CN115770602A - High-entropy nitrogen oxide material and preparation method and application thereof - Google Patents
High-entropy nitrogen oxide material and preparation method and application thereof Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 8
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- -1 lanthanide metal oxide Chemical class 0.000 claims description 9
- 238000005121 nitriding Methods 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 7
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012702 metal oxide precursor Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 23
- 238000000498 ball milling Methods 0.000 description 21
- 229910010413 TiO 2 Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 11
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of high-entropy materials, and particularly relates to a high-entropy nitrogen oxide material and a preparation method and application thereof. The chemical composition formula of the nitrogen oxide material is HETiO x N y Wherein HE is at least three of lanthanide series metal elements La, ce, sm, pr, nd, gd, yb, tb, eu, ho, er, tm, lu and Dy; the percentage of the mole number of each HE metal element to the total mole number of all HE metal elements is 5 to 35 percent; the mol ratio of all HE metal elements to titanium elements is 0.8-1.2; x is more than 0 and less than 3, and y is more than 0 and less than 3. The metal species in the high-entropy nitrogen oxide material prepared by the invention is easy to modulate, and can be components with different species, numbers and proportions, and the preparation method has universality, is simple and controllable, and has higher product yield.
Description
Technical Field
The invention belongs to the technical field of high-entropy materials, and particularly relates to a high-entropy nitrogen oxide material as well as a preparation method and application thereof.
Background
High-entropy materials have attracted considerable attention in recent years as a new material. The concept of high entropy was originally developed from high entropy alloys, which were first proposed in 2004 by professors of the root of the Chinese patent application of Yi in the universe, and then gradually expanded to other material systems. At present, such materials mainly refer to single-phase alloy or solid solution materials containing four or more components and similar contents of elements (Science, 2022,376, eabn3103, sci.adv.,2021,7, eabg1600, j.mater.chem.a,2020,8, 3814-3821. The diversity and adjustable denaturation of the components of the high-entropy material endow the high-entropy material with unique properties, such as a thermodynamic high-entropy effect, a structural lattice distortion effect, a kinetic delayed diffusion effect and a performance cocktail effect, so that the high-entropy material has great application potential in the fields of materials, energy sources, environments, catalysis and the like.
Nitrogen oxide materials have a broad spectrum visible light response capability and exhibit excellent performance in the fields of solar energy utilization, catalysis, and the like (j.am. Chem.soc.,2012,134,20, 8348-8351. The high-entropy nitrogen oxide material not only has high stability, but also can provide multifunctional active sites for complex catalytic reaction by the cooperation of multiple elements, thereby laying a foundation for the precise regulation and control of catalytic activity and selectivity. However, the high-entropy perovskite oxynitride material and the preparation thereof are not reported. The development of cheap, efficient and stable high-entropy nitrogen oxide materials still has great challenges.
Disclosure of Invention
The invention aims to solve the problems and provide a high-entropy nitrogen oxide material, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a high-entropy nitrogen oxide material, and the chemical composition formula of the nitrogen oxide material is HETiO x N y Wherein HE is at least three of lanthanide elements La, ce, sm, pr, nd, gd, yb, tb, eu, ho, er, tm, lu and Dy; each HThe percentage of the mole number of the E metal element to the total mole number of all the HE metal elements is 5 to 35 percent; the mol ratio of all HE metal elements to titanium elements is 0.8-1.2; x is more than 0 and less than 3, and y is more than 0 and less than 3.
In the above technical solution, further, the oxynitride material has a perovskite structure and has a broad-spectrum solar energy absorption characteristic.
In the above technical solution, further, in the nitrogen oxide material, the molar ratio of nitrogen to oxygen is 0.3 to 2.2:1.
in another aspect, the present invention provides a preparation method of the above high-entropy nitrogen oxide material, including the following steps:
(1) According to the chemical composition formula of the nitrogen oxide material, lanthanide metal oxide and titanium oxide are uniformly mixed with alkali metal carbonate;
(2) Roasting the mixture obtained in the step (1), and then washing and drying to obtain a metal oxide precursor;
(3) And (3) nitriding the metal oxide precursor obtained in the step (2) by using ammonia gas to obtain the high-entropy nitrogen oxide material.
The invention mixes lanthanide series metal oxide with titanium oxide and alkali carbonate, and prepares high entropy nitrogen oxide material by using a mixing-roasting-nitriding method. Specifically, different lanthanide series metal oxides, titanium oxides and alkali metal carbonates are utilized to form precursors, and the precursors are nitrided in an ammonia atmosphere to obtain the target product. The uniform mixing of lanthanide series metal oxide, titanium oxide and alkali carbonate is regulated and controlled by regulating a mixing method; synthesis of a regulation precursor is realized by regulating alkali metal; the regulation and control synthesis of the high-entropy nitrogen oxide is realized by regulating the nitridation process.
In the above technical solution, further, in the step (1), the lanthanide metal oxide is any at least three oxides of La, ce, sm, pr, nd, gd, yb, tb, eu, ho, er, tm, lu, and Dy;
the alkali metal carbonate is at least one of carbonates of Li, na, K, rb and Cs;
the molar ratio of the metal elements of the lanthanide metal oxide to the titanium oxide is 0.8-1.2;
the ratio of the number of moles of alkali metal carbonate to the total number of moles of lanthanide metal oxide is greater than 1.
In the above technical solution, further, in the step (2), the temperature of the programmed temperature end point of the roasting process is 800-1300 ℃, preferably 900-1100 ℃, and the holding time is 1-48 h, preferably 6-12 h.
In the above technical solution, further, in the step (3), the flow rate of the ammonia gas is 50 to 500mL/min, preferably 200 to 300mL/min, the temperature at the end of the temperature programming is 800 to 1200 ℃, preferably 850 to 950 ℃, and the holding time is 1 to 48 hours, preferably 3 to 6 hours.
The invention further provides an application of the high-entropy nitrogen oxide material in photocatalysis.
The invention has the following beneficial effects:
1. the prepared high-entropy nitrogen oxide material has the advantages of uniform particles, high stability and high crystallinity.
2. The metal species in the prepared high-entropy nitrogen oxide material is easy to modulate, and can be components with different species, numbers and proportions, and the preparation method has universality, is simple and controllable, has mild conditions and has higher product yield.
3. The prepared high-entropy nitrogen oxide material has a perovskite structure and a broad-spectrum solar energy absorption characteristic.
Drawings
FIG. 1 is an XRD characterization of samples made in example 1, example 2, example 3 and comparative example 1, comparative example 2;
FIG. 2 is a UV-Vis spectrum of the samples prepared in example 1, example 2 and comparative example 1.
FIG. 3 is a graph showing photocatalytic hydrogen production performance of the sample prepared in example 1.
Detailed Description
The whole material preparation process is described in detail by the following examples, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be met for achieving the purpose.
The materials of examples 1-10 of the present invention were tested by the following instruments and methods:
the structural information of the examples was analyzed by X-ray diffraction spectroscopy (XRD);
the spectral absorption properties of the examples were analyzed by ultraviolet-visible absorption spectroscopy (UV-Vis);
examples 1-3 modulate metal type and number; examples 4-6 were conducted by adjusting the baking temperature and time; examples 7-10 were conducted by adjusting the nitriding temperature and the nitrogen gas introduction time.
Example 1
(1) 0.6g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 、Gd 2 O 3 Each 1mmol and 0.33mmol of Pr 6 O 11 And 10mmol of TiO 2 Uniformly mixing by a ball milling method, wherein the ball-material ratio is 10, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast at 1000 ℃ for 10 hours, wherein the heating rate is 5 ℃/min, cooling to room temperature, washing with water, performing centrifugal separation to obtain a precipitate, and drying at 60 ℃ for 12 hours;
(3) Placing the dried sample obtained in the step (2) in a tubular furnace, raising the temperature to 900 ℃ at a program of 5 ℃/min in an ammonia gas atmosphere with a flow rate of 250mL/min, and keeping the temperature for 3 hours to obtain the high-entropy oxynitride (LaSmNdPrGd) TiO 2 N。
Example 2
(1) 0.5g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Gd 2 O 3 1mmol and 0.33mmol of each Pr 6 O 11 And 8mmol TiO 2 Uniformly mixing by a ball milling method, wherein the ball material ratio is 12, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) And (2) roasting the mixture obtained in the step (1) in a muffle furnace at 1000 ℃ for 10 hours at the heating rate of 5 ℃/min, cooling to room temperature, washing with water, performing centrifugal separation to obtain a precipitate, and drying at 60 ℃ for 12 hours.
(3) Putting the dried sample obtained in the step (2) into a tube furnace, heating to 900 ℃ at a temperature of 5 ℃/min in an ammonia gas atmosphere with a flow rate of 250mL/min, and keeping for 3 hours to obtain the high-entropy oxynitride (LaSmPrGd) TiO 2 N。
Example 3
(1) 0.6g of anhydrous potassium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 1.25mmol and 0.42mmol of Pr each 6 O 11 And 10mmol TiO 2 Uniformly mixing by a ball milling method, wherein the ball-material ratio is 10, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) And (2) roasting the mixture obtained in the step (1) in a muffle furnace at 1000 ℃ for 10 hours at the heating rate of 5 ℃/min, cooling to room temperature, washing with water, performing centrifugal separation to obtain a precipitate, and drying at 60 ℃ for 12 hours.
(3) Placing the dried sample obtained in the step (2) into a tubular furnace, raising the temperature to 900 ℃ at a program of 5 ℃/min in an ammonia gas atmosphere with a flow rate of 250mL/min, and keeping the temperature for 3 hours to obtain the high-entropy nitrogen oxide (LaSmNdPr) TiO 2 N。
Discussion of the results: in examples 1 to 3, on the premise of keeping the other conditions (the roasting temperature is 1000 ℃, and the nitriding temperature is 900 ℃ for 3 hours), the high-entropy oxynitride material can be prepared by adjusting the metal types, has a perovskite structure, and has a broad-spectrum solar energy absorption characteristic.
Example 4
(1) 0.6g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 、Gd 2 O 3 1mmol and 0.33mmol of each Pr 6 O 11 And 10mmol of TiO 2 Uniformly mixing by a ball milling method, wherein the ball material ratio is 10;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast at 1100 ℃ for 10 hours, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr.
(3) And (3) placing the dried sample obtained in the step (2) into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min in an ammonia gas atmosphere with the flow rate of 250mL/min, and keeping for 3 hours.
Example 5
(1) 0.6g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 、Gd 2 O 3 1mmol and 0.33mmol of each Pr 6 O 11 And 10mmol of TiO 2 Uniformly mixing by a ball milling method, wherein the ball-material ratio is 10, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast at 900 ℃ for 10 hours, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr.
(3) And (3) placing the dried sample obtained in the step (2) into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min in an ammonia gas atmosphere with the flow rate of 250mL/min, and keeping for 3 hours.
Example 6
(1) 0.6g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 、Gd 2 O 3 1mmol and 0.33mmol of each Pr 6 O 11 And 10mmol of TiO 2 Uniformly mixing by a ball milling method, wherein the ball material ratio is 10;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast for 8 hours at 1000 ℃, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr.
(3) And (3) placing the dried sample obtained in the step (2) into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min in an ammonia gas atmosphere with the flow rate of 250mL/min, and keeping for 3 hours.
Discussion of the results: examples 3-6 under the premise of other conditions being consistent (nitriding temperature and time are kept unchanged), the high-entropy perovskite oxynitride material can be obtained by changing the roasting temperature and time, and the obtained material has the characteristic of broad-spectrum solar energy absorption.
Example 7
(1) 0.6g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 、Gd 2 O 3 1mmol and 0.33mmol of each Pr 6 O 11 And 10mmol of TiO 2 Uniformly mixing by a ball milling method, wherein the ball-material ratio is 10, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast for 10 hours at 1000 ℃, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr.
(3) And (3) placing the dried sample obtained in the step (2) into a tubular furnace, heating to 800 ℃ at a programmed temperature of 5 ℃/min in an ammonia gas atmosphere with a flow rate of 250mL/min, and keeping for 3 hours.
Example 8
(1) 0.6g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 、Gd 2 O 3 Each 1mmol and 0.33mmol of Pr 6 O 11 And 10mmol TiO 2 Uniformly mixing by a ball milling method, wherein the ball-material ratio is 10, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast at 1000 ℃ for 10 hours, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr.
(3) And (3) placing the dried sample obtained in the step (2) into a tube furnace, heating to 950 ℃ at the programmed temperature of 5 ℃/min in an ammonia gas atmosphere with the flow rate of 250mL/min, and keeping for 3 hours.
Example 9
(1) 0.6g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 、Gd 2 O 3 Each 1mmol and 0.33mmol of Pr 6 O 11 And 10mmol of TiO 2 Uniformly mixing by a ball milling method, wherein the ball material ratio is 10;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast at 1000 ℃ for 10 hours, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr.
(3) And (3) placing the dried sample obtained in the step (2) into a tube furnace, heating to 900 ℃ at the speed of 5 ℃/min in an ammonia gas atmosphere with the flow rate of 250mL/min, and keeping for 4 hours.
Example 10
(1) 0.6g of anhydrous sodium carbonate, sm 2 O 3 、La 2 O 3 、Nd 2 O 3 、Gd 2 O 3 1mmol and 0.33mmol of each Pr 6 O 11 And 10mmol TiO 2 Uniformly mixing by a ball milling method, wherein the ball-material ratio is 10, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast for 10 hours at 1000 ℃, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr.
(3) And (3) placing the dried sample obtained in the step (2) into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min in an ammonia gas atmosphere with the flow rate of 250mL/min, and keeping for 1 hour.
Discussion of the results: examples 7-10 the nitrogen oxide formation was controlled by adjusting the time of ammonia gas introduction and the nitriding temperature under otherwise identical conditions. The nitriding time is prolonged, the nitriding temperature is increased, the formation process of the nitrogen oxide can be promoted, and the crystallinity is improved.
Comparative example 1
(1) 0.6g of anhydrous sodium carbonate, 5mmol of Nd 2 O 3 And 10mmol TiO 2 Uniformly mixing by a ball milling method, wherein the ball-material ratio is 10, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast at 1000 ℃ for 10 hours, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr;
(3) And (3) placing the dried sample obtained in the step (2) into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min in an ammonia gas atmosphere with the flow rate of 250mL/min, and keeping for 3 hours.
Comparative example 2
(1) 0.6g of anhydrous sodium carbonate, 5mmol of Gd 2 O 3 And 10mmol TiO 2 Uniformly mixing by a ball milling method, wherein the ball-material ratio is 10, the rotating speed is 600r/min, and the ball milling is carried out for 0.5 hour;
(2) Placing the mixture obtained in the step (1) in a muffle furnace to roast at 1000 ℃ for 10 hours, wherein the heating rate is 5 ℃/min; cooling to room temperature, washing with water, centrifuging to obtain precipitate, and drying at 60 deg.C for 12 hr;
(3) And (3) placing the dried sample obtained in the step (2) into a tube furnace, heating to 900 ℃ at the speed of 5 ℃/min in an ammonia gas atmosphere with the flow rate of 250mL/min, and keeping for 3 hours.
Discussion of the results: compared with the high-entropy nitrogen oxide material, the single lanthanide metal can not obtain the perovskite structure nitrogen oxide, or the purity and the crystallinity of the obtained sample at the same temperature are lower, which shows that the high-entropy nitrogen oxide material is simple and easy to obtain, and has high purity and high crystallinity.
Application example 1
The high-entropy nitrogen oxide obtained in example 1 was used as a catalyst material for a photocatalytic water splitting system, and the performance of hydrogen production reaction by photocatalytic water splitting was examined after loading platinum thereon.
1. Auxiliary agent modification: the high-entropy oxynitride with 1wt% of Pt loading capacity, namely Pt/(LaSmNdPrGd) TiO, is prepared by adopting an impregnation method 2 And N is added. Immersing the high-entropy nitrogen oxide material in the solution containing chloroplatinic acid, stirring, drying, grinding, and accounting for 5% H 2 Heating to 200 ℃ in Ar atmosphere and keeping for 1h.
2. Evaluation of catalytic performance: 30mg of Pt/(LaSmNdPrGd) TiO 2 N and 30mg La 2 O 3 Dispersed in 15mL of an aqueous solution containing methanol as sacrificial agent. Under the irradiation condition of visible light (lambda is more than 420 nm), a hydrogen product is detected by using a photocatalytic online evaluation device and gas chromatography together, and the hydrogen production performance by decomposing water of the high-entropy oxynitride photocatalyst is evaluated.
Claims (8)
1. A high-entropy nitrogen oxide material is characterized in that the nitrogen oxide materialThe chemical composition formula of the material is HETiO x N y Wherein HE is at least three of lanthanide series metal elements La, ce, sm, pr, nd, gd, yb, tb, eu, ho, er, tm, lu and Dy; the percentage of the mole number of each HE metal element to the total mole number of all HE metal elements is 5-35%; the mol ratio of all HE metal elements to titanium elements is 0.8-1.2; x is more than 0 and less than 3, and y is more than 0 and less than 3.
2. A high entropy oxynitride material as claimed in claim 1 wherein the oxynitride material has a perovskite structure and has broad spectrum solar absorption characteristics.
3. A high entropy nitrogen oxide material in accordance with claim 1, wherein a molar ratio of nitrogen to oxygen in the nitrogen oxide material is in a range of 0.3 to 2.2:1.
4. a method for producing a high-entropy nitrogen oxide material as defined in claims 1 to 3, characterized in that,
the method comprises the following steps:
(1) According to the chemical composition formula of the nitrogen oxide material, lanthanide metal oxide and titanium oxide are uniformly mixed with alkali metal carbonate;
(2) Roasting the mixture obtained in the step (1), and then washing and drying to obtain a metal oxide precursor;
(3) And (3) nitriding the metal oxide precursor obtained in the step (2) by using ammonia gas to obtain the high-entropy nitrogen oxide material.
5. A method of producing a high entropy nitrogen oxide material according to claim 4,
in the step (1), the lanthanide metal oxide is at least three of La, ce, sm, pr, nd, gd, yb, tb, eu, ho, er, tm, lu and Dy oxides;
the alkali metal carbonate is at least one of carbonates of Li, na, K, rb and Cs;
the molar ratio of the metal elements of the lanthanide metal oxide to the titanium oxide is 0.8-1.2;
the ratio of the number of moles of alkali metal carbonate to the total number of moles of lanthanide metal oxide is greater than 1.
6. A preparation method of a high-entropy nitrogen oxide material according to claim 4, wherein in the step (2), the temperature programming end point temperature of the roasting process is 800-1300 ℃, and the holding time is 1-48 h.
7. A preparation method of a high-entropy nitrogen oxide material according to claim 4, wherein in the step (3), the flow rate of the ammonia gas is 50-500 mL/min, the temperature programming end point temperature is 800-1200 ℃, and the holding time is 1-48 h.
8. Use of a high entropy nitrogen oxide material as defined in any one of claims 1 to 3 in photocatalysis.
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