CN112495411A - Carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst and preparation and application thereof - Google Patents
Carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst and preparation and application thereof Download PDFInfo
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 181
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 169
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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
- 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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- 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
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst as well as preparation and application thereof, wherein the preparation method of the catalyst specifically comprises the following steps: (1) respectively dissolving indium trichloride tetrahydrate and sodium orthovanadate in deionized water to obtain an indium chloride aqueous solution and a sodium orthovanadate aqueous solution, dropwise adding the indium chloride aqueous solution into the sodium orthovanadate aqueous solution, and regulating the pH value to be clear to obtain InVO4Precursor solution; (2) taking g-C3N4Ultrasonic dispersion to InVO4And carrying out hydrothermal reaction in the precursor solution, centrifuging, washing and drying the obtained product to obtain the target product. Compared with the prior art, the catalyst prepared by the invention has a wider light absorption range, and can reduce CO under visible light2The capability is greatly improved, and the excellent CO reduction performance is shown2Selectivity of reduction to carbon monoxide, low resistivity, fast carrier transfer, high carrier separation, low carrier recombination rate, and good CO reduction2Cyclic stability, etc.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and relates to a carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst, and preparation and application thereof.
Background
With the rapid development of industrialization and population growth, the demand for energy consumption is increasing worldwide, mainly through the large-scale consumption of non-renewable fossil fuels, resulting in excessive amounts of CO2And (4) generating. Large amount of CO2The emission results in atmospheric CO2The increase in concentration from 280ppm before the industrial revolution to over 410ppm in 2019 has raised public concern about global warming. The global average temperature has risen from the pre-industrial level by more than 1 ℃, which has an adverse effect on a series of environmental and anthropological problems. It is therefore of critical importance to reduce CO considerably2And (4) discharging. In the process of simulating natural photosynthesis, CO in photosynthesis is catalyzed by photocatalyst2And H2The conversion of O to chemicals and fuels is believed to reduce atmospheric CO2One of the most promising approaches to emissions helps to mitigate climate change while providing a renewable fuel. CO generation by sunlight2The fuel is hopeful to synchronously solve two problems of global warming and energy shortage. Therefore, it is crucial to design a highly efficient photocatalyst. Efficient photocatalysts need to have strong light trapping capacity, strong redox potential, high charge separation and excellent cycling performance. Researchers have therefore been working on finding high performance, low cost photocatalysts for reducing CO2。
With H2Solar photocatalytic CO with O as electron source2Two major problems facing conversion technology are low efficiency and insufficient product selectivity, especially for high value-added chemicals. In addition to the high endothermic nature of the reaction, the main reason for the low yield consists in the use of wide-bandgap semiconductors as the photocatalysts, which are generally capable of obtaining UV spectra corresponding to only-4% of the solar spectrumLight, and simultaneously has higher electron-hole recombination rate. Furthermore, the common visible light catalysts, such as titanium dioxide, sulfides, selenides, carbides or nitrides, do not satisfy the simultaneous CO evolution due to the photo-corrosive action in the reaction medium2Reduction and H2The thermodynamic potential required for O oxidation, or the presence of serious stability problems under the reaction conditions. At present, although the CO can be reduced directly under illumination by using a semiconductor photocatalyst2But the efficiency and selectivity are still low.
Graphitized carbon nitride (g-C)3N4) Is a polymer semiconductor, has excellent chemical stability and a unique energy band structure (2.7eV), is a cheap and stable visible light response type catalyst, and is widely used in solar photocatalytic conversion. But g-C3N4The following problems limit its application: (1) poor visible light absorption, (2) highly susceptible recombination of electron-hole pairs generated by photoinduction, and (3) small specific surface area and limited active sites.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to provide a carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst as well as preparation and application thereof, and aims to solve the problems of CO photocatalytic reduction caused by limited light absorption range, few surface active sites, extremely easy recombination of photogenerated carriers and the like of carbon nitride serving as a photocatalytic material2The prepared catalyst has a wide light absorption range, the light absorption edge can reach 600nm, the carriers are not easy to recombine, and the molecular structure of the catalyst is in lambda range>The CO is reduced to CO with the highest speed of 69.8 mu mol.h under the irradiation of simulated sunlight with the wavelength of 420nm-1·g-1。
The purpose of the invention can be realized by the following technical scheme:
on one hand, the invention provides a preparation method of a carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst, which comprises the following steps:
(1) respectively dissolving indium trichloride tetrahydrate and sodium orthovanadate in deionized water to obtain an indium chloride aqueous solutionAnd adding an aqueous solution of sodium orthovanadate, dropwise adding an aqueous solution of indium chloride into the aqueous solution of sodium orthovanadate, and regulating the pH value to be clear to obtain InVO4Precursor solution;
(2) taking g-C3N4Ultrasonic dispersion to InVO4And carrying out hydrothermal reaction in the precursor solution, centrifuging, washing and drying the obtained product to obtain the target product.
Further, in the step (1), the concentration of the aqueous solution of indium chloride is preferably 0.1mmol/ml, and the concentration of the aqueous solution of sodium orthovanadate is preferably 0.05 mmol/ml. Of course, the concentration can be adjusted according to the preparation requirement. Meanwhile, in the dropping process, the dropping rate is controlled to be 0.5 ml/min.
Further, in the step (1), the molar ratio of the indium trichloride tetrahydrate to the sodium orthovanadate is 1: 1.
Further, in the step (1), the pH is adjusted to 1-3. The reagent used for the adjustment is preferably dilute nitric acid, and the concentration can be 1-3M.
Further, in step (2), InVO4The concentration of the precursor solution is 0.3mmol/mL, and g-C3N4And InVO4The addition ratio of the precursor solution is 15-100 mg: 30 mL.
Further, in the step (2), the temperature of the hydrothermal reaction is 180 ℃ and the time is 18 h.
Further, in the step (2), g to C3N4Prepared by pyrolysis of melamine at high temperature.
Further, in step (2), g to C3N4The preparation process specifically comprises the following steps: weighing melamine, heating to 500-550 ℃ in air atmosphere, and calcining for 2-6h to obtain g-C3N4. Calcination is preferably carried out at 520 ℃ for 4 h.
The preparation principle and process of the invention refer to the following:
firstly, the raw material for preparing the carbon nitride is melamine with a triazine ring structure, and the principle of high-temperature pyrolysis is applied to obtain the material with-NH by calcining the melamine2Carbon nitride of (2);
preparing indium vanadate from indium chloride tetrahydrate and sodium orthovanadate through a chemical combination reaction to obtain an indium vanadate aqueous solution;
thirdly, treating the water solution of the indium vanadate by dilute nitric acid by using the principles of acid etching and ultrasonic intercalation to obtain a clear solution, adding carbon nitride into the clear solution of the indium vanadate at room temperature, and performing ultrasonic treatment for a period of time to ensure that the indium vanadate intercalation enters the carbon nitride; wherein, the adjustment of pH has a determining function on the micro-morphology of the prepared catalyst;
fourthly, embedding indium vanadate into the two-dimensional ultrathin carbon nitride nanosheets subjected to intercalation and layering in a quantum dot form under a hydrothermal reaction environment at a certain temperature by using a chemical solution growth method, and prefabricating to form a heterostructure;
indium vanadate and carbon nitride form a Z-shaped heterojunction, so that the recombination of photo-generated electron-hole pairs is effectively inhibited;
the electronic structure of indium vanadate/carbon nitride theoretically conforms to the reduction of CO2The formation of the heterostructure for CO energy greatly enhances the photocatalytic reduction of CO2And (4) performance.
On the other hand, the invention provides a carbon nitride nanosheet-loaded indium vanadate quantum dot photocatalyst, which is prepared by the preparation method. The catalyst contains five elements of In, V, O, C and N, the carbon nitride is of a nanosheet structure, the total thickness of the rice-flake structure is about 1.5nm, the indium vanadate is of a quantum dot structure, the particle size is about 2-3 nm, indium vanadate quantum dots are embedded In the carbon nitride nanosheets, the carbon nitride nanosheets are loaded with indium vanadate quantum dot photocatalysts, and InVO (indium VO) is adopted4And g-C3N4In an amount of InVO4:g-C3N41 mmol: 25-100mg, preferably 1 mmol: the 25mg ratio was calculated. Its absorption edge can be up to 600nm, and its carrier is not easy to recombine, and its lambda value is high>The CO is reduced to CO with the highest speed of 69.8 mu mol.h under the irradiation of simulated sunlight with the wavelength of 420nm-1·g-1And the quantum efficiency reaches 7.24% when lambda is 450 +/-20 nm.
Because the two-dimensional ultrathin carbon nitride nanosheets are synthesized by the room cost of ultrasonic intercalation and acid etching in the preparation process, the carbon nitride nanosheets with the two-dimensional ultrathin structures have unique atomic structures, and compared with bulk phase materials, the carbon nitride nanosheets with the two-dimensional ultrathin structures have ultrathin thicknesses and overlarge specific surface areas, so that a large number of surface atoms can be used as active sites, the catalytic process is improved, the catalytic activity is improved, and a clear atomic structure model is favorably constructed. First, the enlarged surface area associated with ultra-thin thicknesses is very beneficial for light harvesting, mass transport of electrons, and exposure of abundant surface active sites. Second, the ultra-thin nature of the ultra-thin nanomaterials significantly reduces the volume-to-surface charge transfer distance, improving charge separation. More importantly, the two-dimensional ultrathin material can be used as an ideal platform for reasonable design of multi-component light-splitting catalysts so as to meet the requirements of various photocatalysis applications. The two-dimensional ultrathin nanosheet structure is used for constructing a hybrid material of carbon nitride and indium vanadate, so that the hybrid material has a larger active area and good photoproduction charge separation efficiency.
On the other hand, the invention also provides application of the carbon nitride nanosheet loaded indium vanadate quantum dot, which is characterized in that the carbon nitride nanosheet loaded indium vanadate quantum dot is used for photocatalytic reduction of CO2Is CO.
Further, the sunlight with lambda larger than 420nm is used for irradiating light to catalyze and reduce CO2。
The carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst is used as a novel photocatalyst and is used for photocatalytic reduction of CO2The application of (A) has the following advantages:
the two-dimensional ultrathin sheet layer structure has the characteristic of large specific surface area, and provides more surface active sites;
the ultrathin thickness of the two-dimensional ultrathin sheet layer structure is beneficial to charge transfer and promotes the transfer of current carriers;
the existence of quantum dots enables more active sites to be exposed;
indium vanadate is used as a ternary metal oxide semiconductor, and has a narrow band gap (2.0eV), so that the light absorption range of the catalyst is widened;
indium vanadate has excellent chemical stability;
sixth, indium vanadate to CO2Has excellent adsorption capacity and is beneficial to reducing more CO2；
Seventhly acidThe energy band structure of indium can form a Z-type catalyst with carbon nitride, which is beneficial to inhibiting the recombination of electron-hole pairs, thereby promoting CO2Reduction of (2).
According to the carbon nitride supported molybdenum nitride nanoparticle photocatalyst, a molybdenum-based catalyst and the traditional photocatalytic material carbon nitride are combined, and a molybdenum nitride/carbon nitride heterojunction is obtained through an oil bath method, so that the ultraviolet-visible light is absorbed and utilized, the development of the photocatalyst is promoted, and the photocatalyst has remarkable practical application in more fully utilizing sunlight.
Compared with pure graphitized carbon nitride, the carbon nitride nanosheet-loaded indium vanadate quantum dot photocatalyst has a wide light absorption range and high reduction of CO2Performance, low resistivity, ability to rapidly transfer self-current carriers, high ability to separate photogenerated carriers, low carrier recombination rate, and good reduction of CO2The characteristic of cycle stability.
The carbon nitride nanosheet-loaded indium vanadate quantum dot photocatalyst provided by the invention takes a two-dimensional ultrathin nanosheet as a basic framework, indium vanadate quantum dots are embedded into the nanosheet, the morphological characteristics are uniformly and regularly distributed, a high specific surface area is provided for the material to better absorb sunlight, and the existence of the quantum dots is CO2The reduction reaction exposes more reactive sites; the molybdenum nitride and the indium vanadate form a Z-type heterostructure, so that the Z-type heterostructure has photocatalytic activity while absorbing light in a wider range. Therefore, the preparation process is very simple, is suitable for industrial scale production, and has higher economic and practical values.
According to the carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst, indium vanadate is applied to photocatalytic reduction of CO2The material is a ternary metal oxide semiconductor, is a visible light-absorbing noble metal-free photocatalytic material, effectively promotes the separation and transfer of photoproduction electrons and holes, inhibits the recombination of the photoproduction electrons and the holes, and shows that CO is efficiently and selectively reduced2The photocatalyst has CO performance, shows better photocatalytic activity in an ultraviolet-visible light region, and has excellent cycle stability. Under the irradiation of visible light, reducing CO2The highest CO rate can beUp to 69.8 mu mol/h-1·g-1And the quantum efficiency reaches 7.24% when lambda is 450 +/-20 nm. .
Compared with the prior art, the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst has the advantages of ultraviolet-visible light absorption, low photoproduction electron-hole recombination rate, no noble metal and high reduction of CO2Performance, excellent reduction selectivity. The preparation method has the advantages of simple operation, low cost, nontoxic raw materials and production according with the environmental protection concept.
Drawings
FIG. 1a is a scanning electron microscope image of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1 at 30 k;
FIG. 1b is a scanning electron microscope image of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1 at 35 k;
FIG. 1c is a transmission electron microscope image of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1 at 2 μm;
FIG. 1d is a transmission electron microscope image of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1 at 200 nm;
fig. 1e is a high-resolution transmission electron microscope image of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1 at 5 nm;
fig. 1f is a transmission electron microscope image of element distribution of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1 at 500 nm;
FIG. 1g is an atomic force microscope image of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1 at 2.3 μm;
FIG. 2a shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4The precursor of (a), the X-ray electron diffraction pattern of the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in examples 1, 2, 3 and 4;
FIG. 2b shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4Precursor of (2), examples 1, 2, 3 and 4A Fourier infrared graph of the obtained carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst;
FIG. 2C shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4The precursor of (a), and the raman spectrogram of the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in examples 1, 2, 3 and 4;
FIG. 2d shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4The precursor of (a), the ultraviolet-visible diffuse reflection diagram of the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in the embodiments 1, 2, 3 and 4;
FIG. 2e shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4The Kubelka-Munk diagram of the precursor, the carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst obtained in the embodiments 1, 2, 3 and 4;
FIG. 3a shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4Precursor of (a), and indium vanadate quantum dot photocatalyst supported on carbon nitride nanosheet obtained in examples 1, 2, 3 and 4 at λ>Photocurrent plot at 420 nm;
FIG. 3b shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4The precursor of (a), the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in examples 1, 2, 3 and 4 has electrochemical impedance;
FIG. 3C shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4The precursor of (a), the linear cyclic voltammogram of the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in examples 1, 2, 3 and 4;
FIG. 4a shows g-C obtained in step (1) of example 13N4InVO obtained in step (2)4Precursor of (a), and reduction of CO by the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in examples 1, 2, 3 and 4 under irradiation of visible light2Is a graph of CO versus time;
FIG. 4b shows the result of step (1) of example 1g-C3N4InVO obtained in step (2)4Precursor of (a), and reduction of CO by the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in examples 1, 2, 3 and 4 under irradiation of visible light2A rate comparison graph;
fig. 4c is a performance diagram of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1 after being recycled;
FIG. 4d shows CO reduction of the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 12Is a graph of the photon yield of CO;
FIG. 5 is a scanning electron micrograph of the carbon nitride/indium vanadate obtained in comparative example 1 at 8K;
FIG. 6 is a scanning electron micrograph of the carbon nitride/indium vanadate obtained in comparative example 2 at 9K.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the starting materials or processing techniques are conventional and commercially available starting materials or conventional processing techniques in the art.
In the present invention, the electrochemical performance was tested by an electrochemical workstation, which was Chenghua electrochemical workstation, model number CHI 760E.
The ultraviolet-visible diffuse reflectance passes the shmatzu-UV 2600 test;
x-ray electron diffraction passes the D8 advance test;
reduction of CO2The performance test was performed using a Thermofish Trace 1310 gas chromatograph.
The electrochemical performance test method in each embodiment of the invention is as follows:
mixing 7.5mg of carbon nitride nanosheet-loaded indium vanadate quantum dot photocatalyst, 1mg of ethyl cellulose, 1mL of alpha-terpineol and 0.5mL of ethanol, and then carrying out ultrasonic treatment for 12 hours at the power of 60W and the frequency of 40KHz to obtain slurry;
coating the obtained slurry on FTO glass, controlling the coating thickness to be 0.5-1mm, drying in an oven at 60 ℃ to obtain an electrochemical testing working electrode, and then testing at an electrochemical workstation to carry out electrochemical performance.
Example 1
The carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst mainly contains five main elements of In, V, O, C and N, and is prepared by the method comprising the following steps:
(1) carbon nitride (hereinafter referred to as g-C)3N4) Preparation of
Putting 3g of melamine into a tube furnace, heating to 520 ℃ for calcination, wherein the gas atmosphere is air, the heating rate is 5 ℃/min, and the temperature is kept for 4h to obtain g-C3N4；
(2) Indium vanadate (hereinafter referred to as InVO)4) Preparation of the precursor
Dissolving 1mmol of indium trichloride tetrahydrate in 10mL of deionized water, and dissolving 1mmol of sodium orthovanadate in 20mL of deionized water to obtain a 0.1mmol/mL indium chloride aqueous solution and a 0.05mmol/mL sodium orthovanadate aqueous solution respectively;
then, controlling the dropping speed to be 0.5ml/min, dropping 0.1mmol/ml indium chloride aqueous solution into 0.05mmol/ml sodium orthovanadate aqueous solution to obtain mixed solution;
and adjusting the pH of the obtained mixed solution to 2-3 by using 2M dilute nitric acid to obtain a clear solution. Thereby obtaining InVO4The precursor solution of (1);
(3) carbon nitride nanosheet-loaded indium vanadate quantum dot (hereinafter referred to as InVO for short)4Preparation of/CN-II)
25mg of g-C3N4Ultrasonically dispersing the InVO prepared in the step (2)4In a clear solution;
after ultrasonic treatment, transferring the dispersion liquid to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 180 ℃, and the reaction time is 18 hours;
then the g-C obtained by the hydrothermal reaction3N4And InVO4Centrifuging the mixed solution at 8000r/min for 10min, and centrifuging the obtained precipitate with deionized water at 8000r/min for 10 min;
and repeating the centrifugal washing for 7-8 times, and controlling the temperature of the obtained filter cake to be-20 ℃ for freeze drying to obtain the carbon nitride loaded indium vanadate quantum dot nanosheet.
Scanning the obtained carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst under 35000 and 30000 multiplying factors by using a scanning electron microscope (model number is FEI XL 30 SEM-FEG, and the manufacturer is JEOL electronics Co., Ltd., Japan), wherein the obtained scanning electron microscope image is shown in FIGS. 1a and 1b, and the carbon nitride two-dimensional ultrathin sheet layer structure can be seen from FIGS. 1a and 1 b.
Scanning the obtained carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst at 2 μm and 200nm by using a transmission electron microscope (model is JEOL JEM-2100F, the manufacturer is JEOL Electron Co., Ltd., Japan), and the obtained transmission electron microscope image is shown in FIGS. 1c and 1d, and the carbon nitride is a two-dimensional ultrathin sheet structure and no particles are formed in FIGS. 1c and 1d, thereby indicating that the indium vanadate is not a nanoparticle.
Scanning the obtained carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst under 5nm by adopting a transmission electron microscope (the model is JEOL JEM-2100F, the manufacturer is JEOL electron company, and the obtained transmission electron microscope is shown in figure 1e, so that the obtained transmission electron microscope figure is shown in figure 1e, and the figure 1e shows that the carbon nitride has no lattice stripes, is amorphous, the indium vanadate obviously presents lattice stripes, and the lattice stripes present the size of 2-3 nm, thereby indicating that the indium vanadate exists in the form of quantum dots and forms a heterostructure with the carbon nitride.
Scanning the obtained carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst at 500nm by adopting a transmission electron microscope (model is JEOL JEM-2100F, and the manufacturer is JEOL electronics company In Japan), wherein the obtained element distribution is shown In figure 1F, and the figure 1F shows that the material contains five elements of In, V, O, C and N and the element distribution is uniform;
an atomic force microscope instrument (model: 5500AFM, Agilent company, manufacturer) is adopted to measure the obtained carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst at 2.3 mu m, an obtained atomic force microscope picture is shown in figure 1g, and a two-dimensional ultrathin sheet structure of the carbon nitride can be seen from figure 1g to be a nanosheet structure, wherein the total thickness of the nanosheet structure is about 1.5 nm.
g-C was obtained by using an X-ray diffractometer (model: D8 advance, manufacturer: Bruker, Germany) for the procedure (1) of example 13N4Obtaining InVO in step (2)4The XRD patterns obtained by measuring the precursor, the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalysts obtained in example 1, example 2, example 3 and example 4 are shown in fig. 2a, wherein in fig. 2a, the abscissa is the angle of 2 theta, the ordinate is the diffraction peak intensity, and g-C is3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4The symbol,/CN-II, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 1, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4The symbol,/CN-III, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 3, InVO4the/CN-IV represents the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 4, and g-C can be seen from FIG. 2a3N4And InVO4All are pure phases.
g-C obtained in step (1) of example 1 by means of a Fourier Infrared spectrometer (model: IS10, manufacturer: Shimadzu corporation, Japan)3N4Obtaining InVO in step (2)4The obtained fourier infrared spectrogram of the photocatalyst with indium vanadate supported by the carbon nitride nanosheets obtained by the precursor, the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4 is shown in fig. 2b, wherein in fig. 2b, the abscissa is the wave number, the ordinate is the transmittance, and g-C is3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4The expression of/CN-II shows that the carbon nitride nanosheet obtained in example 1 supports indium vanadate quantum dots for photocatalysisAgent, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4The symbol,/CN-III, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 3, InVO4The result of FIG. 2b shows that the indium vanadate quantum dot photocatalyst supported on carbon nitride nanosheets obtained in example 4 is represented by/CN-IV, and that the indium vanadate quantum dot photocatalyst supported on carbon nitride nanosheets obtained in examples 1, 2, 3 and 4 all have g-C3N4And InVO4The characteristic functional group of (1).
g-C was obtained by applying a Raman spectrometer (model: LabRAM, manufacturer: Horiba Jobin Yvon, France) to the sample obtained in the step (1) of example 13N4Obtaining InVO in step (2)4The precursor, the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 1, example 2, example 3 and example 4 are respectively measured, and the obtained raman spectrogram is shown in fig. 2C, wherein in fig. 2C, the abscissa is raman shift, the ordinate is intensity, and g-C is3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4The symbol,/CN-II, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 1, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4The symbol,/CN-III, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 3, InVO4The term "/CN-IV" means the indium vanadate quantum dot photocatalyst supported on the carbon nitride nanosheet obtained in example 4, and it can be seen from FIG. 2c that the indium vanadate quantum dot photocatalyst supported on the carbon nitride nanosheet obtained in examples 1, 2, 3 and 4 all have InVO4Characteristic peak of (2).
g-C was obtained by subjecting the product of step (1) of example 1 to an ultraviolet-visible spectrophotometer (model: UV-2400, manufactured by Shimadzu corporation, Japan)3N4Obtaining InVO in step (2)4The precursor, and the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalysts obtained in example 1, example 2, example 3 and example 4 were measured respectively to obtainThe resulting UV-visible diffuse reflectance is shown in FIG. 2d, where in FIG. 2d, the abscissa is wavelength and the ordinate is absorbance, where g-C3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4The symbol,/CN-II, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 1, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4The symbol,/CN-III, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 3, InVO4The reason why the absorption range of the indium vanadate/carbon nitride composite material is widened after the indium vanadate is loaded is probably analyzed because the indium vanadate is a narrow band gap substance, and the band gap of the indium vanadate/carbon nitride is narrowed due to band gap hybridization after the indium vanadate is added, so that the absorption edge red shift is caused.
g-C was obtained from step (1) of example 1 using an electrochemical workstation (model: CHI760E, manufacturer: Shanghai Chen Hua)3N4Obtaining InVO in step (2)4The photocurrent performance graphs of the obtained photocurrents under the bias voltage of 0.2V are shown in fig. 3a, wherein the abscissa is time and the ordinate is the photocurrent, and g-C is g-C3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4The symbol,/CN-II, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 1, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4The symbol,/CN-III, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 3, InVO4The expression of/CN-IV indicates that the carbon nitride nanosheet obtained in example 4 supports indium vanadate quantum dotsThe oxidant, as can be seen from fig. 3a, has no current generated when the lamp is off and has a photocurrent generated when the lamp is on, thus indicating that under excitation of visible light, the photo-generated electron-hole pairs of indium vanadate/carbon nitride separate, causing current to be generated.
g-C was obtained from step (1) of example 1 using an electrochemical workstation (model: CHI760E, manufacturer: Shanghai Chen Hua)3N4Obtaining InVO in step (2)4When the precursor, the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4 are respectively measured, and the alternating current impedance graph obtained when the frequency is 1000000-0.01Hz is shown in fig. 3b, wherein the abscissa is real part impedance, the ordinate is imaginary part impedance, and g-C is3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4The symbol,/CN-II, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 1, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4The symbol,/CN-III, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 3, InVO4the/CN-IV shows that the indium vanadate quantum dot photocatalyst is loaded on the carbon nitride nanosheet obtained in the example 4, and as can be seen from the graph in FIG. 3b, the radius of the half circle of the Quite spectrum of the indium vanadate/carbon nitride composite material is smaller than that of carbon nitride, so that the impedance of the indium vanadate/carbon nitride composite material is smaller than that of the carbon nitride, and the indium vanadate/carbon nitride composite material is beneficial to transferring photon-generated carriers.
g-C was obtained from step (1) of example 1 using an electrochemical workstation (model: CHI760E, manufacturer: Shanghai Chen Hua)3N4Obtaining InVO in step (2)4Precursor, and the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheets obtained in example 1, example 2, example 3 and example 4 were measured respectively, and a linear voltammogram is shown in fig. 3C, wherein the abscissa is voltage and the ordinate is current density, and g-C is3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4Example is shown by/CN-II1 the obtained carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4The symbol,/CN-III, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 3, InVO4the/CN-IV shows that the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 4, and it can be seen from FIG. 3c that the current of indium vanadate/carbon nitride is larger than that of carbon nitride under the same voltage, thereby indicating that the indium vanadate/carbon nitride can more easily separate photon-generated carriers and is not easy to recombine, and the reason for analyzing the current is probably that the recombination of photon-generated electrons and holes is inhibited to some extent due to the addition of indium vanadate.
G-C was obtained by gas chromatography (model: Trace 1310, manufacturer: Thermofoisher) in step (1) of example 13N4Obtaining InVO in step (2)4Reduced CO of precursor, and indium vanadate quantum dot photocatalyst supported by carbon nitride nanosheets obtained in example 1, example 2, example 3, and example 42Respectively measuring the performance and testing the reduced CO2The process is as follows: taking 10mg of g-C obtained in the step (1)3N4And (3) respectively placing the finally obtained carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst in a sealed reactor, respectively adding 2mL of triethanolamine, 4mL of acetonitrile and 6mL of deionized water, then controlling the power to be 60W and the frequency to be 40KHz, carrying out ultrasonic treatment for 10min, sealing the reactor, vacuumizing the reactor, and introducing CO2The reactor is placed under the irradiation of a 300W xenon lamp (with a 420nm cut-off filter) under the condition of adding circulating cooling water for reducing CO2And (6) testing. The reduction to CO is determined by gas chromatography at 1h per illumination and is shown in FIG. 4a, where g-C3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4The symbol,/CN-II, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 1, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4CN-III denotes the nitridation obtained in example 3Carbon nanosheet-loaded indium vanadate quantum dot photocatalyst InVO4The result of the description of the example 4 shows that the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst is represented by/CN-IV, and the CO reduction catalyzed by the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst can be seen from FIG. 4a2The yield of CO is obviously higher than that of carbon nitride, wherein the carbon nitride nanosheet obtained in the example 1 with the best performance is catalyzed by the indium vanadate quantum dot supported photocatalyst, and the catalyst reduces CO2The yield of CO and hydrogen is about 18.2 times that of pure carbon nitride, thereby showing that the addition of indium vanadate greatly improves the reduction of CO of carbon nitride2The reason for this property may be that the addition of indium vanadate inhibits the recombination of photogenerated electron-hole to some extent.
G-C was obtained by gas chromatography (model: Trace 1310, manufacturer: Thermofoisher) in step (1) of example 13N4Obtaining InVO in step (2)4Reduced CO of precursor, and indium vanadate quantum dot photocatalyst supported by carbon nitride nanosheets obtained in example 1, example 2, example 3, and example 42Respectively measuring the performance and testing the reduced CO2The process is as follows: taking 10mg of g-C obtained in the step (1)3N4And (3) respectively placing the finally obtained carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst in a sealed reactor, respectively adding 2mL of triethanolamine, 4mL of acetonitrile and 6mL of deionized water, then controlling the power to be 60W and the frequency to be 40KHz, carrying out ultrasonic treatment for 10min, sealing the reactor, vacuumizing the reactor, and introducing CO2The reactor is placed under the irradiation of a 300W xenon lamp (with a 420nm cut-off filter) under the condition of adding circulating cooling water for reducing CO2And (6) testing. The reduction to CO is determined by gas chromatography at 1h per illumination and is shown in FIG. 4b, where g-C3N4Is the carbon nitride, InVO, obtained in step (1)4Shows that the InVO obtained in the step (2)4Precursor, InVO4The symbol,/CN-II, denotes the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 1, InVO4The symbol/CN-I represents the indium vanadate quantum dot photocatalyst supported by the carbon nitride nanosheet obtained in example 2, InVO4CN-III denotes the nitridation obtained in example 3Carbon nanosheet-loaded indium vanadate quantum dot photocatalyst InVO4The result of the description of the method is that/CN-IV represents the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained in example 4, and FIG. 4b shows that CO is reduced by the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst2The yield of CO is obviously higher than that of carbon nitride, thereby showing that the addition of indium vanadate greatly improves the hydrogen evolution performance of carbon nitride, probably because the addition of indium vanadate inhibits the recombination of photo-generated electron-hole to a certain extent.
The carbon nitride nanosheet-loaded indium vanadate quantum dot photocatalyst obtained in example 1 is subjected to photocatalytic reduction of CO after being recycled by adopting gas chromatography (model: Trace 1310, manufacturer: Thermofisher)2Performance is measured, and the carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst obtained in example 1 is used for catalytic reduction of CO2In the process, the photocatalyst is recycled once every 10 hours, the total usage is 4 times, the performance graph of CO generated in the recycling process is shown in fig. 4c, and it can be seen from fig. 4c that the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst can still keep high CO yield after being recycled for four times, so that the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst obtained by the method has good stability.
Photocatalytic reduction of CO2Performance testing
10mg of g-C obtained in the step (1) above were weighed out separately3N4And (3) respectively placing the finally obtained carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst in a sealed reactor, respectively adding 2mL of triethanolamine, 4mL of acetonitrile and 6mL of deionized water, then controlling the power to be 60W and the frequency to be 40KHz, carrying out ultrasonic treatment for 10min, sealing the reactor, vacuumizing the reactor, and introducing CO2The reactor is placed under the irradiation of a 300W xenon lamp (with a 420nm cut-off filter) under the condition of adding circulating cooling water for reducing CO2And (6) testing. Wherein the triethanolamine acts as a sacrificial agent for sacrificing holes, thereby favoring electrons and CO2The corresponding reduction product is formed by combination.
The indium vanadate quantum dot light loaded by the carbon nitride nanosheetCatalyst for photocatalytic reduction of CO2The dosage of the catalyst is10 mg, and the catalyst is used for catalyzing and reducing CO under the irradiation of visible light2The CO yield in 10h was 697.98. mu. mol g-1At a rate of 69.79. mu. mol. g-1·h-1；
g-C obtained in step (1)3N4As a control, g-C3N4The catalyst is10 mg, and can be used for catalytic reduction of CO under irradiation of visible light2The CO yield in 10h was 38.29. mu. mol g-1At a rate of 3.83. mu. mol. g-1·h-1。
The results show that the CO is reduced by the indium vanadate/carbon nitride composite material loaded with the indium vanadate quantum dots2The performance is much higher than that of carbon nitride, probably because the addition of indium vanadate greatly improves the electronic structure of carbon nitride, enhances light absorption and CO2Adsorption, thereby greatly promoting the reduction of CO2And (4) performance.
Example 2
The carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst mainly contains five main elements of In, V, O, C and N, and is prepared by the method comprising the following steps:
(1) carbon nitride (hereinafter referred to as g-C)3N4) Preparation of
Putting 3g of melamine into a tube furnace, heating to 520 ℃ for calcination, wherein the gas atmosphere is air, the heating rate is 5 ℃/min, and the temperature is kept for 4h to obtain g-C3N4；
(2) Indium vanadate (hereinafter referred to as InVO)4) Preparation of the precursor
Dissolving 1mmol of indium trichloride tetrahydrate in 10mL of deionized water, and dissolving 1mmol of sodium orthovanadate in 20mL of deionized water to obtain a 0.1mmol/mL indium chloride aqueous solution and a 0.05mmol/mL sodium orthovanadate aqueous solution respectively;
then, controlling the dropping speed to be 0.5ml/min, dropping 0.1mmol/ml indium chloride aqueous solution into 0.05mmol/ml sodium orthovanadate aqueous solution to obtain mixed solution;
adjusting the pH of the obtained mixed solution to 2-3 by using 2M dilute nitric acid to obtainTo a clear solution to obtain InVO4A precursor of (a);
(3) carbon nitride nanosheet-loaded indium vanadate quantum dot (hereinafter referred to as InVO for short)4Preparation of/CN-I)
15mg of g-C3N4Ultrasonically dispersing the InVO prepared in the step (2)4In a clear solution;
after ultrasonic treatment, transferring the dispersion liquid to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 180 ℃, and the reaction time is 18 hours;
then the g-C obtained by the hydrothermal reaction3N4And InVO4Centrifuging the mixed solution at 8000r/min for 10min, and centrifuging the obtained precipitate with deionized water at 8000r/min for 10 min;
and repeating the centrifugal washing for 7-8 times, and controlling the temperature of the obtained filter cake to be-20 ℃ for freeze drying to obtain the carbon nitride loaded indium vanadate quantum dot nanosheet.
The electrochemical performance test and the method are the same as the example 1, the obtained results are that the photocurrent response degree is weaker than that of the example 1, the impedance is slightly larger, and the current density is lower than that of the example 1 under the same voltage, thereby showing that the catalyst of the example 1 is easier to separate and transfer the photo-generated electron-hole pair than the catalyst of the example 2, and the reason is probably because the InVO in the example 14：g-C3N4The ratio of (1 mmol): at 25mg, InVO4And g-C3N4The bonding is better.
Photocatalytic reduction of CO2Performance testing
The carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst is used for photocatalytic reduction of CO2The procedure is as in example 1, resulting in g-C obtained in step (1)3N4Can only generate 38.29 mu mol g-1The carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst finally obtained in the step (3) is used for catalytically reducing CO under the irradiation of visible light2The CO yield in 10h was 319.76. mu. mol g-1The rate was 31.98. mu. mol. g-1·h-1。
The CO production decreased somewhat compared to example 1 and the production rate also decreased.
Example 3
The carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst mainly contains five main elements of In, V, O, C and N, and is prepared by the method comprising the following steps:
(1) carbon nitride (hereinafter referred to as g-C)3N4) Preparation of
Putting 3g of melamine into a tube furnace, heating to 520 ℃ for calcination, wherein the gas atmosphere is air, the heating rate is 5 ℃/min, and the temperature is kept for 4h to obtain g-C3N4；
(2) Indium vanadate (hereinafter referred to as InVO)4) Preparation of the precursor
Dissolving 1mmol of indium trichloride tetrahydrate in 10mL of deionized water, and dissolving 1mmol of sodium orthovanadate in 20mL of deionized water to obtain a 0.1mmol/mL indium chloride aqueous solution and a 0.05mmol/mL sodium orthovanadate aqueous solution respectively;
then, controlling the dropping speed to be 0.5ml/min, dropping 0.1mmol/ml indium chloride aqueous solution into 0.05mmol/ml sodium orthovanadate aqueous solution to obtain mixed solution;
adjusting the pH of the obtained mixed solution to 2-3 by using 2M dilute nitric acid to obtain a clear solution, thereby obtaining InVO4A precursor of (a);
(3) carbon nitride nanosheet-loaded indium vanadate quantum dot (hereinafter referred to as InVO for short)4Preparation of/CN-III)
50mg of g-C3N4Ultrasonically dispersing the InVO prepared in the step (2)4In a clear solution;
after ultrasonic treatment, transferring the dispersion liquid to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 180 ℃, and the reaction time is 18 hours;
then the g-C obtained by the hydrothermal reaction3N4And InVO4Centrifuging the mixed solution at 8000r/min for 10min, and centrifuging the obtained precipitate with deionized water at 8000r/min for 10 min;
and repeating the centrifugal washing for 7-8 times, and controlling the temperature of the obtained filter cake to be-20 ℃ for freeze drying to obtain the carbon nitride loaded indium vanadate quantum dot nanosheet.
Electrochemical performance tests, which are performed by the same method as example 1, result in that the photocurrent response degree is stronger than that of example 1 and example 2, the impedance is between example 1 and example 2, and the current density is lower than that of example 1 and larger than that of example 2 under the same voltage, thereby indicating that the catalyst of example 3 is easier to separate and transfer the photo-generated electron-hole pairs than that of example 2, but is slightly worse than that of example 1.
Photocatalytic reduction of CO2Performance testing
The carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst is used for photocatalytic reduction of CO2The procedure is as in example 1, resulting in g-C obtained in step (1)3N4Can only generate 38.29 mu mol g-1The carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst finally obtained in the step (3) is used for catalytically reducing CO under the irradiation of visible light2The CO yield in 10h was 360.89. mu. mol g-1At a rate of 36.09. mu. mol. g-1·h-1。
The CO yield is reduced compared with example 1 and slightly improved compared with example 2, and the production rate is between example 1 and example 2.
Example 4
The carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst mainly contains five main elements of In, V, O, C and N, and is prepared by the method comprising the following steps:
(1) carbon nitride (hereinafter referred to as g-C)3N4) Preparation of
Putting 3g of melamine into a tube furnace, heating to 520 ℃ for calcination, wherein the gas atmosphere is air, the heating rate is 5 ℃/min, and the temperature is kept for 4h to obtain g-C3N4；
(2) Indium vanadate (hereinafter referred to as InVO)4) Preparation of the precursor
Dissolving 1mmol of indium trichloride tetrahydrate in 10mL of deionized water, and dissolving 1mmol of sodium orthovanadate in 20mL of deionized water to obtain a 0.1mmol/mL indium chloride aqueous solution and a 0.05mmol/mL sodium orthovanadate aqueous solution respectively;
then, controlling the dropping speed to be 0.5ml/min, dropping 0.1mmol/ml indium chloride aqueous solution into 0.05mmol/ml sodium orthovanadate aqueous solution to obtain mixed solution;
adjusting the pH of the obtained mixed solution to 2-3 by using 2M dilute nitric acid to obtain a clear solution, thereby obtaining InVO4A precursor of (a);
(3) carbon nitride nanosheet-loaded indium vanadate quantum dot (hereinafter referred to as InVO for short)4Preparation of/CN-IV)
100mg of g-C3N4Ultrasonically dispersing the InVO prepared in the step (2)4In a clear solution;
after ultrasonic treatment, transferring the dispersion liquid to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 180 ℃, and the reaction time is 18 hours;
then the g-C obtained by the hydrothermal reaction3N4And InVO4Centrifuging the mixed solution at 8000r/min for 10min, and centrifuging the obtained precipitate with deionized water at 8000r/min for 10 min;
and repeating the centrifugal washing for 7-8 times, and controlling the temperature of the obtained filter cake to be-20 ℃ for freeze drying to obtain the carbon nitride loaded indium vanadate quantum dot nanosheet.
Electrochemical performance tests and methods similar to example 1 show that the photocurrent response degree is higher than that of example 1, examples 2 and 3 are weaker, the impedance is higher than that of example 1 and lower than that of examples 2 and 3, and the current density is lower than that of example 1 and higher than that of examples 2 and 3 under the same voltage, so that the catalyst of example 4 is easier to separate and transfer than the photo-generated electron-hole pairs of the catalysts of examples 2 and 3, but is slightly poorer than that of example 1.
Photocatalytic reduction of CO2Performance testing
The carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst is used for photocatalytic reduction of CO2The procedure is as in example 1, resulting in g-C obtained in step (1)3N4Can only generate 38.29 mu mol g-1CO, the carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst finally obtained in the step (3) is subjected to visible light irradiationCatalytic reduction of CO by injection2The CO yield in 10h was 323.03. mu. mol g-1At a rate of 32.30. mu. mol. g-1·h-1。
The CO yield is reduced slightly compared with example 1 and is improved slightly compared with examples 2 and 3, and the production rate is also reduced slightly compared with example 1 and is improved slightly compared with examples 2 and 3.
Comparative example 1:
compared with example 1, the method is mostly the same except that the process of adding dilute nitric acid to adjust the pH is omitted.
When no dilute nitric acid is added to adjust the pH, as can be seen from the combination of FIG. 5, the obtained indium vanadate/carbon nitride is in a blocky shape, and cannot form a unique shape that quantum dots are loaded on nanosheets, so that the catalyst has more surface active sites.
Comparative example 2:
compared with the embodiment 1, the method is mostly the same except that dilute nitric acid is added to adjust the pH to be 3-4.
When the pH value is adjusted to be about 4 by using dilute nitric acid, as can be seen from the combination of fig. 6, the indium vanadate/carbon nitride is in the shape of small blocks stacked into large spheres, and cannot form the unique shape that quantum dots are loaded on nanosheets, so that the catalyst has more surface active sites.
In conclusion, the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst disclosed by the invention is excellent in electrochemical performance, and can be applied to photocatalytic reduction of CO2The product has better selectivity to CO, and the CO generation rate can reach 69.79 mu mol g at most-1·h-1. And the preparation method has the characteristics of simple operation and low production cost.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst is characterized by comprising the following steps:
(1) respectively dissolving indium trichloride tetrahydrate and sodium orthovanadate in deionized water to obtain an indium chloride aqueous solution and a sodium orthovanadate aqueous solution, dropwise adding the indium chloride aqueous solution into the sodium orthovanadate aqueous solution, and regulating the pH value to be clear to obtain InVO4Precursor solution;
(2) taking g-C3N4Ultrasonic dispersion to InVO4And carrying out hydrothermal reaction in the precursor solution, centrifuging, washing and drying the obtained product to obtain the target product.
2. The method for preparing a carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst according to claim 1, wherein in step (1), the molar ratio of indium trichloride tetrahydrate to sodium orthovanadate is 1: 1.
3. The method for preparing the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst according to claim 1, wherein in step (1), the pH is adjusted to 1-3.
4. The method for preparing the indium vanadate quantum dot photocatalyst supported by carbon nitride nanosheets according to claim 1, wherein in step (2), InVO4The concentration of the precursor solution is 0.3mmol/mL, and g-C3N4And InVO4The addition ratio of the precursor solution is 15-100 mg: 30 mL.
5. The method for preparing the carbon nitride nanosheet-supported indium vanadate quantum dot photocatalyst according to claim 1, wherein in the step (2), the hydrothermal reaction is carried out at 180 ℃ for 18 hours.
6. According toThe method for preparing the indium vanadate quantum dot photocatalyst loaded on carbon nitride nanosheets as claimed in claim 1, wherein in step (2), g-C3N4Prepared by pyrolysis of melamine at high temperature.
7. The method for preparing the indium vanadate quantum dot photocatalyst supported by carbon nitride nanosheets as claimed in claim 6, wherein in step (2), g-C is3N4The preparation process specifically comprises the following steps: weighing melamine, heating to 500-550 ℃ in air atmosphere, and calcining for 2-6h to obtain g-C3N4。
8. An indium vanadate quantum dot photocatalyst supported by carbon nitride nanosheets, which is prepared by the preparation method of any one of claims 1 to 7.
9. Application of carbon nitride nanosheet-supported indium vanadate quantum dots according to claim 8, wherein the indium vanadate quantum dots are used for photocatalytic reduction of CO2Is CO.
10. The application of the carbon nitride nanosheet-supported indium vanadate quantum dot as claimed in claim 9, wherein sunlight with lambda > 420nm is used for irradiating light to catalyze and reduce CO2。
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