CN114602528B - Cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material and preparation method and application thereof - Google Patents

Cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material and preparation method and application thereof Download PDF

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CN114602528B
CN114602528B CN202210358377.9A CN202210358377A CN114602528B CN 114602528 B CN114602528 B CN 114602528B CN 202210358377 A CN202210358377 A CN 202210358377A CN 114602528 B CN114602528 B CN 114602528B
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indium oxide
composite material
cadmium sulfide
carbon nitride
phosphorus
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CN114602528A (en
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朱蓓蓓
周杰
刘泽珏
吴颖泊
杜锐
吴斌
冯国峰
张海滨
丁邦琴
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Nantong Vocational College
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • C02F2101/40—Organic compounds containing sulfur
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Abstract

The invention provides a cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material, a preparation method and application thereof, relates to the technical field of composite semiconductor photocatalytic materials, and adopts a step-by-step method to prepare the cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride composite material, wherein the composite material has excellent visible light catalytic performance and simple preparation steps. The band gap regulation and control of the carbon nitride are realized through the doping of phosphorus and oxygen, and the ternary composite material forms a three-dimensional electric field space, so that the efficient migration and separation of photogenerated electrons and holes are facilitated. The ternary composite material has good photodegradation effect on common environmental pollutants such as rhodamine B and methyl orange and good visible light reduction performance on Cr (VII).

Description

Cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite semiconductor photocatalytic materials, and particularly relates to a cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material, and a preparation method and application thereof.
Background
Environmental and energy are two of the most prominent problems that limit human economic and social sustainable development. On the one hand, most of the energy sources for human social activities come from fossil fuels, but their reserves are very limited. With the acceleration of industrialization, human production and life are consuming such non-renewable fossil resources every day, which eventually faces exhaustion. This is an urgent requirement for people to take long-term measures and actively develop new energy sources to meet the demands of economic and social development. On the other hand, with the rapid development of global economy, the industrialization degree is continuously advancing, and the environmental pollution becomes a great threat to public health of countries around the world. The environmental pollution problems mainly comprise water pollution and air pollution, especially textile dye, surfactant, pesticide, antibiotics, heavy metal and other pollution in aquatic environment and greenhouse effect of air, and the environmental pollution problems cause great damage to natural and ecological systems and seriously affect survival and development of human beings. In order to solve the above energy and environmental problems, scientists in various countries have been actively exploring for more than half a century in the past. Among all developed and applied solutions, the photocatalytic technology can achieve both thorough removal of contaminants and clean generation of renewable resources, and is considered to be one of the most potential technologies. The core of the photocatalysis technology is the development and preparation of the photocatalyst. In the form of TiO 2 Among the typical semiconductor photocatalysts, indium oxide is widely applied to the fields of solar cells, solid-state optoelectronic devices and gas sensors as a wide-forbidden-band transparent n-type semiconductor material. However, indium oxide is used as a photocatalytic material, has partial response to ultraviolet light only, and photo-generated electrons and holes are easy to recombine, so that further application of the material in the field of photocatalysis is seriously hindered.
The Chinese patent CN20201047637. X discloses a cerium-doped zinc oxide nanoflower-loaded indium oxide photocatalytic degradation material and a preparation method thereof, wherein cerium-doped zinc oxide and indium oxide are compounded, the contact area and the visible light absorption efficiency of the composite material and rhodamine B are improved through the synergistic effect of surface activity, and the existence of cerium element enhances the capture capability of photo-generated electrons and improves the photocatalytic degradation rate.
Chinese patent CN202011285490.6 discloses a preparation method and application of a double-function photocatalytic nickel phosphide/indium oxide nanocomposite material, and Ni prepared by simple hydrothermal method 2 P/In 2 O 3 The nano composite material can be simultaneously used for photocatalytic water decomposition hydrogen production reaction and photocatalytic organic pollutant degradation reaction under simulated sunlight.
Scientific research team at university of Nanyang (10.1021/jacs.8b 02200) In 2 O 3 Growth of ZnIn on inner and outer surfaces of microtubes 2 S 4 Nanosheets as high efficiency CO 2 Photo-reduced photocatalyst exhibiting sandwich ZnIn 2 S 4 -In 2 O 3 Rational design and construction of layered tubular heterostructures. This design accelerates the separation and transfer of photo-generated charge, CO 2 Adsorption provides a large surface area and exposes rich surface catalytically active sites.
However, to date, no report has been made on the preparation and application of cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composites.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a cadmium sulfide nano particle/indium oxide nanowire/phosphorus-oxygen doped carbon nitride ternary composite material, wherein a three-dimensional space electric field is formed by constructing a heterojunction structure, the three-dimensional space electric field provides important guarantee for efficient separation and transmission of photo-generated electrons, the service life of photo-generated charges is effectively prolonged, meanwhile, the phosphorus and oxygen doping realizes band gap regulation and control of carbon nitride, the visible light response performance of the material is effectively improved, and the heterojunction construction and band gap regulation become important conditions that the ternary composite material has higher visible light catalytic activity.
The second purpose of the invention is to provide a preparation method of the ternary composite material, which has simple preparation steps and low cost.
The invention further aims to provide an application of the ternary composite material in removing environmental pollutants.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, the present invention provides a cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material comprising: cadmium sulfide cubic nano particles, indium oxide nano wires and phosphorus-oxygen doped carbon nitride porous structures;
the cadmium sulfide cubic nano particles are uniformly modified on the surface of the indium oxide nano wire, and the cadmium sulfide cubic nano particles and the indium oxide nano wire are distributed in the phosphorus-oxygen doped carbon nitride porous structure.
The invention relates to a cadmium sulfide/indium oxide/phosphorus-oxygen doped carbon nitride ternary composite material, which is a material compounded by cadmium sulfide, indium oxide and phosphorus-oxygen doped carbon nitride, wherein the cadmium sulfide is in a cubic nanoparticle shape, the indium oxide is in a nanowire shape, and the phosphorus-oxygen doped carbon nitride is in a porous net shape.
In some preferred embodiments, the indium oxide nanowires have a diameter of 20 to 50nm and a length of 500nm to 5 μm, preferably 1 to 5 μm, more preferably 2 to 3 μm;
the size of the cadmium sulfide cubic nano particles is 10-15 nm.
In a second aspect, the invention provides a method for preparing a cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material, which comprises the following steps:
(1) Preparing indium oxide nanowires: weighing an indium source, oxalic acid and alkaline hydroxide, dissolving in water, continuously stirring to form a white flocculent solution, transferring into a hydrothermal kettle for reaction, cooling, washing with water, washing with alcohol, drying to obtain a precursor indium hydroxide, and calcining the precursor in a muffle furnace to obtain indium oxide nanowires;
(2) Preparing a cadmium sulfide/indium oxide composite material: weighing the indium oxide nanowire obtained in the step (1), adding the indium oxide nanowire into absolute ethyl alcohol, adding a cadmium source and a sulfur source, stirring, transferring into a hydrothermal kettle for reaction to obtain yellow precipitate, washing, and vacuum drying to obtain a cadmium sulfide/indium oxide composite material;
(3) Preparing a cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material: and (3) weighing the cadmium sulfide/indium oxide composite material obtained in the step (2), a nitrogen source and ammonium dihydrogen phosphate in a mortar, grinding uniformly, then placing in a muffle furnace for pyrolysis, preserving heat, and cooling to obtain the cadmium sulfide/indium oxide/phosphorus-oxygen doped carbon nitride ternary composite material.
Step (1)
Sources of indium include, but are not limited to, hydrated indium nitrate, indium chloride, indium sulfate, and the like.
The alkaline hydroxides include, but are not limited to, sodium hydroxide, potassium hydroxide.
In some embodiments, the molar ratio of the indium source to the alkaline hydroxide is 2:3 to 4 and the molar ratio of the alkaline hydroxide to oxalic acid is 3:1 to 1.5;
preferably, the molar ratio of indium source, oxalic acid and alkaline hydroxide is 2:1:3.
In some embodiments, the reaction temperature in the hydrothermal kettle is 160-200 ℃ and the reaction time is 24-36 hours; the calcination temperature of the muffle furnace is 350-400 ℃ and the calcination time is 5-10 minutes.
Step (2)
Cadmium sources include, but are not limited to, cadmium acetate, cadmium chloride, cadmium nitrate.
Sulfur sources include, but are not limited to, thiourea, thioacetamide, sodium persulfate.
In some embodiments, the molar ratio of the cadmium source to the indium oxide nanowire is 1-2:4 and the molar ratio of the sulfur source to the cadmium source is 1.5-2:1.
In some embodiments, the hydrothermal kettle reaction temperature is 150 to 180 ℃ and the reaction time is 80 to 120 minutes.
Step (3)
In some embodiments, the nitrogen source is melamine or/and dicyandiamide or/and urea.
In some embodiments, the mass ratio of cadmium sulfide/indium oxide composite material to melamine or/and dicyandiamide or/and urea is 1:5 to 10 (e.g., 1:5, 1:6, 1:7, 1:8, 1:9, 1:10), and the mass ratio of monoammonium phosphate to melamine or/and dicyandiamide or/and urea is 1:8 to 10 (e.g., 1:8, 1:9, 1:10).
In some embodiments, the muffle furnace temperature program is: heating to 520-550 ℃ at the speed of 2.5-10 ℃/min, and preserving heat for 1-3 hours.
As a preferred embodiment, the preparation method of the cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material comprises the following steps:
(1) Preparing indium oxide nanowires: weighing a certain amount of hydrated indium nitrate, oxalic acid and sodium hydroxide, dissolving in deionized water, continuously stirring to form a white flocculent solution, transferring into a hydrothermal kettle for reaction, cooling, washing with water, washing with alcohol, drying to obtain a precursor indium hydroxide, and calcining the precursor in a muffle furnace to obtain the indium oxide nanowire;
wherein, in the step, the mol ratio of the hydrated indium nitrate to the sodium hydroxide is 2:3, and the mol ratio of the sodium hydroxide to the oxalic acid is 2:1.
Wherein, in the step, the molar ratio of the hydrated indium nitrate, oxalic acid and sodium hydroxide is 2:1:3.
Wherein, in the step, the reaction temperature in the hydrothermal kettle is 160-200 ℃ and the reaction time is 24-36 hours; the calcination temperature of the muffle furnace is 350-400 ℃ and the calcination time is 5-10 minutes.
(2) Preparing a cadmium sulfide/indium oxide composite material: weighing a certain amount of indium oxide nanowires obtained in the step (1), adding a certain amount of absolute ethyl alcohol, adding a certain amount of cadmium source and sulfur source, stirring, transferring into a hydrothermal kettle for reaction to obtain yellow precipitate, washing, and vacuum drying to obtain a cadmium sulfide/indium oxide composite material;
wherein, in the step, the reaction temperature of the hydrothermal kettle is 150-180 ℃ and the reaction time is 80-120 minutes.
(3) Preparing a cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material: weighing a certain amount of cadmium sulfide/indium oxide composite material obtained in the step (2), a certain amount of melamine or/and dicyandiamide or/and urea, and ammonium dihydrogen phosphate in a mortar, grinding uniformly, then placing in a muffle furnace for pyrolysis, preserving heat, and cooling to obtain the cadmium sulfide/indium oxide/phosphorus oxygen doped carbon nitride ternary composite material.
In the step, the mass ratio of the cadmium sulfide/indium oxide composite material to melamine or/and dicyandiamide or/and urea is 1:5-10, and the mass ratio of ammonium dihydrogen phosphate to melamine or/and dicyandiamide or/and urea is 1:8-10.
In this step, the temperature-raising program of the muffle furnace is as follows: heating to 520-550 ℃ at the speed of 2.5-10 ℃/min, and preserving heat for 1-3 hours.
The cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride composite material is prepared by adopting a step-by-step method, and the composite material has excellent visible light catalytic performance and simple preparation steps. The band gap regulation and control of the carbon nitride are realized through the doping of phosphorus and oxygen, and the ternary composite material forms a three-dimensional electric field space, so that the efficient migration and separation of photogenerated electrons and holes are facilitated.
In a third aspect, the invention provides an application of the cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material or the cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material prepared by the preparation method in removing environmental pollutants.
Such environmental contaminants include, but are not limited to, rhodamine B, methyl orange, cr (VII), and the like.
The technical scheme provided by the invention has the following beneficial effects: the invention designs and constructs a cadmium sulfide/indium oxide/phosphorus-oxygen doped carbon nitride ternary composite material and a preparation method thereof, a space electric field is constructed through the ternary material, a space path is provided for separation and transmission of charges, the service life of photo-generated charges is prolonged, phosphorus and oxygen are doped for replacing carbon nitride, a visible light response interval of the material can be expanded through band gap regulation, and the light absorption performance is improved.
Drawings
FIG. 1 is an XRD pattern of a sample obtained in example 1 of the present invention;
FIG. 2 is an SEM/TEM photograph of a sample obtained according to example 1 of the present invention;
FIG. 3 is an XPS spectrum of a sample obtained in example 1 of the present invention;
FIG. 4 is a UV-vis DRS spectrum of the sample obtained in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further illustrated by the following examples. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
The reagents and raw materials used in the present invention are shown in table 1 below:
TABLE 1 reagents and raw materials used in the invention
Example 1
Accurately weighing 0.63 g of indium nitrate hydrate, 0.134 g of oxalic acid and 0.128 g of sodium hydroxide, dissolving in 40 ml of deionized water, and forming a white flocculent solution under continuous stirring. Transferring the solution into a 50 ml hydrothermal kettle, reacting for 30 hours at 180 ℃ to obtain a product, washing with water, washing with alcohol, and vacuum drying at 60 ℃ to obtain a precursor In (OH) 3 . Calcining the precursor In a muffle furnace at 400 ℃ for 5 minutes to obtain In 2 O 3 A nanowire. Accurately weigh the In 2 O 3 Adding 0.24 g of nanowire into a certain amount of absolute ethyl alcohol, adding 0.0828 g of cadmium acetate, continuously stirring for 30 minutes, adding excessive thiourea, stirring for 30 minutes, transferring into a 100 ml hydrothermal kettle, and carrying out hydrothermal reaction at 180 ℃ for 90 minutes to obtain yellow colorAnd (3) precipitating, washing, and vacuum drying to obtain the cadmium sulfide/indium oxide. Weighing 0.2 g of cadmium sulfide/indium oxide composite material, 2 g of urea and 0.1 g of monoammonium phosphate in a mortar, grinding uniformly, then placing in a muffle furnace for pyrolysis, preserving heat, and cooling to obtain the cadmium sulfide/indium oxide/phosphorus-oxygen doped carbon nitride ternary composite material.
Taking 0.1 g of the prepared cadmium sulfide/indium oxide/phosphorus oxygen doped carbon nitride ternary composite material, placing the material into a beaker containing 100 ml of rhodamine B solution with the concentration of 10 mg/L, carrying out ultrasonic treatment for 2 minutes, carrying out dark absorption for 30 minutes, illuminating the material for 60 minutes at a position 20 cm away from the liquid level by a 300-watt xenon lamp light source under stirring, centrifuging the degraded solution, measuring the absorbance of the degraded solution at 553 nanometers by an ultraviolet-visible spectrophotometer, and calculating the degradation rate (1-C/C 0 Wherein C is the instantaneous concentration of the sample, C 0 Initial concentration of sample) was 99.0%.
Example 2
Accurately weighing 0.63 g of indium nitrate hydrate, 0.134 g of oxalic acid and 0.128 g of sodium hydroxide, dissolving in 40 ml of deionized water, and forming a white flocculent solution under continuous stirring. Transferring the solution into a 50 ml hydrothermal kettle, reacting for 30 hours at 180 ℃ to obtain a product, washing with water, washing with alcohol, and vacuum drying at 60 ℃ to obtain a precursor In (OH) 3 . Calcining the precursor In a muffle furnace at 400 ℃ for 5 minutes to obtain In 2 O 3 A nanowire. Accurately weigh the In 2 O 3 Adding 0.2 g of nanowire into a certain amount of absolute ethyl alcohol, adding 0.0828 g of cadmium acetate, continuously stirring for 30 minutes, adding excessive thiourea, stirring for 30 minutes, transferring into a 100 ml hydrothermal kettle, carrying out hydrothermal reaction for 90 minutes at 180 ℃ to obtain yellow precipitate, washing, and then carrying out vacuum drying to obtain the cadmium sulfide/indium oxide. Weighing 0.15 g of cadmium sulfide/indium oxide composite material, 2 g of urea and 0.1 g of monoammonium phosphate in a mortar, grinding uniformly, then placing in a muffle furnace for pyrolysis, preserving heat, and cooling to obtain the cadmium sulfide/indium oxide/phosphorus-oxygen doped carbon nitride ternary composite material.
0.1 g of the prepared cadmium sulfide/indium oxide/phosphorus oxygen doped carbon nitride ternary composite material is placed in a beaker containing 100 ml of methyl orange solution with the concentration of 10 mg/L, ultrasonic treatment is carried out for 2 minutes, after dark absorption is carried out for 30 minutes, illumination is carried out for 80 minutes from a position, 20 cm away from the liquid surface, of a 300-watt xenon lamp light source under a stirring state, after degradation, the absorbance of the solution at 463 nm is measured by an ultraviolet-visible spectrophotometer after centrifugation, and the degradation rate is calculated to be 89.3%.
Example 3
Accurately weighing 0.63 g of indium nitrate hydrate, 0.134 g of oxalic acid and 0.128 g of sodium hydroxide, dissolving in 40 ml of deionized water, and forming a white flocculent solution under continuous stirring. Transferring the solution into a 50 ml hydrothermal kettle, reacting for 30 hours at 180 ℃ to obtain a product, washing with water, washing with alcohol, and vacuum drying at 60 ℃ to obtain a precursor In (OH) 3 . Calcining the precursor In a muffle furnace at 400 ℃ for 5 minutes to obtain In 2 O 3 A nanowire. Accurately weigh the In 2 O 3 Adding 0.24 g of nanowire into a certain amount of absolute ethyl alcohol, adding 0.0828 g of cadmium acetate, continuously stirring for 30 minutes, adding excessive thiourea, stirring for 30 minutes, transferring into a 100 ml hydrothermal kettle, carrying out hydrothermal reaction for 90 minutes at 180 ℃ to obtain yellow precipitate, washing, and then carrying out vacuum drying to obtain the cadmium sulfide/indium oxide. Weighing 0.2 g of cadmium sulfide/indium oxide composite material, 2 g of urea and 0.1 g of monoammonium phosphate in a mortar, grinding uniformly, then placing in a muffle furnace for pyrolysis, preserving heat, and cooling to obtain the cadmium sulfide/indium oxide/phosphorus-oxygen doped carbon nitride ternary composite material.
Taking 0.1 g of the prepared cadmium sulfide/indium oxide/phosphorus oxygen doped carbon nitride ternary composite material, placing the material into a beaker containing 100 ml of Cr (VI) with the concentration of 10 mg/L, adding 1 g of oxalic acid, carrying out ultrasonic treatment for 2 minutes, carrying out dark absorption for 30 minutes, illuminating for 80 minutes from a position 20 cm away from the liquid surface by a 300-watt xenon lamp light source under a stirring state, centrifuging the degraded solution, measuring the absorbance of the degraded solution at 540 nm by an ultraviolet-visible spectrophotometer according to a diphenyl carbohydrazide method, and calculating the reduction rate (1-C/C) 0 ) 92.7%.
Characterization of cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material
The invention adopts a German Bruker spectrometer company D8 advanced type X-ray diffractometer to dope cadmium sulfide/indium oxide/phosphorus oxide with nitrogen prepared in the embodiment 1 of the inventionXRD analysis is carried out on the carbon composite catalytic material, the obtained result is shown in figure 1, and the test conditions are as follows: the Cu target is K alpha line, lambda=0.15406 nm,2 theta is 10-70 degrees, and the scanning speed is 5 degrees/min. In FIG. 1 c, it is shown that the characteristic peaks of the prepared phosphorus-oxygen doped carbon nitride and bulk phosphorus-oxygen doped carbon nitride remain the same, and there are two diffraction peaks at 13.1℃and 27.0℃corresponding to the (100) crystal plane and (002) crystal plane of the phosphorus-oxygen doped carbon nitride due to the superposition of the repeating units of the continuous triazine ring skeleton in the plane and the conjugated aromatic structure with a pitch of about 0.32nm, respectively. The broader and weaker diffraction peaks indicate shorter inter-layer periodic correlation lengths of triazine ring structures in phosphorus-oxygen doped carbon nitrides. In FIG. 1 a, the diffraction peaks of cadmium sulfide are related to several crystal planes of the hexagonal-phase cadmium sulfide ore CdS (JCPDS No. 41-1049). Also, in (OH) 3 Diffraction peaks at 22.3 °,31.7 °,35.6 °,39.1 °,42.5 °,45.5 °,51.2 °,56.5 °, and 66.3 °, respectively, correspond to pure body-centered cubic phase In (OH) 3 (200), (220), (013), (222), (321), (400), (420), (422) and (440) crystal planes (JCPLDS No. 85-1338), in (OH) 3 Has higher purity and crystallinity. When In (OH) 3 After calcination, in is formed 2 O 3 The diffraction angle was 21.5 °,30.6 °,35.5 °,37.7 °,41.9 °,45.8 °,51.0 °,56.0 °,60.7 ° the characteristic peak and body-centered cubic structure In 2 O 3 (JCPDS No. 06-0416) In the In, in relation to the (211), (222), (400), (411), (332), (431), (440), (611) and (622) crystal planes 2 O 3 In (OH) was not found In the spectra 3 Illustrating the diffraction peaks of In prepared 2 O 3 The sample is purer. When CdS and In 2 O 3 After compounding, the characteristic peak position and peak form are as follows with In 2 O 3 Consistent, description In 2 O 3 The structure remains unchanged before and after hydrothermal treatment, and a partial enlarged view of the diffraction angle at 25-30 degrees is shown as b in fig. 1, and weak peaks around 27 degrees indicate successful doping of CdS, but the characteristic peaks are not obvious due to the lower content of CdS. Similarly, in is mainly shown In the spectrogram of cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride 2 O 3 Characteristic peaks of (2) phosphorus-oxygen doped carbon nitride andthe content of CdS is low, and the characteristic peak is not obvious.
The microstructure and crystal structure of the material obtained in example 1 were tested by using a JSM-6510 scanning electron microscope and a JEM-2100F high-resolution field emission transmission electron microscope, which are manufactured by JSM-6510, and a photograph is shown in FIG. 2. SEM pictures are shown in fig. 2 a, in which it is evident that the phosphorus-oxygen doped carbon nitride has a rich pore structure. FIG. 2 b is In 2 O 3 A TEM photograph of (c). In (In) 2 O 3 Is a nanowire structure with a diameter of about 40nm and a length of about several μm, and can load more nano particles and hold In 2 O 3 Is exposed to the atmosphere. In FIG. 2, c is a TEM photograph of CdS nanoparticles, and CdS has a cubic structure and a size of about 10 nm. FIG. 2 d is CdS/In 2 O 3 In (In) is shown In the TEM photograph, and CdS particles are uniformly modified In 2 O 3 The surface of the nanowire. The FETEM photographs of f and g In fig. 2 clearly show the lattice fringes d=0.29 nm and d=0.34 nm, in respectively 2 O 3 (222) crystal face and (111) crystal face of CdS, cdS and In 2 O 3 Forming close contact provides important conditions for good electron transfer. FIG. 2 is a TEM photograph of cadmium sulfide/indium oxide/phosphorus oxygen doped carbon nitride showing the porous structure of phosphorus oxygen doped carbon nitride, cdS nanoparticles and In 2 O 3 The nanowire and other structures are clear, which indicates that the phosphorus-oxygen doped carbon nitride composite material is successfully prepared.
The elemental composition and chemical state of the material prepared in example 1 were analyzed by using a sammer EscaLab 250Xi X-ray photoelectron spectrometer in the united states, and the results are shown in fig. 3. Diffraction peaks of Cd 3d, S2P, in 3d, O1S, P2P, C1S and N1S appear In the sample, which illustrate that the main constituent elements of the composite material are Cd, S, in, O, P, C and N. Characteristic peaks in the Cd 3d high-resolution spectrogram of FIG. 3 a, which are respectively located at 411.1eV and 404.4eV in binding energy, respectively correspond to Cd 3d 3/2 And Cd 3d 5/2 Description of Cd element in Cd 2+ Is present. FIG. 3 b is a high resolution spectrum of S2 p with binding energies at characteristic peak fractions of 161.8eV and 160.7eV, respectivelyRespectively correspond to S2 p 1/2 And S2 p 3/2 Proving that S element is S 2- Is present in the form of (c). Meanwhile, the analysis results of the above XPS also indicate the presence of CdS. FIG. 3 c shows a high resolution spectrum of In 3d, with characteristic peaks at 451.5eV and 443.9eV, respectively, attributed to In 3d 3/2 And In 3d 5/2 In is shown to have a valence of +3. Meanwhile, the characteristic peak of O1 s is shown In the graph d of FIG. 3, and can be divided into 531.4eV and 529.5eV, which correspond to the substituted O element and In the structure of the carbotriazine nitride respectively 2 O 3 In-O bonds In the structure. The characteristic peak of P2P at 133.4eV is shown in FIG. 3e, corresponding to the P-N structure, illustrating that part of C in the C-N structure is replaced by phosphorus. The above results demonstrate that some of the elements in carbon nitride are replaced with O and P. High resolution spectra of f in FIG. 3 and g in FIG. 3 for C1 s and N1 s, respectively, with characteristic peaks at 288.5eV,287.7eV,286.4eV and 284.6eV for binding energy in C1 s spectra, respectively, bonded to O-C=O, sp 2 Hybridized N-c=n, C-N, C-C bond. The characteristic peaks in the N1 s spectrum at 398.3eV,399.5eV and 401.0eV respectively are respectively bonded with C-N=C bond and N- (C) in the triazine ring structure 3 The bond, N-H bond, is related, whereas the distinct characteristic peak at 404.3eV belongs to pi bond of c=n structure. By combining the analysis results, the CdS, in the sample is illustrated 2 O 3 And phosphorus-oxygen doped carbon nitride, and the like, and the presence of the valence states of the respective elements.
The ultraviolet-visible diffuse reflection absorption spectrum is tested by using a Lambda 650S ultraviolet-visible spectrophotometer (optical polytetrafluoroethylene coating) of PE company in the United states, and the obtained spectrogram is shown in figure 4. As is obvious from the figure, the phosphorus-oxygen doped carbon nitride has remarkable absorption capacity in the visible light region, which indicates that the doping of phosphorus and oxygen effectively improves the light absorption performance of the carbon nitride and realizes the band gap regulation of the carbon nitride. And the absorption spectrum of CdS also shows that the CdS has good visible light absorption characteristics. When CdS is combined with In having a part of visible light absorption characteristics 2 O 3 After compounding, in is greatly expanded 2 O 3 Is a visible light absorption range of (a). Thus, cdS is not only mixed with In 2 O 3 Forming heterojunction, accelerating separation of photon-generated carriers, or improving light absorptionImportant components of the recovery performance. Similarly, the ternary component cadmium sulfide/indium oxide/phosphorus-oxygen doped carbon nitride constructed by introducing phosphorus-oxygen doped carbon nitride shows extremely high visible light response performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (4)

1. A cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material, comprising:
cadmium sulfide cubic nano particles, indium oxide nano wires and phosphorus-oxygen doped carbon nitride porous structures;
the cadmium sulfide cubic nano particles are uniformly modified on the surface of the indium oxide nano wire, and the cadmium sulfide cubic nano particles and the indium oxide nano wire are distributed in the phosphorus-oxygen doped carbon nitride porous structure; the diameter of the indium oxide nanowire is 20-50 nm, and the length of the indium oxide nanowire is 500-5 mu m; the size of the cadmium sulfide cubic nano particles is 10-15 nm;
the preparation method of the cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material comprises the following steps:
(1) Preparing indium oxide nanowires: weighing an indium source, oxalic acid and alkaline hydroxide, dissolving in water, continuously stirring to form a white flocculent solution, transferring into a hydrothermal kettle for reaction, cooling, washing with water, washing with alcohol, drying to obtain a precursor indium hydroxide, and calcining the precursor in a muffle furnace to obtain indium oxide nanowires; wherein the molar ratio of the indium source to the alkaline hydroxide is 2:3-4, and the molar ratio of the alkaline hydroxide to oxalic acid is 3:1-1.5; the reaction temperature in the hydrothermal kettle is 160-200 ℃ and the reaction time is 24-36 hours; the calcination temperature of the muffle furnace is 350-400 ℃, and the calcination time is 5-10 minutes;
(2) Preparing a cadmium sulfide/indium oxide composite material: weighing the indium oxide nanowire obtained in the step (1), adding the indium oxide nanowire into absolute ethyl alcohol, adding a cadmium source and a sulfur source, stirring, transferring into a hydrothermal kettle for reaction to obtain yellow precipitate, washing, and vacuum drying to obtain a cadmium sulfide/indium oxide composite material; wherein, the molar ratio of the cadmium source to the indium oxide nanowire is 1-2:4, and the molar ratio of the sulfur source to the cadmium source is 1.5-2:1; the reaction temperature of the hydrothermal kettle is 150-180 ℃, and the reaction time is 80-120 minutes;
(3) Preparing a cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material: weighing the cadmium sulfide/indium oxide composite material obtained in the step (2), a nitrogen source and ammonium dihydrogen phosphate in a mortar, grinding uniformly, then placing in a muffle furnace for pyrolysis, preserving heat, and cooling to obtain the cadmium sulfide/indium oxide/phosphorus-oxygen doped carbon nitride ternary composite material; the mass ratio of the cadmium sulfide/indium oxide composite material to the nitrogen source is 1:5-10, and the mass ratio of the ammonium dihydrogen phosphate to the nitrogen source is 1:8-10; the temperature rise program of the muffle furnace is as follows: and heating to 520-550 ℃ at a speed of 2.5-10 ℃/min, and preserving heat for 1-3 hours.
2. The cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material of claim 1 wherein in step (1), the molar ratio of indium source, oxalic acid and alkaline hydroxide is 2:1:3.
3. Use of a cadmium sulfide/indium oxide/phosphorus oxide doped carbon nitride ternary composite material according to claim 1 or 2 for removing environmental contaminants.
4. The use according to claim 3, wherein the environmental pollutants comprise rhodamine B, methyl orange and Cr (VI).
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Publication number Priority date Publication date Assignee Title
CN108212195A (en) * 2018-02-09 2018-06-29 信阳师范学院 Petal-shaped cadmium sulfide carbonitride heterojunction nanometer material and preparation method thereof

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