CN109289875B - ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen, preparation method and application - Google Patents
ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen, preparation method and application Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention discloses a ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen, which comprises an insulating substrate, wherein a ZnO nanorod array is distributed on the substrate and consists of a plurality of ZnO nanorods; the outer layers of a plurality of ZnO nanorods are WS2Film of ZnO-WS2A composite system; the ZnO-WS2CdS nano-particles are loaded on the outer layer of the composite system to form ZnO-WS2-a CdS core-shell nanorod array. The invention also provides a preparation method of the photocatalyst and application of the photocatalyst in hydrogen production under visible light catalysis. The photocatalyst has effective electron transfer energy level, and realizes rapid carrier separation so as to improve the hydrogen production activity.
Description
Technical Field
The invention relates to a photocatalytic material, in particular to a ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen, a preparation method and application.
Background
The photocatalytic technology is always considered to be an effective technology for solving the problems of environment and energy, wherein the photocatalytic hydrogen production technology utilizes solar energy to directly decompose water into clean hydrogen, so researchers are dedicated to developing efficient semiconductor photocatalysts, and the research on structure and performance is an important research direction. The ZnO one-dimensional structure has high specific surface area, a fast carrier transmission path and excellent light absorption performance and is widely concerned, but meanwhile, the ZnO wide band gap can only absorb ultraviolet light accounting for 5% of sunlight and fast recombination of semiconductor photon-generated electron holes to influence the catalytic efficiency. The forbidden band width of CdS is 2.4eV, good visible light hydrogen production activity is shown, ZnO and CdS are compounded to form a heterojunction, so that the spectrum absorption of ZnO can be widened, photo-generated electron holes of CdS can be effectively separated, and the photo-catalytic activity is improved. WS2As a typical transition metal sulfide, the catalyst has good catalytic performance.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems of narrow light absorption range, low sunlight utilization rate and rapid recombination of semiconductor photo-generated electron holes of the conventional ZnO, the invention provides a high-efficiency hydrogen-production ZnO core-shell nanorod array photocatalyst. The invention also aims to provide a preparation method of the high-efficiency hydrogen production ZnO core-shell nanorod array photocatalyst. The invention also provides application of the ZnO core-shell nanorod array photocatalyst for efficiently producing hydrogen in visible light.
The technical scheme is as follows: the invention relates to a ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen, which comprises an insulating substrate, wherein a ZnO nanorod array is distributed on the substrate and consists of a plurality of ZnO nanorods; the outer layers of a plurality of ZnO nanorods are WS2Film of ZnO-WS2A composite system; the ZnO-WS2CdS nano-particles are loaded on the outer layer of the composite system to form ZnO-WS2-a CdS core-shell nanorod array.
The insulating substrate can be made of the existing substrate material and can resist the high temperature of 1000-1200 ℃.
The ZnO nanorod array grown on the substrate is distributed in a direction basically perpendicular to the substrate, and the average diameter of the ZnO nanorod array is preferably 300-1000 nm.
Said WS of the invention2The thin film is distributed on the outer layer of ZnO nano-rod, preferably WS2The average thickness of the film is 1-10 nm.
ZnO-WS of the invention2The outer layer of the composite system is loaded with CdS nano-particles, and preferably, the average particle size of the CdS nano-particles is 5-15 nm.
In a preferred embodiment of the present invention, the substrate is a sapphire substrate.
In another preferred mode of the invention, the ZnO nanorod array is grown on the sapphire substrate by a vapor deposition method.
The specific growth method of the ZnO nanorod array comprises the following steps: mixing ZnO powder and carbon powder according to the mass ratio of 1:1-3 to obtain mixed powder, and placing the mixed powder at the bottom of a quartz tube; cutting and cleaning a sapphire substrate to be used as a growth substrate; putting the mixed powder and the sapphire substrate into a quartz tube with an opening at one end, horizontally pushing the quartz tube into a tube furnace, vacuumizing, introducing 130-plus-180 sccm argon and 13-18sccm oxygen for high-temperature reaction at the temperature of 1000-plus-1200 ℃ for 10-60min, and generating the ZnO nanorod array after the reaction is finished.
Preferably, WS as defined above2The film is loaded on the outer layer of the ZnO nano-rod in a sputtering mode, the equipment used for sputtering is a magnetron sputtering instrument, and the sputtering target material is WS2The target material has the specification of 60 multiplied by 3mm, the cavity air pressure is 1-4Pa, the argon flow is 30-50sccm, the nitrogen flow is 5-10sccm, the sputtering power is 80-150W, and the sputtering time is 5-30 min.
Preferably, the CdS nano-particles are loaded on ZnO-WS in a sputtering mode2The outer layer of the composite system, the equipment used for sputtering is a magnetron sputtering instrument, the sputtering target material is a CdS target material with the specification of 60 multiplied by 3mm, the air pressure of a cavity is 1-4Pa, the flow of argon is 30-50sccm, the flow of nitrogen is 5-10sccm, the sputtering power is 80-150W, and the sputtering time is 5-30 min.
The preparation method of the ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen comprises the following steps:
(1) growing a ZnO nanorod array on an insulating substrate by adopting a vapor deposition method; (2) sputtering a layer of WS on the ZnO nanorod array obtained in the step (1)2Film of ZnO-WS2A composite system; (3) ZnO-WS in the composite system obtained in step (2)2Sputtering CdS nanoparticles to form ZnO-WS2-a CdS complex system.
Preferably, in the step (1), the growth method of the ZnO nanorod array is as follows: mixing ZnO powder and carbon powder according to the mass ratio of 1:1-3 to obtain mixed powder, and placing the mixed powder at the bottom of a quartz tube; cutting and cleaning a sapphire substrate to be used as a growth substrate; putting the mixed powder and the sapphire substrate into a quartz tube with an opening at one end, horizontally pushing the quartz tube into a tube furnace, vacuumizing, introducing 130-plus-180 sccm argon and 13-18sccm oxygen for high-temperature reaction at the temperature of 1000-plus-1200 ℃ for 10-60min, and generating the ZnO nanorod array after the reaction is finished.
Preferably, in step (2), the WS2The specific preparation method of the film is as follows: the used equipment is a magnetron sputtering instrument, and the sputtering target material is WS2The target material has the specification of 60 multiplied by 3mm, the cavity air pressure is 1-4Pa, the argon flow is 30-50sccm, the nitrogen flow is 5-10sccm, the sputtering power is 80-150W, and the sputtering time is 5-30 min.
Preferably, in the step (3), the CdS nanoparticles are loaded on ZnO-WS in a sputtering mode2The outer layer of the composite system is sputtered by a magnetron sputtering instrument by using CdS target material of 60 x 3mm, the pressure of a cavity is 1-4Pa, the flow of argon gas is 30-50sccm, the flow of nitrogen gas is 5-10sccm, the sputtering power is 80-150W, and the sputtering time is 5-30 min.
The ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen is used for producing hydrogen under visible light.
Has the advantages that: the invention synthesizes ZnO-WS2CdS core-shell nanorods, ZnO absorption can be broadened to visible light, WS by modifying CdS2Effectively improves the hydrogen production activity of visible light, and simultaneously ZnO uniformly disperses WS2And CdS to form an effective electron transfer energy level, so that the high-efficiency visible light hydrogen production catalyst is obtained.
Drawings
FIG. 1 shows ZnO-WS synthesized in example 1 of the present invention2-a schematic scanning electron microscope of a CdS core-shell nanorod array;
FIG. 2 shows ZnO-WS synthesized in example 1 of the present invention2-a transmission electron microscopy schematic of a CdS core-shell nanorod;
FIG. 3 shows ZnO-WS synthesized in example 1 of the present invention2A schematic diagram of visible light hydrogen production of the CdS core-shell nanorod array.
Detailed Description
The technical scheme of the invention is further illustrated by the following examples.
Example 1: the first step is as follows: mixing and grinding ZnO powder with the purity of 99.99% and carbon powder according to the mass ratio of 1:1, and filling the mixture into a ceramic boat; cutting the sapphire substrate into 1.5cm multiplied by 1cm, carrying out ultrasonic cleaning on the sapphire substrate by acetone, absolute ethyl alcohol and deionized water in sequence, drying the sapphire substrate by using nitrogen to be used as a growth substrate, then placing the sapphire substrate into a quartz tube with an opening at one end, a length of 30cm and a diameter of 3cm, and placing the cleaned sapphire substrate into the quartz tube at a position 5cm away from the tube opening. Pushing the quartz tube into a horizontal tube furnace with the set temperature of 1050 ℃, closing the tube furnace, vacuumizing, introducing argon flow of 150sccm and oxygen flow of 15sccm, and reacting for 30min to grow the ZnO nano-rod array on the surface of the sapphire;
the second step is that: sputtering a layer of WS in a ZnO nanorod array by using a magnetron sputtering instrument2Film of, with WS2The target material is a sputtering source with the specification of 60 multiplied by 3mm, the cavity air pressure is 2Pa, the argon flow is 50sccm, the nitrogen flow is 10sccm, the sputtering power is 100W, the sputtering time is 8min, and ZnO-WS is obtained2A complex;
the third step: in which ZnO-WS is present by means of a magnetron sputtering apparatus2Sputtering a CdS film on the composite, using a CdS target as a sputtering source, with the specification of 60 × 3mm, the cavity pressure of 2Pa, the argon flow of 50sccm, the nitrogen flow of 10sccm, the sputtering power of 100W, and the sputtering time of 8min to obtain ZnO-WS2-CdS core-shell nanorod arrays, see figures 1 and 2;
the fourth step: weighing a certain amount of the product obtained in the third step, transferring the weighed product into a photocatalytic reactor, carrying out photocatalytic reaction under simulated sunlight (adding an optical filter with the wavelength of 420 nm), and producing hydrogen by photocatalytic water splitting as the activity of the photocatalyst for evaluation, wherein the activity is shown in figure 3.
Example 2: the method is the same as example 1, except that the high temperature reaction time of the first step is 10min, the sputtering time of the second step is 10min, the sputtering time of the third step is 10min, and the obtained ZnO-WS2The morphology of the-CdS core-shell nanorod array is similar to that of example 1.
Example 3: the method is the same as example 1, except that the high temperature reaction time of the first step is 15min, the sputtering time of the second step is 8min, the cavity volume is 1.5Pa, the sputtering time of the third step is 15min, the cavity air pressure is 1.5Pa, and the obtained ZnO-WS is2-CdS core-shell nanorod array morphologySimilar to example 1.
Example 4: the method is the same as example 1, except that the high temperature reaction time of the first step is 45min, the sputtering time of the second step is 20min, the sputtering time of the third step is 15min, and the obtained ZnO-WS is obtained2The morphology of the-CdS core-shell nanorod array is similar to that of example 1.
Example 5: the method is the same as example 1, except that in the first step, the mass ratio of the ZnO powder to the carbon powder is 1: 3 mixing to obtain mixed powder, wherein the reaction temperature of the high-temperature reaction is 1000 ℃, and the reaction time is 60 min; the argon flow is 130sccm, and the oxygen flow is 13 sccm. In the second step, the pressure of the cavity is 1Pa, the flow of argon is 30sccm, the flow of nitrogen is 5sccm, the sputtering power is 150W, and the sputtering time is 30min during the sputtering of the magnetron sputtering instrument. In the third step, the sputtering power of the ion sputtering instrument is 80W, the air pressure of the cavity is 3Pa, the sputtering time is 5min, and the obtained ZnO-WS2The morphology of the-CdS core-shell nanorod array is similar to that of example 1.
Example 6: the method is the same as example 1, except that the reaction temperature of the high-temperature reaction in the first step is 1100 ℃, and the reaction time is 10 min; the argon flow is 180sccm and the oxygen flow is 18 sccm. In the second step, the cavity pressure is 4Pa, the argon flow is 50sccm, the nitrogen flow is 10sccm, the sputtering power is 80W, and the sputtering time is 5min during the magnetron sputtering. In the third step, the sputtering power of the ion sputtering instrument is 120W during sputtering, the air pressure of the cavity is 1.6Pa, the sputtering time is 15min, and the obtained ZnO-WS is obtained2The morphology of the-CdS core-shell nanorod array is similar to that of example 1.
Comparative example 1: the method is the same as example 1, except that only the ZnO nanorod array prepared in the first step is used, and visible light hydrogen production is shown in figure 3.
Comparative example 2: the method is the same as example 1, except that only the first step and the third step are needed to form the ZnO-CdS photocatalyst, and visible light hydrogen production is shown in figure 3.
As can be seen from FIG. 3, the present invention magnetron-sputters a layer of WS on ZnO nano-rods2A film; in ZnO-WS2CdS nano particles are magnetically sputtered on the core-shell nanorod to form a three-dimensional core-shell nanorod array, and ZnO absorption can be widened by modifying CdSVisible light, modifying WS2Effectively improves the hydrogen production activity of visible light, and simultaneously ZnO uniformly disperses WS2And CdS form an effective electron transfer energy level, so that the rapid carrier separation is realized, the hydrogen production activity is improved, and the hydrogen production catalytic capability is improved to a great extent.
Claims (8)
1. The ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen is characterized by comprising an insulating substrate, wherein a ZnO nanorod array is distributed on the insulating substrate and consists of a plurality of ZnO nanorods; the outer layers of a plurality of ZnO nanorods are WS2Film of ZnO-WS2A composite system; the ZnO-WS2The outer layer of the composite system is loaded with CdS nano-particles; the ZnO core-shell nanorod array photocatalyst is prepared by the following method: growing a ZnO nanorod array on an insulating substrate by adopting a vapor deposition method; sputtering a layer of WS on the obtained ZnO nano-rod array2Film of ZnO-WS2A composite system; in ZnO-WS2Sputtering CdS nanoparticles to form ZnO-WS2-a CdS complex system; the average diameter of the ZnO nano-rod is 300-1000 nm; the WS2The average thickness of the film is 1-10 nm; the average particle size of the CdS nano-particles is 5-15 nm; the WS2Loading the film on the outer layer of the ZnO nanorod in a sputtering mode: the equipment used for sputtering is a magnetron sputtering instrument, and the sputtering target material is WS2The target material has the specification of 60 multiplied by 3mm, the cavity air pressure is 1-4Pa, the argon flow is 30-50sccm, the nitrogen flow is 5-10sccm, the sputtering power is 80-150W, and the sputtering time is 5-30 min; the CdS nano-particles are loaded on ZnO-WS in a sputtering mode2Outer layer of the composite system: the equipment used for sputtering is a magnetron sputtering instrument, the sputtering target material is a CdS target material with the specification of 60 multiplied by 3mm, the air pressure of the cavity is 1-4Pa, the flow of argon is 30-50sccm, the flow of nitrogen is 5-10sccm, the sputtering power is 80-150W, and the sputtering time is 5-30 min.
2. The ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen according to claim 1, wherein the insulating substrate is a sapphire substrate.
3. The ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen according to claim 1, wherein the specific growth method of the ZnO nanorod array is as follows: mixing ZnO powder and carbon powder according to the mass ratio of 1:1-3 to obtain mixed powder, and placing the mixed powder at the bottom of a quartz tube; cutting and cleaning a sapphire substrate to be used as a growth substrate; putting the mixed powder and the sapphire substrate into a quartz tube with an opening at one end, horizontally pushing the quartz tube into a tube furnace, vacuumizing, introducing 130-plus-180 sccm argon and 13-18sccm oxygen for high-temperature reaction at the temperature of 1000-plus-1200 ℃ for 10-60min, and generating the ZnO nanorod array after the reaction is finished.
4. A preparation method of the ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen according to any one of claims 1 to 3 is characterized by comprising the following steps:
(1) growing a ZnO nanorod array on an insulating substrate by adopting a vapor deposition method;
(2) sputtering a layer of WS on the ZnO nanorod array obtained in the step (1)2Film of ZnO-WS2A composite system;
(3) ZnO-WS in the composite system obtained in step (2)2Sputtering CdS nanoparticles to form ZnO-WS2-a CdS complex system.
5. The preparation method of the ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen according to claim 4, wherein in the step (1), the growth method of the ZnO nanorod array is as follows: mixing ZnO powder and carbon powder according to the mass ratio of 1:1-3 to obtain mixed powder, and placing the mixed powder at the bottom of a quartz tube; cutting and cleaning a sapphire substrate to be used as a growth substrate; putting the mixed powder and the sapphire substrate into a quartz tube with an opening at one end, horizontally pushing the quartz tube into a tube furnace, vacuumizing, introducing 130-plus-180 sccm argon and 13-18sccm oxygen for high-temperature reaction at the temperature of 1000-plus-1200 ℃ for 10-60min, and generating the ZnO nanorod array after the reaction is finished.
6. The preparation method of ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen according to claim 4, wherein in the step (2), the WS is2The specific preparation method of the film is as follows: the used equipment is a magnetron sputtering instrument, and the sputtering target material is WS2The target material has the specification of 60 multiplied by 3mm, the cavity air pressure is 1-4Pa, the argon flow is 30-50sccm, the nitrogen flow is 5-10sccm, the sputtering power is 80-150W, and the sputtering time is 5-30 min.
7. The preparation method of the ZnO core-shell nanorod array photocatalyst with high hydrogen production efficiency according to claim 4, wherein in the step (3), the CdS nanoparticles are loaded on ZnO-WS in a sputtering manner2The outer layer of the composite system is sputtered by a magnetron sputtering instrument by using CdS target material of 60 x 3mm, the pressure of a cavity is 1-4Pa, the flow of argon gas is 30-50sccm, the flow of nitrogen gas is 5-10sccm, the sputtering power is 80-150W, and the sputtering time is 5-30 min.
8. The ZnO core-shell nanorod array photocatalyst capable of efficiently producing hydrogen according to any one of claims 1 to 3 is used for producing hydrogen under visible light.
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