CN113546659A - Highly dispersed CeCN-urea-N by coordination method2Material, preparation method and application thereof - Google Patents
Highly dispersed CeCN-urea-N by coordination method2Material, preparation method and application thereof Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
Abstract
The invention discloses a CeCN-urea-N treated by a coordination method2A material, a preparation method and application thereof, belonging to the field of material preparation and photocatalytic reduction of CO2The technical field of resource utilization. The method comprises (1) reacting Ce (NO)3)3·6H2And respectively adding O and urea into absolute ethyl alcohol to obtain dispersion liquid A and dispersion liquid B, slowly dropwise adding the dispersion liquid A into the dispersion liquid B, and uniformly stirring to obtain a solution C. (2) G to C3N4Adding into anhydrous ethanol to obtain dispersion solution D, adding dropwise solution C into dispersion solution D, and heating in water bath to obtainA solid; (3) the solid is placed in a tube furnace at N2Calcining, cooling to obtain CeCN-urea-N2. The invention adopts a coordination method to obtain the high-dispersion heterojunction material, the preparation process is simple and convenient, and the raw materials are cheap; the material has strong practicability and high environmental stability, and can be used for reducing CO in photocatalysis2Has potential application prospect in the aspect.
Description
Technical Field
The invention belongs to material preparation and photocatalytic reduction of CO2The technical field of resource utilization, in particular to a high-dispersion CeCN-urea-N adopting a coordination method2A material and a preparation method and application thereof.
Background
In recent years, in order to solve the problems of rapid consumption of fossil fuels and global warming, many methods have been proposed to reduce carbon emissions. Wherein CO is reduced in sustainable solar energy2Discharging or mixing CO2Solutions for conversion to valuable carbon derivatives (e.g. methane, formic acid, methanol, etc.) are receiving a lot of attention. In recent years, photocatalytic CO2Emission reduction is one of the most mature solutions today due to its sustainability, environmental friendliness and high efficiency. At present, many photocatalysts have the problems of large size, easy agglomeration of particles and the like, so that the reaction center is reduced, and the photocatalytic performance is influenced. In recent years, a monatomic catalyst in which metal atoms are highly dispersed on a carrier has attracted much attention in the field of catalysis, and methods for synthesizing the monatomic catalyst have been increasing. Atomic Layer Deposition (ALD) and mass selective soft landing techniques are the two most effective methods for achieving precise and controlled synthesis of monatomic catalysts. However, the high cost and low yield of the synthesis equipment prevent the large-scale production of the monatomic catalyst. Therefore, from the practical application point of view, the application of the wet chemical method with the advantages of simple operation and mass production in the synthesis of the monatomic catalyst is explored and developed. In the case of the wet-chemical process,the dispersion of synthetic precursors and the prevention of the migration and aggregation of monoatomic atoms are very important, and there are some reported strategies such as the construction of suitable defects on the surface of the support, the design of controlling coordinatively unsaturated sites to enhance the interaction with metal atoms, the steric confinement of metal atoms in molecular cages of framework materials, i.e. zeolites, MOFs and COFs, the introduction of site-anchored metal precursors, etc.
Wherein graphene carbon nitride (g-C)3N4) The graphene carbon nitride (g-C) with a two-dimensional layered structure has an advantageous structure that N atoms on a triazine ring have lone pair electrons3N4) Is a ligand suitable for anchoring and coordinating isolated metal atoms. CeO (CeO)2As rare earth oxide, the rare earth oxide has the characteristics of rich oxygen vacancy, good oxidation-reduction capability, alkaline surface and the like, and is beneficial to CO in the photocatalysis process2Adsorption and activation. In the past work on CeO2Photo-reduction of CO2Some studies have been conducted to find that oxygen vacancies and surface functional groups can act as lewis acidic and basic sites, respectively, both of which contribute to CO2Adsorption and activation. However, no preparation at g-C by chelation of urea and cerium salt precursors has been achieved so far by complexation3N4Ce species with high dispersibility (denoted as CeCN-urea-N)2) Preparation method and photocatalytic CO2Reduction applications are reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a high-dispersion CeCN-urea-N adopting a coordination method2A method for preparing the material. Another technical problem to be solved by the present invention is to provide a highly dispersed CeCN-urea-N using a coordination method2A material. The invention also provides a highly dispersed CeCN-urea-N using coordination method2Photocatalytic reduction of CO in materials2The use of (1).
In order to solve the problems, the technical scheme adopted by the invention is as follows:
highly dispersed CeCN-urea-N by coordination method2Method for producing a materialThe method specifically comprises the following steps:
(1) solid Ce (NO)3)3·6H2Respectively putting O and urea into absolute ethyl alcohol to respectively obtain dispersion liquid A and dispersion liquid B, after completely dissolving, slowly dropwise adding the dispersion liquid A into the dispersion liquid B, and uniformly stirring to obtain a solution C;
(2) the solid g-C3N4Adding into anhydrous ethanol, stirring to obtain dispersion solution D, slowly dropwise adding the solution C into the dispersion solution D, heating in water bath, and stirring to obtain solid;
(3) the solids were placed in a porcelain boat and the boat was placed in a tube furnace in N2Calcining in the atmosphere, cooling to room temperature to obtain the catalyst CeCN-urea-N2。
The high-dispersion CeCN-urea-N adopting the coordination method2Method for preparing material, solid g-C3N4The preparation of (1): putting urea into a muffle furnace, heating to 550-600 ℃, and calcining for 4-6 h to obtain g-C3N4(ii) a The heating rate is 2-3 ℃/min.
The high-dispersion CeCN-urea-N adopting the coordination method2The preparation method of the material comprises the following steps of 1-4 g/L of dispersion liquid A, 3-10 g/L of dispersion liquid B and 17-20 g/L of dispersion liquid D; the ultrasonic dispersion time is 0.5-1 h when the dispersion solution is prepared.
The high-dispersion CeCN-urea-N adopting the coordination method2Method for preparing material, solid Ce (NO)3)3·6H2O, urea and solids g-C3N4The mass ratio of (A) to (B) is 1: 1-2: 4-6.
The high-dispersion CeCN-urea-N adopting the coordination method2The preparation method of the material comprises the step (2), wherein the water bath heating temperature is 100 ℃.
The high-dispersion CeCN-urea-N adopting the coordination method2The preparation method of the material comprises the following steps of calcining at the temperature of 450-550 ℃; n is a radical of2The gas flow rate is 150-250 mL/min.
The high-dispersion CeCN-urea-N prepared by the method2A material.
The high dispersion CeCN-urea-N2Photocatalytic reduction of CO in materials2The use of (1).
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) high dispersion CeCN-urea-N of coordination method of the invention2The preparation process of the material is green and simple, the cost is low, the practicability is high, the material has excellent environmental stability, and the problem of solving CO is solved2Has potential application prospect in the aspect of environmental problems such as greenhouse effect and the like.
(2) High dispersion CeCN-urea-N of coordination method of the invention2The Ce particles are highly dispersed on the material, not forming CeO2The particles are agglomerated in g-C3N4A surface. Highly dispersed Ce species with g-C3N4Interface interaction is enhanced, the transfer of photogenerated electrons is promoted, and the Ce species is taken as Lewis base sites to be beneficial to CO2Adsorption and activation. In addition, in CeCN-urea-N2More CO formed thereon2H in which the free radicals are surface-enriched2O/OH proton attack in favor of CH4Selectivity of (a); provides a simple method for designing high-efficiency photocatalyst.
Drawings
FIG. 1 is XRD, STEM-HAADF and STEM-EDX mapping spectra of the prepared sample, wherein FIG. 1A is XRD map, FIG. 1B is STEM-HAADF map, and FIGS. 1C-1F are STEM-EDX mapping spectra;
FIG. 2 is N1s XPS (FIG. 2A) and DFT (FIG. 2B) of the prepared samples;
FIG. 3 is the ESR (FIG. 3A) and water contact angle (FIGS. 3B and 3C) of the prepared samples;
FIG. 4 is a graph of O1s XPS (FIG. 4A) and O of the prepared sample2-TPD (fig. 4B) diagram;
FIG. 5 is a graph of the prepared samples under full spectrum illumination for CO2And (5) reducing the effect graph.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
Highly dispersed CeCN-urea-N by coordination method2The preparation method of the material comprises the following steps:
(1) preparation of solid g-C3N4Photocatalyst: weighing 15g of urea, putting the urea into a crucible, covering the crucible with a crucible cover, horizontally placing the urea into a muffle furnace, calcining in air atmosphere, raising the temperature to 560 ℃, reacting for 4 hours at the temperature, and cooling to room temperature after calcination to obtain solid g-C3N4；
(2) 0.2g of solid Ce (NO)3)3·6H2Adding O into 50mL of absolute ethyl alcohol, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid A; adding 0.3g of urea into 50mL of absolute ethyl alcohol, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid B; slowly dripping the dispersion liquid A into the dispersion liquid B, and uniformly stirring to obtain a solution C;
(3) 0.93g of solid g-C3N4Adding the mixture into 50mL of absolute ethyl alcohol, performing ultrasonic dispersion for 1h, and fully stirring and uniformly mixing to obtain a dispersion liquid D; slowly dropwise adding the solution C into the dispersion liquid D, heating the solution C to 100 ℃ in a water bath in a fume hood, and uniformly stirring to obtain a solid;
(4) the collected solid powder was placed in a porcelain boat and the porcelain boat was placed in a tube furnace in N2Calcining to 520 ℃ for 5h at the heating rate of 2 ℃/min, cooling to room temperature after the reaction is finished, and obtaining the catalyst CeCN-urea-N2。
Preparation of CeCN-N2A material comprising the steps of:
(1) preparation of g-C3N4Photocatalyst: weighing 15g of urea, putting the urea into a crucible, covering the crucible with a crucible cover, horizontally placing the urea into a muffle furnace, calcining in air atmosphere, raising the temperature to 560 ℃, reacting for 4 hours at the temperature, and cooling to room temperature after calcination to obtain g-C3N4A photocatalyst;
(2) 10g of Ce (NO)3)3·6H2Calcining O in a muffle furnace at 560 ℃ for 4h (the temperature rise rate is 2 ℃/min) to prepare CeO2。
(3) 0.06g of urea was added to 50mLH2In O, ultrasonic analysisDispersing for 1h, fully stirring and uniformly mixing to obtain a dispersion liquid A;
(4) 0.94g g-C3N4Adding into 50mLH2In O, ultrasonically dispersing for 1h, fully stirring and uniformly mixing to obtain a dispersion liquid B;
(5) slowly dripping the dispersion liquid A into the dispersion liquid B, and uniformly stirring to obtain a solution C;
(6) heating the solution C to 100 ℃ in a fume hood by a water bath, and uniformly stirring to obtain a solid; the collected solid powder was placed in a porcelain boat and the porcelain boat was placed in a tube furnace in N2Calcining to 520 deg.C for 5h at a heating rate of 2 deg.C/min, cooling to room temperature to obtain catalyst named CeCN-N2。
FIG. 1 is CeCN-urea-N2，CeCN-N2And g-C3N4An X-ray diffraction pattern (XRD) of the sample, wherein FIG. 1A is an XRD pattern, FIG. 1B is a STEM-HAADF pattern, and FIGS. 1C-1F are STEM-EDX mapping patterns. As can be seen from FIG. 1A, sample CeCN-urea-N2Only the peak at 27.3 ℃ appears, which is attributed to g-C3N4The (002) plane of (a); the peaks which did not appear at 28.7 °, 33.3 °, 47.8 ° and 56.8 ° were CeO, respectively2(111) Characteristic peaks of (200), (220) and (311) crystal planes. FIGS. 1B and 1C-1F are CeCN-urea-N2STEM-HAADF and STEM-EDX mapping of (1). As can be seen from FIGS. 1B and 1C-1F, the Ce species are highly dispersed in g-C3N4Instead of forming CeO2The particles are agglomerated in g-C3N4A surface.
FIG. 2 is CeCN-urea-N2，CeCN-N2And g-C3N4N1s XPS (FIG. 2A) and DFT (FIG. 2B) of the sample, from which it can be observed that a large number of electrons are concentrated at the N atom (g-C)3N4) The number of Ce electrons decreased, indicating that electrons were transferred from Ce to g-C3N4On N of (3) results in CeCN-urea-N2A strong built-in electric field is formed, consistent with the XPS results.
FIG. 3 is CeCN-urea-N2And CeCN-N2Fig. 3A shows ESR (fig. 3A) and water contact angle (fig. 3B and fig. 3C) of the sample, and it is found from fig. 3A that signals when g is 2.03 and g is 1.96 correspond to superoxideFree radical and Ce3+Species of the species. By comparison of the intensities of the two peaks (I)1/I2) Discovery of CeCN-urea-N2Ce of3+Species ratio CeCN-N2Poly of (A) to (B), Ce3+The species are hydroxyl groups and lewis basic sites to which water molecules adsorb. On the basis of the above, CeCN-urea-N2Has good Ce species dispersibility, Ce and g-C3N4Has strong built-in electron field among N atoms, more surface adsorbs hydroxyl and water molecules, and catalyzes CO2Photochemical Properties of reduction and CH4The selectivity has a positive influence. As can be seen from FIG. 3B, the results of the water contact angles (FIGS. 3B and 3C) show that CeCN-urea-N2Has a lower contact angle of water, which indicates better hydrophilicity and more oxygen-containing substances adsorbed on the CeCN-urea-N2On the surface.
FIG. 4 is CeCN-urea-N2，CeCN-N2And g-C3N4O1s XPS plot (FIG. 4A) and O of samples2TPD plot (FIG. 4B), from FIG. 4A it can be seen that the broad peak consists of two peaks at the binding energy, each belonging to lattice oxygen (O)L) And adsorbing oxygen (O)C) 530 and 532.6eV, respectively. Generally, the species of surface oxygen include surface hydroxyl groups and adsorbed water molecules. According to the calculated AC/A(C+L) Peak area value, CeCN-urea-N2More water molecules and hydroxyl groups are adsorbed on the surface. As shown in FIG. 4B, the width between 100-. Wherein, CeCN-urea-N2The peak intensity of (A) is greater and moves slightly to higher temperatures, indicating that CeCN-urea-N2The adsorption interaction of surface oxygen is stronger. In combination with the results of O1s XPS, the surface adsorbed oxygen species were strongly attributed to hydroxyl groups and water molecules. Thus, CeCN-urea-N2More hydroxyl groups and water molecules are adsorbed on the surface.
Example 2
Application of the photocatalyst prepared in example 1 to CO2In the reduction, the experimental steps are as follows:
CO2the photoreduction reaction of (2) was carried out in a 100ml autoclave, and CO was measured2Photoreductive property. Weighing 20mg of sample, and placing in quartzIn a glass sand reactor. 1ml of distilled water was dropped on the catalyst surface to soak the catalyst. After exhausting, 4bar of high-purity CO is added2The autoclave was charged and the xenon lamp was turned on for 8h, and the resulting gas was detected by gas chromatography. The used samples were washed several times with distilled water and then dried in an oven at 80 ℃. FIG. 5 is a graph of the prepared samples under full spectrum illumination for CO2And (5) reducing the effect graph.
As can be seen from FIG. 5, g-C was observed after 8 hours of light irradiation3N4Only CO was detected, while both CeCN catalysts detected CO and CH4The activity is all compared with g-C3N4Is improved. Wherein, CeCN-urea-N2The CO yield of the sample was CeCN-N2About 2 times of the sample, CH4The yield is CeCN-N2More than 10 times of the sample, indicating that the CeCN-urea-N2CH of sample4The selectivity is greatly improved.
Claims (8)
1. Highly dispersed CeCN-urea-N by coordination method2The preparation method of the material is characterized by comprising the following steps:
(1) solid Ce (NO)3)3·6H2Respectively putting O and urea into absolute ethyl alcohol to respectively obtain dispersion liquid A and dispersion liquid B; after the dispersion liquid A is completely dissolved, slowly dropwise adding the dispersion liquid A into the dispersion liquid B, and uniformly stirring to obtain a solution C;
(2) the solid g-C3N4Adding into anhydrous ethanol, stirring to obtain dispersion solution D, slowly dropwise adding the solution C into the dispersion solution D, heating in water bath, and stirring to obtain solid;
(3) the solids were placed in a porcelain boat and the boat was placed in a tube furnace in N2Calcining in the atmosphere, cooling to room temperature to obtain the catalyst CeCN-urea-N2。
2. The highly dispersed CeCN-urea-N by coordination according to claim 12A process for the preparation of a material, characterized in that the solid g-C3N4The preparation of (1): putting urea into a muffle furnace, heating to 550-600 ℃, and calcining for 4-6 h to obtain g-C3N4(ii) a The heating rate is 2-3 ℃/min.
3. The highly dispersed CeCN-urea-N by coordination according to claim 12The preparation method of the material is characterized in that the concentration of the dispersion liquid A is 1-4 g/L, the concentration of the dispersion liquid B is 3-10 g/L, and the concentration of the dispersion liquid D is 17-20 g/L; the ultrasonic dispersion time is 0.5-1 h when the dispersion solution is prepared.
4. The highly dispersed CeCN-urea-N by coordination according to claim 12A method for producing a material, characterized in that solid Ce (NO) is used3)3·6H2O, urea and solids g-C3N4The mass ratio of (A) to (B) is 1: 1-2: 4-6.
5. The highly dispersed CeCN-urea-N by coordination according to claim 12The preparation method of the material is characterized in that in the step (2), the water bath heating temperature is 100 ℃.
6. The highly dispersed CeCN-urea-N by coordination according to claim 12The preparation method of the material is characterized in that the calcination temperature is 450-550 ℃; n is a radical of2The gas flow rate is 150-250 mL/min.
7. Highly dispersed CeCN-urea-N prepared by the method of any one of claims 1 to 62A material.
8. The highly disperse CeCN-urea-N of claim 72Photocatalytic reduction of CO in materials2The use of (1).
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| CN115555010A (en) * | 2022-08-17 | 2023-01-03 | 广州大学 | Oxygen vacancy-rich mesoporous nanorod photocatalyst, preparation method and application |
| CN115636944A (en) * | 2022-10-10 | 2023-01-24 | 厦门大学附属心血管病医院 | Erbium ion doped metal coordination polymer nanogel material and preparation method and application thereof |
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| CN112023974A (en) * | 2020-09-22 | 2020-12-04 | 南京大学 | P-CeO2/g-C3N4Heterojunction material, preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115555010A (en) * | 2022-08-17 | 2023-01-03 | 广州大学 | Oxygen vacancy-rich mesoporous nanorod photocatalyst, preparation method and application |
| CN115555010B (en) * | 2022-08-17 | 2024-02-02 | 广州大学 | Mesoporous nanorod photocatalyst rich in oxygen vacancies, preparation method and application |
| CN115636944A (en) * | 2022-10-10 | 2023-01-24 | 厦门大学附属心血管病医院 | Erbium ion doped metal coordination polymer nanogel material and preparation method and application thereof |
| CN115636944B (en) * | 2022-10-10 | 2023-11-17 | 厦门大学附属心血管病医院 | Erbium ion doped metal coordination polymer nanogel material and preparation method and application thereof |
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