Monatomic iron / triazole-graphyne@non-woven fabric composite material and preparation method thereof

Abstract

The application provides a single-atom iron / triazographite@non-woven fabric composite material and a preparation method thereof. Single-atom iron in the single-atom iron / triazographite@non-woven fabric composite material is anchored on a triazographite@non-woven fabric carrier, and the valence of the single-atom iron is +3. The single-atom iron / triazographite@non-woven fabric composite material can be used as a whole catalyst to realize high-efficiency catalytic performance and automatic loading.

Description

Technical Field

[0001] This invention relates to the field of catalyst materials technology, and in particular to a single-atom iron / trinitrogen graphdiyne@nonwoven fabric composite material and its preparation method. Background Technology

[0002] Single-atom catalysts offer unique advantages over traditional nanocatalysts. Because single-atom catalysts have a single atom as the active center, they possess more active sites compared to nanocatalysts, while avoiding clustering effects and thus enhancing catalytic activity. Single-atom catalysts exhibit highly uniformly dispersed active sites, and different reactants display varying adsorption and catalytic capacities on the catalyst surface, enabling selective catalysis of specific reactants. Furthermore, single-atom catalysts can fully utilize the activity of catalyst atoms, achieving near 100% atom utilization, thereby reducing catalyst preparation costs.

[0003] Monolithic catalysts refer to catalysts in which the catalytically active components are completely supported on a monolithic carrier. Compared with powder, granular, and extruded catalysts, monolithic catalysts have significant advantages such as ease of handling and separation, and good reproducibility. In terms of heat transfer, the porous structure of monolithic catalysts facilitates rapid radial heat transfer. Regarding mass transfer, monolithic catalysts can uniformly disperse the catalytically active components on the surface, shortening the mass diffusion path from reactants to the active centers. In terms of momentum transfer, at the same bed height and space velocity, monolithic catalysts exhibit a smaller pressure drop than traditional granular catalysts.

[0004] Graphdiyne possesses an easily tunable electronic structure. Compared to the sp² hybrid carbon of traditional graphene and carbon nanotubes, the unique sp² hybrid carbon in graphdiyne can serve as anchoring sites for metal single atoms. Compared to graphdiyne, trinitrogen graphdiyne, by introducing nitrogen atoms, generates numerous heteroatom defects and active sites. However, trinitrogen graphdiyne powder is relatively dense, often resulting in significant pressure drops during industrial production, limiting its large-scale application. Therefore, obtaining novel monolithic trinitrogen graphdiyne catalysts with high catalytic performance remains a significant technological challenge. Summary of the Invention

[0005] The purpose of this invention is to provide a single-atom iron / trinitrogen graphdiyne@nonwoven fabric composite material and its preparation method, thereby solving the technical problem of how to obtain a new monolithic catalyst with good mechanical stability in the prior art.

[0006] To solve the above technical problems, the present invention provides a single-atom iron / triazine graphdiyne@nonwoven fabric composite material, wherein the single-atom iron is anchored on the triazine graphdiyne@nonwoven fabric carrier, and the single-atom iron has a valence state of +3.

[0007] Preferably, the triazine graphdiyne@nonwoven carrier includes a triazine graphdiyne layer and a nonwoven carrier layer, with a portion of the triazine graphdiyne layer located on the upper surface of the nonwoven carrier layer and another portion of the triazine graphdiyne layer embedded in the nonwoven carrier layer; single-atom iron is anchored at the yne bond sites of the triazine graphdiyne layer and at the defects of the triazine graphdiyne layer.

[0008] Preferably, the nonwoven carrier layer includes any one of nylon fabric or linen fabric.

[0009] Preferably, the nitrogen doping configuration of the trinitrogen graphdiyne layer is any one of pyridine nitrogen, imine nitrogen, pyrrole nitrogen, amino nitrogen, nitrile nitrogen, and graphitic nitrogen.

[0010] Accordingly, the present invention also provides a method for preparing a single-atom iron / trinitrogen graphdiyne@nonwoven composite material as described in any of the above claims, comprising the following steps:

[0011] S10, copper salt solution is immersed in nonwoven fabric roll to obtain nonwoven fabric carrier;

[0012] S20, the non-woven fabric carrier is impregnated in the first solution tank of the catalyst automated loading device to obtain triazine graphdiyne@non-woven fabric carrier, the first solution tank including hexaazanaphthalene solution;

[0013] S30, a single-atom iron / triazine graphdiyne@nonwoven fabric carrier is impregnated in a second solution tank in an automated catalyst loading device to obtain a single-atom iron / triazine graphdiyne@nonwoven fabric composite material, wherein the second solution tank includes a ferrous salt chloroform solution.

[0014] Preferably, in step S10, the copper salt solution is copper sulfate pentahydrate, and the soaking time is 30 min to 60 min; in step S20, the solution temperature in the first solution tank is greater than 0℃ and ≤300℃.

[0015] Preferably, the automated catalyst loading device also includes a base, a metal plate, an unwinding unit, and a winding unit;

[0016] The bottom of the unwinding unit, the bottom of the first solution pool, the bottom of the second solution pool, and the bottom of the winding unit are all threadedly connected to the base, and the side of the unwinding unit and the side of the winding unit are all threadedly connected to the metal plate.

[0017] Preferably, the winding unit includes a first metal frame, on which a first pulley assembly and a second pulley assembly spaced apart are fixedly mounted, and a first metal crossbar passes through the first pulley assembly and the second pulley assembly respectively.

[0018] Preferably, a servo motor is also fixed on the first metal frame, and the servo motor is used to drive the first metal crossbar to rotate; the speed of the servo motor is greater than 0 and ≤300 rad / min.

[0019] Preferably, in step S30, the ferrous salt in the ferrous salt chloroform solution is one or more of ferrous chloride, ferrous sulfate, and ferrous bromide.

[0020] The beneficial effects of this invention are as follows: Unlike the prior art, this invention provides a single-atom iron / triazine graphdiyne@nonwoven fabric composite material and its preparation method. In the single-atom iron / triazine graphdiyne@nonwoven fabric composite material, the single-atom iron is anchored on the triazine graphdiyne@nonwoven fabric carrier, and the single-atom iron has a valence state of +3. The above-mentioned single-atom iron / triazine graphdiyne@nonwoven fabric composite material can be used as an integral catalyst to achieve high catalytic performance and can also achieve automated loading. Attached Figure Description

[0021] Figure 1 This is a schematic diagram illustrating the reaction principle of the preparation method of the single-atom iron / trinitrogen graphdiyne@nonwoven fabric composite material in a specific embodiment of the present invention;

[0022] Figure 2 This is a flowchart illustrating the preparation method of the single-atom iron / trinitrogen graphdiyne@nonwoven fabric composite material in a specific embodiment of the present invention;

[0023] Figure 3 This is a schematic diagram of the automatic catalyst loading device used in the embodiments of the present invention;

[0024] Figure 4 A schematic diagram of the unwinding unit of the automatic catalyst loading device provided in an embodiment of the present invention;

[0025] Figure 5 A schematic diagram of the winding unit of the automatic catalyst loading device provided in an embodiment of the present invention;

[0026] Figure 6 This is a scanning electron microscope image of a blank nonwoven fabric provided in Embodiment 1 of the present invention;

[0027] Figure 7 This is a high-magnification scanning electron microscope image of the trinitrogen-graphetry@nonwoven carrier composite material provided in Example 1 of the present invention;

[0028] Figure 8 The X-ray diffraction pattern of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material provided in Example 1 of the present invention;

[0029] Figure 9 The Raman spectrum of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material provided in Example 1 of the present invention;

[0030] Figure 10 The mechanical stability diagram of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material provided in Example 1 of the present invention;

[0031] Figure 11 The graph shows the propylene degradation stability of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material provided in Example 1 of the present invention. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0034] The present invention first provides a single-atom iron / triazine graphdiyne@nonwoven fabric composite material, wherein the single-atom iron is anchored on the triazine graphdiyne@nonwoven fabric carrier, and the single-atom iron has a valence state of +3.

[0035] Preferably, the triazine graphdiyne@nonwoven carrier includes a triazine graphdiyne layer and a nonwoven carrier layer, with a portion of the triazine graphdiyne layer located on the upper surface of the nonwoven carrier layer and another portion of the triazine graphdiyne layer embedded in the nonwoven carrier layer; single-atom iron is anchored to the yne bond sites of the triazine graphdiyne layer.

[0036] Preferably, the nonwoven carrier layer includes any one of nylon fabric or linen fabric.

[0037] Preferably, the nitrogen-doped configuration of the triazine graphdiyne layer is any one of pyridine nitrogen, imine nitrogen, pyrrole nitrogen, amino nitrogen, nitrile nitrogen, and graphitic nitrogen. Different nitrogen-doped configurations of the above-mentioned triazine graphdiyne layer can be generated by controlling the coupling reaction conditions of hexaazanaphthalene.

[0038] Please see Figure 1 as well as Figure 2 , Figure 1 This is a schematic diagram illustrating the reaction principle of the preparation method of the single-atom iron / trinitrogen graphdiyne@nonwoven fabric composite material in a specific embodiment of the present invention; Figure 2 The flowchart below shows the preparation method of the single-atom iron / triazine graphdiyne@nonwoven fabric composite material in a specific embodiment of the present invention; wherein, the preparation method of the single-atom iron / triazine graphdiyne@nonwoven fabric composite material includes the following steps:

[0039] S10, the copper salt solution is immersed in the nonwoven fabric roll to obtain the nonwoven fabric carrier.

[0040] Specifically, step S10 also includes:

[0041] First, a small amount of copper salt solution is prepared and then immersed in a nonwoven fabric roll to obtain a nonwoven fabric carrier, so that the nonwoven fabric carrier is loaded with copper ions.

[0042] Preferably, the nonwoven fabric roll is soaked in a 0.1 mmol / L copper sulfate solution for 30 min.

[0043] S20, the nonwoven fabric carrier is impregnated in the first solution tank 30 of the catalyst automated loading device to obtain triazine graphdiyne@nonwoven fabric carrier, the first solution tank 30 including hexaazanaphthalene solution.

[0044] Specifically, step S20 also includes:

[0045] First, an automated catalyst loading device is provided, such as... Figures 3 to 5 As shown, Figure 3 This is a schematic diagram of the automatic catalyst loading device used in the embodiments of the present invention. Figure 4 This is a schematic diagram of the unwinding unit according to an embodiment of the present invention. Figure 5 This is a schematic diagram of a winding unit according to a specific embodiment of the present invention; wherein, the automatic catalyst loading device includes a base 10, a metal plate 20, a first solution tank 30, a second solution tank 40, an unwinding unit, and a winding unit;

[0046] The bottom of the unwinding unit, the bottom of the first solution pool 30, the bottom of the second solution pool 40, and the bottom of the winding unit are all threadedly connected to the base 10, and the side of the unwinding unit and the side of the winding unit are all threadedly connected to the metal plate 20.

[0047] Specifically, please refer to Figure 3 as well as Figure 5 The winding unit includes a first metal frame 50, which includes two first support frames 51 that are vertically fixed to the base 10 and are 2m apart. The two first support frames 51 are welded and fixed together by a first metal rod 52, and the top of the two first support frames 51 is welded and fixed together by a second metal rod 53. One end of the second metal rod 53 is also threadedly connected to the metal plate 20.

[0048] Furthermore, a first pulley assembly 54 and a second pulley assembly 55 spaced apart from the first pulley assembly 54 are fixedly installed on the first metal frame 50, and the first metal crossbar 56 passes through the first pulley assembly 54 and the second pulley assembly 55 respectively; a non-woven catalyst roll 57 is also sleeved on the first metal crossbar 56, and the two ends of the non-woven catalyst roll 57 are fixedly connected by a first limiting and correcting device 58.

[0049] The first pulley assembly 54 and the second pulley assembly 55 are each equipped with three pulleys, which are 4cm apart and are fixed by an inverted triangular threaded connection; the length of the first metal crossbar 56 is 2.5m.

[0050] Furthermore, a servo motor 59 is also fixed on the first metal frame 50. The servo motor 59 is used to drive the first metal crossbar 56 to rotate. The rotational speed of the servo motor 59 is greater than 0 and ≤300 rad / min.

[0051] Specifically, please refer to Figure 3 as well as Figure 4 The unwinding unit includes a second metal frame 60, which includes two second support frames 61 that are vertically fixed to the base 10 and are 2m apart. The two second support frames 61 are welded and fixed together by a third metal rod 62, and the top of the two second support frames 61 is welded and fixed together by a fourth metal rod 63. One end of the fourth metal rod 63 is also threadedly connected to the metal plate 20.

[0052] Furthermore, a third pulley assembly 64 and a fourth pulley assembly 65 spaced apart from the third pulley assembly 64 are fixedly installed on the second metal frame 60, and the third pulley assembly 64 and the fourth pulley assembly 65 are respectively passed through the second metal crossbar 66; a blank non-woven fabric roll 67 is also sleeved on the second metal crossbar 66, and the two ends of the blank non-woven fabric roll 67 are fixedly connected by the second limit correction device 68.

[0053] The third pulley assembly 64 and the fourth pulley assembly 65 are each equipped with three pulleys, which are 4cm apart and are fixed by an inverted triangular threaded connection; the second metal crossbar 66 is 2.5m long.

[0054] Specifically, a first solution pool 30 is placed 0.2m vertically from the second metal frame 60, a second solution pool 40 is placed 1.2m vertically from the second metal frame 60, and a first metal frame 50 is placed 2.0m vertically from the second metal frame 60.

[0055] The first solution tank 30 includes a hexaazanaphthalene solution, and the second solution tank 40 includes a ferrous salt chloroform solution, wherein the ferrous salt in the ferrous salt chloroform solution is one or more of ferrous chloride, ferrous sulfate, and ferrous bromide.

[0056] Furthermore, the winding unit also includes a first auxiliary rod 70, the unwinding unit also includes a second auxiliary rod 80, and a limiting rod 90 is installed in both the first solution pool 30 and the second solution pool 40; the first auxiliary rod 70, the second auxiliary rod 80 and the limiting rod 90 are all used to transport the nonwoven fabric roll on the blank nonwoven fabric roll 67 to the nonwoven catalyst roll 57.

[0057] Specifically, step S20 includes:

[0058] A nonwoven fabric carrier is placed on a blank nonwoven fabric roll 67, and a servo motor 59 is activated to immerse the nonwoven fabric carrier on the blank nonwoven fabric roll 67 in the first solution pool 30 to obtain a triazine graphdiyne@nonwoven fabric carrier. The copper ions adsorbed on the nonwoven fabric carrier in the copper salt solution promote a coupling reaction of hexaazanaphthalene on the surface of the nonwoven fabric carrier, ensuring that hexaazanaphthalene forms a triazine graphdiyne@nonwoven fabric carrier on the nonwoven fabric carrier in a manner similar to in-situ growth of graphdiyne. Simultaneously, the copper ions dissolve in the hexaazanaphthalene solution and are not anchored by the triazine graphdiyne@nonwoven fabric carrier. Figure 1 As shown.

[0059] Furthermore, compared to graphyne, trinitrogen graphyne with the introduction of N atoms generates many heteroatom defects and active sites, which is beneficial to improving the catalytic performance of the catalyst.

[0060] Furthermore, in step S10, the copper salt solution is copper sulfate pentahydrate, and the soaking time is 30 min to 60 min; in step S20, the solution temperature in the first solution tank 30 is greater than 0℃ and ≤300℃.

[0061] S30, a single-atom iron / triazine graphdiyne@nonwoven fabric carrier is impregnated in a second solution tank 40 in an automated catalyst loading device to obtain a single-atom iron / triazine graphdiyne@nonwoven fabric composite material, wherein the second solution tank 40 includes a ferrous salt chloroform solution.

[0062] Specifically, step S30 also includes:

[0063] Servo motor 59 continues to operate, causing the triazine graphdiyne@nonwoven fabric carrier, which has been impregnated in the first solution pool 30, to be immersed in the second solution pool 40 to obtain a single-atom iron / triazine graphdiyne@nonwoven fabric composite material. The second solution pool 40 includes a ferrous salt chloroform solution, such as... Figure 1 As shown. The ferrous salt in the ferrous salt chloroform solution is one or more of ferrous chloride, ferrous sulfate, and ferrous bromide. This step, using excess hydrochloric acid, effectively prevents the aggregation of iron ions, helping to anchor monatomic iron atoms at the alkyne bond sites and defects of triazine graphdiyne.

[0064] Preferably, the nonwoven fabric roll passes through the highest and lowest limiting rods 90 in the first solution pool 30 in a staggered manner to obtain a triazine graphdiyne@nonwoven fabric carrier; the triazine graphdiyne@nonwoven fabric carrier passes through the second solution pool 40 via an automated catalyst loading device to obtain a single-atom iron / triazine graphdiyne@nonwoven fabric composite material, and the rotation speed of the servo motor 59 is preferably 0.1 rad / min.

[0065] This invention can be carried out under normal pressure and nitrogen atmosphere, with mild reaction conditions, and can be prepared in large quantities and automatically; Figure 1 This demonstrates the adsorption of Cu on the nonwoven fabric carrier in copper sulfate solution. 2+ This process promotes the coupling reaction of hexaazanaphthalene on the surface of the nonwoven fabric carrier, ensuring the in-situ growth of triazagraphyne formed after the hexaazanaphthalene coupling reaction on the nonwoven fabric to form triazagraphyne@nonwoven fabric carrier. At this time, all copper ions are dissolved in the hexaazanaphthalene solution and will not be loaded on the triazagraphyne@nonwoven fabric carrier. Subsequently, single-atom iron is anchored on the triazagraphyne@nonwoven fabric carrier, forming a single-atom iron / triazagraphyne@nonwoven fabric composite material. In addition, this invention prevents the agglomeration of iron by using excess hydrochloric acid, which helps to anchor the single-atom iron.

[0066] The technical solution of this application will now be described in conjunction with specific embodiments.

[0067] Example 1:

[0068] This embodiment 1 presents a single-atom iron / trinitrogen graphdiyne@nonwoven fabric carrier composite material, which is prepared by the following steps:

[0069] First, 0.8 mmol of copper sulfate pentahydrate was dissolved in 80 L of water and immersed in the nonwoven fabric roll for 60 min. Then, the resulting nonwoven fabric was placed on the second metal crossbar 66 of the unwinding unit, and the nonwoven fabric was pulled out and fixed on the first metal crossbar 56 of the winding unit after passing through the first solution pool 30 and the second solution pool 40. Then, the servo motor 59 of the winding unit was set to a speed of 0.1 rad / min, and the molar ratio of hexaazanaphthalene in the first solution pool 30 to ferrous ions in the second solution pool 40 was set to 1:1. At this time, hexaazanaphthalene under the catalysis of copper ions underwent a coupling reaction on the surface of the nonwoven fabric carrier.

[0070] In Example 1, the triazine graphdiyne@nonwoven fabric carrier, driven by an automatic catalyst loading device, passed through a first solution tank 30 and a second solution tank 40, and was finally washed and dried to obtain a single-atom iron / triazine graphdiyne@nonwoven fabric carrier composite material. The iron in this material exists in the form of trivalent iron, with an iron loading of approximately 5 wt.%.

[0071] Specifically, please refer to Figures 6 to 11 , Figure 6 This is a scanning electron microscope image of a blank nonwoven fabric from Embodiment 1 of the present invention; Figure 7 This is a high-magnification scanning electron microscope image of the trinitrogen-graphoxydiene@nonwoven fabric carrier composite material of Example 1 of the present invention; Figure 8 The X-ray diffraction pattern of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material provided in Example 1 of the present invention; Figure 9 The Raman spectrum of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material provided in Example 1 of the present invention; Figure 10The mechanical stability diagram of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material provided in Example 1 of the present invention; Figure 11 The graph shows the propylene degradation stability of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material provided in Example 1 of the present invention.

[0072] The characterization results of the single-atom iron / trinitrogen graphdiyne@nonwoven fabric carrier composite material prepared in Example 1 are as follows: Figure 6-11 As shown in the figure, the characterization results demonstrate the successful preparation of the single-atom iron / trinitrogen graphylene@nonwoven carrier composite material.

[0073] Specifically, by Figure 6 It can be seen that the surface of blank nonwoven fabric is relatively smooth; from Figure 7 It can be seen that the carrier surface of the trinitrogen-graphyne@nonwoven carrier composite material has a nano-wall structure.

[0074] Specifically, the mechanical stability of the single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material prepared in Example 1 was evaluated under ultrasonic conditions of 50 kHz and 150 kW. Figure 10 It can be seen that after 60 minutes, the mass loss of the single-atom iron / triazine graphdiyne@nonwoven carrier composite material is only 5%, which proves that the single-atom iron / triazine graphdiyne@nonwoven carrier composite material has good mechanical stability.

[0075] Specifically, the catalytic activity of the single-atom iron / trinitrogen graphdiyne@nonwoven fabric carrier composite material prepared in Example 1 was evaluated under the conditions of 1% volume fraction C3H6, 5% volume fraction O2, and a N2 balance gas flow rate of 600 ml / min. Figure 11 It can be seen that the single-atom iron / trinitrogen graphdiyne@nonwoven fabric carrier composite material has excellent stability in propylene catalytic oxidation (conversion rate is guaranteed to be around 60%).

[0076] Example 2:

[0077] This embodiment proposes a single-atom iron / trinitrogen graphdiyne@nonwoven fabric carrier composite material, which is prepared by the following steps:

[0078] First, 0.8 mmol of copper sulfate pentahydrate was dissolved in 80 L of water and immersed in a nonwoven fabric roll for 30 min. Then, the resulting nonwoven fabric was placed on the second metal crossbar 66 of the unwinding unit, pulled out, and passed through the first solution tank 30 and the second solution tank 40 before being fixed on the first metal crossbar 56 of the winding unit. Next, the servo motor 59 of the winding unit was set to a speed of 0.5 rad / min, and the molar ratio of hexaazanaphthalene in the first solution tank 30 to ferrous ions in the second solution tank 40 was set to 2:1. At this point, hexaazanaphthalene underwent a coupling reaction on the surface of the nonwoven fabric carrier under the catalysis of copper ions. The blank nonwoven fabric carrier passed through the first solution tank 30 and the second solution tank 40 under the drive of an automatic catalyst loading device. Finally, it was washed with water and dried to obtain a single-atom iron / triazine graphdiyne@nonwoven fabric carrier composite material. The iron in this material exists in the form of trivalent iron, with an iron loading of approximately 8 wt.%.

[0079] Example 3:

[0080] This embodiment 3 presents a single-atom iron / trinitrogen graphdiyne@nonwoven carrier composite material, which is prepared by the following steps:

[0081] First, 50 mmol of copper sulfate pentahydrate was dissolved in 80 L of water and immersed in a nonwoven fabric roll for 10 min. Then, the resulting nonwoven fabric was placed on the second metal crossbar 66 of the unwinding unit, pulled out, and passed through the first solution tank 30 and the second solution tank 40 before being fixed on the first metal crossbar 56 of the winding unit. Next, the servo motor 59 of the winding unit was set to a speed of 1 rad / min, and the molar ratio of hexaazanaphthalene in the first solution tank 30 to ferrous ions in the second solution tank 40 was set to 1.5:1. At this point, hexaazanaphthalene underwent a coupling reaction on the surface of the nonwoven fabric carrier under the catalysis of copper ions. The blank nonwoven fabric carrier was driven by an automatic catalyst loading device, passing through the first solution tank 30 and the second solution tank 40. Finally, it was washed with water and dried to obtain a single-atom iron / triazine graphdiyne@nonwoven fabric carrier composite material. The iron in this material exists in the form of trivalent iron, with an iron loading of approximately 4 wt.%.

[0082] In summary, unlike existing technologies, this invention provides a single-atom iron / triazine graphdiyne@nonwoven fabric composite material and its preparation method. In the single-atom iron / triazine graphdiyne@nonwoven fabric composite material, the single-atom iron is anchored on the triazine graphdiyne@nonwoven fabric carrier, and the single-atom iron has a valence state of +3. The above-mentioned single-atom iron / triazine graphdiyne@nonwoven fabric composite material can be used as an integral catalyst to achieve high catalytic performance and can also achieve automated loading.

[0083] It should be noted that all the above embodiments belong to the same inventive concept, and the descriptions of each embodiment have different focuses. Where the description in a particular embodiment is not detailed, please refer to the description in other embodiments.

[0084] The above embodiments merely illustrate implementation methods of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing a single-atom iron / trinitrogen graphdiyne@nonwoven fabric composite material, characterized in that, Includes the following steps: S10, copper salt solution is immersed in nonwoven fabric roll to obtain nonwoven fabric carrier; S20, the nonwoven fabric carrier is immersed in the first solution tank in the catalyst automated loading device to obtain triazine graphdiyne@nonwoven fabric carrier, the first solution tank including hexaazanaphthalene solution; S30, the triazine graphdiyne@nonwoven fabric carrier is impregnated in the second solution tank of the catalyst automated loading device to obtain a single-atom iron / triazine graphdiyne@nonwoven fabric composite material, the second solution tank including ferrous salt chloroform solution; the single-atom iron of the single-atom iron / triazine graphdiyne@nonwoven fabric composite material is anchored on the triazine graphdiyne@nonwoven fabric carrier, and the single-atom iron has a valence state of +3.

2. The method for preparing the single-atom iron / trinitrogen graphdiyne@nonwoven composite material according to claim 1, characterized in that, In step S10, the copper salt solution is copper sulfate pentahydrate, and the soaking time is 30 min to 60 min; in step S20, the solution temperature in the first solution tank is greater than 0℃ and ≤300℃.

3. The method for preparing the single-atom iron / trinitrogen graphdiyne@nonwoven composite material according to claim 1, characterized in that, The automated catalyst loading device also includes a base, a metal plate, an unwinding unit, and a winding unit; The bottom of the unwinding unit, the bottom of the first solution pool, the bottom of the second solution pool, and the bottom of the winding unit are all threadedly connected to the base, and the side of the unwinding unit and the side of the winding unit are all threadedly connected to the metal plate.

4. The method for preparing the single-atom iron / trinitrogen graphdiyne@nonwoven composite material according to claim 3, characterized in that, The winding unit includes a first metal frame, on which a first pulley assembly and a second pulley assembly spaced apart are fixedly mounted, and a first metal crossbar passes through the first pulley assembly and the second pulley assembly respectively.

5. The method for preparing the single-atom iron / trinitrogen graphdiyne@nonwoven composite material according to claim 4, characterized in that, A servo motor is also fixed on the first metal frame, and the servo motor is used to drive the first metal crossbar to rotate; the rotational speed of the servo motor is greater than 0 and ≤300 rad / min.

6. The method for preparing the single-atom iron / trinitrogen graphdiyne@nonwoven composite material according to claim 1, characterized in that, In step S30, the ferrous salt in the ferrous salt chloroform solution is one or more of ferrous chloride, ferrous sulfate, and ferrous bromide.

7. The method for preparing the single-atom iron / trinitrogen graphdiyne@nonwoven composite material according to claim 1, characterized in that, The triazine graphdiyne@nonwoven carrier includes a triazine graphdiyne layer and a nonwoven carrier layer. A portion of the triazine graphdiyne layer is located on the upper surface of the nonwoven carrier layer, and another portion of the triazine graphdiyne layer is embedded in the nonwoven carrier layer. The monatomic iron is anchored at the alkyne bond sites of the triazine graphdiyne layer and at the defects of the triazine graphdiyne layer.

8. The method for preparing the single-atom iron / trinitrogen graphdiyne@nonwoven composite material according to claim 7, characterized in that, The nonwoven carrier layer includes either nylon or linen.

9. The method for preparing the single-atom iron / trinitrogen graphdiyne@nonwoven composite material according to claim 7, characterized in that, The nitrogen-doped configuration of the trinitrogen graphdiyne layer is any one of pyridine nitrogen, imine nitrogen, pyrrole nitrogen, amino nitrogen, nitrile nitrogen, and graphitic nitrogen.

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