CN114887646A - Fe monatomic-loaded porous carbon nitride photocatalytic material and preparation method and application thereof - Google Patents
Fe monatomic-loaded porous carbon nitride photocatalytic material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 52
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/391—Physical properties of the active metal ingredient
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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Abstract
The invention relates to the technical field of semiconductor photocatalytic materials, in particular to a Fe monatomic loaded porous carbon nitride photocatalytic material and a preparation method and application thereof. The preparation method comprises the following steps: placing 1-4 parts by weight of nano Fe particles, 500-1500 parts by weight of dicyandiamide and 500-1500 parts by weight of ammonium chloride in a mortar, grinding in a glove box and uniformly mixing to form a mixture; and transferring the mixture into a quartz boat, calcining the quartz boat in a tubular muffle furnace for 2-6 hours in a vacuum environment at the temperature of 300-600 ℃, and naturally cooling the quartz boat to room temperature after the calcination is finished to obtain the Fe monatomic loaded porous carbon nitride photocatalytic material. The photocatalytic material is prepared by the method. The photocatalytic material can be applied to photocatalytic nitrogen reduction synthesis of ammonia. The method has the characteristics of simple and mild process conditions, low cost, greenness, no pollution and suitability for large-scale production.
Description
Technical Field
The invention relates to the technical field of semiconductor photocatalytic materials, in particular to a Fe monatomic loaded porous carbon nitride photocatalytic material and a preparation method and application thereof.
Background
Ammonia gas, as an essential active nitrogen source in the agricultural and chemical industries, has long been recognized as a potential energy carrier and fertilizer precursor. The current haber-bo construction process for industrially synthesizing ammonia uses Fe-based catalyst as core and reduces N under high temperature and high pressure 2 Producing ammonia gas. However, in the process of producing ammonia gas by the Haber-Bosch process, the consumed energy accounts for more than 1% of the world energy supply annually, and the released CO 2 More than 3 hundred million tons is not favorable for the sustainable development of ammonia industry. Monatomic photocatalysts (SAPs) are considered as one of the ideal alternatives to the Haber-Bosch process as a green emerging technology for converting solar energy. The selection of an appropriate substrate is critical to the successful preparation of SAPs. Carbon nitride (g-C) 3 N 4 ) Having a "nitrogen cavity" in the structure formed by 6 nitrogen atoms, which can form a Metal-Nx bond to anchor a single Metal atom, is an ideal substrate for constructing SAPs. The prior art of SAPs is mainly wet chemical methods, which usually require complex steps to adsorb and reduce precursors and finally stabilize the isolated atoms, and top-down methods. The top-down thermal diffusion/emission method is simple in step, can confine multiple atomic metals directly to the support, however, this method does not require high temperatures of about 900 ℃ and cannot coordinate and optimize individual atoms.
At present, Fe element can effectively weaken N [ identical to ] N and has a remarkable promoting effect on nitrogen reduction, and the preparation of Fe single-atom photocatalyst is the key research field at present. The prior art generally uses Fe 2 O 3 Loaded at g-C 3 N 4 In addition, the graphite carbon nitride prepared by the conventional method is generally blocky, and g-C prepared by the traditional high-temperature calcination process 3 N 4 Serious agglomeration, few active sites, small specific surface area, weak light absorption capacity and rapid recombination of photo-generated electron-hole pairs, so that the photocatalytic performance is limited.
Disclosure of Invention
In view of the above, the present invention aims to provide a Fe monatomic supported porous carbon nitride photocatalytic material and a preparation method thereof, so as to solve the problems of a complex process for synthesizing a monatomic photocatalyst, serious traditional carbon nitride agglomeration, small specific surface area, weak light absorption capacity, and incapability of reducing N at normal temperature and normal pressure 2 The problem of producing ammonia.
In order to achieve the purpose, the invention prepares Fe monatomic load porous carbon nitride by using a one-step calcination method, and mainly provides the following technical scheme:
the preparation method of the Fe monatomic loaded porous carbon nitride photocatalytic material comprises the following steps:
step 1, putting 1-4 parts by weight of nano Fe particles, 500-1500 parts by weight of dicyandiamide and 500-1500 parts by weight of ammonium chloride into a mortar, grinding in a glove box and uniformly mixing to form a mixture;
and 2, transferring the mixture into a quartz boat, placing the quartz boat in a tubular muffle furnace, calcining for 2-6 hours in a vacuum environment at the temperature of 300-600 ℃, and naturally cooling to room temperature after calcining to obtain the Fe monatomic load porous carbon nitride photocatalytic material.
The temperature rise rate of the muffle furnace affects the carbonization degree, and if the temperature rise is too fast, the material is not completely carbonized, and the formation of a carbon nitride structure is affected. Therefore, in the above preparation method, the temperature rise rate of the tubular muffle furnace is set to 5 ℃/min.
According to the preparation method, the gaseous protonic acid can oxidize Fe particles to generate Fe salt, Fe ions are dispersed on carbon nitride and captured by defects in the carbon nitride to form isolated Fe sites. The preparation method can simultaneously form a pore-shaped structure and Fe single atoms by using a one-step calcination method.
The porous structure can expose more active sites, the Fe monoatomic atom can enable the local electronic structure of the carbon nitride to be redistributed, the bandwidth of the photocatalytic material prepared by the method is 2.95-3.02 eV, so that the catalyst can more easily utilize visible light, and the introduction of the Fe monoatomic atom enables the photocatalytic nitrogen reduction path of the catalyst to be converted from association far ends into association alternation, so that the photocatalytic nitrogen reduction reaction is more easily generated.
In the above preparation method, the Fe particles are Fe particles having a diameter of 50 nm.
Since the Fe particles are doped too much and are liable to agglomerate together in a specific preparation process, and cannot form Fe single atoms, which has an influence on the photocatalytic performance, the amount of the Fe nanoparticles in the embodiment of the present application is greatly different from the amounts of the other two substances. In addition, in order to prevent oxidation of Fe particles, nano Fe particles, dicyandiamide, and ammonium chloride were ground in a glove box.
In the above preparation method, the mass ratio of the dicyandiamide to the ammonium chloride is 1: 1.
In the preparation method, the weight of the nano Fe particles is 10-40 mg, the weight of the dicyandiamide is 5-15 g, and the weight of the dicyandiamide is 5-15 g.
In the above preparation method, the mass of the Fe nanoparticles is 30mg, the mass of the dicyandiamide is 10g, and the mass of the dicyandiamide is 10 g.
In the above-mentioned production method, the temperature at the time of the calcination is 550 ℃.
The Fe monatomic load porous carbon nitride photocatalytic material prepared by the method has the advantages that Fe monatomic load porous carbon nitride photocatalytic material Fe is connected to porous carbon nitride in a Fe-N4 coordination mode, and the Fe-N1 bond length is
Fe-N2 has a bond length of
Fe-N3 has a bond length of
Fe-N4 has a bond length of
The Fe monatomic load porous carbon nitride photocatalytic material is a porous material, and the response wavelength of the Fe monatomic load porous carbon nitride photocatalytic material is 390nm-780 nm.
In the Fe monatomic load porous carbon nitride photocatalytic material, the response wavelength of the Fe monatomic load porous carbon nitride photocatalytic material is from 395 nm to 620nm when ammonia is synthesized by photocatalytic nitrogen reduction, and the bandwidth of the Fe monatomic load porous carbon nitride photocatalytic material is 2.95eV to 3.02 eV;
preferably, the response wavelength of the Fe monatomic loaded porous carbon nitride photocatalytic material in the process of synthesizing ammonia by photocatalytic nitrogen reduction is 425-500 nm;
in the above Fe monatomic-supported porous carbon nitride photocatalytic material, the photocatalytic nitrogen reduction pathway of the Fe monatomic-supported porous carbon nitride photocatalytic material is an associated alternate pathway.
The Fe monatomic load porous carbon nitride photocatalytic material is applied to the synthesis of ammonia through photocatalytic nitrogen reduction.
By the technical scheme, the Fe monatomic loaded porous carbon nitride photocatalytic material and the preparation method provided by the invention have the following advantages:
(1) the Fe monatomic loaded porous carbon nitride photocatalytic material prepared by the preparation method can improve the photocatalytic nitrogen reduction activity from three aspects. Firstly, the porous structure can provide additional active sites, improve the specific surface area of the photocatalyst, and increase the photocatalyst and N 2 The contact area of (a); second, the bandwidth ratio of Fe/PCN is conventional g-C 3 N 4 Narrow, and thus the visible light absorption range can be expanded. Functional groups such as amino groups and hydrogen bonds of electron donors (recombination sites of photogenerated electrons) in the carbon nitride structure are also reduced due to the formation of a porous structure, so that the separation of photogenerated carriers is promoted, and the photocatalytic performance is promoted. Finally, under the action of Fe single atom, the redistributed electrons make the material more easily obtain visible light, and the nitrogen is adsorbed by Fe/PCN in a chemical adsorption mode, which is beneficial to the occurrence of photocatalytic nitrogen reduction reaction.
(2) The preparation method of the Fe monatomic-loaded porous carbon nitride composite photocatalyst can form a porous structure and Fe monatomic simultaneously by a one-step calcination method, and has the characteristics of simple and mild process conditions, low cost, environmental friendliness, no pollution, suitability for large-scale production and the like.
(3) In the preparation method for preparing the Fe/PCN composite photocatalyst, ammonium chloride is used as a double template. Specifically, dicyandiamide decomposes into NH under heat 3 And HCl gas in g-C 3 N 4 Bubbles are formed during the polymerization process, so that a porous structure is formed, and the porous structure is a bubble template. The acidic HCl gas can oxidize Fe particles and generate Fe salt, Fe ions are dispersed on the carbon nitride and captured by a nitrogen cavity to form isolated Fe sites which are used as acidic gas templates. Not only increases the reaction active site and the photocatalytic reaction center of the composite photocatalytic system, but also realizes the Fe monoatomic ion in the porous g-C 3 N 4 The above stable load. More importantly, the Fe monoatomic atom is formed by directly atomizing metal, so that the complicated process of conventionally synthesizing the monoatomic atom is greatly reduced.
(4) The Fe monatomic loaded porous carbon nitride composite photocatalytic material prepared by the method can reduce N at normal temperature and normal pressure 2 And (4) synthesizing ammonia.
(5) The Fe monatomic load porous carbon nitride composite photocatalytic material prepared by the method changes the traditional carbon nitride photocatalytic reduction of N 2 The pathway for ammonia synthesis (changing from an associative distant pathway to an associative alternate pathway). The main reason is that after Fe single atom is introduced, electrons in the carbon nitride structure are redistributed and the band gap is narrowed, so that the material can obtain visible light more easily, the recombination of photogenerated electrons and holes is inhibited, and the PCNRR activity is improved. In addition, nitrogen gas is converted from physisorption to chemisorption and reduced to NH by an associated alternative pathway in the presence of Fe 3 。
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is an XRD diffraction pattern of bulk carbon nitride, porous carbon nitride and Fe monatomic supported porous carbon nitride composite photocatalytic materials prepared in comparative examples 1-2 and examples 1-4;
in FIG. 2, (a), (b), (c) and (d) are SEM images of the photocatalytic materials prepared in comparative example 1, comparative example 2, example 3 and example 4, respectively;
FIG. 3 is a graph showing the photocatalytic nitrogen reduction performance of the photocatalytic materials prepared in comparative examples 1-2 and examples 1-4 at all light;
FIG. 4 is a band gap diagram of photocatalytic materials prepared in comparative example 2 and examples 1 to 4;
FIG. 5 shows (a) a DOS diagram of comparative example 2 and (b) a DOS diagram of a theoretical configuration calculated by DFT of an Fe monatomic-supported porous carbon nitride composite photocatalytic material according to an example of the present application;
FIG. 6 is a PDOS diagram of a Fe monatomic supported porous carbon nitride composite photocatalytic material according to an embodiment of the present application;
fig. 7 is a diagram of photocatalytic nitrogen reduction pathways of comparative example 2 and examples of the present application.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects of the Fe monatomic supported porous carbon nitride photocatalytic material and the preparation method thereof according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Example 1
A preparation method of a Fe monatomic loaded porous carbon nitride composite photocatalytic material comprises the following steps: firstly, weighing 10mg of nano Fe particles, 10g of dicyandiamide and 10g of ammonium chloride, grinding and uniformly mixing the nano Fe particles, 10g of dicyandiamide and 10g of ammonium chloride in a mortar (operating in a glove box), then transferring the mixture into a quartz boat, placing the quartz boat in a tubular muffle furnace vacuum environment, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 3 hours, and naturally cooling to room temperature after calcining is finished to obtain the Fe monatomic load porous carbon nitride composite photocatalytic material.
Wherein, the purchase manufacturer of the nano Fe particles is Shanghai Chaowei nanometer technology company, and the specific specification is 50nm Fe particles.
The XRD diffraction pattern of the composite photocatalytic material prepared by the preparation method of the embodiment is shown in figure 1. As can be seen from the XRD pattern, the two characteristic peaks of the composite photocatalytic materials (100) and (002) prepared by the preparation method of the embodiment illustrate the successful preparation of the carbon nitride. In addition, the composite photocatalytic material prepared by the preparation method of the embodiment has no new characteristic peak, particularly no characteristic peak belonging to Fe, which indicates that the structure of carbon nitride is not damaged by the load of Fe monoatomic atoms and Fe is highly dispersed on carbon nitride.
The graph of the performance of the photocatalytic material prepared in the example for photocatalytic nitrogen reduction at full light is shown in fig. 3. The specific ammonia yield (ammonia production rate) was: 25.47. + -. 0.64. mu. mol g -1 cat h -1 。
The bandwidth ratio of Fe/PCN of the photocatalytic material prepared by the embodiment to conventional g-C 3 N 4 The band gap is narrow, so that the visible light absorption range can be expanded, specifically, as shown in a band gap diagram of the material shown in fig. 4, the band gap calculated by DRS data is as follows: 3.02 eV.
In this embodiment, the specific operation process of the photocatalytic nitrogen reduction experiment is as follows: 30mg of photocatalyst was mixed with 30mL of 0.1mol/L Na 2 SO 4 The solutions were added together to a 100mL reactor and stirred to uniformly disperse the photocatalyst in the reaction solution. Followed by feeding N at a rate of 40mL/min 2 Bubbling for 30min to remove gas impurities in the reaction solution and reach nitrogen saturation. Then irradiating the reactor by a 300W xenon lamp, and continuously introducing N during the irradiation 2 And stirred. After illumination for 1 hour, 4mL of reaction solution is collected to detect the content of the synthetic ammonia.
This example uses indophenol blue spectrophotometry to measure ammonia production. Specifically, 4mL of standard NH4Cl solution (solvent is 0.1mol/L Na) with a series of concentrations are respectively added 2 SO 4 Solution) was mixed with 50 μ L of an oxidizing solution (NaClO solution), 500 μ L of a coloring solution (salicylic acid-potassium sodium tartrate solution) and 50 μ L of a catalyst solution (sodium nitroferricyanide solution). At the same time, 4mL of the collected reaction solution was treated as described aboveAnd (5) operating. The resulting mixture was allowed to stand for two hours, and then UV-vis measurement was carried out in the range of 800nm to 500 nm. A calibration curve, the ammonia Yield (YNH) of the sample in the photocatalytic nitrogen reduction reaction (PCNRR), was obtained from the absorbance at 660nm 3 ) Calculated using the following formula:
YNH 3 ＝(CNH 4 Cl×0.318×V)/(17×t×m)
wherein: CNH 4 Cl is the measured concentration, V is the solution volume, t is the photocatalytic time, and m is the mass of the catalyst.
Example 2
A preparation method of a Fe monatomic loaded porous carbon nitride composite photocatalytic material comprises the following steps: firstly, weighing 20mg of nano Fe particles, 10g of dicyandiamide and 10g of ammonium chloride, grinding and uniformly mixing the nano Fe particles, 10g of dicyandiamide and 10g of ammonium chloride in a mortar (operating in a glove box), then transferring the mixture into a quartz boat, placing the quartz boat in a tubular muffle furnace vacuum environment, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 3 hours, and naturally cooling to room temperature after calcining is finished to obtain the Fe monatomic load porous carbon nitride composite photocatalytic material.
The XRD diffraction pattern of the composite photocatalytic material prepared by the preparation method of the embodiment is shown in figure 1. Similarly, as can be seen from the XRD chart, the two characteristic peaks of the composite photocatalytic materials (100) and (002) prepared by the preparation method of this example illustrate the successful preparation of carbon nitride. Further, the loading of Fe single atoms does not destroy the structure of carbon nitride and Fe is highly dispersed on carbon nitride.
The graph of the performance of the photocatalytic material prepared in the example for photocatalytic nitrogen reduction at full light is shown in fig. 3. The specific ammonia yield was: 40.66. + -. 2.02. mu. mol g -1 cat h -1 . The photocatalytic nitrogen reduction experiment and the measurement of ammonia production were performed as in example 1.
According to the bandgap diagram of the material shown in fig. 4, the bandgap of the photocatalytic material prepared in this embodiment is calculated from DRS data as follows: 3.01 eV.
Example 3
A preparation method of a Fe monatomic loaded porous carbon nitride composite photocatalytic material comprises the following steps: firstly, weighing 30mg of nano Fe particles, 10g of dicyandiamide and 10g of ammonium chloride, grinding and uniformly mixing the nano Fe particles, 10g of dicyandiamide and 10g of ammonium chloride in a mortar (operating in a glove box), then transferring the mixture into a quartz boat, placing the quartz boat in a tubular muffle furnace vacuum environment, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 3 hours, and naturally cooling to room temperature after calcining is finished to obtain the Fe monatomic load porous carbon nitride composite photocatalytic material.
The nitrogen adsorption isotherm data of the composite photocatalytic material prepared by the preparation method of the embodiment are shown in table 1.
Table 1: nitrogen adsorption isotherm data
Table 1.Data of N 2 -Sorption Isotherms.
Table 1 shows the pore volumes and pore diameters of comparative example 1, comparative example 2 and example 3. Comparative example 2, which has a larger specific surface area than example 3 than comparative example 1, illustrates the successful synthesis of a porous structure with an increase in g-C 3 N 4 Thereby enabling more photocatalytic active centers to be exposed. The pore size of example 3 was larger than that of comparative example 2, but the pore size was smaller than that of comparative example 2, which is probably because part of the pores of PCN was blocked by Fe ions during the process of supporting Fe, and thus, successful supporting of Fe monoatomic atoms was also verified from the side. Comparative example 2 has a larger specific surface area than example 3, but the photocatalytic effect is not as good as example 3 because the porous structure can improve the photocatalytic nitrogen reduction performance to some extent, but it is the load of Fe that is dominant.
The time-resolved fluorescence spectrum data of the composite photocatalytic material prepared by the preparation method of the embodiment is shown in table 2, wherein τ is the fluorescence lifetime data of the material, and the shorter the time, the higher the separation efficiency of the photon-generated carrier.
Table 2: time resolved fluorescence spectroscopy data of a sample
The XRD diffraction pattern of the composite photocatalytic material prepared by the preparation method of the embodiment is shown in figure 1. Similarly, as can be seen from the XRD chart, the two characteristic peaks of the composite photocatalytic materials (100) and (002) prepared by the preparation method of this example illustrate the successful preparation of carbon nitride. Further, the support of Fe single atoms does not destroy the structure of carbon nitride and Fe is highly dispersed on carbon nitride.
FIG. 2c is a scanning electron micrograph of the photocatalytic material prepared in this example. As can be seen from fig. 2c, the photocatalytic material has a porous structure, which illustrates that the preparation method of this embodiment successfully prepares porous carbon nitride by using ammonium chloride as a bubble template.
The graph of the performance of the photocatalytic material prepared in the example for photocatalytic nitrogen reduction at full light is shown in fig. 3. The specific ammonia yield was: 59.74. + -. 2.26. mu. mol g -1 cat h -1 . As can be seen from FIG. 3, the prepared Fe monatomic supported porous carbon nitride composite photocatalytic material has excellent photocatalytic activity, wherein the photocatalytic nitrogen reduction rate of the material of example 3 is the highest. The photocatalytic nitrogen reduction experiment and the measurement of ammonia production were performed as in example 1.
When the catalyst is exposed to light with energy larger than the band gap of the catalyst, electrons are excited and form photon-generated carriers to participate in reaction. The porous structure exposes a large number of active centers. In addition, after the Fe monoatomic group is introduced, redistributed electrons and band gaps are narrowed, so that the material can more easily obtain visible light, the recombination of photogenerated electrons and holes is inhibited, and the activity of synthesizing ammonia by photocatalytic nitrogen reduction is improved. In the presence of Fe, nitrogen is converted from physical adsorption to chemical adsorption and reduced to NH through an association alternative pathway 3 。
According to the bandgap diagram of the material shown in fig. 4, the bandgap of the photocatalytic material prepared in this embodiment is calculated from DRS data as follows: 2.97 eV.
FIG. 5a is a side view of Fe/PCN calculated by first principles of Performance (DFT) as it adsorbs nitrogen, and it can be seen that Fe/PCN adsorbs nitrogen by chemisorption.
From FIG. 6, it can be seen from the DOS plot that the valence band of PCN is composed primarily of the N-2p orbital and the conduction band is composed primarily of the C-2p orbital. The valence band of FPx consists primarily of the Fe-3d orbital and the conduction band consists primarily of the C-2p orbital. Therefore, the introduction of Fe single atoms can change the local electronic structure of the carbon nitride.
Under the action of Fe single atom, the photocatalytic nitrogen reduction reaction is easier to carry out. One reason is that due to the introduction of Fe, the nitrogen adsorption mode of the material is changed from physical adsorption to chemical adsorption, so that nitrogen can be better utilized, and specific data are shown in fig. 3. And secondly, the introduction of Fe changes the reaction path of the porous carbon nitride photocatalysis nitrogen reduction, so that the porous carbon nitride photocatalysis nitrogen reduction can be carried out more easily.
As can be seen from fig. 5 and 6, the valence band for comparative example 2 is mainly contributed by the N2 p orbital, with a small amount coming from the C2 p orbital. The conduction band of comparative example 2 is mainly contributed by the C2 p orbital, and a small amount is derived from the N2 p orbital. For the present example, the valence band consists mainly of the Fe 3p orbital, and the conduction band is contributed by the C2 p and N2 p orbitals. This indicates that the introduction of Fe alters g-C 3 N 4 The conduction band and the valence band of the material are changed. In connection with FIG. 4, g-C 3 N 4 The local electrons are redistributed so that the band gap is narrowed, thereby making the material more accessible to visible light.
As can be seen from FIG. 7, in the present example, NNH was formed when the second hydrogenation step of the photocatalytic nitrogen reduction reaction occurred 2 More free energy was required to overcome the distal path of association than the alternate path of association to form NHNH. Illustrating N adsorbed on Fe/PCN 2 The molecules are more likely to undergo photocatalytic nitrogen reduction reactions in associated alternating pathways. In contrast to comparative example 2, NNH was formed during the second hydrogenation step of the photocatalytic nitrogen reduction reaction 2 The distal path of association occurs more readily than the alternate path of association that forms NHNH. Illustrating N adsorbed on PCN 2 The molecules are more likely to undergo photocatalytic nitrogen reduction reactions in associated remote pathways. In addition, N adsorbed on the examples during the first hydrogenation step of the photocatalytic nitrogen reduction reaction 2 The molecule is more easily hydrogenated to N 2 H. The above results show that the introduction of Fe is improvedThe path of the photocatalytic nitrogen reduction is changed and the photocatalytic nitrogen reduction reaction is carried out towards a more favorable direction.
Example 4
A preparation method of a Fe monatomic loaded porous carbon nitride composite photocatalytic material comprises the following steps: firstly, weighing 40mg of nano Fe particles, 10g of dicyandiamide and 10g of ammonium chloride, grinding and uniformly mixing the nano Fe particles, 10g of dicyandiamide and 10g of ammonium chloride in a mortar (operating in a glove box), then transferring the mixture into a quartz boat, placing the quartz boat in a tubular muffle furnace vacuum environment, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 3 hours, and naturally cooling to room temperature after calcining is finished to obtain the Fe monatomic load porous carbon nitride composite photocatalytic material.
The XRD diffraction pattern of the composite photocatalytic material prepared by the preparation method of the embodiment is shown in figure 1. Similarly, as can be seen from the XRD chart, the two characteristic peaks of the composite photocatalytic materials (100) and (002) prepared by the preparation method of this example illustrate the successful preparation of carbon nitride. Further, the loading of Fe single atoms does not destroy the structure of carbon nitride and Fe is highly dispersed on carbon nitride.
FIG. 2d is a scanning electron micrograph of the photocatalytic material prepared in this example. As can be seen from fig. 2d, the photocatalytic material has a porous structure, which illustrates that the preparation method of this embodiment successfully prepares porous carbon nitride by using ammonium chloride as a bubble template.
The graph of the performance of the photocatalytic material prepared in the example for photocatalytic nitrogen reduction at full light is shown in fig. 3. The specific ammonia production yield is: 47.65. + -. 1.05. mu. mol g -1 cat h -1 . The photocatalytic nitrogen reduction experiment and the measurement of ammonia production were performed as in example 1.
According to the bandgap diagram of the material shown in fig. 4, the bandgap of the photocatalytic material prepared in this embodiment is calculated from DRS data as follows: 2.95 eV.
The reason why the photocatalytic performance of example 4 is weaker than that of example 3 is that an excessive amount of Fe nanoparticles may be enriched to form Fe — Fe bonds. And our goal is to form isolated Fe sites to form Fe-N 4 Coordinate, rather than form Fe-Fe bonds. And excessive iron nanoparticles may act as photogenerationThe recombination center of the electron-hole pair influences the performance of photocatalytic reduction of nitrogen.
Comparative example 1
A method for preparing a blocky carbon nitride photocatalytic material comprises the following steps: firstly, weighing 10g of dicyandiamide, fully grinding, then transferring into a quartz boat, placing in a tubular muffle furnace under a vacuum environment, heating at a heating rate of 5 ℃/min to 550 ℃, calcining for 3h, and naturally cooling to room temperature after calcining to obtain the blocky carbon nitride.
The nitrogen adsorption isotherm data of the bulk carbon nitride photocatalytic material prepared by the preparation method of the comparative example are shown in table 1.
The time-resolved fluorescence spectrum data of the bulk carbon nitride photocatalytic material prepared by the preparation method of the comparative example are shown in table 2.
The XRD diffraction pattern of the composite photocatalytic material prepared by the preparation method of the embodiment is shown in figure 1. From the XRD patterns, it can be seen that the bulk carbon nitride photocatalytic material prepared by the comparative example has two characteristic peaks (100) and (002), indicating the successful preparation of carbon nitride without the characteristic peak belonging to Fe, while the bulk carbon nitride photocatalytic material prepared by the comparative example 1 is pure carbon nitride (no Fe is added in the comparative example 1).
FIG. 2a is a scanning electron micrograph of the photocatalytic material prepared in this example. As can be seen from fig. 2a, the photocatalytic material exhibits a bulk structure.
The graph of the performance of the photocatalytic material prepared in the example for photocatalytic nitrogen reduction at full light is shown in fig. 3. The specific ammonia yield was: 11.66. + -. 0.49. mu. mol g -1 cat h -1 。
Comparative example 2
A preparation method of a porous carbon nitride photocatalytic material comprises the following steps: firstly, weighing 10g of dicyandiamide and 10g of ammonium chloride in a mortar according to the mass ratio of 1:1, grinding and uniformly mixing the dicyandiamide and the ammonium chloride, then transferring the mixture into a quartz boat, placing the quartz boat in a tubular muffle furnace under a vacuum environment, heating the quartz boat to 550 ℃ at the heating rate of 5 ℃/min, calcining the quartz boat for 3 hours, and naturally cooling the quartz boat to room temperature after the calcination is finished to obtain the porous carbon nitride.
The nitrogen adsorption isotherm data of the porous carbon nitride photocatalytic material prepared by the preparation method of this comparative example are shown in table 1.
The time-resolved fluorescence spectrum data of the porous carbon nitride photocatalytic material prepared by the preparation method of the comparative example are shown in table 2.
The graph of the performance of the photocatalytic material prepared in the example for photocatalytic nitrogen reduction at full light is shown in fig. 3. The specific ammonia yield was: 22.32. + -. 0.43. mu. mol g -1 cat h -1 。
According to the bandgap diagram of the material shown in fig. 4, the bandgap of the photocatalytic material prepared in this embodiment is calculated from DRS data as follows: 3.03 eV. When the light with energy larger than the band gap irradiates the catalyst, the electrons are excited and form photon-generated carriers to participate in the reaction. The porous structure exposes a large number of active centers. In addition, after the Fe monoatomic group is introduced, redistributed electrons and band gaps are narrowed, so that the material can more easily obtain visible light, the recombination of photogenerated electrons and holes is inhibited, and the PCNRR activity is improved. In the presence of Fe, nitrogen gas is converted from physisorption to chemisorption and reduced to NH3 by the association-alternate pathway.
From fig. 7, we can see that comparative example 2 is more susceptible to association remote (digital) routes.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
- A preparation method of the Fe monatomic supported porous carbon nitride photocatalytic material is characterized by comprising the following steps:step 1, putting 1-4 parts by weight of nano Fe particles, 500-1500 parts by weight of dicyandiamide and 500-1500 parts by weight of ammonium chloride into a mortar, grinding in a glove box and uniformly mixing to form a mixture;and 2, transferring the mixture into a quartz boat, placing the quartz boat in a tubular muffle furnace, calcining for 2-6 hours in a vacuum environment at the temperature of 300-600 ℃, and naturally cooling to room temperature after calcining to obtain the Fe monatomic load porous carbon nitride photocatalytic material.
- 2. The production method according to claim 1,the temperature rise rate of the tubular muffle furnace is 5 ℃/min.
- 3. The production method according to claim 1,the Fe particles are Fe particles with the diameter of 50 nm.
- 4. The production method according to claim 1,the mass ratio of the dicyandiamide to the ammonium chloride is 1: 1.
- 5. The production method according to claim 1,the mass of the nano Fe particles is 10-40 mg, the mass of the dicyandiamide is 5-15 g, and the mass of the dicyandiamide is 5-15 g.
- 6. The production method according to claim 5,the mass of the nano Fe particles is 30mg, the mass of the dicyandiamide is 10g, and the mass of the dicyandiamide is 10 g.
- 7. The production method according to claim 1,the temperature during the calcination was 550 ℃.
- The Fe monatomic-supported porous carbon nitride photocatalytic material is characterized by being prepared by the preparation method of any one of claims 1 to 7, being a porous material, and having a response wavelength of 390nm to 780 nm.
- 9. The Fe monatomic-supported porous carbon nitride photocatalytic material according to claim 8, characterized in that,the response wavelength of the Fe monatomic load porous carbon nitride photocatalytic material is 395-620 nm when ammonia is synthesized by photocatalytic nitrogen reduction, and the bandwidth of the Fe monatomic load porous carbon nitride photocatalytic material is 2.95-3.02 eV;fe is connected to the porous carbon nitride in a Fe-N4 coordinated manner, and the Fe-N1 bond length isFe-N2 has a bond length of
Fe-N3 has a bond length of
Fe-N4 has a bond length of
The photocatalytic nitrogen reduction path of the Fe monatomic supported porous carbon nitride photocatalytic material is an associated alternate path. - Use of a Fe monatomic-supported porous carbon nitride photocatalytic material in the photocatalytic reduction of nitrogen to ammonia, said photocatalytic material being the photocatalytic material in claim 8 or 9.
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