CN111013579A - Limited-area carbon material loaded with palladium single atom or palladium nano-particles and preparation method thereof - Google Patents

Limited-area carbon material loaded with palladium single atom or palladium nano-particles and preparation method thereof Download PDF

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CN111013579A
CN111013579A CN201911139648.6A CN201911139648A CN111013579A CN 111013579 A CN111013579 A CN 111013579A CN 201911139648 A CN201911139648 A CN 201911139648A CN 111013579 A CN111013579 A CN 111013579A
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palladium
graphene oxide
carbon
amorphous carbon
particles
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CN111013579B (en
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王帅
殷杰
徐睿
陈欣
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Zhuhai Fudan Innovation Research Institute
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract

The invention belongs to the technical field of advanced nano materials, and particularly relates to a limited-area carbon material loaded with palladium single atoms or palladium nano particles and a preparation method thereof. The method comprises the step of adsorbing a cucurbituril which is a supermolecule compound with a positive port potential on the surface of Graphene Oxide (GO) by utilizing the characteristic that the Zeta potential of the Graphene Oxide (GO) is negative. The cucurbituril is a special super-molecular Cavity (CB) which is tightly coated on the surface of GO and then calcined at high temperature, so that the CB forms N-doped amorphous carbon with a special aperture and is firmly adsorbed on a graphene sheet layer; meanwhile, GO can be cracked by oxygen-containing groups after high-temperature calcination to form rGO with good conductivity. A limited interface is formed between the two, and the palladium nano-particles and the palladium single atoms are successfully loaded under the low-temperature condition. The material prepared by the invention is applied to the fields of electrochemical catalysis, organic catalysis, biosensors, supercapacitors, lithium ion batteries and the like, and has good performance.

Description

Limited-area carbon material loaded with palladium single atom or palladium nano-particles and preparation method thereof
Technical Field
The invention belongs to the technical field of advanced nano materials, and particularly relates to a limited-area carbon material loaded with palladium single atoms or palladium nano particles and a preparation method thereof.
Background
Graphene (GO) can be understood as a single or few layer of graphite, sp carbon channels2The hybridized 6-edge repeating units are linked to form the two-dimensional nano material which has a conjugated structure. Graphene can be said to be "gold" hidden in the carbonaceous surface, which was discovered by geom et al, a student at manchester university, 2004. The unprecedented emergence of graphene has led scientists to pay unprecedented attention. Due to the unique structure of the graphene material, the graphene material has excellent conductivity, ultrahigh specific surface area, excellent mechanical property and carrier mobility. Due to the unique two-dimensional structure, the graphene has the performance similar to that of a semiconductor, so that the graphene has a huge application prospect in the aspects of energy storage, biosensing, energy conversion, electrochemical catalysis and the like.
The term confinement is usually used in the field of catalysis, but in a broad sense, a confinement is more like a spatial confinement, such as a ball cage, a ring cage, etc. A constrained interface is a progression of constrained space that not only narrows the space to a certain extent, but also exhibits two distinct properties at the interface. The well-known heterojunction is a special phenomenon formed by the interface between an n-type semiconductor and a p-type semiconductor. In the limited space, because the space for the particles to move is limited and different interfaces can mutually influence each other, a special electronic system is formed, so that a magic effect can generally occur in the limited space.
The concept of single atom catalysis was a completely new concept first proposed by the academy of tension at the university of Qinghua. Compared with larger nanoparticles, the monatomic catalyst is said to have 100% atomic utilization and to take advantage of the atomic orbitals to the greatest extent, thus having unexpected catalytic activity.
At present, many methods for preparing monoatomic compounds have been reported. Generally, it is required to undergo a series of high-temperature reduction processes. At higher temperatures, most metals tend to agglomerate, so the spacing between metal atoms is usually elongated to avoid agglomeration at high temperatures. This method has a disadvantage in that it greatly limits the monoatomic content in the material due to the enlarged interatomic distance. Therefore, it is necessary to develop a simple and direct method, or a method capable of directly preparing a single atom at a low temperature.
Nanoparticles, while not as reactive as single atoms, have found wide application in composites. At present, the preparation research of nano particles mainly focuses on forming nano particles with uniform structure size and designing the nano particles with controllable size according to application requirements.
Disclosure of Invention
The invention aims to provide a domain-limited carbon material loaded with palladium monoatomic atoms or palladium nanoparticles and a preparation method thereof.
Aiming at the technical problems, the invention deeply researches the confinement effect between the amorphous carbon containing special holes and the high-crystalline reduced graphene, explores the influence of the concentration on palladium monoatomic ions or palladium nanoparticles, and provides a method for directly preparing the palladium monoatomic ions or the palladium nanoparticles at low temperature in a confinement interface.
The invention provides a limited-domain carbon material of a load palladium single atom or a palladium nano particle, which is characterized in that a layer of compact amorphous carbon is paved on the surface of graphene to form a limited-domain interface; wherein the amorphous carbon is obtained by in-situ calcination of cucurbituril with a material with a special cavity, has a special aperture reserved by the original cavity of the cucurbituril, and contains a large amount of N elements for anchoring single atoms, and the content of the N elements is 1-15%; the palladium atom or the palladium nano particle can be directly reduced in a confinement interface at 0-20 ℃, the load capacity of palladium is 0.1-10%, and is determined by the concentration of initial reaction liquid, reaction temperature and reaction time.
The invention provides a preparation method of a limited-area carbon material loaded with palladium single atoms or palladium nano particles, which comprises the following specific steps:
preparing a confinement interface, which comprises the following steps:
(1) uniformly mixing cucurbiturils with a Graphene Oxide (GO) aqueous solution according to a certain molar ratio, and then fully stirring to coat the cucurbiturils on the GO with a lamellar shape through electrostatic action (the mixed solution obviously changes color (is gray brown), which indicates that the coating is successful, and the stirring time is generally 1-24 h);
(2) fully washing the composite material with GO coated with cucurbituril by acetone and deionized water in sequence; freeze-drying the composite material to avoid structural collapse; in particular, in the case of a large molar ratio of cucurbiturils, carefully picking out a white part of the freeze-dried composite material, wherein the part is the cucurbituril which is not loaded on GO;
(3) and (3) placing the prepared composite material (solid) in a quartz crucible, and calcining in a tube furnace under the protection of inert gas to obtain the composite carbon with a limited domain interface, namely the composite carbon material of reduced graphene oxide @ amorphous carbon.
The calcining process comprises the following steps: before calcination, it is ensured that the air in the tube furnace has been completely removed and that an inert gas (for example N) is maintained2Or Ar) gas flow of 100-200 cc/s; during calcination, the calcination temperature in the first stage is 300-500 ℃, the heating rate is 1-5 ℃/min, and the holding time is 0.5-2 h, wherein the stage is to reserve the special cavity aperture of the cucurbituril; the calcination temperature of the second stage is 700-The section is to break the oxygen-containing group of the graphene oxide to obtain reduced graphene oxide and increase the conductivity of the amorphous carbon; after calcination, naturally cooling, and mixing the obtained composite material with acetone: water: fully washing with a washing solution with ethanol being 1:1:1 to remove oily byproducts such as high-grade saturated alkane and the like generated in the carbonization process; and then washing with ultrapure water and freeze-drying to obtain the material, namely the reduced graphene oxide @ amorphous carbon composite carbon material.
(II) loading of monatomic palladium and nanoparticles:
the method comprises the following specific steps of loading the monoatomic material:
(1) fully grinding the reduced graphene oxide @ amorphous carbon prepared by the raw material ratio of (1.5-2): 1, mixing the ground reduced graphene oxide @ amorphous carbon into ice water, fully stirring the mixture and keeping ice bath; then 0.1-4 mL of K with the concentration of 0.1-1 mol/L is dropwise added2PdCl4Adding water solution, and increasing rotation speed to mix thoroughly; the reaction time is 1-5 h;
(2) repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and then carrying out reduced pressure suction filtration and drying to obtain the palladium monoatomic-supported restricted carbon material;
the load of palladium single atom is 0.1-1%.
The method for loading the palladium nano-particles comprises the following specific steps:
(1) fully grinding the reduced graphene oxide @ amorphous carbon prepared by the raw material ratio of (0.5-2): 1, mixing the ground reduced graphene oxide @ amorphous carbon into ice water, fully stirring the mixture and keeping ice bath; then dropwise adding 1-4 mL of K with the concentration of 1mol/L2PdCl4Adding water solution, and increasing rotation speed to mix thoroughly; the reaction time is 4-5 h;
(2) repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and then carrying out reduced pressure suction filtration and drying to obtain the limited-area carbon material loaded with the palladium nanoparticles;
the loading of the palladium nano-particles is 1-10%.
In the invention, the cucurbituril is selected from CB [6] or CB [8] or a mixture of the two, which are insoluble in water.
According to the invention, the supermolecule special cavity of the cucurbituril and the characteristics of the port electropositivity of the cucurbituril are utilized to spontaneously coat the cucurbituril on the GO with the Zeta electronegativity, and the port coating mode enables a porous structure formed by the special cavity to be opened; in addition, by utilizing a one-step reduction method, under the high-temperature condition of filling inert atmosphere, the cucurbituril is calcined into amorphous carbon, meanwhile, oxygen-containing groups in GO are thermally broken, and finally, the composite material coated by the amorphous carbon with special pores and rGO and having a limited interface is successfully prepared.
The invention obtains a confined structure formed by porous amorphous carbon and crystalline carbon with special aperture, so that monoatomic and nano-particles can directly and spontaneously form a stable structure in a confined interface under a low-temperature condition; the main reason for this is that a more stable anchor site is provided for the reduction of palladium atoms in the confinement interface, so that the palladium reduction has a lower work function, and thus palladium can spontaneously aggregate in the confinement interface formed by amorphous carbon and crystalline carbon.
The special composite material prepared by the invention is loaded with a large amount of palladium monoatomic atoms or palladium nanoparticles with multiple active sites, has wide application prospect, and can be directly applied to the fields of electrochemical catalysis, organic catalysis, biosensors, supercapacitors, lithium ion batteries and the like.
The invention provides a brand new thought for the preparation of the monoatomic particles, and can prepare more monoatomic/nanoparticle-loaded composite carbon materials with high performance by utilizing the stable effect of the limited-area interface.
Drawings
Fig. 1 is a transmission electron micrograph of the confined carbon material supporting palladium nanoparticles in example 1.
FIG. 2 is a transmission electron micrograph of the confined carbon material supporting palladium nanoparticles of example 1 at high magnification. Palladium nanoparticles are clearly observed in the material.
FIG. 3 is a TEM image of the surface of rGO coated with amorphous carbon in example 2.
FIG. 4 is a transmission electron micrograph (magnified) of the amorphous carbon coated on the surface of rGO in example 2. No significant agglomerated particles were present in the material.
FIG. 5 is STEM-ADF testing of amorphous carbon coated rGO in example 3.
FIG. 6 is a solution of uncatalyzed p-nitrobenzene. The solution was visibly yellow in color.
FIG. 7 is a reaction diagram of the material of example 3 if used as a catalyst. The reaction liquid faded rapidly in color.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a method for preparing palladium monoatomic atoms and nano-particles thereof in a limited domain interface, which directly avoids a high-temperature reduction process which is easy to cause agglomeration of metal nano-particles. According to the method, cucurbituril is used as a coating material and directly coated on GO to form a special coating structure, cucurbituril is used as a carbon source of amorphous carbon, GO is reduced into rGO at a high temperature and used as a carbon source of crystalline carbon, and the special structure with amorphous carbon-coated crystalline carbon is directly formed in an inert atmosphere through a one-step method. Wherein the amorphous carbon with the special structure has a special aperture reserved by a calcined cucurbituril cavity. Then, the K is directly added at the interface by ice bath by utilizing the characteristic of lower work function of metal ions in a limited domain interface2PdCl4Reducing to palladium single atoms and palladium nano particles with different particle diameters.
The invention provides a method for preparing palladium monoatomic atoms and nano-particles thereof in a limited domain interface, which specifically comprises the following steps:
(1) weighing uniformly mixed solution of CB 6 or CB 8 or a mixture of the two with different molar ratios and GO aqueous solution, wherein the molar ratios are respectively 0.5:1, 0.75:1, 1:1, 1.25:1, 1.5:1, 1.75:1 and 2:1, fully stirring the mixture to enable cucurbiturils to be coated on GO with a lamellar shape through electrostatic interaction, and the required stirring time is 1-24 h;
(2) fully washing the coated cucurbituril and GO composite material by acetone and then deionized water, and performing freeze drying treatment;
(3) the prepared gray-brown solid was placed in a quartz crucible to calcine into composite carbon containing a confined interface. Before calcination, it is ensured that the air in the tube furnace has been completely removed and that an inert gas (in particular, N) is maintained2Or Ar) gas flow of 100-200 cc/s; the calcination temperature in the first stage is 300-500 ℃, the heating rate is 1-5 ℃/min, and the holding time is 0.5-2 h, wherein the stage is to reserve the special cavity aperture of the cucurbituril; the calcination temperature of the second stage is 700-; after natural cooling, the obtained composite material is prepared by using acetone: water: and (3) fully washing with a washing solution with ethanol ratio of 1:1:1, washing with ultrapure water, and freeze-drying to obtain the material, namely the reduced graphene oxide @ amorphous carbon composite carbon material.
In the present invention, the use of CB 6, CB 8 or a mixture of both has a certain effect on the final properties; in addition, in the process of coating GO by cucurbiturils, the molar ratio of the cucurbiturils and the GO needs to be strictly controlled, the molar ratio of the cucurbiturils and the GO directly determines the quality of carbon formation of a limited interface, the subsequent drying treatment needs to be freeze-drying, and if the drying is carried out at a constant temperature of more than 60 ℃, the structure can be damaged. The calcining process needs to be carried out in two stages, and the calcining at 300-500 ℃ aims at keeping the special aperture of the cucurbituril cavity; the calcination at 700-900 ℃ is to improve the conductivity of the composite material and to break the oxygen-containing groups in GO to form rGO.
The preparation steps of the monatomic palladium are as follows:
(1) fully grinding the amorphous carbon-coated reduced graphene oxide composite material prepared by the raw material ratio of 1.5:1, 1.75:1 and 2:1, mixing the ground amorphous carbon-coated reduced graphene oxide composite material into ice water, fully stirring and keeping ice bath; then 0.1-4 mL of K with the concentration of 0.1-1 mol/L is dropwise added2PdCl4Mixing the aqueous solution thoroughly;
(2) and repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and drying after reduced pressure suction filtration to obtain the palladium monoatomic-supported restricted carbon material. In particular, the loading of palladium monoatomic atoms is 0.1 to 1%.
In the process of preparing the monatomic palladium, the monatomic supported palladium can be obtained more efficiently only by loading the monatomic supported palladium on the composite carbon material prepared according to the raw material ratio; otherwise, the palladium nano-particles are easily formed because the content of the amorphous carbon in the formed composite material is too low. In addition, K2PdCl4Control of the concentration of the aqueous solution is also critical.
The preparation steps of the palladium nano-particles are as follows:
(1) fully grinding reduced graphene oxide @ amorphous carbon prepared by the raw material ratio of 0.5:1, 0.75:1, 1:1, 1.25:1, 1.5:1, 1.75:1 and 2:1, mixing the ground reduced graphene oxide @ amorphous carbon into ice water, fully stirring and keeping ice bath; then 1-4 mL of K with the concentration of 1mol/L is dropwise added2PdCl4Adding water solution, and increasing rotation speed to mix thoroughly;
(2) and repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and drying after reduced pressure suction filtration to obtain the limited-area carbon material loaded with the palladium nanoparticles. Specifically, the loading of the palladium nanoparticles is 1 to 10%.
In the preparation process of the palladium nano-particles, the concentration ratio needs to be reasonably controlled to obtain different nano-particle diameters.
The following are example analyses:
example 1:
(1) weighing 0.05 mol of CB [6] hydrate and 14.2 mL of 7 mol/L GO aqueous solution, uniformly mixing, and stirring for 24 hours to ensure that no obvious white powder exists in the mixed solution;
(2) fully washing the coated cucurbituril and GO composite material by acetone and then deionized water, and performing freeze drying treatment;
(3) the resulting solid was placed in a quartz crucible to calcine into composite carbon containing a confined interface. Before calcination, introducing Ar gas, and keeping the gas flow at 200 cc/s; the calcining temperature of the first stage is 500 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1h, so that the special cavity aperture of the cucurbituril is reserved; the calcination temperature of the second stage is 900 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 2 h; after natural cooling, the obtained composite material is prepared by using acetone: water: fully washing with a washing solution with ethanol at a ratio of 1:1:1, washing with ultrapure water, and freeze-drying to obtain the amorphous carbon @ reduced graphene oxide composite carbon material;
(4) mixing the composite material into ice water, fully stirring and keeping ice bath; then 1 mL of K with the concentration of 1mol/L is dropwise added2PdCl4And repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, performing reduced pressure suction filtration, and drying to obtain the limited-area carbon material loaded with the palladium nanoparticles.
In the embodiment, a domain-limited carbon material loaded with palladium nanoparticles, which is shot by a transmission electron microscope, is shown in fig. 1, wherein amorphous carbon is obviously coated on rGO. Whereas small amounts of palladium nanoparticles were observed where the amorphous carbon was in contact with rGO. The particles can be observed to be formed by stacking a plurality of palladium nano particles of 2-5 nm by transmission electron microscope shooting under higher resolution, which proves that the palladium nano particles are successfully loaded.
Example 2:
(1) weighing 0.075 mol of CB [6] hydrate and 14.2 mL of 7 mol/L GO aqueous solution, uniformly mixing, and stirring for 24 hours to ensure that no obvious white powder exists in the mixed solution;
(2) fully washing the coated cucurbituril and GO composite material by acetone and then deionized water, and performing freeze drying treatment;
(3) the resulting solid was placed in a quartz crucible to calcine into composite carbon containing a confined interface. Before calcination, introducing Ar gas, and keeping the gas flow at 200 cc/s; the calcining temperature of the first stage is 500 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1h, so that the special cavity aperture of the cucurbituril is reserved; the calcination temperature of the second stage is 900 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 2 h; after natural cooling, the obtained composite material is prepared by using acetone: water: fully washing with a washing solution with ethanol at a ratio of 1:1:1, washing with ultrapure water, and freeze-drying to obtain the amorphous carbon @ reduced graphene oxide composite carbon material;
(4) mixing the composite material into ice water, fully stirring and keeping ice bath; then 2 mL of K with the concentration of 1mol/L is dropwise added2PdCl4Water solution and increasing the rotation speed to fully mix the water solution. And repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and drying after reduced pressure suction filtration to obtain the limited-area carbon material loaded with the palladium nanoparticles. In this example, the number of palladium nanoparticles is significantly increased, and the particle size of the nanoparticles tends to increase.
Example 3:
(1) weighing 0.15 mol CB [6] hydrate and 14.2 mL 7 mol/L GO aqueous solution, uniformly mixing, stirring for 24 h to ensure that no obvious white powder exists in the mixed solution;
(2) fully washing the coated cucurbituril and GO composite material by acetone and then deionized water, and performing freeze drying treatment;
(3) the resulting solid was placed in a quartz crucible to calcine into composite carbon containing a confined interface. Before calcination, introducing Ar gas, and keeping the gas flow at 200 cc/s; the calcining temperature of the first stage is 500 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1h, so that the special cavity aperture of the cucurbituril is reserved; the calcination temperature of the second stage is 900 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 2 h; after natural cooling, the obtained composite material is prepared by using acetone: water: fully washing with a washing solution with ethanol at a ratio of 1:1:1, washing with ultrapure water, and freeze-drying to obtain the amorphous carbon @ reduced graphene oxide composite carbon material;
(4) mixing the composite material into ice water, fully stirring and keeping ice bath; then 0.1 mL of K with the concentration of 1mol/L is dropwise added2PdCl4Aqueous solution and increasing the rotation speedAnd (4) fully mixing. And repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and drying after reduced pressure suction filtration to obtain the limited-area carbon material loaded with the palladium nanoparticles.
In this example, as shown in fig. 3, it can be observed through transmission electron microscope shooting that amorphous carbon is more fully wrapped on the surface of rGO, as shown in fig. 4, no obvious agglomerated particles appear in the material; the Pd content in the material is 0.73 percent through element analysis; as shown in fig. 5, the presence of palladium monoatomic atoms in the material was directly observed via STEM-ADF testing. In addition, the material shows excellent organic catalytic performance, as shown in fig. 6, 5 mg of the sample is weighed for a water solution of p-nitrobenzene, and after 100 mg of sodium borohydride is added, the solution rapidly fades (as shown in fig. 7), and the experimental result shows that the material has excellent application prospect.
Example 4:
(1) weighing 0.2 mol of CB [6] hydrate and 14.2 mL of 7 mol/L GO aqueous solution, uniformly mixing, and stirring for 24 hours to ensure that no obvious white powder exists in the mixed solution;
(2) fully washing the coated cucurbituril and GO composite material by acetone and then deionized water, and performing freeze drying treatment;
(3) the resulting solid was placed in a quartz crucible to calcine into composite carbon containing a confined interface. Before calcination, introducing Ar gas, and keeping the gas flow at 200 cc/s; the calcining temperature of the first stage is 500 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1h, so that the special cavity aperture of the cucurbituril is reserved; the calcination temperature of the second stage is 900 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 2 h; after natural cooling, the obtained composite material is prepared by using acetone: water: fully washing with a washing solution with ethanol at a ratio of 1:1:1, washing with ultrapure water, and freeze-drying to obtain the amorphous carbon @ reduced graphene oxide composite carbon material;
(4) mixing the composite material into ice water, fully stirring and keeping ice bath; then 0.5 mL of K with the concentration of 1mol/L is dropwise added2PdCl4Aqueous solution and increasing the rotation speedSo that it is fully mixed. And repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and drying after reduced pressure suction filtration to obtain the limited-area carbon material loaded with the palladium nanoparticles. In this example, the Pd monoatomic content is significantly increased due to the complete coating of the amorphous carbon on rGO and due to the increased concentration.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (5)

1. A preparation method of a domain-limited carbon material loaded with palladium single atoms or palladium nano particles is characterized by comprising the following specific steps:
preparing a confinement interface, which comprises the following steps:
(1) uniformly mixing cucurbiturils with a GO aqueous solution according to a certain molar ratio, and then fully stirring to enable the cucurbiturils to be coated on GO with a lamellar shape through electrostatic action;
(2) fully washing the composite material with GO coated with cucurbituril by acetone and deionized water in sequence; freeze-drying the composite material; picking out the cucurbituril which is not loaded on GO;
(3) placing the prepared composite material in a quartz crucible, calcining in a tubular furnace under the protection of inert gas to obtain composite carbon with a limited domain interface, and marking as a composite carbon material of reduced graphene oxide @ amorphous carbon;
(II) loading of monatomic palladium and nanoparticles:
the method comprises the following specific steps of loading the monoatomic material:
(1) fully grinding the reduced graphene oxide @ amorphous carbon prepared by the raw material ratio of (1.5-2): 1, mixing the ground reduced graphene oxide @ amorphous carbon into ice water, fully stirring the mixture and keeping ice bath; then 0.1-4 mL of K with the concentration of 0.1-1 mol/L is dropwise added2PdCl4Adding water solution, and increasing rotation speed to mix thoroughly; the reaction time is 1-5 h;
(2) repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and then carrying out reduced pressure suction filtration and drying to obtain the palladium monoatomic-supported restricted carbon material; the load capacity of the palladium single atom is 0.1-1%;
the method for loading the palladium nano-particles comprises the following specific steps:
(1) fully grinding the reduced graphene oxide @ amorphous carbon prepared by the raw material ratio of (0.5-2): 1, mixing the ground reduced graphene oxide @ amorphous carbon into ice water, fully stirring the mixture and keeping ice bath; then dropwise adding 1-4 mL of K with the concentration of 1mol/L2PdCl4Adding water solution, and increasing rotation speed to mix thoroughly; the reaction time is 4-5 h;
(2) repeatedly washing the obtained reactant with ultrapure water to remove unreacted residual ions, and then carrying out reduced pressure suction filtration and drying to obtain the limited-area carbon material loaded with the palladium nanoparticles; the loading of the palladium nano-particles is 1-10%.
2. The process according to claim 1, wherein said cucurbituril is selected from water-insoluble CB [6] or CB [8], or a mixture of both.
3. The method of claim 1, wherein the calcining comprises: removing air in the tubular furnace before calcination, and controlling the flow rate of the inert gas to be 100-200 cc/s; the calcination is divided into two stages: the calcination temperature in the first stage is 300-; the calcination temperature of the second stage is 700-; after calcination, naturally cooling, and mixing the obtained composite material with acetone: water: fully washing with a washing solution with ethanol being 1:1:1 to remove oily byproducts such as high-grade saturated alkane and the like generated in the carbonization process; and then washing with ultrapure water and freeze-drying to obtain the material, namely the reduced graphene oxide @ amorphous carbon composite carbon material.
4. A confined carbon material carrying palladium monoatomic or palladium nanoparticle obtained by the production method according to any one of claims 1 to 3.
5. The confined carbon material supporting palladium monoatomic or palladium nanoparticle according to claim 4, which uses palladium as an active site for applications in electrochemical catalysis, organic catalysis, biosensors, supercapacitors and lithium ion batteries.
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