CN112354555A - Metal monatomic supported carbon-nitrogen polymer catalyst and preparation method thereof - Google Patents
Metal monatomic supported carbon-nitrogen polymer catalyst and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 130
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000001354 calcination Methods 0.000 claims abstract description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims description 27
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 229920000877 Melamine resin Polymers 0.000 claims description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
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- 229910021641 deionized water Inorganic materials 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 125000004429 atom Chemical group 0.000 description 15
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- 239000007787 solid Substances 0.000 description 8
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- 239000010935 stainless steel Substances 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 6
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- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
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- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 230000004298 light response Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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Classifications
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/391—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
A metal monatomic supported carbon-nitrogen polymer catalyst and a preparation method thereof are disclosed, wherein a carbon-nitrogen polymer is mixed with water and then is subjected to hydrothermal treatment for 10-15h at the temperature of 150-200 ℃ to obtain a carbon-nitrogen polymer containing hydroxyl; mixing the carbon-nitrogen polymer containing hydroxyl with water, performing ultrasonic treatment, adding a metal source solution, stirring for 8-24h in a dark place, separating, drying, and calcining to obtain the metal monatomic supported carbon-nitrogen polymer catalyst. The preparation method of the metal monoatomic carbon nitrogen loaded polymer is simple, the universality is strong, the loading position at the monoatomic position is accurate and controllable, and the prepared metal monoatomic carbon nitrogen loaded polymer catalyst is high in loading amount, rapid in-plane charge transmission, excellent in photocatalytic performance and strong in stability.
Description
Technical Field
The invention belongs to the field of composite material preparation, and particularly relates to a metal monatomic supported carbon-nitrogen polymer catalyst and a preparation method thereof.
Background
Carbon-nitrogen polymer (P-CN) is one of the oldest materials reported in the literature and consists of carbon and nitrogen elements rich in earth crust. P-CN is non-toxic and harmless, has low production cost and visible light response (the energy band width is about 2.7 eV), and is widely concerned and researched by the scientific community as a photocatalyst. However, the charge in the plane of the photocatalyst is slowly and disorderly transferred, so that the photoexcited electrons cannot be effectively and accurately transferred to the periphery of the active site of the catalytic reaction to complete the photocatalytic reaction, thereby greatly limiting the application of the photocatalyst in the field of photocatalysis, and urgently seeking a method for directly and directionally transferring the excited electrons to the periphery of the active site.
It is reported in the literature (Chemical Reviews 119,1806-1854) that the size of the metal particles is reduced to an atomic size, the electron orbitals of which will change from a continuous state to a discrete state. If such metal units are sub-assembled on a base material, the electronic structure of the base material will be changed, thereby changing the electron transport properties of the base material. This provides a way to modify the charge transport properties of the carrier material on an atomic scale: if metal monoatomic atoms can be accurately loaded around the active sites of P-CN, the energy band structure of the carrier is changed through the interaction between the metal and the carrier, the electron transmission direction is changed, and the purpose of electron directional transmission is achieved.
However, as the size decreases, the surface energy of the metal particles will increase dramatically and will spontaneously agglomerate into larger metal particles. Although various "top-down" or "bottom-up" metal monoatomic loading methods have been reported from a large number of documents, none of them is capable of accurately loading monoatomic atoms around active sites. Therefore, the difficulty of accurately loading a large content of metal monoatomic atoms around the active site of P-CN is extremely high, and no report is made.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a catalyst of metal monoatomic supported carbon-nitrogen polymer and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a metal monatomic supported carbon-nitrogen polymer catalyst comprises the steps of mixing a carbon-nitrogen polymer with water, and carrying out hydrothermal treatment for 10-15h at the temperature of 150-200 ℃ to obtain a carbon-nitrogen polymer containing hydroxyl;
mixing the carbon-nitrogen polymer containing hydroxyl with water, performing ultrasonic treatment, adding a metal source solution, stirring for 8-24h in a dark place, separating, drying, and calcining to obtain the metal monatomic supported carbon-nitrogen polymer catalyst.
In a further development of the invention, the carbon-nitrogen polymer is produced by the following process: the nitrogen-containing precursor is calcined at the temperature of 520 ℃ and 580 ℃ for 2-5 h.
The invention has the further improvement that the nitrogen-containing precursor is one or more of urea, melamine and cyanuric acid; when two of urea, melamine and cyanuric acid are used, the two are mixed according to the mass ratio of 1:1, and when three are used, the three are mixed according to the mass ratio of 1:1: 1.
The invention is further improved in that the temperature is increased from room temperature to 520-580 ℃ at a temperature increase rate of 1-5 ℃.
The invention is further improved in that the ratio of carbon-nitrogen polymer to water is 0.1-0.5 g: 20-70 mL; hydroxyl group-containing carbon nitrogen polymer and water 0.1 to 0.5 g: 30-80 mL.
The invention further improves that the ratio of the carbon nitrogen polymer containing hydroxyl groups to the metal source solution is 0.1-0.5 g: 10-20 mL; the concentration of the metal source solution is 0.1-0.5 mol/L.
The further improvement of the invention is that the power of the ultrasound is 200W, and the time is 30-60 min; the metal source solution is a metal source solution containing Pt, Pd, Au, Fe, Ni, Cu or Ag metal cations.
In a further improvement of the invention, the metal source containing the Pt metal cation is H2PtCl6·6H2O and Pt (NH)3)4Cl2One of (1);
the metal source containing Pd metal cations is PdCl4With Na2PdCl4One of (1);
the metal source of the Au-containing metal cation is HAuCl4；
The metal source containing Ag metal cations is AgNO3；
The metal source containing Fe metal cations is FeCl3With FeCl2One of (1);
the metal source containing Ni metal cations is NiCl2；
The metal source containing Cu metal cations is CuCl2With Cu (NO)3)2One kind of (1).
The further improvement of the invention is that the calcining temperature is 120-200 ℃ and the time is 2-5 h.
A metal monoatomic supported carbon nitrogen polymer catalyst prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a metal monatomic supported carbon-nitrogen polymer catalyst, which can generate the interaction of metal and a carrier due to the fact that the surface of the catalyst is supported with metal monatomic, and has a larger light absorption range and stronger light absorption capacity. Because the metal monoatomic and the atom around the carrier active site are hybridized, the energy band structure of the carrier carbon-nitrogen polymer is changed, a built-in electric field is generated, the electron excited by light is promoted to be directionally transmitted to the periphery of the active site, and the photocatalysis performance of the catalyst is stronger.
According to the preparation method of the metal monatomic supported carbon-nitrogen polymer catalyst, oxygen-containing group hydroxyl is introduced to the surface of the carbon-nitrogen polymer, and the metal cation or the ion group is accurately adsorbed to the periphery of the active site of the carbon-nitrogen polymer containing hydroxyl in the form of single atom under the electrostatic action and the coordination action of the metal cation and the oxygen-containing group anion. Because the carbon-nitrogen polymer has a pair of lone-pair electrons, N atoms and metal atoms can be hybridized with each other through low-temperature calcination, so that metal single atoms are stably loaded on the surface of the carbon-nitrogen polymer. Compared with the traditional preparation method, the preparation method provided by the invention has the advantages of accurate load, simple operation, large single atom load capacity and stable structure, and can be used for mass production.
Drawings
For a further understanding of the invention, reference is made to the accompanying drawings.
FIG. 1 is an AC-STEM diagram of the dispersion of a monatomic catalyst on the surface of a catalyst.
FIG. 2 is an infrared spectrum of P-CN and P-CN-OH.
FIG. 3 is a diagram of the catalytic reduction of CO with monatomic Pt supported P-CN2And pure P-CN catalytic reduction of CO2Comparative plot of performance.
FIG. 4 is a diagram of the catalytic reduction of CO with monatomic Pt supported P-CN2The cycle stability diagram of (1).
Detailed Description
The technical solutions, objects and advantages of the present invention will be described in further detail below with reference to specific embodiments.
The main component of the metal monatomic supported carbon-nitrogen polymer catalyst provided by the invention is a metal monatomic and carbon-nitrogen polymer base material.
Further, the metal single atom is one or more of Pt, Pd, Au, Fe, Ni, Cu and Ag.
The preparation method of the metal monatomic supported carbon-nitrogen polymer catalyst provided by the invention comprises the following steps:
(1) 1-10g of nitrogen-containing precursor is placed into a 10-100mL alumina crucible with a cover, then the crucible is placed into a muffle furnace, the temperature is raised to 520-580 ℃ from the room temperature at the temperature raising rate of 1-5 ℃, and the calcination is carried out for 2-5h at the temperature.
The nitrogen-containing precursor is one or more of urea, melamine and cyanuric acid, when two of the urea, the melamine and the cyanuric acid are adopted, the two are mixed according to the mass ratio of 1:1, and when the three are adopted, the three are mixed according to the mass ratio of 1:1: 1.
(2) The resulting solid cake obtained after calcination was ground to 200 mesh or less to obtain a carbon-nitrogen polymer, designated as P-CN.
(3) Adding 0.1-0.5g P-CN into a 30-100mL reaction kettle, adding 20-70mL deionized water, carrying out hydrothermal treatment in an oven at the temperature of 150-.
According to the invention, the carbon-nitrogen polymer containing a large amount of hydroxyl can be obtained only by carrying out hydrothermal treatment at 150-200 ℃, the carbon-nitrogen polymer containing a large amount of hydroxyl can not be obtained at a low temperature, the carbon-nitrogen polymer can be reacted at a high temperature, and the obtained carbon-nitrogen polymer containing a large amount of hydroxyl is completely hydrolyzed to become ammonia gas.
(4) 0.1-0.5g P-CN-OH is put into a 100-200mL beaker, 30-80mL deionized water is added, and ultrasonic treatment is carried out for 30-60min with 200W power, so that the P-CN-OH is uniformly dispersed in the water.
(5) Adding 10-20mL of metal source solution into the uniformly dispersed solution, stirring at room temperature of 500-.
Wherein the metal source solution is a Pt, Pd, Au, Fe, Ni, Cu or Ag metal salt solution.
The molar concentration of the metal source solution may be 0.1 to 0.5 mol/L.
The metal source containing Pt metal cations can be H2PtCl6·6H2O and Pt (NH)3)4Cl2One kind of (1).
The metal source containing Pd metal cations can be PdCl4With Na2PdCl4One kind of (1).
The metal source of the Au-containing metal cation can be HAuCl4。
The metal source containing Ag metal cations may be AgNO3。
The metal source containing Fe metal cations may be FeCl3With FeCl2One kind of (1).
The metal source comprising Ni metal cations may be NiCl2。
The metal source containing Cu metal cations can be CuCl2With Cu (NO)3)2One kind of (1).
(6) And (3) putting 0.1-0.5g of the dried product obtained in the step (5) into a 5-10mL porcelain boat, putting the porcelain boat into a tubular furnace, calcining the porcelain boat for 2-5h at the temperature of 200 ℃ under the protection of inert gas, naturally cooling the porcelain boat to room temperature, and recovering a calcined sample, namely the metal monatomic supported carbon-nitrogen polymer catalyst which is marked as P-CN-O-M (M represents a metal species).
Because of the interaction of the metal source and the hydroxyl groups, the metal and substrate loading can be achieved with lower calcination temperatures. The invention reduces the calcining temperature by adopting the temperature of more than 400 ℃ in the prior art.
The inert gas is one of argon and helium.
The following are specific examples.
Example 1
(1) 5g of melamine were placed in a 100mL alumina crucible with a lid and calcined in a muffle furnace for 3h at a temperature rise rate of 5 ℃ and a calcination temperature of 550 ℃.
(2) The cake solid obtained by the calcination of the former was ground to 200 mesh or less to obtain P-CN.
(3) Adding 0.3g of P-CN prepared by the former into a 100mL reaction kettle, adding 70mL of deionized water, carrying out hydrothermal treatment for 12h in an oven at 180 ℃, carrying out centrifugal treatment on the solution after the reaction is finished, alternately cleaning with absolute ethyl alcohol and deionized water for 3 times, drying for 12h at 80 ℃, and grinding to below 200 meshes to obtain a carbon-nitrogen polymer containing a large amount of hydroxyl, which is marked as P-CN-OH.
(4) 0.3g of P-CN-OH prepared by the former method is put into a 200mL beaker, 40mL of deionized water is added, and ultrasonic treatment is carried out for 30min at the power of 200W, so that the P-CN-OH is uniformly dispersed in the water.
(5) To the solution obtained in the former, 10mL of 0.1mol/L Pt (NH) was added3)4Cl2Stirring the solution at room temperature of 500r/min for 10h in a dark place, centrifuging after stirring, alternately cleaning the obtained product ethanol and deionized water for 3 times, and vacuum-drying in a vacuum drying oven at 60 ℃ for 12 h.
(6) And putting 0.3g of the dried product in a 10mL porcelain boat, putting the porcelain boat in a tubular furnace, calcining for 2h at 150 ℃ under the protection of helium, naturally cooling to room temperature, and recovering a calcined sample, namely the metal Pt monatomic supported carbon-nitrogen polymer catalyst which is recorded as P-CN-O-Pt.
0.1g P-CN-O-Pt is uniformly dispersed at the bottom of a 50mL cylindrical reactor, the periphery and the bottom of the reactor are made of stainless steel, the top end of the reactor is provided with a quartz window, and ports for adding and extracting gas are reserved. Injecting 1MPa of CO into the reactor2Gas, providing a 300W xenon lampThe light source vertically irradiates the surface of the catalyst, and CO and CH in the gas are detected after 1h of illumination4The concentration of the P-CN-O-Pt is calculated to obtain the P-CN-O-Pt photoreduction CO2Production of CO and CH4The efficiencies of (a) were 4.5 and 8.6. mu. mol g, respectively-1h-1。
It can be seen from fig. 1 that the Pt monoatomic atoms are dispersed as a single atom on the catalyst surface.
As can be seen from FIG. 2, the P-CN-OH sample was at 3600cm at 2500--1A stronger infrared absorption peak appears, which indicates that hydroxyl groups are successfully introduced on the surface of the catalyst.
From FIG. 3, it can be seen that the methane yield of P-CN after Pt monatomic loading is improved by 5 times, and the photocatalytic performance is better.
As can be seen from FIG. 4, the catalytic performance of the catalyst is not significantly reduced after 3 times of cycle tests, which indicates that the metal monatomic supported P-CN has better stability.
The single atom loading amount measured by inductively coupled plasma mass spectrometry (ICP-MS) is about 1%, and the single atom loading amount is generally aggregated into particles when the reported loading amount is 0.2%, so that the single atom loading amount is larger.
Example 2
(1) 5g of melamine were placed in a 100mL alumina crucible with a lid and calcined in a muffle furnace for 3h at a temperature rise rate of 5 ℃ and a calcination temperature of 550 ℃.
(2) The cake solid obtained by the calcination of the former was ground to 200 mesh or less to obtain P-CN.
Adding 0.3g P-CN into a 100mL reaction kettle, adding 70mL deionized water, carrying out hydrothermal treatment for 12h in an oven at 180 ℃, carrying out centrifugal treatment on the solution after the reaction is finished, alternately cleaning with absolute ethyl alcohol and deionized water for 3 times, drying for 12h at 80 ℃, and grinding to below 200 meshes to obtain a carbon-nitrogen polymer containing a large amount of hydroxyl, which is marked as P-CN-OH.
(3) 0.3g P-CN-OH is placed into a 200mL beaker, 40mL deionized water is added, and ultrasonic treatment is carried out for 30min at 200W power, so that the P-CN-OH is uniformly dispersed in the water.
(4) To the solution obtained in the former, 10mL of 0.1mol/L CuCl was added2Solution, 500Stirring at room temperature at r/min in dark place for 10h, centrifuging after stirring, alternately cleaning the obtained product with ethanol and deionized water for 3 times, and vacuum drying in a vacuum drying oven at 60 deg.C for 12 h.
(5) And putting 0.3g of the dried product in a 10mL porcelain boat, putting the porcelain boat in a tubular furnace, calcining for 2h at 150 ℃ under the protection of helium, naturally cooling to room temperature, and recovering a calcined sample, namely the metal Cu monatomic supported carbon nitrogen polymer catalyst which is marked as P-CN-O-Cu.
(6) 0.1g P-CN-O-Cu is uniformly dispersed at the bottom of a 50mL cylindrical reactor, the periphery and the bottom of the reactor are made of stainless steel, the top end of the reactor is provided with a quartz window, and ports for adding and extracting gas are reserved. Injecting 1MPa of CO-2Gas, vertically irradiating a light source provided by a 300W xenon lamp onto the surface of the catalyst, and detecting CO and CH in the gas after 1h of illumination4The concentration of the P-CN-O-Cu is calculated to obtain the P-CN-O-Cu photo-reduction CO2Production of CO and CH4The efficiencies of (a) were 3.1 and 6.5. mu. mol g, respectively-1h-1。
Example 3
(1) 5g of melamine were placed in a 100mL alumina crucible with a lid and calcined in a muffle furnace for 3h at a temperature rise rate of 5 ℃ and a calcination temperature of 550 ℃.
(2) The cake solid obtained by the calcination of the former was ground to 200 mesh or less to obtain P-CN.
(3) Adding 0.3g P-CN into a 100mL reaction kettle, adding 70mL deionized water, carrying out hydrothermal treatment for 12h in an oven at 180 ℃, carrying out centrifugal treatment on the solution after the reaction is finished, alternately cleaning with absolute ethyl alcohol and deionized water for 3 times, drying for 12h at 80 ℃, and grinding to below 200 meshes to obtain a carbon-nitrogen polymer containing a large amount of hydroxyl, which is marked as P-CN-OH.
(4) 0.3g P-CN-OH is placed into a 200mL beaker, 40mL deionized water is added, and ultrasonic treatment is carried out for 30min at 200W power, so that the P-CN-OH is uniformly dispersed in the water.
(5) To the solution obtained by the former was added 10mL of 0.1mol/L FeCl3Stirring the solution at room temperature of 500r/min for 10h in a dark place, centrifuging after stirring, alternately cleaning the obtained product with ethanol and deionized water for 3 times, and washing the product with deionized waterVacuum drying at 60 deg.C for 12 hr.
(6) And putting 0.3g of the dried product in a 10mL porcelain boat, putting the porcelain boat in a tubular furnace, calcining for 2h at 150 ℃ under the protection of helium, naturally cooling to room temperature, and recovering a calcined sample, namely the metallic Fe monatomic supported carbon-nitrogen polymer catalyst which is marked as P-CN-O-Fe.
0.1g P-CN-O-Fe was uniformly dispersed in the bottom of a 50mL cylindrical reactor, which was surrounded and at the bottom by stainless steel, with a quartz window at the top and a port for gas addition and extraction reserved. Injecting 1MPa of CO into the reactor2Gas, vertically irradiating a light source provided by a 300W xenon lamp onto the surface of the catalyst, and detecting CO and CH in the gas after 1h of illumination4The concentration of (A) is calculated to obtain the photo-reduced CO of P-CN-O-Fe2Production of CO and CH4The efficiencies of (a) were 4.1 and 6.6. mu. mol g, respectively-1h-1。
Example 4
(1) 5g of melamine were placed in a 100mL alumina crucible with a lid and calcined in a muffle furnace for 3h at a temperature rise rate of 5 ℃ and a calcination temperature of 550 ℃.
(2) The cake solid obtained by the calcination of the former was ground to 200 mesh or less to obtain P-CN.
(3) Adding 0.3g P-CN into a 100mL reaction kettle, adding 70mL deionized water, carrying out hydrothermal treatment for 12h in an oven at 180 ℃, carrying out centrifugal treatment on the solution after the reaction is finished, alternately cleaning with absolute ethyl alcohol and deionized water for 3 times, drying for 12h at 80 ℃, and grinding to below 200 meshes to obtain a carbon-nitrogen polymer containing a large amount of hydroxyl, which is marked as P-CN-OH.
(4) 0.3g P-CN-OH is placed into a 200mL beaker, 40mL deionized water is added, and ultrasonic treatment is carried out for 30min at 200W power, so that the P-CN-OH is uniformly dispersed in the water.
(5) To the solution obtained by the former, 10mL of 0.1mol/L NiCl was added2Stirring the solution at room temperature of 500r/min for 10h in a dark place, centrifuging after stirring, alternately cleaning the obtained product ethanol and deionized water for 3 times, and vacuum-drying in a vacuum drying oven at 60 ℃ for 12 h.
(6) And putting 0.3g of the dried product in a 10mL porcelain boat, putting the porcelain boat in a tubular furnace, calcining for 2h at 150 ℃ under the protection of helium, naturally cooling to room temperature, and recovering a calcined sample, namely the metal Ni monatomic supported carbon nitrogen polymer catalyst which is marked as P-CN-O-Ni.
0.1g P-CN-O-Ni was uniformly dispersed in the bottom of a 50mL cylindrical reactor, which was surrounded and at the bottom by stainless steel, with a quartz window at the top and a port for gas addition and extraction reserved. Injecting 1MPa of CO into the reactor2Gas, vertically irradiating a light source provided by a 300W xenon lamp onto the surface of the catalyst, and detecting CO and CH in the gas after 1h of illumination4The concentration of the P-CN-O-Ni is calculated to obtain the P-CN-O-Ni photo-reduction CO2Production of CO and CH4The efficiencies of (a) were 3.5 and 7.4. mu. mol g, respectively-1h-1。
Example 5
And heating the nitrogen-containing precursor from room temperature to 520 ℃ at the heating rate of 1 ℃, and calcining for 5h to obtain the carbon-nitrogen polymer. Wherein the nitrogen-containing precursor is urea.
Mixing 0.1g of carbon-nitrogen polymer with 20mL of water, and performing hydrothermal treatment for 15h at 150 ℃ to obtain a hydroxyl-containing carbon-nitrogen polymer;
mixing 0.1g of hydroxyl-containing carbon-nitrogen polymer with 80mL of water, then performing ultrasonic treatment at 200W for 30min, then adding 10mL of 0.1mol/L metal source solution, stirring for 24h in a dark place, separating, drying, and then calcining for 5h at 120 ℃ to obtain the metal monatomic supported carbon-nitrogen polymer catalyst. Wherein the metal source solution is Cu (NO)3)2An aqueous solution.
Example 6
And heating the nitrogen-containing precursor from room temperature to 580 ℃ at the heating rate of 5 ℃, and calcining for 2h to obtain the carbon-nitrogen polymer. Wherein the nitrogen-containing precursor is cyanuric acid.
Mixing 0.5g of carbon-nitrogen polymer with 70mL of water, and performing hydrothermal treatment at 200 ℃ for 10h to obtain a hydroxyl-containing carbon-nitrogen polymer;
mixing 0.1g of hydroxyl-containing carbon-nitrogen polymer with 30mL of water, performing ultrasonic treatment at 200W for 60min, adding 10mL of 0.5mol/L metal source solution, stirring for 20h in a dark place, separating, drying, and calcining at 200 ℃ for 2h to obtain metal monogenA sub-supported carbon nitrogen polymer catalyst. Wherein the metal source solution is FeCl3An aqueous solution.
Example 7
And heating the nitrogen-containing precursor from room temperature to 550 ℃ at the heating rate of 2 ℃, and calcining for 3h to obtain the carbon-nitrogen polymer. Wherein the nitrogen-containing precursor is a mixture of urea and melamine in a mass ratio of 1: 1;
mixing 0.1g of carbon-nitrogen polymer with 50mL of water, and performing hydrothermal treatment for 14h at 170 ℃ to obtain a hydroxyl-containing carbon-nitrogen polymer;
mixing 0.3g of hydroxyl-containing carbon-nitrogen polymer with 50mL of water, then performing ultrasonic treatment for 40min at 200W, then adding 15mL of 0.3mol/L metal source solution, stirring for 15h in a dark place, separating, drying, and then calcining for 3h at 160 ℃ to obtain the metal monatomic supported carbon-nitrogen polymer catalyst. Wherein the metal source solution is HAuCl4An aqueous solution.
Example 8
And heating the nitrogen-containing precursor from room temperature to 540 ℃ at the heating rate of 4 ℃, and calcining for 3h to obtain the carbon-nitrogen polymer. Wherein the nitrogen-containing precursor is a mixture of urea, melamine and cyanuric acid in a mass ratio of 1:1: 1;
mixing 0.4g of carbon-nitrogen polymer with 60mL of water, and performing hydrothermal treatment for 14h at 160 ℃ to obtain a hydroxyl-containing carbon-nitrogen polymer;
mixing 0.5g of hydroxyl-containing carbon-nitrogen polymer with 60mL of water, then performing ultrasonic treatment for 50min at 200W, then adding 20mL of 0.5mol/L metal source solution, stirring for 24h in a dark place, separating, drying, and then calcining for 2.5h at 180 ℃ to obtain the metal monatomic supported carbon-nitrogen polymer catalyst. Wherein the metal source solution is PdCl4An aqueous solution.
Example 9
And heating the nitrogen-containing precursor from room temperature to 570 ℃ at the heating rate of 3 ℃, and calcining for 2.5h to obtain the carbon-nitrogen polymer. Wherein the nitrogen-containing precursor is a mixture of melamine and cyanuric acid in a mass ratio of 1: 1.
Mixing 0.1g of carbon-nitrogen polymer with 40mL of water, and performing hydrothermal treatment at 180 ℃ for 11h to obtain a hydroxyl-containing carbon-nitrogen polymer;
0 is added.2g of hydroxyl-containing carbon-nitrogen polymer is mixed with 40mL of water, then ultrasonic treatment is carried out for 60min under 200W, then 16mL of 0.4mol/L metal source solution is added, the mixture is stirred for 8h in a dark place, separated and dried, and then calcined for 4h at 150 ℃, so as to obtain the metal monatomic supported carbon-nitrogen polymer catalyst. Wherein the metal source solution is H2PtCl6·6H2And (4) O aqueous solution.
Comparative example 1
(1) 5g of melamine in a 100mL alumina crucible with a lid are calcined in a muffle furnace for 3 hours at a rate of 5 ℃ and a calcination temperature of 550 ℃.
(2) The cake solid obtained by the calcination of the former was ground to 200 mesh or less to obtain P-CN.
0.1g P-CN was uniformly dispersed in the bottom of a 50mL cylindrical reactor, which was made of stainless steel around and at the bottom, with a quartz window at the top and a port reserved for gas addition and extraction. Injecting 1MPa of CO into the reactor2Gas, vertically irradiating a light source provided by a 300W xenon lamp onto the surface of the catalyst, and detecting CO and CH in the gas after 1h of illumination4The concentration of (A) is calculated to obtain P-CN photo-reduction CO2Production of CO and CH4The efficiencies of (a) were 3.2 and 1.7. mu. mol g, respectively-1h-1。
Comparative example 2
(1) 5g of melamine in a 100mL alumina crucible with a lid are calcined in a muffle furnace for 3 hours at a rate of 5 ℃ and a calcination temperature of 550 ℃.
(2) The cake solid obtained by the calcination of the former was ground to 200 mesh or less to obtain P-CN.
(3) Adding 0.3g P-CN into a 100mL reaction kettle, adding 70mL deionized water, carrying out hydrothermal treatment for 12h in an oven at 180 ℃, carrying out centrifugal treatment on the solution after the reaction is finished, alternately cleaning with absolute ethyl alcohol and deionized water for 3 times, drying for 12h at 80 ℃, and grinding to below 200 meshes to obtain a carbon-nitrogen polymer containing a large amount of hydroxyl, which is marked as P-CN-OH.
0.1g P-CN-OH is uniformly dispersed at the bottom of a 50mL cylindrical reactor, stainless steel is arranged at the periphery and the bottom of the reactor, a quartz window is arranged at the top end, and ports for adding and extracting gas are reserved. Towards the reactionInjecting 1MPa CO into the reactor2Gas, vertically irradiating a light source provided by a 300W xenon lamp onto the surface of the catalyst, and detecting CO and CH in the gas after 1h of illumination4The concentration of (A) is calculated to obtain P-CN-OH photo-reduction CO2Production of CO and CH4The efficiencies of (a) were 1.7 and 1.3. mu. mol g, respectively-1h-1。
Comparative example 3
(1) 5g of melamine in a 100mL alumina crucible with a lid are calcined in a muffle furnace for 3 hours at a rate of 5 ℃ and a calcination temperature of 550 ℃.
(2) The cake solid obtained by the calcination of the former was ground to 200 mesh or less to obtain P-CN.
(3) 0.3g P-CN was placed in a 200mL beaker, 40mL deionized water was added and sonication was performed at 200W for 30min to disperse P-CN-OH in water uniformly.
(4) To the solution obtained in (3) was added 10mL of 0.1M Pt (NH)3)4Cl2Stirring the solution at room temperature of 500r/min for 10h in a dark place, centrifuging after stirring, alternately cleaning the obtained product ethanol and deionized water for 3 times, and vacuum-drying in a vacuum drying oven at 60 ℃ for 12 h.
(5) And putting 0.3g of the dried product in a 10mL porcelain boat, putting the porcelain boat in a tubular furnace, calcining for 2h at 150 ℃ under the protection of helium, naturally cooling to room temperature, and recovering a calcined sample, namely the metal Pt monatomic supported carbon-nitrogen polymer catalyst, which is recorded as P-CN-Pt.
0.1g P-CN-Pt is uniformly dispersed at the bottom of a 50mL cylindrical reactor, stainless steel is arranged at the periphery and the bottom of the reactor, a quartz window is arranged at the top end, and ports for adding and extracting gas are reserved. Injecting 1MPa of CO into the reactor2Gas, vertically irradiating a light source provided by a 300W xenon lamp onto the surface of the catalyst, and detecting CO and CH in the gas after 1h of illumination4The concentration of (A) is calculated to obtain the photo-reduced CO of the P-CN-Pt2Production of CO and CH4The efficiencies of (a) were 3.8 and 2.5. mu. mol g, respectively-1h-1。
By comparing comparative example 1 with examples 1 to 4, it can be seen that the supported metal monoatomic post-carbonitride polymer photocatalytically reduces CO2Production of CO and CH4The efficiency of the method is obviously improved compared with pure P-CN.
By comparing comparative example 2 with examples 1-4, it can be seen that the acting supported carbon nitrogen polymer photocatalytically reduces CO2Production of CO and CH4The efficiency improvement is caused by the metal monoatomic load, and the hydroxyl group alone does not play a role in improving the catalytic activity.
By comparing comparative example 3 with examples 1 to 4, it can be seen that the hydrothermal treatment introduced hydroxyl groups to the surface of p-CN to facilitate the metal monoatomic support and the improvement of catalytic activity.
The invention prepares the carbon-nitrogen polymer by calcining the nitrogen-containing precursor; hydrothermally treating the carbon-nitrogen polymer to make the surface thereof rich in hydroxyl groups; adsorbing metal cations around active sites through electrostatic and coordination of oxygen-containing groups such as hydroxyl groups and the like and the metal cations; the metal is loaded around the active sites in the form of single atoms by a low temperature calcination process. The preparation method of the metal monoatomic carbon nitrogen loaded polymer is simple, the universality is strong, the loading position at the monoatomic position is accurate and controllable, and the prepared metal monoatomic carbon nitrogen loaded polymer catalyst is high in loading amount, rapid in-plane charge transmission, excellent in photocatalytic performance and strong in stability.
Claims (10)
1. A preparation method of a metal monatomic supported carbon-nitrogen polymer catalyst is characterized in that a carbon-nitrogen polymer and water are mixed and then subjected to hydrothermal treatment at the temperature of 150-200 ℃ for 10-15h to obtain a carbon-nitrogen polymer containing hydroxyl;
mixing the carbon-nitrogen polymer containing hydroxyl with water, performing ultrasonic treatment, adding a metal source solution, stirring for 8-24h in a dark place, separating, drying, and calcining to obtain the metal monatomic supported carbon-nitrogen polymer catalyst.
2. The method for preparing a metal monatomic supported carbon-nitrogen polymer catalyst according to claim 1, wherein the carbon-nitrogen polymer is prepared by the following process: the nitrogen-containing precursor is calcined at the temperature of 520 ℃ and 580 ℃ for 2-5 h.
3. The method for preparing the metal monatomic supported carbon-nitrogen polymer catalyst according to claim 2, wherein the nitrogen-containing precursor is one or more of urea, melamine and cyanuric acid; when two of urea, melamine and cyanuric acid are used, the two are mixed according to the mass ratio of 1:1, and when three are used, the three are mixed according to the mass ratio of 1:1: 1.
4. The method as claimed in claim 2, wherein the temperature is raised from room temperature to 520-580 ℃ at a temperature raising rate of 1-5 ℃.
5. The method for preparing a metal monatomic supported carbon-nitrogen polymer catalyst as claimed in claim 1, wherein the ratio of the carbon-nitrogen polymer to water is 0.1 to 0.5 g: 20-70 mL; hydroxyl group-containing carbon nitrogen polymer and water 0.1 to 0.5 g: 30-80 mL.
6. The method for preparing a metal monatomic supported carbon-nitrogen polymer catalyst as claimed in claim 1, wherein the ratio of the hydroxyl group-containing carbon-nitrogen polymer to the metal source solution is 0.1 to 0.5 g: 10-20 mL; the concentration of the metal source solution is 0.1-0.5 mol/L.
7. The preparation method of the metal monatomic supported carbon-nitrogen polymer catalyst according to claim 1, wherein the power of ultrasound is 200W, and the time is 30-60 min; the metal source solution is a metal source solution containing Pt, Pd, Au, Fe, Ni, Cu or Ag metal cations.
8. The method for preparing the metal monatomic carbon nitrogen-supported polymer catalyst according to claim 7, wherein the metal source containing the Pt metal cation is H2PtCl6·6H2O and Pt (NH)3)4Cl2One of (1);
the metal source containing Pd metal cations is PdCl4With Na2PdCl4In (1)One kind of the material is selected;
the metal source of the Au-containing metal cation is HAuCl4；
The metal source containing Ag metal cations is AgNO3；
The metal source containing Fe metal cations is FeCl3With FeCl2One of (1);
the metal source containing Ni metal cations is NiCl2；
The metal source containing Cu metal cations is CuCl2With Cu (NO)3)2One kind of (1).
9. The method for preparing a metal monatomic supported carbon-nitrogen polymer catalyst as recited in claim 1, wherein the calcination temperature is 120-200 ℃ and the calcination time is 2-5 h.
10. A metal monatomic supported carbon nitrogen polymer catalyst produced by the method according to any one of claims 1 to 9.
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