CN113181907B - Sandwich structure catalyst, space separation double-promoter structure photocatalyst, preparation method and application - Google Patents
Sandwich structure catalyst, space separation double-promoter structure photocatalyst, preparation method and application Download PDFInfo
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- CN113181907B CN113181907B CN202110468373.1A CN202110468373A CN113181907B CN 113181907 B CN113181907 B CN 113181907B CN 202110468373 A CN202110468373 A CN 202110468373A CN 113181907 B CN113181907 B CN 113181907B
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- photocatalyst
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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Abstract
The invention provides a catalyst with a sandwich structure and a preparation method thereof, and a photocatalyst with a spatial separation double-promoter structure and a preparation method and application thereof, and belongs to the technical field of photocatalytic materials. The preparation method comprises the steps of taking a carbon nano material as a template, sequentially depositing a first oxide nano layer, an oxide nano particle layer and a second oxide nano layer on the outer surface of the carbon nano material by utilizing an Atomic Layer Deposition (ALD) method, and then calcining and reducing to obtain the catalyst with the sandwich structure. The catalyst with the sandwich structure prepared by the method provided by the invention has excellent photogenerated carrier separation performance, more hydrogen evolution active sites and high photocatalytic hydrogen evolution activity. According to the invention, the space separation double-assistant structure photocatalyst is obtained by further constructing a space separation double-assistant structure on the basis of the sandwich structure catalyst, and the space separation double-assistant structure photocatalyst has high separation efficiency of photon-generated carriers and excellent photocatalytic hydrogen evolution and full water splitting activity.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a catalyst with a sandwich structure and a preparation method thereof, a photocatalyst with a spatial separation double-promoter structure and a preparation method and application thereof.
Background
Semiconductor photocatalytic water splitting hydrogen production (H) 2 ) The device is one of solar energy utilization technologies with great prospect, can convert intermittent solar energy into storable and pollution-free hydrogen energy, has important significance for relieving energy crisis and protecting the environment, and is widely concerned by researchers in various countries. However, the recombination rate of photogenerated carriers in the semiconductor is high, and the efficiency of hydrogen production by photocatalytic water decomposition is low. In order to reduce the recombination of photogenerated carriers in a semiconductor, a supported promoter (such as a reductive promoter of platinum, copper or nickel, and an oxidative promoter of manganese oxide, ruthenium oxide, nickel oxide or cobalt oxide) is an effective method for promoting the separation of photogenerated charges and manufacturing reaction sites with high surface activity. The fact that the cocatalyst has a suitable particle size and can be stably anchored to the carrier is an essential factor for ensuring high activity and long-term stability of the supported catalyst. However, the cocatalyst supported on the surface of the semiconductor is not only easy to aggregate during the preparation and reaction of the catalyst, thereby reducing the activity and stability of the catalyst, but also has less contact surface between the cocatalyst and the semiconductor, which is not beneficial to the transmission of photon-generated carriers and the occurrence of photocatalytic redox reaction.
In order to increase the stability of the catalyst and the transmission channel of photo-generated electrons and reduce the transmission distance of photo-generated carriers, the preparation of the catalyst with a sandwich structure by embedding the cocatalyst in the semiconductor is a method for solving the problems. However, in the prior art, sol-gel and hydrothermal methods are usually adopted to prepare the sandwich structure catalyst, the preparation method is complex, the thickness of materials of inner and outer layers of the sandwich, the size and distribution of the redox assistant nanoparticles and the metal-semiconductor interface structure are difficult to accurately control, and the activity of the catalyst needs to be improved.
Disclosure of Invention
The invention aims to provide a sandwich structure catalyst and a preparation method thereof, a space separation double-promoter structure photocatalyst and a preparation method and application thereof, and the sandwich structure catalyst prepared by the method can maximize hydrogen evolution active sites and reduce photon-generated carrier recombination; the space separation double-promoter structure photocatalyst obtained based on the sandwich structure catalyst can further reduce the recombination of photon-generated carriers in a semiconductor, and has excellent photocatalytic hydrogen evolution and full hydrolytic activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a sandwich structure catalyst, which comprises the following steps:
depositing a first oxide nano layer on the outer surface of a carbon nano material by using the carbon nano material as a template and utilizing an atomic layer deposition method, wherein the chemical composition of the first oxide nano layer comprises titanium dioxide or zinc oxide;
depositing an oxide nanoparticle layer on the outer surface of the first oxide nanoparticle layer by using an atomic layer deposition method, wherein the chemical composition of the oxide nanoparticle layer comprises copper oxide, nickel oxide or platinum oxide;
depositing a second oxide nano-layer on the outer surface of the oxide nano-particle layer by utilizing an atomic layer deposition method to obtain a first catalyst precursor, wherein the chemical composition of the second oxide nano-layer comprises titanium dioxide or zinc oxide;
subjecting the first catalyst precursor to a calcination treatment to crystallize the first oxide nanolayer and the second oxide nanolayer while removing carbon nanomaterials in the first catalyst precursor to obtain a second catalyst precursor;
and reducing the oxide nanoparticle layer in the second catalyst precursor to form metal nanoparticles between the first oxide nanoparticle layer and the second oxide nanoparticle layer to obtain the catalyst with the sandwich structure, wherein the metal nanoparticles comprise nano copper, nano nickel or nano platinum.
Preferably, the raw material for depositing the first oxide nanolayer comprises a titanium tetraisopropoxide-water system, a titanium tetrachloride-water system or a diethyl zinc-water system; the deposition conditions include: the temperature is 100-200 ℃, and the pressure is 10-100 Pa.
Preferably, the raw material used to deposit the oxide nanoparticle layer comprises a bis (2, 6-tetramethyl-3, 5-heptanedionate) copper-ozone system, a nickelocene-ozone system, or a trimethyl (methylcyclopentadienyl) platinum-ozone system; the deposition conditions include: the temperature is 200-300 ℃, and the pressure is 10-100 Pa.
Preferably, the starting materials used to deposit the second oxide nanolayer include a titanium tetraisopropoxide-water system, a titanium tetrachloride-water system, or a diethyl zinc-water system; the deposition conditions include: the temperature is 100-200 ℃, and the pressure is 10-100 Pa.
The invention provides a catalyst with a sandwich structure prepared by the preparation method in the technical scheme, which comprises a first oxide nano layer, a second oxide nano layer sleeved outside the first oxide nano layer and metal nano particles distributed between the first oxide nano layer and the second oxide nano layer.
Preferably, the total thickness of the first oxide nano layer and the second oxide nano layer is 10 to 22nm, and the inner diameter of the first oxide nano layer is 20 to 150nm; the particle size of the metal nano particles is less than or equal to 5nm; the load capacity of the metal nano particles is 0.1-10.0 wt%.
The invention provides a space separation double-promoter structured photocatalyst, which comprises a sandwich structured catalyst and an oxidation promoter loaded on the surface of the sandwich structured catalyst, wherein the sandwich structured catalyst is the sandwich structured catalyst in the technical scheme; the oxidation auxiliary agent is a nano-scale metal oxide.
Preferably, the metal element in the oxidation assistant is manganese, ruthenium, cobalt or nickel.
The invention provides a preparation method of the space separation double-promoter structured photocatalyst in the technical scheme, which comprises an atomic layer deposition method or a photochemical deposition method;
the method for preparing the space separation double-promoter structured photocatalyst by utilizing the atomic layer deposition method comprises the following steps:
depositing an oxidation auxiliary agent on the surface of the catalyst with the sandwich structure by utilizing an atomic layer deposition method to obtain a photocatalyst with a spatially separated double-auxiliary agent structure;
the method for preparing the space separation double-promoter structure photocatalyst by using the photochemical deposition method comprises the following steps:
mixing a precursor corresponding to the oxidation auxiliary agent, the catalyst with the sandwich structure and a solvent, and depositing the oxidation auxiliary agent on the surface of the catalyst with the sandwich structure by using an in-situ photo-deposition method to obtain the photocatalyst with the spatially separated double-auxiliary-agent structure.
The invention provides an application of a sandwich-structure catalyst or a space separation double-promoter structure photocatalyst in a photocatalytic full-hydrolysis reaction or a photocatalytic water-splitting hydrogen-analysis reaction, wherein the sandwich-structure catalyst is the sandwich-structure catalyst in the technical scheme, and the space separation double-promoter structure photocatalyst is the space separation double-promoter structure photocatalyst in the technical scheme or the space separation double-promoter structure photocatalyst prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a catalyst with a sandwich structure, which comprises the following steps: depositing a first oxide nano layer on the outer surface of a carbon nano material by using the carbon nano material as a template and utilizing an atomic layer deposition method, wherein the chemical composition of the first oxide nano layer comprises titanium dioxide or zinc oxide; depositing an oxide nanoparticle layer on the outer surface of the first oxide nanoparticle layer by using an atomic layer deposition method, wherein the chemical composition of the oxide nanoparticle layer comprises copper oxide, nickel oxide or platinum oxide; depositing a second oxide nano-layer on the outer surface of the oxide nano-particle layer by utilizing an atomic layer deposition method to obtain a first catalyst precursor, wherein the chemical composition of the second oxide nano-layer comprises titanium dioxide or zinc oxide; subjecting the first catalyst precursor to a calcination treatment to crystallize the first oxide nanolayer and the second oxide nanolayer while removing carbon nanomaterials in the first catalyst precursor to obtain a second catalyst precursor; and reducing the oxide nanoparticle layer in the second catalyst precursor to form metal nanoparticles between the first oxide nanoparticle layer and the second oxide nanoparticle layer to obtain the sandwich structure catalyst, wherein the metal nanoparticles comprise nano copper, nano nickel or nano platinum.
The preparation method comprises the steps of taking a carbon nano material as a template, utilizing an Atomic Layer Deposition (ALD) method to sequentially deposit and form a first oxide nano layer, an oxide nano particle layer and a second oxide nano layer on the outer surface of the carbon nano material, and then carrying out calcination treatment and reduction treatment to obtain the catalyst with the sandwich structure. By adopting the method provided by the invention, under the condition of ensuring that the light absorption properties of the catalysts are consistent, the composition and the surface interface structure of the composite photocatalytic material can be accurately regulated and controlled from the atomic level by changing the deposition times when the first oxide nano layer and the second oxide nano layer are formed, the optimal carrier separation efficiency and the maximized hydrogen evolution active site can be realized, and the prepared catalyst with the sandwich structure has excellent photogenerated carrier separation performance, more hydrogen evolution active sites and high photocatalytic hydrogen evolution activity. In addition, the invention adopts the atomic layer deposition method to prepare the catalyst with the sandwich structure, thereby overcoming the defects that the traditional method in the prior art can not finely regulate and control the position, the thickness, the particle size and the distribution of the semiconductor-auxiliary agent, and the prepared catalyst with the sandwich structure has more fine and definite structure.
According to the invention, a space separation double-assistant structure is further constructed on the basis of the catalyst with the sandwich structure to obtain the photocatalyst with the space separation double-assistant structure, and the photocatalyst with the space separation double-assistant structure has high separation efficiency of photon-generated carriers and excellent photocatalytic hydrogen evolution activity.
Drawings
FIG. 1 shows 150TiO prepared in example 1 2 /100Cu/150TiO 2 Transmission electron microscopy of the catalyst;
FIG. 2 shows 150TiO prepared in example 3 2 /100Cu/150TiO 2 @1.0％RuO x Transmission electron microscopy of the catalyst.
Detailed Description
The invention provides a preparation method of a catalyst with a sandwich structure, which comprises the following steps:
depositing a first oxide nano layer on the outer surface of the carbon nano material by using an atomic layer deposition method by taking the carbon nano material as a template, wherein the chemical composition of the first oxide nano layer comprises titanium dioxide or zinc oxide;
depositing an oxide nanoparticle layer on the outer surface of the first oxide nanoparticle layer by using an atomic layer deposition method, wherein the chemical composition of the oxide nanoparticle layer comprises copper oxide, nickel oxide or platinum oxide;
depositing a second oxide nano-layer on the outer surface of the oxide nano-particle layer by utilizing an atomic layer deposition method to obtain a first catalyst precursor, wherein the chemical composition of the second oxide nano-layer comprises titanium dioxide or zinc oxide;
subjecting the first catalyst precursor to a calcination treatment to crystallize the first oxide nanolayer and the second oxide nanolayer while removing carbon nanomaterials in the first catalyst precursor to obtain a second catalyst precursor;
and reducing the oxide nanoparticle layer in the second catalyst precursor to form metal nanoparticles between the first oxide nanoparticle layer and the second oxide nanoparticle layer to obtain the catalyst with the sandwich structure, wherein the metal nanoparticles comprise nano copper, nano nickel or nano platinum.
The method takes a carbon nano material as a template, and utilizes an atomic layer deposition method to deposit and form a first oxide nano layer on the outer surface of the carbon nano material, wherein the chemical composition of the first oxide nano layer comprises titanium dioxide or zinc oxide. The invention takes a carbon nano material as a template, and particularly, the outer diameter of the carbon nano material is consistent with the inner diameter of the first oxide nano layer. In the present invention, the carbon nanomaterial preferably includes a carbon nanoball or a carbon nanowire, and in the present invention, the diameters of the carbon nanoball and the carbon nanowire are independently preferably 60 to 70nm. The carbon nano-material is not particularly limited in source, and can be prepared by methods well known to those skilled in the art, and in the examples of the present invention, the carbon nano-sphere is preferably prepared by reference to the literature (Zhou, l.l.; zhang, g.l.; wang, m.g., wang, d.f.; cai, d.q.; wu, z.y.instant removal of a monovalent chromium from water and soil using a magnetic series coated by functionalized nano carbon fiber spheres.chemical engineering journal2018,334, 400); the carbon nanofibers are preferably helical carbon nanorods (simply referred to as carbon helices) which are preferably prepared by reference to the literature (Qin, y.; zhang, z.; cui, z. Helical carbon nanofibers prepared by gasification of ethylene with a catalyst derived from the composition of copperperplate. Carbon 2003,41 (15), 3072).
After the carbon nano material is obtained, the carbon nano material is used as a template, and a first oxide nano layer is deposited on the outer surface of the carbon nano material by utilizing an atomic layer deposition method. For convenience of operation, the present invention preferably disperses the carbon nanomaterial in an organic solvent, coats the resulting dispersion on the surface of a substrate, dries to obtain a substrate with the carbon nanomaterial attached thereto, and then performs a subsequent deposition step on the substrate with the carbon nanomaterial attached thereto. In the present invention, the organic solvent is preferably ethanol; the invention has no special limit on the dosage of the ethanol, and ensures that the coating is smoothly carried out; in the embodiment of the present invention, the ratio of the carbon nanomaterial to ethanol is preferably 25mg: (1-3) mL. In the present invention, the substrate is preferably a quartz plate, and the size of the quartz plate is preferably 80mm × 80mm. The present invention preferably applies the dispersion to one side of the substrate. In the present invention, the amount of the carbon nanomaterial supported on the surface of the substrate is preferably 0.25 to 0.50mg/cm 2 More preferably 0.30 to 0.40mg/cm 2 (ii) a In the embodiment of the present invention, the supported amount of the carbon nanomaterial on one surface of the substrate is preferably 25mg in terms of the substrate having a size of 80mm × 80mm. The drying mode is not particularly limited, and the drying can be carried out by airing.
After the substrate attached with the carbon nano material is obtained, the substrate attached with the carbon nano material is placed in a vacuum reaction cavity of atomic layer deposition equipment, and a first oxide nano layer is formed on the outer surface of the carbon nano material through deposition by an atomic layer deposition method. In the present invention, the chemical composition of the first oxide nanolayer includes titanium dioxide or zinc oxide; the invention selects corresponding raw materials according to the chemical composition of the first oxide nano layer, and particularly, the raw materials for depositing the first oxide nano layer preferably comprise a titanium tetraisopropoxide-water system, a titanium tetrachloride-water system or a diethyl zinc-water system. In the present invention, when depositing the first oxide nanolayer, the deposition conditions include: the temperature is preferably 100 to 200 ℃, and more preferably 150 ℃; the pressure is preferably 10 to 100Pa, and more preferably 50Pa. In the invention, when the first oxide nano layer is deposited, the carrier gas is continuously introduced into the vacuum reaction cavity, specifically, the ratio of the carrier gas flow to the volume of the vacuum reaction cavity is 1: (5-10) introducing a carrier gas, preferably 1:8; the carrier gas is preferably high purity nitrogen.
The thickness of the first oxide nano layer is preferably controlled by controlling the deposition cycle number, specifically, water is used as a first precursor, a metal compound (namely titanium tetraisopropoxide, titanium tetrachloride or diethyl zinc) is used as a second precursor, the substrate attached with the carbon nano material is placed in a vacuum reaction cavity of the atomic layer deposition equipment, the first precursor is firstly pulsed into the vacuum reaction cavity, the first precursor is adsorbed on the surface of the substrate attached with the carbon nano material, and after the first precursor is adsorbed and saturated, carrier gas is introduced to bring the remaining first precursor and reaction products out of the vacuum reaction cavity; then, a second precursor is pulsed into the vacuum reaction cavity, after the second precursor and the first precursor are completely reacted, carrier gas is introduced, and the unreacted second precursor and reaction products are taken out of the vacuum reaction cavity and are recorded as 1 cycle number; repeating the above operation until the first oxide nano-layer with the required thickness is obtained. In the present invention, the thickness of the first oxide nanolayer is preferably 5 to 11nm, and the number of cycles for depositing the first oxide nanolayer is preferably 10 to 290, more preferably 50 to 250, even more preferably 100 to 200, and even more preferably 150.
After the first oxide nano-layer is obtained, an oxide nano-particle layer is formed on the outer surface of the first oxide nano-layer in a deposition mode through an atomic layer deposition method, and the chemical composition of the oxide nano-particle layer comprises copper oxide, nickel oxide or platinum oxide. According to the invention, corresponding raw materials are selected according to the chemical composition of the oxide nanoparticle layer, and particularly, the raw materials for depositing the oxide nanoparticle layer preferably comprise a bis (2, 6-tetramethyl-3, 5-heptanedionate) copper-ozone system, a nickelocene-ozone system or a trimethyl (methylcyclopentadienyl) platinum-ozone system. In the present invention, when depositing the oxide nanoparticle layer, the deposition conditions include: the temperature is preferably 200 to 300 ℃, and more preferably 250 ℃; the pressure is preferably 10 to 100Pa, more preferably 50Pa. In the present invention, when depositing the oxide nanoparticle layer, a carrier gas is continuously introduced into the vacuum reaction chamber, and the types and the selectable ranges of the carrier gas and the flow rate are preferably consistent with those of the carrier gas and the flow rate when depositing the first oxide nanoparticle layer, which is not described herein again.
The method preferably controls the thickness of the oxide nanoparticle layer by controlling the number of cycles of deposition, and further controls the particle size and the loading capacity of nanoparticles in the finally obtained sandwich structure catalyst, specifically, ozone is used as a first precursor, a metal compound (namely bis (2, 6-tetramethyl-3, 5-heptanedionato) copper, nickelocene or trimethyl (methylcyclopentadienyl) platinum) is used as a second precursor to obtain a first oxide nanoparticle layer, the first precursor is firstly pulsed into a vacuum reaction cavity, the first precursor is adsorbed on the surface of the first oxide nanoparticle layer, after the first precursor is adsorbed and saturated, a carrier gas is introduced, and the remaining first precursor and reaction products are taken out of the vacuum reaction cavity; then, a second precursor is pulsed into the vacuum reaction cavity, after the second precursor and the first precursor are completely reacted, carrier gas is introduced, and the unreacted second precursor and reaction products are taken out of the vacuum reaction cavity and are recorded as 1 cycle number; repeating the operation to obtain the oxide nanoparticle layer with the required thickness. In the present invention, the thickness of the oxide nanoparticle layer is preferably 1 to 3nm, and the number of cycles for depositing the oxide nanoparticle layer is preferably 5 to 600, more preferably 50 to 400, and still more preferably 100 to 200.
After the oxide nanoparticle layer is obtained, depositing a second oxide nanoparticle layer on the outer surface of the oxide nanoparticle layer by using an atomic layer deposition method to obtain a first catalyst precursor, wherein the second oxide nanoparticle layer comprises titanium dioxide or zinc oxide in chemical composition. In the present invention, the chemical composition of the second oxide nano layer includes titanium dioxide or zinc oxide, specifically, the chemical composition of the second oxide nano layer may be the same as or different from that of the first oxide nano layer, and the present invention is not limited to this; the invention selects corresponding raw materials according to the chemical composition of the second oxide nano layer, and particularly, the raw materials for depositing the second oxide nano layer preferably comprise a titanium tetraisopropoxide-water system, a titanium tetrachloride-water system or a diethyl zinc-water system. In the present invention, when depositing the second oxide nano-layer, the selectable ranges of the deposition conditions, the carrier gas types and the flow rates are preferably consistent with those of the first oxide nano-layer, and thus, detailed description thereof is omitted.
The present invention preferably controls the thickness of the second oxide nanolayer by controlling the number of cycles of deposition, and specifically, the specific operation manner of 1 cycle number when depositing the second oxide nanolayer is preferably the same as the specific operation manner of 1 cycle number when depositing the first oxide nanolayer, and by controlling the appropriate number of cycles, the second oxide nanolayer having a desired thickness can be obtained. In the present invention, the thickness of the second oxide nanolayer is preferably 5 to 11nm, and the number of cycles for depositing the second oxide nanolayer is preferably 10 to 290, more preferably 50 to 250, even more preferably 100 to 200, and even more preferably 150. In the present invention, the thickness of the second oxide nanolayer may or may not be the same as the thickness of the first oxide nanolayer, and preferably the thickness of the second oxide nanolayer is the same as the thickness of the first oxide nanolayer.
After obtaining the first catalyst precursor, the present invention subjects the first catalyst precursor to a calcination treatment to crystallize the first oxide nanolayer and the second oxide nanolayer while removing carbon nanomaterials in the first catalyst precursor, to obtain a second catalyst precursor. In the present invention, the calcination treatment is preferably performed in an air atmosphere; the temperature of the calcination treatment is preferably 400-600 ℃, and more preferably 500 ℃; the holding time is preferably 1 to 3 hours, more preferably 2 hours. The invention preferably heats from room temperature to the temperature of calcination treatment at the heating rate of 3-7 ℃/min, and then the calcination treatment is carried out by heat preservation; the temperature increase rate is more preferably 5 ℃/min. The calcination treatment is preferably performed under the above conditions in the present invention, which can ensure sufficient removal of the carbon nanomaterial in the first catalyst precursor while crystallizing the first oxide nanolayer and the second oxide nanolayer.
After the second catalyst precursor is obtained, the oxide nanoparticle layer in the second catalyst precursor is subjected to reduction treatment, and metal nanoparticles are formed between the first oxide nanoparticle layer and the second oxide nanoparticle layer, so that the catalyst with the sandwich structure is obtained, wherein the metal nanoparticles comprise nano copper, nano nickel or nano platinum. In the present invention, the reduction treatment is preferably performed in H 2 In a mixed atmosphere of-Ar, wherein H 2 H in-Ar gas mixture 2 Is preferably 3 to 7%, more preferably 5%; the temperature of the reduction treatment is preferably 400-600 ℃, and more preferably 500 ℃; the heat preservation time is preferably 1.5 to 2.5 hours, and more preferably 2 hours; the invention preferably heats from room temperature to the temperature of reduction treatment at the heating rate of 3-7 ℃/min, and carries out reduction treatment by heat preservation; the temperature increase rate is more preferably 5 ℃/min. In the present invention, the reduction treatment is preferably performed under the above conditions, which can ensure that the oxide in the oxide nanoparticle layer in the second catalyst precursor is reduced to a simple substance without reducing the oxide in the first oxide nanoparticle layer and the second oxide nanoparticle layer, and finally nanoparticles are formed between the first oxide nanoparticle layer and the second oxide nanoparticle layer, thereby obtaining the catalyst with a sandwich structure.
The preparation method comprises the steps of taking a carbon nano material as a template, utilizing an Atomic Layer Deposition (ALD) method to sequentially deposit and form a first oxide nano layer, an oxide nano particle layer and a second oxide nano layer on the outer surface of the carbon nano material, and then carrying out calcination treatment and reduction treatment to obtain the catalyst with the sandwich structure. By adopting the method provided by the invention, the regulation and control of the composition and the surface interface can be realized by changing the deposition sequence and the deposition times of the oxide nano layer and the oxide nano particles. Under the condition that the total deposition times of the oxide nano-layers are fixed (the light absorption performance of each catalyst is ensured to be consistent), the composition and the surface interface are regulated and controlled by changing the deposition times of the first oxide nano-layer and the second oxide nano-layer. Specifically, taking carbon nano materials as carbon nano fibers as an example, the tube inner structure is prepared when only the second oxide nano layer is deposited; when the deposition times of the first oxide nano layer and the second oxide nano layer are consistent, a sandwich structure with the metal nano particles being consistent with the inner wall and the outer wall of the oxide nano layer is prepared; preparing an out-of-tube structure when only the first oxide nanolayer is deposited; because the interface and the relative position of the catalyst cannot be accurately adjusted on an atomic scale by the existing method, the influence of the interface and the relative position on photocatalytic hydrogen evolution is not researched yet at present. The method can accurately research the specific influence of the interface area of the oxide layer-metal nanoparticle layer and the position of the metal particle layer in the oxide layer on the photocatalytic hydrogen evolution activity.
The invention provides a catalyst with a sandwich structure prepared by the preparation method in the technical scheme, which comprises a first oxide nano layer, a second oxide nano layer sleeved outside the first oxide nano layer and nano particles distributed between the first oxide nano layer and the second oxide nano layer; wherein the total thickness of the first oxide nano layer and the second oxide nano layer is preferably 10 to 22nm, more preferably 13 to 16nm, and the inner diameter of the first oxide nano layer is 20 to 150nm, preferably 50 to 100nm, more preferably 60 to 70nm; the particle size of the nano particles is less than or equal to 5nm, preferably ranges from atomic clusters to 3nm, and the atomic clusters specifically refer to atomic clusters formed by 20-70 atoms; the supported amount of the nanoparticles is preferably 0.1 to 10.0wt%, more preferably 1.0 to 6.0wt%.
The invention provides a space separation double-promoter structured photocatalyst, which comprises a sandwich-structured catalyst and an oxidation promoter loaded on the surface of the sandwich-structured catalyst, wherein the sandwich-structured catalyst is the sandwich-structured catalyst in the technical scheme; the oxidation auxiliary agent is a nano-scale metal oxide. In the invention, the whole sandwich structure catalyst is in a hollow structure, and the surfaces of the sandwich structure catalyst specifically refer to the inner surface and the outer surface of the sandwich structure catalyst. In the invention, the photocatalyst with the spatial separation double-promoter structure specifically comprises two promoters, wherein one promoter is a metal nanoparticle in the catalyst with the sandwich structure, and the other promoter is an oxidation promoter loaded on the surface of the catalyst with the sandwich structure, and the two promoters form a spatial separation state based on a second oxide nanoparticle in the catalyst with the sandwich structure, so that the composition of a photogenerated carrier in a semiconductor can be further reduced, and the photocatalyst with the spatial separation double-promoter structure has excellent photocatalytic hydrogen evolution activity.
In the invention, the metal element in the oxidation assistant is preferably manganese, ruthenium, cobalt or nickel, and the loading amount of the oxidation assistant is preferably 0.5-2.5 wt%, and more preferably 1.0-1.5 wt%; the size of the oxidation assistant is preferably 1 to 100nm. In the present invention, the morphology of the oxidation assistant is related to the type of the metal oxide and the preparation method (the preparation method includes an atomic layer deposition method or a photochemical deposition method, which will be described in detail later), and specifically, when the oxidation assistant is ruthenium oxide, the morphology of the ruthenium oxide is nanoparticles, and the diameter of the nanoparticles is preferably 1 to 3nm. When the oxidation auxiliary agent is manganese oxide, the manganese oxide prepared by a photochemical deposition method is a nanorod, the diameter of the nanorod is preferably 5-10 nm, and the length of the nanorod is preferably 30-50 nm; the manganese oxide prepared by the atomic layer deposition method is in the shape of nanoparticles, and the diameter of the nanoparticles is preferably 3-4 nm.
In the present invention, the oxidation assistant may be represented by MO x M is Mn, ru, co or Ni.
The invention provides a preparation method of the space separation double-promoter structured photocatalyst in the technical scheme, which comprises an atomic layer deposition method or a photochemical deposition method;
the method for preparing the space separation double-promoter structured photocatalyst by utilizing the atomic layer deposition method comprises the following steps:
depositing an oxidation auxiliary agent on the surface of the catalyst with the sandwich structure by utilizing an atomic layer deposition method to obtain a photocatalyst with a spatial separation double-auxiliary-agent structure;
the method for preparing the space separation double-promoter structure photocatalyst by using the photochemical deposition method comprises the following steps:
and mixing a precursor corresponding to the oxidation auxiliary agent, the catalyst with the sandwich structure and a solvent, and depositing the oxidation auxiliary agent on the surface of the catalyst with the sandwich structure by using an in-situ photo-deposition method to obtain the photocatalyst with the spatial separation double-auxiliary-agent structure.
In the invention, the method for preparing the space separation double-promoter structured photocatalyst by utilizing the atomic layer deposition method comprises the following steps:
and depositing an oxidation auxiliary agent on the surface of the catalyst with the sandwich structure by utilizing an atomic layer deposition method to obtain the photocatalyst with the spatial separation double-auxiliary agent structure.
In the invention, the raw material for depositing the oxidation auxiliary agent preferably comprises an N, N' -diisopropyl acetamidine manganese-water system, a diethyl ruthenocene-oxygen system, a cobaltocene-ozone system or a nickelocene-ozone system; the deposition conditions preferably include: the temperature is 100-300 ℃, and the pressure is 10-100 Pa. In the present invention, the method of depositing the oxidation assistant on the surface of the sandwich-structured catalyst is preferably performed with reference to the method of depositing the first oxide nanolayer, which will not be described herein.
In the invention, the photochemical deposition method is used for preparing the space separation double-promoter structure photocatalyst, and the method comprises the following steps:
and mixing a precursor corresponding to the oxidation auxiliary agent, the catalyst with the sandwich structure and a solvent, and depositing the oxidation auxiliary agent on the surface of the catalyst with the sandwich structure by using an in-situ photo-deposition method to obtain the photocatalyst with the spatial separation double-auxiliary-agent structure.
In the invention, the precursor corresponding to the oxidation auxiliary agent preferably comprises manganese salt, ruthenium salt, cobalt salt or nickel salt, and more preferably manganese nitrate, ruthenium chloride, cobalt nitrate or nickel nitrate; the solvent is preferably water. In the invention, a precursor corresponding to the oxidation auxiliary agent is preferably mixed with a solvent to obtain a precursor solution; and then mixing the precursor solution with a catalyst with a sandwich structure to obtain a reaction solution. The invention preferably controls the load capacity of the oxidation auxiliary agent in the space separation dual-auxiliary-agent structure photocatalyst by controlling the proportioning relation of the precursor corresponding to the oxidation auxiliary agent and the catalyst with the sandwich structure, and the method can be selected according to actual needs. In the present invention, the concentration of the sandwich catalyst in the reaction solution is preferably 0.3 to 1.0mg/mL.
After reaction liquid is obtained, the invention uses an in-situ light deposition method to deposit and form an oxidation auxiliary agent on the surface of the catalyst with the sandwich structure, and the photocatalyst with a space separation double-auxiliary agent structure is obtained. In the present invention, the conditions of the in-situ photo-deposition method include: the light source is preferably a 300W xenon lamp; the deposition time is preferably 4 to 6 hours, and more preferably 5 hours; the deposition temperature is preferably 25-50 ℃, and in the embodiment of the invention, in-situ light deposition can be carried out under room temperature conditions. In the invention, when in-situ light deposition is carried out, under the illumination condition, metal ions, holes generated in the titanium oxide nanotube and water react to generate corresponding metal oxide on the surface of the catalyst with the sandwich structure, and finally the photocatalyst with the space separation double-assistant structure is obtained. After the in-situ light deposition is finished, the obtained system is preferably filtered, the solid material is washed by ultrapure water and then dried, and the space separation double-promoter structured photocatalyst is obtained.
The invention provides an application of a sandwich structure catalyst or a space separation double-promoter structure photocatalyst in a photocatalytic full-hydrolysis reaction or a photocatalytic water-splitting hydrogen-splitting reaction, wherein the sandwich structure catalyst is the sandwich structure catalyst in the technical scheme, and the space separation double-promoter structure photocatalyst is the space separation double-promoter structure photocatalyst in the technical scheme or the space separation double-promoter structure photocatalyst prepared by the preparation method in the technical scheme. The method for using the sandwich structure catalyst and the space separation dual promoter structure photocatalyst is not particularly limited, and the method known by the person skilled in the art can be adopted.
In the embodiment of the invention, the sandwich-structure catalyst or the space separation double-promoter structure photocatalyst is used for photocatalytic water decomposition hydrogen analysis reaction, and the using method specifically comprises the following steps:
dispersing a catalyst in a methanol aqueous solution, stirring for 25-35 min under a dark condition, and introducing high-purity argon into a reaction system in the stirring process so as to achieve the purposes of uniformly dispersing the catalyst, replacing air in the reaction system and establishing adsorption-desorption balance on the surface of the catalyst; then, the photocatalytic water decomposition hydrogen analysis reaction is carried out under the conditions of illumination and high-purity argon gas introduction.
In the embodiment of the present invention, the volume fraction of methanol in the methanol aqueous solution is preferably 8 to 12%, and more preferably 10%; the methanol is used as a sacrificial agent, which is beneficial to the consumption of photogenerated holes in the catalyst and the proceeding of hydrogen evolution reaction. In the examples of the present invention, the ratio of the amount of the catalyst to the aqueous methanol solution is preferably 30mg: (200 to 250) mL, more preferably 30mg:220mL. In the embodiment of the invention, the high-purity argon is preferably introduced at a rate of 15.6mL min -1 (ii) a The light source providing the illumination condition is preferably a 300W mercury lamp, the reaction temperature is preferably 20 ℃, the hydrogen production amount in the reaction process is preferably analyzed by gas chromatography every 1h in the reaction process, and the hydrogen production rate is calculated to represent the photocatalytic hydrogen evolution activity of the catalyst.
In the embodiment of the present invention, when the sandwich-structured catalyst or the spatial separation dual-promoter structured photocatalyst is used in a photocatalytic full water splitting reaction, it is preferably consistent with the above-mentioned conditions of photocatalytic hydrogen splitting reaction, but the difference is only that the methanol aqueous solution is replaced by water, i.e. no sacrificial agent is used, and details are not repeated herein.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The carbon helices used in the following examples and comparative examples of the invention were prepared by reference to the literature (Qin, Y.; zhang, Z.; cui, Z. Simple carbon fibers prepared by gasification of ethylene with a catalyst derived from the composition of copperplate. Carbon 2003,41 (15), 3072).
Example 1
Preparing a sandwich structure catalyst, comprising the following steps:
(1) Taking 25mg of carbon helix, dispersing in 2mL of absolute ethyl alcohol, uniformly coating the obtained carbon helix dispersion liquid on a single surface of a quartz plate with the thickness of 80mm multiplied by 80mm, airing, placing in a vacuum reaction cavity of atomic layer deposition equipment, taking the carbon helix as a template, taking water as a first precursor, taking titanium tetraisopropoxide as a second precursor, and depositing on the surface of the carbon helix by utilizing an atomic layer deposition method to obtain an inner-layer titanium dioxide nanotube; the deposition parameters were set as: the temperature of the cavity is 150 ℃, and the pressure of the cavity is 50Pa; in the deposition process, the ratio of the flow of a carrier gas (specifically high-purity nitrogen) to the volume of the vacuum reaction cavity is 1:8, introducing carrier gas, wherein the flow rate of the carrier gas is 50mL/min; specifically, a first precursor is pulsed into the vacuum reaction cavity, the first precursor is adsorbed on the surface of a carbon spiral on a quartz plate, and carrier gas is introduced after the first precursor is adsorbed and saturated, so that the residual first precursor and reaction products are taken out of the vacuum reaction cavity; then, a second precursor is pulsed into the vacuum reaction cavity, after the second precursor and the first precursor completely react, carrier gas is introduced, the unreacted second precursor and reaction products are taken out of the vacuum reaction cavity, the number of cycles is recorded as 1, the operation is repeated, and 150 cycles are deposited;
(2) Depositing a copper oxide nanoparticle layer on the surface of the inner-layer titanium dioxide nanotube by using an atomic layer deposition method by taking ozone as a first precursor and bis (2, 6-tetramethyl-3, 5-heptanedionate) copper (II) as a second precursor; the deposition parameters were set as: the temperature of the cavity is 250 ℃, and the pressure of the cavity is 50Pa; in the deposition process, in every minute, the ratio of the flow of a carrier gas (specifically high-purity nitrogen) to the volume of a vacuum reaction cavity is 1:8, introducing carrier gas, wherein the flow rate of the carrier gas is 50mL/min; specifically, a first precursor is pulsed into the vacuum reaction cavity, the first precursor is adsorbed on the surface of the inner-layer titanium dioxide nanotube, after the first precursor is adsorbed and saturated, carrier gas is introduced, and the remaining first precursor and reaction products are taken out of the vacuum reaction cavity; then, a second precursor is pulsed into the vacuum reaction cavity, after the second precursor and the first precursor completely react, carrier gas is introduced, the unreacted second precursor and reaction products are taken out of the vacuum reaction cavity, the number of cycles is recorded as 1, the operation is repeated, and 100 cycles are deposited;
(3) Depositing on the surface of the copper oxide nanoparticle layer by using water and titanium tetraisopropoxide as precursors by utilizing an atomic layer deposition method to obtain an outer-layer titanium dioxide nanotube, wherein the set deposition parameters are consistent with those in the step (1), and 150 cycle numbers of co-deposition are carried out to obtain a first catalyst precursor;
(4) Heating the first catalyst precursor from room temperature (25 ℃) to 500 ℃ at the speed of 5 ℃/min in the air, and carrying out heat preservation and calcination treatment for 2h to remove the carbon helix in the first catalyst precursor and crystallize the inner titanium dioxide nanotube and the outer titanium dioxide nanotube at the same time to obtain a second catalyst precursor;
(5) Reacting said second catalyst precursor in H 2 -Ar mixed atmosphere (H) 2 The volume fraction is 5 percent), heating from room temperature to 500 ℃ at the speed of 5 ℃/min, preserving heat and carrying out reduction treatment for 2h to ensure that the copper oxide nano particles in the copper oxide nano particle layer are reduced into copper nano particles, and the copper nano particles are formed between the inner layer titanium dioxide nano tube and the outer layer titanium dioxide nano tube to obtain a sandwich structure catalyst, which is marked as 150TiO 2 /100Cu/150TiO 2 (ii) a Wherein the total thickness of the inner layer titanium dioxide nanotube and the outer layer titanium dioxide nanotube is 13nm, the particle diameter of the copper nanoparticle is 1.9nm (as shown in figure 1), and the exposed surface area of the copper nanoparticle is 90.1m 2 g-Cu (i.e. 1g of Cu in the catalyst possesses a surface area of 90.1m 2 ) The loading was 1.0wt%. Inner diameter of inner layer titanium dioxide nanotube60 to 70nm.
FIG. 1 shows 150TiO prepared in example 1 2 /100Cu/150TiO 2 The transmission electron microscopic picture of the catalyst, wherein the scale of (a) is 50nm, (b) is an enlarged picture, the scale is 30nm, (c) is a high-resolution transmission electron microscopic picture, the scale is 5nm, and (d) is a particle size statistical picture of the copper nanoparticles. The sandwich structure of the catalyst is clearly shown in fig. 1, and the particle size of the copper nanoparticles is 1.9nm; meanwhile, as can be seen from fig. 1, the distance between the copper nanoparticle layer and the tube wall of the inner layer titanium dioxide nanotube is consistent with that between the copper nanoparticle layer and the tube wall of the outer layer titanium dioxide nanotube.
Example 2
The preparation method of the spatial separation double-promoter structured photocatalyst comprises the following steps:
diluting 1.30 mu L of a 50wt% manganese nitrate aqueous solution to 50mL by using water to obtain a manganese nitrate diluent;
the sandwich structure catalyst 150TiO prepared in example 1 2 /100Cu/150TiO 2 Mixing 30mg and 50mL of manganese nitrate diluent, stirring and reacting for 5 hours at room temperature (25 ℃) under the irradiation condition of a 300W xenon lamp, depositing on the surface of the catalyst with the sandwich structure to form manganese oxide, filtering the obtained system, washing the solid material by adopting ultrapure water, and then drying to obtain the photocatalyst with the spatial separation double-assistant structure, which is recorded as 150TiO 2 /100Cu/150TiO 2 @1.5％MnO x (ii) a Wherein the loading amount of the manganese oxide is 1.5wt%, the manganese oxide is in a nano rod shape, the diameter is 5-10 nm, and the length is 30-50 nm.
Example 3
A spatially-separated two-promoter structured photocatalyst was prepared in the same manner as in example 2, except that "1.30. Mu.L of a 50wt% aqueous solution of manganese nitrate" was replaced with "58. Mu.L of an 0.5mol/L aqueous solution of ruthenium chloride"; the space separation double-assistant structured photocatalyst finally obtained is recorded as 150TiO 2 /100Cu/150TiO 2 @1.0％RuO x Wherein the loading amount of the ruthenium oxide is 1.0wt%, the ruthenium oxide is in a nano particle shape, and the particle diameter is 2nm.
FIG. 2 shows 150TiO prepared in example 3 2 /100Cu/150TiO 2 @1.0％RuO x Transmission electron micrographs of the catalyst, wherein (a) is at 50nm and (b) is a high resolution transmission electron micrograph at 10nm. As can be seen from FIG. 2, the ruthenium oxide nanoparticles are coated on the surface of the spatially-separated dual-promoter structured photocatalyst, and the particle size is 2nm; meanwhile, as can be seen from fig. 2, the size distribution of the ruthenium oxide nanoparticles is narrow.
Example 4
The preparation method of the spatial separation double-promoter structured photocatalyst comprises the following steps:
the sandwich structure catalyst 150TiO prepared in example 1 2 /100Cu/150TiO 2 Placing the precursor into a vacuum reaction cavity of atomic layer deposition equipment, taking water as a first precursor, taking N, N' -diisopropylacetamidinyl manganese as a second precursor, and utilizing an atomic layer deposition method to form a 150TiO precursor 2 /100Cu/150TiO 2 The manganese oxide nanoparticles are obtained by surface deposition; the deposition parameters set were: the temperature of the cavity is 200 ℃, and the pressure of the cavity is 50Pa; in the deposition process, the ratio of the flow of a carrier gas (specifically high-purity nitrogen) to the volume of the vacuum reaction cavity is 1:8, introducing carrier gas, wherein the flow rate of the carrier gas is 50mL/min; specifically, first, a first precursor is pulsed into the vacuum reaction chamber, and the first precursor is adsorbed on 150TiO 2 /100Cu/150TiO 2 After the first precursor is adsorbed and saturated, introducing carrier gas, and taking the remaining first precursor and reaction products out of the vacuum reaction cavity; then, a second precursor is pulsed into the vacuum reaction cavity, after the second precursor and the first precursor completely react, carrier gas is introduced, the unreacted second precursor and reaction products are taken out of the vacuum reaction cavity, the number of cycles is recorded as 1, the operation is repeated, and 50 cycles are deposited; finally obtaining the space separation double-assistant structured photocatalyst which is marked as 150TiO 2 /100Cu/150TiO 2 @1.0％MnO x -50; wherein the loading amount of the manganese oxide is 1.0wt%, and the manganese oxide is in the form of nano particles with the diameter of 3nm.
Example 5
Preparation of a Sandwich construction according to example 1The difference of the catalyst is only that the copper oxide nanoparticle layer is replaced by a nickel oxide nanoparticle layer, and the used precursors are nickelocene and ozone; wherein 100 cycle numbers are deposited when the inner titanium dioxide nanotube, the nickel oxide nanoparticle layer and the outer titanium dioxide nanotube are deposited; the final resulting catalyst with a sandwich structure was recorded as 100TiO 2 /100Ni/100TiO 2 Wherein the total thickness of the inner layer titanium dioxide nanotube and the outer layer titanium dioxide nanotube is 13nm.
Example 6
Preparing a sandwich structure catalyst according to the method of the embodiment 1, wherein the difference is that in the embodiment 1, the inner-layer titanium dioxide nanotube is replaced by an inner-layer zinc oxide nanotube, the copper oxide nanoparticle layer is replaced by a nickel oxide nanoparticle layer, the precursors adopted in the preparation of the inner-layer zinc oxide nanotube are water and diethyl zinc, and the precursors adopted in the preparation of the nickel oxide nanoparticle layer are ozone and nickelocene; specifically, 45 cycle numbers are deposited together when the inner zinc oxide nanotube is deposited, the thickness of the inner zinc oxide nanotube is about 7nm, and 100 cycle numbers are deposited together when the nickel oxide nanoparticle layer is deposited; the finally prepared catalyst with a sandwich structure is marked as 45ZnO/100Ni/150TiO 2 。
Example 7
A sandwich-structured catalyst was prepared according to the method of example 1, except that the copper oxide nanoparticle layer of example 1 was replaced with a platinum oxide nanoparticle layer, and the precursors used in preparing the platinum oxide nanoparticle layer were ozone and trimethyl (methylcyclopentadienyl) platinum, and the platinum oxide nanoparticle layer was deposited for 10 cycles; the final prepared catalyst with sandwich structure was recorded as 150TiO 2 /10Pt/150TiO 2 。
Example 8
A sandwich catalyst was prepared according to the method of example 1, except that the carbon helix support in example 1 was replaced with a carbon nanoball, which is referred to in the literature (Zhou, L.L.; zhang, G.L.; wang, M.; wang, D.F.; cai, D.Q.; wu, Z.Y.efficient removal of hexavalent chromium fromwater and soil using magnetic ceramics coated by functional nano carbon spheres.chemical Engineering Journal2018,334, 400); the final prepared catalyst with sandwich structure was recorded as 150TiO 2 /100Cu/150TiO 2 -s, wherein the total thickness of the inner and outer titania nanotubes is 13nm.
Comparative example 1
A titanium dioxide nanotube catalyst was prepared according to the method of example 1, except that the step of depositing the copper oxide nanoparticle layer was omitted and the titanium dioxide nanotubes were deposited for a total of 300 cycles; the final resulting titanium dioxide nanotube catalyst was recorded as 300TiO 2 Wherein the thickness of the titanium dioxide nanotube is 13nm.
Comparative example 2
Catalyst with additive confinement in a semiconductor nanotube was prepared by reference to the method of example 1, except that a copper oxide nanoparticle layer was first deposited on the surface of a carbon helix (100 cycles of codeposition), then titanium dioxide nanotubes were deposited on the surface of the copper oxide nanoparticle layer (300 cycles of codeposition), and finally the catalyst with additive confinement in a semiconductor nanotube was recorded as 100Cu/300TiO 2 Wherein the particle diameter of the copper nanoparticles is 2.1nm, and the exposed surface area of the copper nanoparticles is 129.7m 2 g-Cu, the thickness of the titanium dioxide nanotube is 13nm.
Comparative example 3
Preparing a catalyst modified outside the semiconductor nanotubes by using the method of example 1, except that the step of depositing the outer titanium dioxide nanotubes is omitted, wherein the inner titanium dioxide nanotubes are deposited for 300 cycles; when the copper oxide nanoparticle layer is deposited, 100 cycles of codeposition are carried out; the catalyst modified outside the semiconductor nanotube by the finally obtained auxiliary agent is marked as 300TiO 2 /100Cu, wherein the thickness of the inner titanium dioxide nanotubes is 13nm.
Comparative example 4
The catalyst was prepared according to the method of example 1, except that the copper nanoparticles were omitted, i.e. no copper oxide was depositedA nanoparticle layer, wherein the inner-layer titanium dioxide nanotube in example 1 is replaced by an inner-layer zinc oxide nanotube, a precursor used in preparing the inner-layer zinc oxide nanotube is water and diethyl zinc, and the inner-layer zinc oxide nanotube is deposited for 45 cycles at the same time, wherein the thickness of the inner-layer zinc oxide nanotube is about 7nm; the catalyst obtained in the final preparation is marked as 45ZnO/150TiO 2 (ii) a Wherein the total thickness of the inner layer zinc oxide nanotube and the outer layer titanium dioxide nanotube is 13nm.
The catalysts in the examples and comparative examples were used for photocatalytic water splitting hydrogen evolution reaction by the following steps:
in a 300mL closed quartz reactor, 30mg of the catalyst was dispersed in 220mL of aqueous methanol (methanol as sacrificial agent, volume fraction of sacrificial agent is 10%), and magnetic stirring was maintained under dark conditions at 15.6mLmin -1 Introducing high-purity Ar for 30min at the rate of the reaction so as to achieve the aims of uniformly dispersing the catalyst, replacing air in a reaction system and establishing adsorption and desorption balance on the surface of the catalyst; then, the photocatalytic water decomposition hydrogen analysis reaction is carried out under the irradiation condition of a full light (300W mercury lamp), the reaction temperature is kept at 20 ℃, and 15.6mL min is carried out in the whole reaction process -1 Continuously introducing high-purity Ar, analyzing the hydrogen production amount in the reaction process by using gas chromatography every 1h, and calculating the hydrogen production rate.
The hydrogen production rates after the reaction was stabilized by photocatalytic water splitting hydrogen analysis reaction using each catalyst are specifically shown in tables 1 and 2.
TABLE 1 Performance test data of the catalysts prepared in the examples for photocatalytic water splitting hydrogen evolution reaction
Table 2 data of performance test of the catalyst prepared in comparative example for photocatalytic water splitting hydrogen evolution reaction
The catalyst prepared in example 2 was used for photocatalytic full-hydrolysis reaction under the same conditions as those for photocatalytic hydrogen-splitting reaction described above, except that "220mL of aqueous methanol solution" was replaced with "220mL of water", i.e., no sacrificial agent was used. The hydrogen production rate and the oxygen production rate after the reaction was stabilized are specifically shown in table 3.
Table 3 data of performance test of the catalyst prepared in example 2 for photocatalytic total hydrolysis reaction
According to the data analysis in tables 1-2, it can be seen that the hydrogen evolution performance of each catalyst in decomposing photocatalytic water into hydrogen is analyzed, in the photocatalytic reaction, the interface between the copper nanoparticles, nickel nanoparticles or platinum nanoparticles and titanium dioxide or zinc oxide and the oxidation assistant are main reduction and oxidation active sites, respectively, and the position of the copper nanoparticles, nickel nanoparticles or platinum nanoparticles in the titanium dioxide nanotubes or the nanotubes composed of the titanium dioxide layer and the zinc oxide layer has a large influence on the photocatalytic hydrogen evolution activity, specifically:
when the particle diameter of the copper nano particle is 1.9nm and the thickness of the titanium dioxide nano tube is 13nm, the position of the copper nano particle in the titanium dioxide nano tube is adjusted, and when the copper nano particle is in the center of the titanium dioxide nano tube, the photocatalytic hydrogen evolution activity is optimal.
Compared with the titanium dioxide nanotube, the nanotube formed by the titanium dioxide layer and the zinc oxide layer has better photocatalytic hydrogen evolution activity; the nickel nano particles are added into two different oxide nano layers, so that the photocatalytic hydrogen evolution activity can be further improved.
When the carrier is carbon helix or carbon nanosphere, the prepared catalyst with the sandwich structure can greatly improve the photocatalytic hydrogen evolution activity.
Furthermore, oxidation assistants of different types and loading quantities are modified on the surface of the catalyst with the sandwich structure, and results show that the oxidation assistants of different types and loading quantities can further improve the photocatalytic hydrogen evolution activity.
The space separation double-auxiliary catalyst is applied to the photocatalytic full-hydrolytic reaction, considerable hydrogen and oxygen can be generated simultaneously, the metering ratio of the hydrogen to the oxygen is 1.99 and is close to 2, and the reaction is the full-hydrolytic reaction.
In conclusion, the results in tables 1 to 3 show that the space separation double-promoter structure catalyst based on the sandwich structure synergistically promotes the photocatalytic water splitting hydrogen analysis reaction and the photocatalytic full water splitting reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A space separation double-promoter structured photocatalyst comprises a sandwich structured catalyst and an oxidation promoter loaded on the surface of the sandwich structured catalyst;
the oxidation auxiliary agent is a nano-scale metal oxide, the metal element in the oxidation auxiliary agent is manganese, ruthenium, cobalt or nickel, the loading capacity of the oxidation auxiliary agent is 0.5-2.5 wt%, and the size of the oxidation auxiliary agent is 1-100 nm;
the preparation method of the catalyst with the sandwich structure comprises the following steps:
depositing a first oxide nano layer on the outer surface of a carbon nano material by using the carbon nano material as a template and utilizing an atomic layer deposition method, wherein the chemical composition of the first oxide nano layer comprises titanium dioxide or zinc oxide;
depositing an oxide nanoparticle layer on the outer surface of the first oxide nanoparticle layer by utilizing an atomic layer deposition method, wherein the chemical composition of the oxide nanoparticle layer comprises copper oxide, nickel oxide or platinum oxide;
depositing a second oxide nano-layer on the outer surface of the oxide nano-particle layer by utilizing an atomic layer deposition method to obtain a first catalyst precursor, wherein the chemical composition of the second oxide nano-layer comprises titanium dioxide or zinc oxide;
subjecting the first catalyst precursor to a calcination treatment to crystallize the first oxide nanolayer and the second oxide nanolayer while removing carbon nanomaterials in the first catalyst precursor, resulting in a second catalyst precursor;
reducing the oxide nanoparticle layer in the second catalyst precursor to form metal nanoparticles between the first oxide nanoparticle layer and the second oxide nanoparticle layer to obtain the catalyst with a sandwich structure, wherein the metal nanoparticles comprise nano copper, nano nickel or nano platinum;
the total thickness of the first oxide nano layer and the second oxide nano layer is 10-22 nm, and the inner diameter of the first oxide nano layer is 20-150 nm; the particle size of the nano particles is less than or equal to 5nm, and the load of the nano particles is 0.1-10.0 wt%.
2. The spatially separated dual promoter structured photocatalyst of claim 1, wherein the starting material for the deposition of said first oxide nanolayer comprises a titanium tetraisopropoxide-water system, a titanium tetrachloride-water system, or a diethyl zinc-water system; the deposition conditions include: the temperature is 100-200 ℃, and the pressure is 10-100 Pa.
3. The spatially separated dual promoter structured photocatalyst as set forth in claim 1, wherein a raw material for depositing the oxide nanoparticle layer comprises a bis (2, 6-tetramethyl-3, 5-heptanedionate) copper-ozone system, a nickelocene-ozone system, or a trimethyl (methylcyclopentadienyl) platinum-ozone system; the deposition conditions include: the temperature is 200-300 ℃, and the pressure is 10-100 Pa.
4. The spatially separated dual promoter structured photocatalyst of claim 1, wherein the starting material for the deposition of the second oxide nanolayer comprises a titanium tetraisopropoxide-water system, a titanium tetrachloride-water system, or a diethyl zinc-water system; the deposition conditions include: the temperature is 100-200 ℃, and the pressure is 10-100 Pa.
5. A method for preparing the spatially-separated dual co-agent structured photocatalyst of any one of claims 1 to 4, comprising atomic layer deposition or photochemical deposition;
the method for preparing the space separation double-promoter structured photocatalyst by utilizing the atomic layer deposition method comprises the following steps:
depositing an oxidation auxiliary agent on the surface of the catalyst with the sandwich structure by utilizing an atomic layer deposition method to obtain a photocatalyst with a spatial separation double-auxiliary-agent structure;
the method for preparing the space separation double-promoter structure photocatalyst by using the photochemical deposition method comprises the following steps:
mixing a precursor corresponding to the oxidation auxiliary agent, the catalyst with the sandwich structure and a solvent, and depositing the oxidation auxiliary agent on the surface of the catalyst with the sandwich structure by using an in-situ photo-deposition method to obtain the photocatalyst with the spatially separated double-auxiliary-agent structure.
6. The use of the spatially-separated dual co-agent structured photocatalyst according to any one of claims 1 to 4 or the spatially-separated dual co-agent structured photocatalyst prepared by the preparation method according to claim 5 in a photocatalytic full water splitting reaction or a photocatalytic water splitting hydrogen splitting reaction.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771972A (en) * | 2016-03-07 | 2016-07-20 | 中国科学院山西煤炭化学研究所 | Preparing method of limited-range catalyst modified through atomic layer deposition and application thereof |
| CN105903480A (en) * | 2016-05-18 | 2016-08-31 | 中国科学院山西煤炭化学研究所 | Preparation method of double-interface catalyst for one-process hydrogen production-hydrogenation coupling reaction and application of catalyst |
| CN107012474A (en) * | 2016-01-28 | 2017-08-04 | 中国科学院大连化学物理研究所 | A kind of method of large-scale solar energy photocatalysis-photoelectrocatalysis hydrogen production by water decomposition |
| CN110038590A (en) * | 2019-05-14 | 2019-07-23 | 中国科学院山西煤炭化学研究所 | A kind of more interlayer composite catalysts and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006016718A2 (en) * | 2004-08-11 | 2006-02-16 | Showa Denko K.K. | Fine particulate titanium dioxide, and production process and use thereof |
| TWI600796B (en) * | 2014-09-05 | 2017-10-01 | 國立清華大學 | Nanoporous thin film and method for fabricating the same |
| CN108147464B (en) * | 2018-02-02 | 2019-12-31 | 陕西科技大学 | Rice-shaped manganese dioxide/titanium carbide composite material and preparation method thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012474A (en) * | 2016-01-28 | 2017-08-04 | 中国科学院大连化学物理研究所 | A kind of method of large-scale solar energy photocatalysis-photoelectrocatalysis hydrogen production by water decomposition |
| CN105771972A (en) * | 2016-03-07 | 2016-07-20 | 中国科学院山西煤炭化学研究所 | Preparing method of limited-range catalyst modified through atomic layer deposition and application thereof |
| CN105903480A (en) * | 2016-05-18 | 2016-08-31 | 中国科学院山西煤炭化学研究所 | Preparation method of double-interface catalyst for one-process hydrogen production-hydrogenation coupling reaction and application of catalyst |
| CN110038590A (en) * | 2019-05-14 | 2019-07-23 | 中国科学院山西煤炭化学研究所 | A kind of more interlayer composite catalysts and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Haojie Liang.Porous TiO2/Pt/TiO2 Sandwich Catalyst for Highly Selective Semihydrogenation of Alkyne to Olefin.《ACS Catal.》.2017,第7卷 * |
| Porous TiO2/Pt/TiO2 Sandwich Catalyst for Highly Selective Semihydrogenation of Alkyne to Olefin;Haojie Liang;《ACS Catal.》;20170821;第7卷;第6567-6572页 * |
| 氧化钛复合材料的结构精确调控及其光催化性能研究;杨帆;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20210115;B014-388 * |
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