/CuO and CuO catalysts of the present invention.
FIG. 7 is a two-dimensional in-plane heterogeneous CuS/CuO photocatalytic reduction of CO with varying degrees of sulfidation 2 Yield C 2 H 5 OH efficiency diagram.
FIG. 8 is a two-dimensional in-plane heterogeneous CuS/CuO photocatalytic reduction of CO with varying degrees of sulfidation 2 Yield C 2 H 5 OH stability diagram.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
The chemical reagents used in the examples below were all analytically pure, and the purity of the carbon dioxide gas used was 99.999%.
Example 1
The preparation method of the two-dimensional in-plane heterogeneous CuS/CuO comprises the following steps:
then the temperature of the system is raised to 100 ℃ and stirred for reaction for 10 hours, and then the precursor is obtained by washing and drying;
Example 2
The preparation method of the two-dimensional in-plane heterogeneous CuS/CuO comprises the following steps:
then the temperature of the system is raised to 150 ℃ and stirred for reaction for 5 hours, and the precursor is obtained by washing and drying;
Example 3
The preparation method of the two-dimensional in-plane heterogeneous CuS/CuO comprises the following steps:
and 2, taking 50mg of the precursor obtained after the drying in the step 1, uniformly dispersing with 5mL of ultrapure water, putting into a beaker for standby, then dropwise adding 50 mu L of ammonium sulfide into the beaker, stirring at a constant temperature of 30 ℃ for reaction for 60 seconds, centrifugally washing, drying and collecting to obtain the two-dimensional in-plane heterogeneous CuS/CuO.
The two-dimensional in-plane heterogeneous CuS/CuO obtained in this example was subjected to phase analysis by XRD, as shown in fig. 2, and the diffraction peak of the two-dimensional in-plane heterogeneous CuS/CuO may be assigned the JCPDS with the card number: 72-0629 CuO and JCPPS: 79-2321, which illustrates that the precursor material synthesized by the method is a CuS/CuO heterojunction.
Characterization of the two-dimensional in-plane heterogeneous CuS/CuO and precursor (CuO) obtained in this example by Raman Spectroscopy, as shown in FIG. 3, the Raman shift was 261.9cm -1 And 471.0cm -1 The peak appearing at the position is a Cu-S vibration peak, and the peak position and the peak type of CuO are not changed along with the improvement of the vulcanization degree, and meanwhile, the CuS peak is continuously increased; further aided by the formation of CuS, i.e., the material synthesized by the present invention is a CuS/CuO heterojunction.
The two-dimensional in-plane heterogeneous CuS/CuO obtained in this example and the precursor (CuO) were transmitted using an electron microscope, as shown in fig. 4 and 5.
As can be seen from the low resolution TEM photograph of fig. 4: the precursor CuO obtained in the embodiment presents a two-dimensional ultrathin sheet shape, and the average size is approximately 100nm multiplied by 50nm; the two-dimensional in-plane heterogeneous CuS/CuO obtained in the embodiment is still in a two-dimensional ultrathin sheet shape, and the average size is approximately 100nm multiplied by 50nm.
As can be seen from the high resolution TEM photograph of fig. 5: the crystal lattices of CuS and CuO appear on the same sheet, which further proves that the substance obtained by the invention is a heterojunction material; the crystal planes exposed by CuO are: (010), (100), and the crystal plane exposed by CuS is (103).
From the UV-vis spectrum of FIG. 6, it can be seen that: the light absorption capacity of the two-dimensional in-plane heterogeneous CuS/CuO obtained by the embodiment is obviously enhanced compared with that of CuO at 700-1500nm, and the light absorption and utilization range is expanded to a near infrared region; this is also an important reason for its great breakthrough in photocatalytic performance.
In view of the characterization results, the method for preparing the two-dimensional in-plane heterogeneous CuS/CuO by adopting the method of refluxing and then partially vulcanizing at normal temperature is greatly improved in light absorption compared with the original CuO nanosheets.
Example 4
The procedure is as in example 3, except that in step 1: solvents (ethylene glycol, buffer solution, n-propylamine); solute [ Cu (Ac) ] 2 Expanding 2-10 times at the same time; the results obtained were similar to those of example 3.
Example 5
The procedure is as in example 3, except that in step 2: dissolving 100-1000mg of CuO powder (i.e. precursor) in 10-100mL of ultrapure water, and adding 100-1000 mu L of ammonium sulfide, wherein the proportion of the ammonium sulfide to CuO is kept unchanged, and other conditions are kept unchanged; the results obtained were similar to those of example 3.
Comparing examples 3-5 found that: the raw materials used in the invention are added in the same proportion to obtain a large amount of catalysts, which shows that the method for preparing the in-plane heterogeneous CuS/CuO photocatalytic material is simple, can realize a large amount of synthesis, and the catalyst yield is limited only by the size of a reaction vessel, as shown in figure 1.
The two-dimensional in-plane heterogeneous CuS/CuO obtained in examples 3-5 was used for the photocatalytic reduction of CO 2 Preparation C 2 H 5 OH：
Weighing 8mg of two-dimensional in-plane heterogeneous CuS/CuO, uniformly dispersing, coating the two-dimensional in-plane heterogeneous CuS/CuO on a glass plate, putting the glass plate coated with the two-dimensional in-plane heterogeneous CuS/CuO into a photocatalytic reaction tank after the solvent is completely volatilized and dried, and adding 20mL of ultrapure water into the reaction tank; after the cyclic condensate water (5 ℃) is opened after the sealing is covered, a vacuum pump is utilized to deoxidize until the system pressure is 1KPa, and then CO is introduced through an air inlet of the reaction tank 2 Until the system pressure is 80KPa; and (5) after the reaction system is stable, utilizing a xenon lamp to irradiate.
And detecting a product by using nuclear magnetism, comparing with a blank experiment of Ar to determine that the produced ethanol is not introduced with impurities, and comparing the photocatalytic performance of the CuO (namely a precursor) obtained in the step 1 and the two-dimensional in-plane heterogeneous CuS/CuO, so that the influence of vulcanization on the performance is shown.
Photocatalytic reduction of CO as in FIG. 7 2 Yield C 2 H 5 The OH efficiency diagram is shown: the two-dimensional in-plane heterogeneous CuS/CuO obtained by the invention has good photocatalytic reduction of CO 2 Preparation of C 2 H 5 Performance of OH, yield of270 mu mol/(g.h) can be achieved, and the catalyst is improved by about 18 times compared with a pure CuO two-dimensional nano-plate catalyst; at the same time for C 2 H 5 OH has very high selectivity and can reach 97 percent.
Photocatalytic reduction of CO as in FIG. 8 2 Yield C 2 H 5 The OH stability diagram is shown: photocatalytic reduction of CO 2 Preparation of C 2 H 5 The stability of OH can reach more than 20h, and has good development prospect.
The photocatalytic test results described above confirm that: the two-dimensional in-plane heterogeneous CuS/CuO obtained by the invention can be well applied to the photocatalytic reduction of CO 2 Yield C 2 H 5 OH, catalytic activity and stability are higher than those of CuO nano-sheets, and the method has good research value and application prospect.
Example 6
The two-dimensional in-plane heterogeneous CuS/CuO coating amount obtained in example 3 is respectively set to 7.0mg, 7.5mg, 8.5mg, 9.0mg, 9.5mg and 10.0mg, and other photocatalysis conditions are all kept unchanged; the results obtained were similar to the photocatalytic test results described above.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. The preparation method of the two-dimensional in-plane heterogeneous CuS/CuO is characterized by comprising the following steps of:
step 1, dissolving copper acetate in water, dropwise adding n-propylamine, stirring at 25-35 ℃ for reaction for 25-35min, then heating to 100-150 ℃ for stirring for reaction for 5-10h, and obtaining a precursor;
step 2, adding the precursor into water for uniform dispersion, and then dropwise adding ammonium sulfide, wherein the volume-mass ratio of the ammonium sulfide to the precursor is 0.8-1.2 mu L:0.8-1.2mg, and stirring and reacting for 10-200s at 25-35 ℃ to obtain the two-dimensional in-plane heterogeneous CuS/CuO.
2. The method for preparing two-dimensional in-plane heterogeneous CuS/CuO according to claim 1, wherein the specific operation of step 1 is as follows: stirring ethylene glycol, dissolving copper acetate in water, dropwise adding the water into the ethylene glycol for stirring, dropwise adding n-propylamine for stirring reaction for 25-35min, adding potassium carbonate-potassium bicarbonate buffer solution for stirring, and maintaining the system temperature at 25-35 ℃; then the temperature of the system is raised to 100-150 ℃ and stirred for reaction for 5-10h, and then the precursor is obtained by washing and drying.
3. The method for preparing the two-dimensional in-plane heterogeneous CuS/CuO according to claim 1, wherein the mass ratio of n-propylamine to copper acetate is 0.8-1.2:0.8-1.2.
4. The method for preparing two-dimensional in-plane heterogeneous CuS/CuO according to claim 2, wherein the sum of the mass of n-propylamine, ethylene glycol, water and potassium carbonate-potassium bicarbonate buffer isaThe mass of the copper acetate isbThena：b=1：2。
5. The method for preparing two-dimensional in-plane heterogeneous CuS/CuO according to claim 1, wherein the specific operation of step 2 is as follows: and (3) dispersing the precursor obtained in the step (1) in water, then dropwise adding ammonium sulfide, stirring at 25-35 ℃ for reacting for 10-200s, centrifugally washing, and drying to obtain the two-dimensional in-plane heterogeneous CuS/CuO.
6. A two-dimensional in-plane heterogeneous CuS/CuO, which is prepared by the two-dimensional in-plane heterogeneous CuS/CuO preparation method according to any one of claims 1 to 5.
7. The two-dimensional in-plane heterogeneous CuS/CuO as claimed in claim 6, which is used as a catalyst for catalyzing carbon dioxide to prepare ethanol.
8. A method of catalyzing the two-dimensional in-plane heterogeneous CuS/CuO according to claim 6, comprising the steps of: the two-dimensional in-plane heterogeneous CuS/CuO is coated on the surface of a glass plate, dried and placed in a photocatalysis reaction tank, water is added into the reaction tank, circulating condensed water is started after sealing, the system is subjected to vacuum suction filtration to remove impurity gas, carbon dioxide is introduced until the pressure of the system is 75-85KPa, and a xenon lamp is adopted for illumination.
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