CN111822025A - Carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material, preparation method and application - Google Patents
Carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material, preparation method and application Download PDFInfo
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 62
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 claims abstract description 36
- 229910001868 water Inorganic materials 0.000 claims abstract description 25
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- 230000007246 mechanism Effects 0.000 claims abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052753 mercury Inorganic materials 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002055 nanoplate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
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- 239000000243 solution Substances 0.000 description 41
- 150000001875 compounds Chemical class 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 229910052573 porcelain Inorganic materials 0.000 description 16
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
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- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 231100000956 nontoxicity Toxicity 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention discloses a tungsten trioxide two-dimensional composite Z-shaped photocatalytic material treated by carbon nitride/hydrogen, a preparation method and application thereof. The material is formed by compounding Pt-loaded ultrathin carbon nitride nanosheets (Pt-CN/NS) and tungsten trioxide (HWO) treated by hydrogen; wherein the Pt-CN/NS has a curled two-dimensional network structure; the tungsten trioxide treated by hydrogen is a two-dimensional nanosheet; the Pt-CN/NS and the HWO are compounded into two-dimensional surface contact type compounding; mass ratio of Pt-CN/NS to HWOIs 0.5:1 to 40: 1. The prepared photocatalytic material is based on a Z-type photocatalytic action mechanism, has high visible light utilization rate, low carrier recombination rate and high-efficiency hydrogen production activity of decomposing water by visible light, and the maximum visible light hydrogen production activity can reach 862 mu mol.h‑1The apparent quantum yield under monochromatic light of 420nm was 16.6%. The method has the advantages of rich raw materials, simple synthesis process, easy operation control, high separation efficiency of photo-generated charges and capability of overcoming g-C to a great extent3N4The carrier recombination problem is serious, and the method has a great application prospect in the field of photolysis of water.
Description
Technical Field
The invention relates to the technical field of preparation of a nano photocatalytic material and hydrogen production application thereof, in particular to a carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material, a preparation method and application thereof.
Background
Energy is the basis for human survival and development, but with the rapid development of all aspects of the current society, traditional fossil energy (coal, oil and natural gas) is gradually exhausted. Therefore, the search for alternative environment-friendly new energy is a problem which needs to be solved urgently in sustainable development of various countries. The hydrogen energy has the advantages of wide sources directly obtained from water, high combustion heat value, clean and pollution-free combustion process, recyclable combustion products of pollution-free water, existence of gaseous or solid metal hydride and the like, and is considered to be an ideal replaceable clean energy source. Fujishima and Honda utilized titanium dioxide (TiO) in 19722) The electrode successfully realizes the photoelectrochemistry hydrogen production by splitting water, and the pioneering work lays a foundation for subsequent researches on hydrogen production by splitting water, hydrogen production by electrolyzing water and hydrogen production by splitting water by photoelectrochemistry. However, compared with the hydrogen production by water photolysis, the hydrogen production by water electrolysis and photoelectrochemistry splitting both need to provide higher electric energy to drive the reaction, and the water photolysis only needs to use sunlight as a driving force in principle. Therefore, hydrogen production by photolysis of water gradually becomes a research hotspot, and hydrogen production by photocatalytic decomposition of water by solar energy is called as a technology of dream of 21 century.
Carbon nitride (g-C)3N4) The material has the advantages of low price, no toxicity, simple preparation method, proper splitting water energy level position and the like, and becomes one of star materials in the field of photocatalysis, but the carrier recombination is serious, so that the application of the material in the field of hydrogen production by water photolysis is limited. Therefore, for g-C3N4Modification and modification to improve the carrier separation efficiency of the catalyst are important points of scientific research and industrial application.
Generally speaking, the Z-type photocatalytic system can effectively separate carriers and simultaneously maintain higher oxidation reduction capability of the catalyst, which is widely researched and very effective for improving the semiconductorA method of catalytically activating a material. Compared with a bulk phase material, the two-dimensional (2D) material can shorten a carrier transfer path, so that the carrier separation efficiency is improved. Thus, 2D ultra-thin g-C was prepared3N4Has become a popular research area. In addition, a Z-type photocatalysis mechanism composite system obtained by compositing different semiconductor materials with matched energy levels can effectively separate photo-generated electrons and holes of the whole system while keeping higher redox capability of the semiconductor materials, thereby improving the separation efficiency of carriers.
Among various semiconductor materials, tungsten trioxide (WO)3) Because of the advantages of low price, no toxicity, strong absorption capability to visible light, strong oxidation capability of valence band holes and the like, the material is often used as a better candidate material for constructing Z-type systems. In particular hydrogen treated 2D nanoplatelet WO3The material has a large specific surface area, can increase the number of active sites and shorten the diffusion distance of carriers, generates a certain oxygen vacancy on the basis, and further improves the light absorption capacity of the material. Thus, WO with hydrogen treatment3Has great application prospect in the field of photocatalysis.
At present, no report about the ultrathin carbon nitride/hydrogen treated tungsten trioxide 2D/2D composite Z-type photocatalytic material related to the invention is found.
Disclosure of Invention
The invention aims to provide a tungsten trioxide 2D/2D composite Z-type photocatalytic material treated by ultrathin carbon nitride/hydrogen, a preparation method and application.
According to the invention, a calcination method is used for the first time to prepare the tungsten trioxide (HWO) two-dimensional/two-dimensional (2D/2D) composite Z-shaped photocatalytic material processed by the close-contact ultrathin carbon nitride/hydrogen, and the carrier separation efficiency of the material is improved from the aspects of morphology regulation and charge transfer mechanism, so that the high-efficiency visible light catalytic hydrogen production activity is obtained. The photocatalytic material has 2D/2D composite characteristics, can effectively separate photogenerated charges, realizes efficient photocatalytic water decomposition hydrogen production driven by visible light, and can reach 862 mu mol h at most-1Hydrogen production activity of (1).
The technical scheme provided by the invention is as follows:
a carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material:
pt-supported ultrathin carbon nitride nanosheets (Pt-C)3N4Pt-CN/NS for short) and tungsten trioxide (HWO) treated by hydrogen;
wherein the Pt-CN/NS has a curled two-dimensional network structure; the tungsten trioxide (HWO) treated by hydrogen is a two-dimensional nanosheet;
the Pt-CN/NS and the HWO are compounded into two-dimensional surface contact type compounding;
the mass ratio of the Pt-CN/NS to the HWO is 0.5: 1-40: 1.
The thickness of the Pt-CN/NS is about 4 nm; the hydrotreated HWO is an ultrathin two-dimensional nanoplate, about 2.5nm thick.
After the two-dimensional composite Z-type photocatalytic carbon nitride/tungsten trioxide material is excited by visible light, the photoproduction charge transfer mode between Pt-CN/NS and HWO follows a Z-type photocatalytic mechanism.
Another object of the present invention is to provide a method for preparing the above-mentioned carbon nitride/tungsten trioxide two-dimensional composite Z-type photocatalytic material, comprising the steps of:
(1) the urea is calcined twice to obtain ultrathin g-C3N4；
(2) Ultra-thin g-C3N4Dispersing in methanol solution, and adding H2PtCl6The solution is irradiated by a high-pressure mercury lamp after ultrasonic dispersion, and the Pt-loaded g-C is obtained by centrifugally washing solid particles3N4(Pt-CN/NS)；
(3) Mixing Na2WO4·2H2Dissolving O in water, and dropwise adding HCl solution while stirring to obtain light yellow floccule; then (NH) is added4)2C2O4·H2O, stirring until the solution is clear and transparent, adding deionized water into the solution, uniformly stirring, carrying out hydrothermal reaction, and washing and drying the product to obtain tungsten trioxide; adding the tungsten trioxide into absolute ethyl alcohol, stirring until the tungsten trioxide is uniformly dispersed, then carrying out alcohol heat treatment, washing, drying and calcining a product to finally obtain the ultrathin tungsten trioxide; finally at Ar andH2hydrogenating the ultra-thin tungsten trioxide in a mixed atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) taking Pt loaded g-C3N4And (Pt-CN/NS) and the hydrogenated tungsten trioxide are annealed in an argon atmosphere to obtain the two-dimensional composite Z-type photocatalytic material of the Pt-CN/NS and the HWO.
In the step (1), the initial temperature of the first calcination is 550 ℃, and the calcination time is 2 h; the second calcination temperature is 520 ℃, and the calcination time is 3 h; the heating rates are both 5 ℃ and min-1。
The temperature of the hydrothermal reaction in the step (3) is 120 ℃, and the treatment time is 1 h; the alcohol heat treatment temperature is 200 ℃, and the treatment time is 24 h.
Ar and H in the above step (3)2The volume ratio of (A) to (B) is 1:9, the hydrotreating temperature is 400 ℃, and the treating time is 6 h.
The annealing temperature in the step (4) is 400 ℃, and the annealing time is 1 h.
The invention also provides application of the carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material in high-efficiency hydrogen production by photocatalytic decomposition of water with visible light.
The invention has the beneficial effects that:
(1) the prepared photocatalytic material is a 2D/2D ultrathin nanosheet, the transfer distance of a current carrier is effectively shortened, and the bulk phase recombination probability of photo-generated charges is reduced;
(2) the prepared photocatalytic material has a photo-generated charge transfer mode belonging to a Z mechanism, so that the carrier separation efficiency of the whole system is improved, and meanwhile, the higher redox capability is kept;
(3) the prepared photocatalytic material has strong light capture capability and high-efficiency photocatalytic hydrogen production activity, and the maximum can reach 862 mu mol.h-1The hydrogen production activity of the catalyst has a wide application prospect;
(4) the preparation raw materials are easy to obtain, the preparation method is simple, the process conditions are easy to control, the reaction activity is high, and the method is suitable for industrial production;
(5) the novel idea of preparing the Z-type photocatalytic material by 2D/2D compounding of ultrathin carbon nitride/tungsten trioxide is provided, and the prepared photocatalytic material has higher reference value for preparation and application of the photocatalytic material.
Drawings
FIG. 1 is a FESEM (a), TEM (b) diagram of ultra-thin carbon nitride (CN/NS) prepared by the present invention;
FIG. 2 is a FESEM (a), TEM (b) and HRTEM (b inset) images of HWOs prepared according to the present invention;
FIG. 3 is an atomic force microscope image of ultra-thin carbon nitride CN/NS (a) and HWO (b) prepared according to the present invention, and the corresponding height images CN/NS (c) and HWO (d);
FIG. 4 is a graph (a) of the diffuse reflection of ultraviolet and visible light of a part of the Pt-CN/HWO-40Z type photocatalytic material prepared by the invention after 1h of illumination, and a graph (b) of the apparent quantum yield of the material; and a photocatalytic hydrogen production activity comparison diagram (c) of different materials,
FIG. 5 shows fluorescence emission spectrum (a) and electrochemical impedance spectrum (b) of Pt-CN/HWO-40 prepared by the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
For simplicity and uniform presentation, a brief description of the materials is now provided:
CN/NS-ultra-thin carbon nitride; Pt-CN/NS-Pt supported ultra-thin carbon nitride; stripping the tungsten oxide nanosheet by a WO/NPs-alcohol thermal method; HWO — tungsten trioxide treated by hydrogenation; Pt-C3N4Carbon nitride supported on Pt, using C without calcination treatment3N4As a raw material; a composite material formed by Pt-CN/HWO-Pt supported ultrathin carbon nitride and tungsten trioxide subjected to hydrogenation treatment; a composite of ultrathin carbon nitride supported on Pt-CN/HWO-X-Pt and hydrogenated tungsten trioxide, wherein X is a number representing the mass ratio of Pt-CN to HWO.
Example 1
The preparation method comprises the following steps:
(1) 12g of urea were placed in a 50mL porcelain crucible at 550 ℃ and 5 ℃ min-1Calcining for 2h under the condition of temperature rising rate, and grinding to obtain g-C3N4Powder; placing 50mg of the powder in a porcelain boat, and heating at 520 deg.C for 5 deg.C/min-1Calcining for 3h under the condition of temperature rise rate to obtain ultrathin carbon nitride (CN/NS);
(2) dispersing the ultrathin product in 40mL of deionized water and 15mL of methanol solution, and then adding a proper amount of 0.08 mol.L-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded carbon nitride (Pt-CN/NS);
(3) 0.5000g of Na is taken2WO4·2H2O was dissolved in 60mL of deionized water, and then 22mLHCl solution (3.0M) was added dropwise with stirring to give a pale yellow floccule, to which was added 0.4500g of (NH)4)2C2O4·H2O, stirring until the solution is clear and transparent, adding 60mL of deionized water, stirring for 30min, carrying out hydrothermal reaction at 120 ℃ for 1h, washing the hydrothermal product, and drying at 70 ℃ in vacuum to obtain tungsten trioxide (WO)3nanoplates, WO/NPs for short). 0.2270g of the tungsten trioxide is dispersed in 40mL of absolute ethyl alcohol, stirred for 30min, thermally stripped for 24h at 200 ℃, centrifuged, washed, dried and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Adding proper amount of the product into Ar + H2(volume ratio is 9:1) carrying out hydrogenation treatment for 6h at 400 ℃ in a mixed gas atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) 50mg of Pt-CN/NS and 100mg of HWO are ultrasonically dispersed in absolute ethyl alcohol, and then the solvent is volatilized under the irradiation of an infrared lamp to obtain a dry compound. Annealing the compound for 1h at 400 ℃ in argon to obtain the 2D/2D composite Z-type photocatalytic material with Pt-CN/HWO-0.5 in different proportions.
FIG. 1 is a FESEM and TEM image of the ultra-thin carbon nitride (CN/NS) prepared in step (1). As can be seen from FIG. 1, the ultra-thin carbon nitride (CN/NS) prepared by the present invention has a two-dimensional curling shape and a net structure.
FIG. 2 is a FESEM (a), TEM (b) and HRTEM (inset b) image of the HWO prepared in step (3). It can be observed from fig. 2a that HWO exhibits a morphologically irregular sheet-like structure with a length and width of about 100nm, and from fig. 2b, clear lattice lines can be seen, indicating a better crystallinity.
FIG. 3 is an ultra-thin g-C film prepared in step (1)3N4And (3) an atomic force microscopy image of the HWO prepared in step (3) and a corresponding height map. From FIGS. 3a and 3b, it can be observed that the thickness of ultra-thin carbon nitride (CN/NS) is around 4 nm. The HWO is subjected to an alcohol thermal stripping reaction, so the nanosheets are relatively small as can be seen from fig. 3c, and the thickness is around 3nm as can be seen from fig. 3 d. From the results of the reaction of FIG. 3, the present invention successfully produced 2D ultra-thin carbon nitride (CN/NS) and HWO. Based on the above results, ultra-thin g-C3N4And successful preparation of HWO provides a good basis for further synthesis of Pt-CN/HWO.
Example 2
(1) 12g of urea were placed in a 50mL porcelain crucible at 550 ℃ and 5 ℃ min-1Calcining for 2h under the condition of temperature rising rate, and grinding to obtain g-C3N4Powder; placing 50mg of the powder in a porcelain boat, and heating at 520 deg.C for 5min-1Calcining for 3h under the condition of temperature rise rate to obtain ultrathin carbon nitride (CN/NS);
(2) dispersing the ultrathin product in 40mL of deionized water and 15mL of methanol solution, and then adding a proper amount of 0.08 mol.L-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded carbon nitride (Pt-CN/NS);
(3) 0.5000g of Na is taken2WO4·2H2O was dissolved in 60mL of deionized water, and then 22mLHCl solution (3.0M) was added dropwise with stirring to give a pale yellow floccule, to which was added 0.4500g of (NH)4)2C2O4·H2And O, stirring until the solution is clear and transparent, adding 60mL of deionized water, stirring for 30min, carrying out hydrothermal reaction at 120 ℃ for 1h, washing a hydrothermal product, and drying in vacuum at 70 ℃ to obtain WO/NPs. 0.2270g of the tungsten trioxide is dispersed in 40mL of absolute ethyl alcohol, stirred for 30min, thermally stripped for 24h at 200 ℃, centrifuged, washed, dried and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Mixing appropriate amount of the aboveThe product is in Ar + H2(volume ratio is 9:1) carrying out hydrogenation treatment for 6h at 400 ℃ in a mixed gas atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) 50mg of Pt-CN/NS and 50mg of HWO were ultrasonically dispersed in absolute ethanol and then irradiated under an infrared lamp to obtain a dry complex. Annealing the compound for 1h at 400 ℃ in argon to obtain the 2D/2D composite Z-type photocatalytic material of Pt-CN/HWO-1 with different proportions.
Example 3
(1) 12g of urea were charged into a 50mL porcelain crucible at 550 ℃ C. at 5 ℃ C. min-1Calcining for 2h under the condition of temperature rising rate, and grinding to obtain g-C3N4Powder; placing 50mg of the powder in a porcelain boat, and heating at 520 deg.C for 5min-1Calcining for 3h under the condition of temperature rise rate to obtain ultrathin carbon nitride (CN/NS);
(2) the thin product is dispersed in 40mL deionized water and 15mL methanol solution, then proper amount of 0.08 mol.L is added-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded carbon nitride (Pt-CN/NS);
(3) 0.5000g of Na is taken2WO4·2H2O was dissolved in 60mL of deionized water, and then 22mLHCl solution (3.0M) was added dropwise with stirring to give a pale yellow floccule, to which was added 0.4500g of (NH)4)2C2O4·H2And O, stirring until the solution is clear and transparent, adding 60mL of deionized water, stirring for 30min, carrying out hydrothermal reaction at 120 ℃ for 1h, washing a hydrothermal product, and drying in vacuum at 70 ℃ to obtain WO/NPs. 0.2270g of the tungsten trioxide is dispersed in 40mL of absolute ethyl alcohol, stirred for 30min, thermally stripped for 24h at 200 ℃, centrifuged, washed, dried and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Adding proper amount of the product into Ar + H2(volume ratio of 9:1) in a mixed gas atmosphere at 400 ℃ for 6h to obtain hydrogenated tungsten trioxide ((HWO);
(4) 100mg of Pt-CN/NS and 20mg of HWO are dispersed in absolute ethyl alcohol by ultrasonic, and then the solvent is volatilized under the irradiation of an infrared lamp to obtain a dry compound. Annealing the compound for 1h at 400 ℃ in argon to obtain the 2D/2D composite Z-type photocatalytic material of Pt-CN/HWO-5 with different proportions.
Example 4
(1) 12g of urea were placed in a 50mL porcelain crucible at 550 ℃ and 5 ℃ min-1Calcining for 2h under the condition of temperature rising rate, and grinding to obtain g-C3N4Powder; placing 50mg of the powder in a porcelain boat, and heating at 520 deg.C for 5min-1Calcining for 3h under the condition of temperature rise rate to obtain ultrathin carbon nitride (CN/NS);
(2) dispersing the ultrathin product in 40mL of deionized water and 15mL of methanol solution, and then adding a proper amount of 0.08 mol.L-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded carbon nitride (Pt-CN/NS);
(3) 0.5000g of Na is taken2WO4·2H2O was dissolved in 60mL of deionized water, and then 22mLHCl solution (3.0M) was added dropwise with stirring to give a pale yellow floccule, to which was added 0.4500g of (NH)4)2C2O4·H2And O, stirring until the solution is clear and transparent, adding 60mL of deionized water, stirring for 30min, carrying out hydrothermal reaction at 120 ℃ for 1h, washing a hydrothermal product, and drying in vacuum at 70 ℃ to obtain WO/NPs. 0.2270g of the tungsten trioxide is dispersed in 40mL of absolute ethyl alcohol, stirred for 30min, thermally stripped for 24h at 200 ℃, centrifuged, washed, dried and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Adding proper amount of the product into Ar + H2(volume ratio is 9:1) carrying out hydrogenation treatment for 6h at 400 ℃ in a mixed gas atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) 100mg of Pt-CN/NS and 10mg of HWO are dispersed in absolute ethyl alcohol by ultrasonic, and then the solvent is volatilized under the irradiation of an infrared lamp to obtain a dry compound. Annealing the compound for 1h at 400 ℃ in argon to obtain the 2D/2D composite Z-type photocatalytic material of Pt-CN/HWO-10 with different proportions.
Example 5
(1) 12g of urea were placed in a 50mL porcelain crucible at 550 ℃ and 5 ℃ min-1Calcining for 2h under the condition of temperature rising rate, and grinding to obtain g-C3N4Powder; placing 50mg of the powder in a porcelain boat, and heating at 520 deg.C for 5min-1Calcining for 3h under the condition of temperature rise rate to obtain ultrathin carbon nitride (CN/NS);
(2) dispersing the ultrathin product in 40mL of deionized water and 15mL of methanol solution, and then adding a proper amount of 0.08 mol.L-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded carbon nitride (Pt-CN/NS);
(3) 0.5000g of Na is taken2WO4·2H2O was dissolved in 60mL of deionized water, and then 22mLHCl solution (3.0M) was added dropwise with stirring to give a pale yellow floccule, to which was added 0.4500g of (NH)4)2C2O4·H2And O, stirring until the solution is clear and transparent, adding 60mL of deionized water, stirring for 30min, carrying out hydrothermal reaction at 120 ℃ for 1h, washing a hydrothermal product, and drying in vacuum at 70 ℃ to obtain WO/NPs. 0.2270g of the tungsten trioxide is dispersed in 40mL of absolute ethyl alcohol, stirred for 30min, thermally stripped for 24h at 200 ℃, centrifuged, washed, dried and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Adding proper amount of the product into Ar + H2(volume ratio is 9:1) carrying out hydrogenation treatment for 6h at 400 ℃ in a mixed gas atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) 100mg of Pt-CN/NS and 5mg of HWO are dispersed in absolute ethyl alcohol by ultrasonic, and then the solvent is volatilized under the irradiation of an infrared lamp to obtain a dry compound. Annealing the compound for 1h at 400 ℃ in argon to obtain 2D/2D composite Z-type photocatalytic materials of Pt-CN/HWO-20 with different proportions.
Example 6
(1) 12g of urea were placed in a 50mL porcelain crucible at 550 ℃ and 5 ℃ min-1Calcining for 2h under the condition of temperature rising rate, and grinding to obtain g-C3N4Powder; placing 50mg of the powder in a porcelain boat, and heating at 520 deg.C for 5min-1Calcining for 3h under the condition of temperature rise rate to obtain ultrathin carbon nitride (CN/NS);
(2) dispersing the ultrathin product in 40mL of deionized water and 15mL of methanol solution, and then adding a proper amount of 0.08 mol.L-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded carbon nitride (Pt-CN/NS);
(3) 0.5000g of Na is taken2WO4·2H2O was dissolved in 60mL of deionized water, and then 22mLHCl solution (3.0M) was added dropwise with stirring to give a pale yellow floccule, to which was added 0.4500g of (NH)4)2C2O4·H2And O, stirring until the solution is clear and transparent, adding 60mL of deionized water, stirring for 30min, carrying out hydrothermal reaction at 120 ℃ for 1h, washing a hydrothermal product, and drying in vacuum at 70 ℃ to obtain the tungsten trioxide WO/NPs. 0.2270g of the tungsten trioxide is dispersed in 40mL of absolute ethyl alcohol, stirred for 30min, thermally stripped for 24h at 200 ℃, centrifuged, washed, dried and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Adding proper amount of the product into Ar + H2(volume ratio is 9:1) carrying out hydrogenation treatment for 6h at 400 ℃ in a mixed gas atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) 150mg of Pt-CN/NS and 5mg of HWO are dispersed in absolute ethyl alcohol by ultrasonic, and then the solvent is volatilized under the irradiation of an infrared lamp to obtain a dry compound. Annealing the compound for 1h at 400 ℃ in argon to obtain the 2D/2D composite Z-type photocatalytic material of Pt-CN/HWO-30 with different proportions.
Example 7
(1) 12g of urea were placed in a 50mL porcelain crucible at 550 ℃ and 5 ℃ min-1Calcining for 2h under the condition of temperature rising rate, and grinding to obtain g-C3N4Powder; placing 50mg of the powder in a porcelain boat, and heating at 520 deg.C for 5min-1Calcining for 3h under the condition of temperature rise rate to obtain ultrathin carbon nitride (CN/NS);
(2) dispersing the ultrathin product in 40mL of deionized water and 15mL of methanol solution, and then adding a proper amount of 0.08 mol.L-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded carbon nitride (Pt-CN/NS);
(3) 0.5000g of Na is taken2WO4·2H2O was dissolved in 60mL of deionized water, and then 22mLHCl solution (3.0M) was added dropwise with stirring to give a pale yellow floccule, to which was added 0.4500g of (NH)4)2C2O4·H2And O, stirring until the solution is clear and transparent, adding 60mL of deionized water, stirring for 30min, carrying out hydrothermal reaction at 120 ℃ for 1h, washing a hydrothermal product, and drying in vacuum at 70 ℃ to obtain WO/NPs. 0.2270g of the tungsten trioxide is dispersed in 40mL of absolute ethyl alcohol, stirred for 30min, thermally stripped for 24h at 200 ℃, centrifuged, washed, dried and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Adding proper amount of the product into Ar + H2(volume ratio is 9:1) carrying out hydrogenation treatment for 6h at 400 ℃ in a mixed gas atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) 160mg of Pt-CN/NS and 4mg of HWO are ultrasonically dispersed in absolute ethyl alcohol, and then the solvent is volatilized under the irradiation of an infrared lamp to obtain a dry compound. Annealing the compound for 1h at 400 ℃ in argon to obtain the 2D/2D composite Z-type photocatalytic material of Pt-CN/HWO-40 with different proportions.
Example 8
(1) 12g of urea were placed in a 50mL porcelain crucible at 550 ℃ and 5 ℃ min-1Calcining for 2h under the condition of temperature rising rate, and grinding to obtain g-C3N4Powder; placing 50mg of the powder in a porcelain boat, and heating at 520 deg.C for 5min-1Calcining for 3h under the condition of temperature rise rate to obtain ultrathin carbon nitride (CN/NS);
(2) dispersing the ultrathin product in 40mL of deionized water and 15mL of methanol solution, and then adding a proper amount of 0.08 mol.L-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded carbon nitride (Pt-CN/NS);
(3) 0.5000g of Na is taken2WO4·2H2O was dissolved in 60mL of deionized water, and then 22mLHCl solution (3.0M) was added dropwise with stirring to give a pale yellow floccule, to which was added 0.4500g of (NH)4)2C2O4·H2O, stirring until the solution is clear and transparent, adding 60mL of deionized water, stirring for 30min, and filteringCarrying out hydrothermal reaction at 120 ℃ for 1h, washing the hydrothermal product, and carrying out vacuum drying at 70 ℃ to obtain WO/NPs. 0.2270g of the tungsten trioxide is dispersed in 40mL of absolute ethyl alcohol, stirred for 30min, thermally stripped for 24h at 200 ℃, centrifuged, washed, dried and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Adding proper amount of the product into Ar + H2(volume ratio is 9:1) carrying out hydrogenation treatment for 6h at 400 ℃ in a mixed gas atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) 200mg of Pt-CN/NS and 4mg of HWO are dispersed in absolute ethyl alcohol by ultrasonic, and then the solvent is volatilized under the irradiation of an infrared lamp to obtain a dry compound. Annealing the compound for 1h at 400 ℃ in argon to obtain the 2D/2D composite Z-type photocatalytic material with Pt-CN/HWO-50 in different proportions.
Comparative example 1
Preparation of Pt-C3N4
0.2g of carbon nitride (g-C) was taken3N4) Dispersing the powder in 40mL deionized water and 15mL methanol solution, and then adding a proper amount of 0.08 mol.L-1H of (A) to (B)2PtCl6Ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing, and drying to obtain 1 wt% Pt-loaded bulk-phase carbon nitride (Pt-C)3N4)。
Comparative example 2
Preparation of Pt-CN/NS
0.2g of ultrathin carbon nitride is taken to be dispersed in 40mL of deionized water and 15mL of methanol solution, and then a proper amount of 0.08 mol.L is added-1H of (A) to (B)2PtCl6And ultrasonically dispersing the solution for 5min, irradiating the suspension for 3h under a high-pressure mercury lamp, centrifugally washing and drying to obtain 1 wt% Pt-loaded ultrathin carbon nitride (Pt-CN/NS).
Comparative example 3
Preparation of HWO
0.2270g of tungsten trioxide (WO/NPs) obtained by hydrothermal reaction is added into 40mL of absolute ethyl alcohol, the mixture is stirred for 30min, the alcohol is thermally stripped for 24h at 200 ℃, and the product is centrifugally separated, washed and calcined for 2h at 300 ℃ to obtain the ultrathin tungsten trioxide. Taking a proper amount of the product in Ar + H2(volume ratio of 9:1) hydrogenation treatment at 400 ℃ for 6h in mixed gas atmosphere to obtain hydrogenationTreated tungsten trioxide (HWO).
Example 9
First, spectrum test
The test method comprises the following steps: the photocatalytic material was detected using gas chromatography.
FIG. 4a shows the UV-visible diffuse reflectance absorption spectrum of some samples prepared according to the present invention, from which it can be seen that HWO has stronger absorption in the 450-800 nm range compared to tungsten trioxide (WO/NPs), and it is possible that hydrogen treatment greatly improves the absorption of visible light. In addition, the absorption intensity of the Z-type compound (Pt-CN/HWO-40) with the mass ratio of Pt-CN/NS to HWO of 40:1 in the range of 400-800 nm is obviously increased compared with that of Pt-CN/NS, and the interaction between the HWO and the Pt-CN/NS can promote the absorption of visible light by the material. FIG. 4b is a graph of the Apparent Quantum Yield (AQY) of Pt-CN/HWO-40 prepared in example 7. The observation shows that the apparent quantum yield of the sample at the monochromatic light of 420nm is 16.6%, and the trend of capturing visible light is the same as that of ultraviolet-visible diffuse reflection absorption spectrum, which indicates that the higher photocatalytic activity of Pt-CN/HWO-40 is driven by visible light.
Second, electrochemical impedance test
The test method comprises the following steps: the Pt-CN/HWO-40 and CN/NS prepared in example 7 were tested using an electrochemical workstation.
FIG. 5a shows the electrochemical impedance spectrum of Pt-CN/HWO-40, from which it can be seen that the resistance to charge transfer at the composite interface is significantly reduced relative to CN/NS. FIG. 5b shows the fluorescence emission spectrum of Pt-CN/HWO-40 prepared by the present invention at 375nm excitation wavelength. As can be observed from FIG. 5b, the fluorescence emission intensity of Pt-CN/HWO-40 is obviously lower than that of pure CN/NS and HWO, which indicates that the carrier recombination rate of the material is obviously inhibited, thereby effectively improving the hydrogen production activity by photolysis. By combining the appearance advantages of the material, a unique charge transfer mechanism and excellent long-acting stability, the Pt-CN/HWO Z type photocatalytic material prepared by the invention has good performance of photocatalytic hydrogen production by water splitting, and has good application prospect in the aspect of realizing high-efficiency photocatalytic hydrogen production.
Application example 1
Photocatalytic hydrogen production and photocatalytic activity detection
The 2D/2D composite Z-type photocatalytic material with high-efficiency visible light response prepared by the embodiments of the invention is subjected to a photocatalytic hydrogen production experiment, and the photocatalytic activity of the photocatalytic hydrogen production experiment is detected.
The photocatalytic hydrogen production steps are as follows:
the prepared Z-type photocatalytic material can be used for photocatalytic hydrogen production in the presence of visible light and an electronic sacrificial reagent (triethanolamine (10 vol%)).
50mg of the photocatalytic material was dispersed in 50mL of an aqueous solution of an electron-sacrificing agent (triethanolamine (10 vol%)), ultrasonically dispersed for 5min to obtain a uniform suspension, and then the suspension was evacuated to remove dissolved air therein, stirred and irradiated with light for 1h (light source 300W xenon lamp).
And (3) detecting the photocatalytic activity: and (3) analyzing the hydrogen generated by the reaction by using a gas chromatograph by using argon as a carrier gas.
FIG. 4c is a graph comparing the hydrogen production activity of the pure product and the compounds with different proportions under visible light. The observation of the figure shows that the hydrogen production activity of the platinum-loaded ultrathin carbon nitride (Pt-CN/NS) is obviously higher than that of Pt-C3N4And HWO alone does not exhibit any hydrogen production activity. When Pt-CN/NS and HWO are prepared into a compound, the activity of the compound in a certain range is increased along with the reduction of the amount of the HWO, but when the mass ratio of the Pt-CN/NS to the HWO is more than 50:1, the activity is reduced, and the Z system formed by the two is unbalanced probably because the content of the HWO is too small, thereby reducing the hydrogen production activity. When the mass ratio of the two is 40:1, the complex has the height of 862 mu mol h-1Hydrogen production activity of (1).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (9)
1. The carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material is characterized in that:
pt-supported ultrathin carbon nitride nanosheets (Pt-C)3N4Pt-CN/NS for short) and tungsten trioxide (HWO) treated by hydrogen;
wherein the Pt-CN/NS has a curled two-dimensional network structure; the tungsten trioxide (HWO) treated by hydrogen is a two-dimensional nanosheet;
the Pt-CN/NS and the HWO are compounded into two-dimensional surface contact type compounding;
the mass ratio of the Pt-CN/NS to the HWO is 0.5: 1-40: 1.
2. The carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material according to claim 1, characterized in that: the thickness of the Pt-CN/NS is about 4 nm; the hydrotreated HWO is an ultrathin two-dimensional nanoplate, about 2.5nm thick.
3. The carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material according to claim 1, characterized in that: upon visible light excitation, the photoproduction charge transfer pattern between Pt-CN/NS and HWO follows the Z-type photocatalytic mechanism.
4. The preparation method of the carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material as claimed in any one of claims 1 to 3, is characterized by comprising the following steps:
(1) the urea is calcined twice to obtain ultrathin g-C3N4；
(2) Ultra-thin g-C3N4Dispersing in methanol solution, and adding H2PtCl6The solution is irradiated by a high-pressure mercury lamp after ultrasonic dispersion, and the Pt-loaded g-C is obtained by centrifugally washing solid particles3N4(Pt-CN/NS)；
(3) Mixing Na2WO4·2H2Dissolving O in water, and dropwise adding HCl solution while stirring to obtain light yellow floccule; then (NH) is added4)2C2O4·H2O, stirring until the solution is clear and transparent, adding deionized water into the solution, stirring uniformly, carrying out hydrothermal reaction, washing and drying the product to obtain the trioxaneTungsten is melted; adding the tungsten trioxide into absolute ethyl alcohol, stirring until the tungsten trioxide is uniformly dispersed, then carrying out alcohol heat treatment, washing, drying and calcining a product to finally obtain the ultrathin tungsten trioxide; finally at Ar and H2Hydrogenating the ultra-thin tungsten trioxide in a mixed atmosphere to obtain hydrogenated tungsten trioxide (HWO);
(4) taking Pt loaded g-C3N4And (Pt-CN/NS) and the hydrogenated tungsten trioxide are annealed in an argon atmosphere to obtain the two-dimensional composite Z-type photocatalytic material of the Pt-CN/NS and the HWO.
5. The production method according to claim 3, characterized in that: in the step (1), the initial temperature of the first calcination is 550 ℃, and the calcination time is 2 h; the second calcination temperature is 520 ℃, and the calcination time is 3 h; the heating rates are both 5 ℃ and min-1。
6. The production method according to claim 3, characterized in that: the temperature of the hydrothermal reaction in the step (3) is 120 ℃, and the treatment time is 1 h; the alcohol heat treatment temperature is 200 ℃, and the treatment time is 24 h.
7. The production method according to claim 3, characterized in that: ar and H in the step (3)2The volume ratio of (A) to (B) is 1:9, the hydrotreating temperature is 400 ℃, and the treating time is 6 h.
8. The production method according to claim 3, characterized in that: the annealing temperature in the step (4) is 400 ℃, and the annealing time is 1 h.
9. The application of the carbon nitride/tungsten trioxide two-dimensional composite Z-shaped photocatalytic material as defined in any one of claims 1-3 in the preparation of hydrogen through the catalytic decomposition of water by high-efficiency visible light.
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| CN115432760A (en) * | 2021-06-03 | 2022-12-06 | 吴昌谋 | Super-efficient full-spectrum photothermal conversion material, membrane layer and composite layer structure thereof, and application thereof |
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