CN117654507A - Monoatomic catalyst and preparation method and application thereof - Google Patents

Monoatomic catalyst and preparation method and application thereof Download PDF

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Publication number
CN117654507A
CN117654507A CN202311375900.XA CN202311375900A CN117654507A CN 117654507 A CN117654507 A CN 117654507A CN 202311375900 A CN202311375900 A CN 202311375900A CN 117654507 A CN117654507 A CN 117654507A
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atom
metal
catalyst
monoatomic
atoms
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成艳
李响
彭乐乐
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Shenzhen International Graduate School of Tsinghua University
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Abstract

The invention provides a single-atom catalyst, a preparation method and application thereof. The single-atom catalyst comprises a carrier and metal single atoms loaded in the carrier, so that excessive accumulation possibly existing in the multi-atom catalyst is avoided. Meanwhile, the distribution and the property of the catalytic center can be controlled more accurately, and a more accurate catalytic effect is realized. The invention also provides a preparation method and application of the single-atom catalyst.

Description

Monoatomic catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a single-atom catalyst, a preparation method and application thereof.
Background
The method is similar to the change brought to the catalysis field by preparing the bulk metal material into nano particles, the size of the metal material is further reduced to be an isolated single atom, and the metal material is embedded into a carrier, so that the design of the catalyst can be optimized, and the understanding of a reaction mechanism can be enhanced.
The atomic dispersion metal catalyst has potential application prospect in the aspects of CO oxidation, hydrogenation, organic reaction, electro-catalysis, photo-catalysis reaction and the like due to higher atomic utilization rate, unique atomic structure and electronic performance. Although the carbon material is used as a most commonly used metal monoatomic carrier at present, the large-scale, simple and efficient preparation of the catalyst with high-density metal monoatomic sites is still quite difficult. During pyrolysis, metal atoms tend to aggregate or form metal carbides with the carbon support, thereby reducing the dispersed sites of the single metal; in addition, the structural instability of the precursor in the high-temperature annealing process leads to uncontrollable chemical composition and structure around the metal monoatoms, and the factors restrict the effective construction and application of the monoatomic catalyst. To limit agglomeration of these isolated atoms under high temperature conditions, strong interactions between the atoms and the support need to be enhanced.
Thus, there remains a need to develop a new monoatomic catalyst.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. To this end, the present invention provides a single-atom catalyst that avoids excessive stacking that may be present in multi-atom catalysts. Meanwhile, the distribution and the property of the catalytic center can be controlled more accurately, and a more accurate catalytic effect is realized.
The invention also provides a method for preparing the monoatomic catalyst.
The invention also provides application of the single-atom catalyst.
The first aspect of the present invention provides a monoatomic catalyst comprising a support and a metal monoatom supported In the support, the metal monoatom including at least one of a Co atom, a Fe atom, a Ni atom, a Zn atom, a Cu atom, a Sn atom, a W atom, a Ga atom, an Ir atom, a Pt atom, a Bi atom, a Cd atom, a Mo atom, a Zr atom, a Cr atom, a Mn atom, a V atom, an In atom, a Pd atom, an Ag atom, a Lu atom, a Rh atom, and an Au atom.
The invention relates to one of the technical schemes of a single-atom catalyst, which has at least the following beneficial effects:
the single-atom catalyst of the present invention, comprising a carrier and a metal single atom supported in the carrier, can provide high catalytic activity because each catalytic center can participate in the reaction, avoiding excessive stacking that may exist in a multi-atom catalyst. Meanwhile, the distribution and the properties of the catalytic center can be controlled more accurately, so that a more accurate catalytic effect is realized.
The single-atom catalyst of the invention is beneficial to improving the selectivity of the reaction and reducing the generation of side reactions, thereby improving the purity of the product. Meanwhile, the catalyst has better catalytic stability, can resist deactivation or poisoning, and prolongs the service life of the catalyst.
According to the single-atom catalyst disclosed by the invention, the metal single atoms comprise at least one of Co atoms, fe atoms, ni atoms, zn atoms, cu atoms, sn atoms, W atoms, ga atoms, ir atoms, pt atoms, bi atoms, cd atoms, mo atoms, zr atoms, cr atoms, mn atoms, V atoms, in atoms, pd atoms, ag atoms, lu atoms, rh atoms and Au atoms, and the specific metal single atoms can be selected according to the requirements, so that the use of expensive metals is reduced, the atomic economy is improved, and the sustainable utilization of resources is facilitated.
According to some embodiments of the invention, the support comprises reduced graphene oxide.
Graphene is a single-layer planar crystal structure material composed of carbon atoms, and has the characteristics of excellent electric conductivity, excellent thermal conductivity, extremely high mechanical property, extremely high chemical stability and the like. However, graphene also has some drawbacks such as flammability, instability, etc. Therefore, graphene derivatives, graphene oxide and reduced graphene, are widely studied and applied.
Graphene oxide is an oxidation product formed after oxidation of graphene. The material has high chemical stability, so that the material can be applied to the fields of drug delivery, advanced energy storage, sensing technology and the like. Graphene oxide can also be surface modified to obtain a variety of different properties and applications. For example, by combining with polymers and biomolecules, it can be used to make tough, elastic nanomaterials.
Reduced graphene oxide is abbreviated as reduced graphene. Reduced graphene is a carbon material prepared by reducing graphene oxide. Compared with graphene and graphene oxide, the reduced graphene has the characteristics of bipolar charge, electron-rich property, high controllability and the like, and is widely researched and applied to the fields of biosensing, energy storage, solid-state capacitors, semiconductors and the like. For example, reduced graphene may be applied to high power energy storage devices by thin film lamination techniques.
The single-atom catalyst comprises a carrier and metal single atoms loaded in the carrier, wherein the term loaded in the carrier means that the metal single atoms are distributed on the surface of the carrier.
According to some embodiments of the invention, the loading of the metal monoatoms is 2wt% to 25wt%.
According to some embodiments of the invention, the loading of the metal monoatoms is from 5wt% to 17wt%.
The single-atom catalyst of the invention avoids the agglomeration phenomenon of metal atoms, and when the metal single atoms are Co atoms, the loading capacity of the metal single atoms can be up to 16.58 weight percent.
In a second aspect the present invention provides a process for preparing a monoatomic catalyst comprising the steps of:
s1: dispersing a carrier raw material in a solvent, adding a pore-forming agent, an anchoring agent and metal salt, stirring, and freeze-drying to obtain a precursor;
s2: and (3) after the precursor is subjected to self-propagating combustion, annealing the product in a protective atmosphere to obtain the monoatomic catalyst.
The invention relates to a technical scheme in a preparation method of a monoatomic catalyst, which at least has the following beneficial effects:
in the preparation of a single-atom carbon material system by pyrolysis, precursor regulation and control are one of key factors for directional construction of pyrolysis products. Therefore, selecting a precursor of a monatomic material with a proper structure, pre-constructing monatomic and surrounding chemical structure sites, is an effective means for efficiently preparing a high-density monatomic/polyatomic carbon material, and therefore, searching a proper ligand is a key for synthesizing a high monatomic load carbon material. According to the preparation method, based on self-propagating combustion reduction carrier raw materials (such as graphene oxide), metal atoms are pre-anchored at surrounding chemical structure sites, and then annealing treatment is carried out, so that the high-load metal monoatomic catalyst (namely the metal monoatomic reduction graphene oxide material) is finally successfully constructed.
The preparation method of the invention does not need expensive equipment and complex process control, has low reaction conditions, easily obtained raw materials, low production cost and easy industrial production.
In step S1:
the pore-forming agent is used for preparing the porous carrier. If the carrier raw material is graphene oxide, the porous graphene is a carbon material with nanoscale pores on a two-dimensional basal plane, so that the porous graphene not only maintains the excellent properties of graphene, but also promotes the improvement of the material transportation efficiency compared with the existence of pores on the surface of inert graphene, and particularly, the pores on the atomic scale can be sieved to different sizes. More importantly, the introduction of the holes also effectively opens the energy band gap of the graphene, and promotes the application of the graphene in the field of electronic devices.
The zero-valent metal monoatoms are extremely unstable and can be agglomerated to finally obtain metal nano particles and the like, so that a solid host material (mainly referred to as reduced graphene oxide) is required to bear O, N, S, P, B and other non-metal atoms to form chemical bonds with the metal monoatoms so as to form stable metal monoatomic sites. Therefore, the anchoring agent in the invention is used for forming stable chemical bonds with metal atoms so as to obtain the uniformly dispersed and stable metal monoatomic material.
In step S2:
the precursor is subjected to self-propagating combustion, and a process of self-propagating high-temperature synthesis (SHS for short), which is also called combustion synthesis (combustion synthesis), is a process of synthesizing a material by utilizing self-heating and self-conduction of high chemical reaction heat between reactants, and when the reactants are ignited, the reactants automatically spread to an unreacted area until the reaction is complete, so that the method is a method for preparing an inorganic compound high-temperature material. According to the self-propagating combustion method, alkali metal is used as an ignition agent, and after the alkali metal is heated, the graphene oxide contacts the surface of the alkali metal to generate self-propagating reaction, so that the alkali metal is not required to be added into a precursor, and the introduction of alkali metal impurities is avoided. The alkali metal acts as only one type of ignition agent and can react subsequently once the precursor is ignited.
The purpose of the annealing treatment is to further increase the graphitization degree of the material and the high temperature stability of the single atoms.
According to some embodiments of the present invention, the self-propagating combustion in step S2 may be performed in a low oxygen environment, such as a glove box.
The high oxygen content in the atmosphere can cause rapid and severe reduction reactions, resulting in the final complete combustion of the grapheme carbon material in the sample to produce carbon dioxide gas, and thus, the sample needs to be ignited in a low oxygen environment such as a glove box. The oxygen content in the glove box is less than 0.1ppm, and there is still a small amount of oxygen in the glove box that is sufficient to ignite the precursor to eventually undergo a self-propagating reaction.
According to some embodiments of the invention, the support material comprises graphene oxide.
According to some embodiments of the invention, the solvent comprises water.
According to some embodiments of the invention, the pore-forming agent comprises H 2 O 2 。
According to some embodiments of the invention, the anchor comprises at least one of a nitrogen-containing anchor, a sulfur-containing anchor, a phosphorus-containing anchor, a boron-containing anchor.
According to some embodiments of the invention, the anchor comprises at least one of urea, dicyandiamide, boric acid, ammonium thiocyanate, sodium hypophosphite, and phytic acid.
According to some embodiments of the invention, in step S1, the mass ratio of carrier raw material to metal monoatoms is 1:0.5 to 0.6.
The carrier material comprises graphene oxide.
According to some embodiments of the invention, in step S1, the carrier material is dispersed in a solvent to form a solution having a concentration of carrier material of 1mg/mL to 10mg/mL.
According to some embodiments of the invention, in step S1, the carrier raw material is dispersed in a solvent to form a solution and a pore-forming agent in a volume ratio of 10 to 100:1.
According to some embodiments of the invention, the molar ratio of the anchor agent to the metal salt is 1-4:1.
According to some embodiments of the invention, the metal salt comprises at least one of nitrate, sulfate, hydrochloride, acetylacetonate, acetate, and oxalate.
The metal salt is a metal salt containing a corresponding metal monoatomic element.
According to some embodiments of the invention, the stirring time is 1h to 24h.
According to some embodiments of the invention, the freeze-drying comprises liquid nitrogen freezing and cold trap freezing.
According to some embodiments of the invention, the lyophilization time is 24h to 72h.
The purpose of freeze-drying is: in this process, the metal compound and the nonmetallic anchoring agent are effectively separated by these large numbers of holes, thereby ensuring that as many metal centers as possible are uniformly distributed in the porous graphene for subsequent pre-anchoring, and finally obtaining a uniformly dispersed monoatomic catalyst.
According to some embodiments of the invention, the self-propagating combustion has a pilot temperature of 200 ℃ to 600 ℃.
According to some embodiments of the invention, the self-propagating combustion time is between 0.01s and 1.00s.
According to some embodiments of the invention, the self-propagating combustion may be initiated by an alkali metal, such as sodium. Alkali metal is only used as a heat source, and only needs to generate transfer heat energy, and the alkali metal does not need to be ignited, so that the combustion temperature of the alkali metal does not need to be reached. The graphene oxide can be ignited only at 200 ℃ at the lowest temperature, belongs to low-temperature self-propagation, and can effectively achieve the effect of energy conservation.
According to some embodiments of the invention, the annealing process comprises: heating to 600-900 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 2-5 h. Further improves the graphitization degree and the high-temperature stability of single atoms of the material, and then naturally cools to room temperature.
The annealing treatment may be performed in a tube furnace.
The invention provides a method for capturing metal ions by utilizing low-temperature self-propagating combustion, and forms rich and uniform metal atoms and non-metal atom anchoring sites, thereby pre-anchoring the metal atoms in a carbon frame. The preparation method can obtain active sites of different metal-nonmetal coordination, greatly weakens the agglomeration phenomenon of metal atoms in the high-temperature annealing process, and obtains the high-load monoatomic catalyst.
In a third aspect the invention provides the use of a single-atom catalyst in fuel cell reactions, waste water and air purification, organic synthesis and gas conversion.
The invention relates to a technical scheme of a monoatomic catalyst in the application of fuel cell reaction, waste water and air purification, organic synthesis and gas conversion, which has at least the following beneficial effects:
the single-atom catalyst is used for catalyzing fuel cell reactions, such as oxidation reactions of hydrogen, methanol and ethanol, and can improve the energy conversion efficiency.
The monoatomic catalyst provided by the invention is used for treating pollutants in wastewater and air, such as nitrogen oxides (NOx) and heavy metals, and has higher treatment efficiency.
The single-atom catalyst is used in organic synthesis, and is favorable for optimizing reaction selectivity and improving catalytic activity.
The single-atom catalyst can improve the reaction efficiency in the gas conversion process, such as converting methane into methanol.
Drawings
Fig. 1 is an XRD pattern of the monoatomic catalyst prepared in example 1.
Fig. 2 is an SEM image of the monoatomic catalyst prepared in example 1.
Fig. 3 is a TEM image of the monoatomic catalyst prepared in example 1.
FIG. 4 is a HADDF-STEM diagram of the monoatomic catalyst prepared in example 1.
FIG. 5 is a Fourier Transform (FT) -EXAFS spectrum at Co K-edge of a single-atom catalyst, co foil, coO and CoPc prepared in example 1.
FIG. 6 is a high-magnification XPS spectrum of Co 2p of the monoatomic catalyst prepared in example 1.
FIG. 7 XPS full spectrum of the monoatomic catalyst prepared in example 1.
FIG. 8 is a HADDF-STEM diagram of the multimetal monoatomic catalyst prepared in example 5.
FIG. 9 is a HADDF-STEM diagram and corresponding elemental distribution of the multimetal monoatomic catalyst prepared in example 5.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
In some embodiments of the present invention, the present invention provides a monoatomic catalyst including a support and a metal monoatom supported In the support, the metal monoatom including at least one of a Co atom, a Fe atom, a Ni atom, a Zn atom, a Cu atom, a Sn atom, a W atom, a Ga atom, an Ir atom, a Pt atom, a Bi atom, a Cd atom, a Mo atom, a Zr atom, a Cr atom, a Mn atom, a V atom, an In atom, a Pd atom, an Ag atom, a Lu atom, a Rh atom, and an Au atom.
It will be appreciated that the single-atom catalysts of the present invention, including the support and the metal single-atoms supported in the support, can provide high catalytic activity because each catalytic center is capable of participating in a reaction, avoiding excessive stacking that may be present in a multi-atom catalyst. Meanwhile, the distribution and the properties of the catalytic center can be controlled more accurately, so that a more accurate catalytic effect is realized.
Furthermore, the single-atom catalyst disclosed by the invention is beneficial to improving the reaction selectivity and reducing the generation of side reactions, so that the product purity is improved. Meanwhile, the catalyst has better catalytic stability, can resist deactivation or poisoning, and prolongs the service life of the catalyst.
It is also understood that the monoatomic catalyst of the present invention, the metal monoatoms include at least one of Co atom, fe atom, ni atom, zn atom, cu atom, sn atom, W atom, ga atom, ir atom, pt atom, bi atom, cd atom, mo atom, zr atom, cr atom, mn atom, V atom, in atom, pd atom, ag atom, lu atom, rh atom and Au atom, and a specific metal monoatom can be selected as needed, so that the use of expensive metals is reduced, the atomic economy is improved, and the sustainable utilization of resources is facilitated.
In some embodiments of the invention, the support comprises reduced graphene oxide.
It should be noted that graphene is a single-layer planar crystal structure material composed of carbon atoms, and has the characteristics of excellent electric conduction and thermal conductivity, extremely high mechanical properties, chemical stability and the like. However, graphene also has some drawbacks such as flammability, instability, etc. Therefore, graphene derivatives, graphene oxide and reduced graphene, are widely studied and applied.
Further, graphene oxide is an oxidation product formed by oxidizing graphene. The material has high chemical stability, so that the material can be applied to the fields of drug delivery, advanced energy storage, sensing technology and the like. Graphene oxide can also be surface modified to obtain a variety of different properties and applications. For example, by combining with polymers and biomolecules, it can be used to make tough, elastic nanomaterials.
Further, the reduced graphene oxide is simply reduced graphene. Reduced graphene is a carbon material prepared by reducing graphene oxide. Compared with graphene and graphene oxide, the reduced graphene has the characteristics of bipolar charge, electron-rich property, high controllability and the like, and is widely researched and applied to the fields of biosensing, energy storage, solid-state capacitors, semiconductors and the like. For example, reduced graphene may be applied to high power energy storage devices by thin film lamination techniques.
In some embodiments of the invention, the loading of metal monoatoms is 2wt% to 25wt%.
In some embodiments of the invention, the loading of metal monoatoms is from 5wt% to 17wt%.
The single-atom catalyst of the invention avoids the agglomeration phenomenon of metal atoms, and when the metal single atoms are Co atoms, the loading capacity of the metal single atoms can be up to 16.58 weight percent.
In other embodiments of the invention, the invention provides a method of preparing a monoatomic catalyst comprising the steps of:
s1: dispersing a carrier raw material in a solvent, adding a pore-forming agent, an anchoring agent and metal salt, stirring, and freeze-drying to obtain a precursor;
s2: and (3) after the precursor is subjected to self-propagating combustion, annealing the product in a protective atmosphere to obtain the monoatomic catalyst.
It can be appreciated that in preparing a monoatomic carbon material system by pyrolysis, precursor regulation is one of the key factors for directional construction of pyrolysis products. Therefore, selecting a precursor of a monatomic material with a proper structure, pre-constructing monatomic and surrounding chemical structure sites, is an effective means for efficiently preparing a high-density monatomic/polyatomic carbon material, and therefore, searching a proper ligand is a key for synthesizing a high monatomic load carbon material. According to the preparation method, based on self-propagating combustion reduction carrier raw materials (such as graphene oxide), metal atoms are pre-anchored at surrounding chemical structure sites, and then annealing treatment is carried out, so that the high-load metal monoatomic catalyst (namely the metal monoatomic reduction graphene oxide material) is finally successfully constructed.
The preparation method of the invention does not need expensive equipment and complex process control, has low reaction conditions, easily obtained raw materials, low production cost and easy industrial production.
In step S1:
the pore-forming agent is used for preparing the porous carrier. If the carrier raw material is graphene oxide, the porous graphene is a carbon material with nanoscale pores on a two-dimensional basal plane, so that the porous graphene not only maintains the excellent properties of graphene, but also promotes the improvement of the material transportation efficiency compared with the existence of pores on the surface of inert graphene, and particularly, the pores on the atomic scale can be sieved to different sizes. More importantly, the introduction of the holes also effectively opens the energy band gap of the graphene, and promotes the application of the graphene in the field of electronic devices.
The zero-valent metal monoatoms are extremely unstable and can be agglomerated to finally obtain metal nano particles and the like, so that a solid host material (mainly referred to as reduced graphene oxide) is required to bear O, N, S, P, B and other non-metal atoms to form chemical bonds with the metal monoatoms so as to form stable metal monoatomic sites. Therefore, the anchoring agent in the invention is used for forming stable chemical bonds with metal atoms so as to obtain the uniformly dispersed and stable metal monoatomic material.
In step S2:
the precursor is subjected to self-propagating combustion, and a process of self-propagating high-temperature synthesis (SHS for short), which is also called as combustion synthesis (combustion synthesis), is a process of synthesizing a material by utilizing self-heating and self-conduction of high chemical reaction heat between reactants, and when the reactants are ignited, the reactants automatically spread to an unreacted area until the reaction is complete, so that the process is a method for preparing an inorganic compound high-temperature material. According to the self-propagating combustion method, alkali metal is used as an ignition agent, and after the alkali metal is heated, the graphene oxide contacts the surface of the alkali metal to perform self-propagating reaction, so that the alkali metal is not required to be added into a precursor, and the introduction of alkali metal impurities is avoided. The alkali metal acts as only one type of ignition agent and can react subsequently once the precursor is ignited.
The purpose of the annealing treatment is to further increase the graphitization degree of the material and the high temperature stability of the single atoms.
In some embodiments of the present invention, the self-propagating combustion in step S2 may be performed in a low oxygen environment, such as a glove box.
The high oxygen content in the atmosphere can cause rapid and severe reduction reactions, resulting in the final complete combustion of the grapheme carbon material in the sample to produce carbon dioxide gas, and thus, the sample needs to be ignited in a low oxygen environment such as a glove box. The oxygen content in the glove box is less than 0.1ppm, and there is still a small amount of oxygen in the glove box that is sufficient to ignite the precursor to eventually undergo a self-propagating reaction.
In some embodiments of the invention, the support material comprises graphene oxide.
In some embodiments of the invention, the solvent comprises water.
In some embodiments of the invention, the pore-forming agent comprises H 2 O 2 。
In some embodiments of the invention, the anchor comprises at least one of a nitrogen-containing anchor, a sulfur-containing anchor, a phosphorus-containing anchor, a boron-containing anchor.
In some embodiments of the invention, the anchoring agent comprises at least one of urea, dicyandiamide, boric acid, ammonium thiocyanate, sodium hypophosphite, and phytic acid.
In some embodiments of the invention, in step S1, the mass ratio of carrier raw material to metal monoatoms is 1:0.5-0.6.
The carrier material comprises graphene oxide.
In some embodiments of the invention, in step S1, the carrier material is dispersed in a solvent to form a solution having a concentration of carrier material of 1mg/mL to 10mg/mL.
In some embodiments of the invention, in step S1, the carrier material is dispersed in a solvent to form a solution and a pore-forming agent in a volume ratio of 10 to 100:1.
In some embodiments of the invention, the molar ratio of anchor to metal salt is 1-4:1.
In some embodiments of the invention, the metal salt comprises at least one of a nitrate, sulfate, hydrochloride, acetylacetonate, acetate, and oxalate.
The metal salt is a metal salt containing a corresponding metal monoatomic element.
In some embodiments of the invention, the stirring time is 1h to 24h.
In some embodiments of the invention, freeze-drying includes liquid nitrogen freezing and cold trap freezing.
In some embodiments of the invention, the lyophilization time is 24 hours to 72 hours.
The purpose of freeze-drying is: in this process, the metal compound and the nonmetallic anchoring agent are effectively separated by these large numbers of holes, thereby ensuring that as many metal centers as possible are uniformly distributed in the porous graphene for subsequent pre-anchoring, and finally obtaining a uniformly dispersed monoatomic catalyst.
In some embodiments of the invention, the ignition temperature of self-propagating combustion is 200 ℃ to 600 ℃.
In some embodiments of the invention, the self-propagating combustion time is 0.01s to 1.00s.
In some embodiments of the invention, the ignition self-propagating combustion may be initiated by an alkali metal, such as sodium. Alkali metal is only used as a heat source, and only needs to generate transfer heat energy, and the alkali metal does not need to be ignited, so that the combustion temperature of the alkali metal does not need to be reached. The graphene oxide can be ignited only at 200 ℃ at the lowest temperature, belongs to low-temperature self-propagation, and can effectively achieve the effect of energy conservation.
In some embodiments of the invention, a method of annealing treatment includes: heating to 600-900 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 2-5 h. Further improves the graphitization degree and the high-temperature stability of single atoms of the material, and then naturally cools to room temperature.
The annealing treatment may be performed in a tube furnace.
The invention provides a method for capturing metal ions by utilizing low-temperature self-propagating combustion, and forms rich and uniform metal atoms and non-metal atom anchoring sites, thereby pre-anchoring the metal atoms in a carbon frame. The preparation method can obtain active sites of different metal-nonmetal coordination, greatly weakens the agglomeration phenomenon of metal atoms in the high-temperature annealing process, and obtains the high-load monoatomic catalyst.
In other embodiments of the invention, the invention provides the use of a single-atom catalyst in fuel cell reactions, wastewater and air purification, organic synthesis, and gas conversion.
It will be appreciated that the single-atom catalyst of the present invention, which is used to catalyze fuel cell reactions such as oxidation of hydrogen, methanol and ethanol, can improve energy conversion efficiency.
The monoatomic catalyst provided by the invention is used for treating pollutants in wastewater and air, such as nitrogen oxides (NOx) and heavy metals, and has higher treatment efficiency.
The single-atom catalyst is used in organic synthesis, and is favorable for optimizing reaction selectivity and improving catalytic activity.
The single-atom catalyst can improve the reaction efficiency in the gas conversion process, such as converting methane into methanol.
The technical solution of the present invention will be better understood by combining the following specific embodiments.
In the examples, all raw materials were obtained from commercial sources, with graphene purchased from the first-come nano company.
Example 1
The embodiment provides a monoatomic catalyst, wherein a carrier is reduced graphene oxide, and Co monoatoms are dispersed on the surface of the reduced graphene oxide.
The specific preparation method comprises the following steps:
step S1: taking 5mL of graphene oxide aqueous solution with mass density of 5mg/mL, and then adding 15 mu LH 2 O 2 5mg of cobalt nitrate and 3mg of dicyandiamide which are respectively an oxidant, a metal source and a nonmetal anchoring agent, and finally stirring for 3 hours to obtain uniformly dispersed liquid, freezing by adopting liquid nitrogen, and then drying in a freeze dryer for 30 hours;
step S2: performing self-propagating on the precursor obtained in the step S1, igniting by adopting sodium metal in a glove box, wherein the ignition temperature is 260 ℃, and obtaining a reduced graphene oxide precursor pre-anchored with metal Co atoms for 20 ms;
step S3: and (3) placing the material obtained in the step (S2) in a high-temperature tube furnace, heating to 600 ℃ at a heating rate of 3 ℃/min under an inert atmosphere, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the high-metal monoatomic Co reduced graphene oxide material.
Example 2
The embodiment provides a monoatomic catalyst, wherein a carrier is reduced graphene oxide, and V monoatoms are dispersed on the surface of the reduced graphene oxide.
The specific preparation method comprises the following steps:
step S1: 5mL of graphene oxide aqueous solution with a mass density of 2mg/mL was taken, followed by addition of 8. Mu.L of H 2 O 2 And 5mg of vanadium chloride and 3mg of ammonium thiocyanate which are respectively an oxidant, a metal source and a nonmetal anchoring agent, stirring for 10 hours finally to obtain uniformly dispersed liquid, freezing by a cold trap, and then drying in a freeze dryer for 24 hours.
Step S2: performing self-propagating on the precursor obtained in the step S1, igniting by adopting Li metal in a glove box, wherein the ignition temperature is 300 ℃, and obtaining a reduced graphene oxide precursor pre-anchored with metal V atoms for 10 ms;
step S3: and (3) placing the material obtained in the step (S2) in a high-temperature tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under an inert atmosphere, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain the catalyst with high monoatomic V loading.
Example 3
The embodiment provides a monoatomic catalyst, wherein a carrier is reduced graphene oxide, and Cr monoatoms are dispersed on the surface of the reduced graphene oxide.
The specific preparation method comprises the following steps:
step S1: 5mL of graphene oxide aqueous solution with a mass density of 6mg/mL was taken, followed by the addition of 18. Mu.L of H 2 O 2 、10mgCr(Ac) 3 And 8mg of boric acid which is respectively an oxidant, a metal source and a nonmetal anchoring agent, stirring for 8 hours finally to obtain uniformly dispersed liquid, freezing by adopting liquid nitrogen, and then placing the liquid into a freeze dryer for drying for 24 hours.
Step S2: self-propagating the precursor obtained in the step S1, igniting the precursor in air by adopting a lighter, wherein the ignition temperature is 400 ℃, and the reduced graphene oxide precursor pre-anchored with metal Cr atoms is obtained for 20 ms;
step S3: and (3) placing the material obtained in the step (S2) in a high-temperature tube furnace, heating to 800 ℃ at a heating rate of 6 ℃/min under an inert atmosphere, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the catalyst with high monoatomic Cr loading.
Example 4
The embodiment provides a monoatomic catalyst, wherein a carrier is reduced graphene oxide, and V monoatoms are dispersed on the surface of the reduced graphene oxide.
The specific preparation method comprises the following steps:
step S1: 5mL of graphene oxide aqueous solution with a mass density of 2mg/mL was taken, followed by addition of 8. Mu.L of H 2 O 2 And 5mg of vanadium chloride and 3mg of ammonium thiocyanate which are respectively an oxidant, a metal source and a nonmetal anchoring agent, stirring for 10 hours finally to obtain uniformly dispersed liquid, freezing by a cold trap, and then drying in a freeze dryer for 24 hours.
Step S2: performing self-propagating on the precursor obtained in the step S1, igniting by adopting Li metal in a glove box, wherein the ignition temperature is 300 ℃, and obtaining a reduced graphene oxide precursor pre-anchored with metal V atoms for 10 ms;
step S3: and (3) placing the material obtained in the step (S2) in a high-temperature tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under an inert atmosphere, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain the catalyst with high monoatomic V loading.
Example 5
The embodiment provides a monoatomic catalyst, wherein the carrier is reduced graphene oxide, and Cr, V, co, mn, ni, zn, cd, sn, pt, W monoatoms are dispersed on the surface of the reduced graphene oxide.
The specific preparation method comprises the following steps:
step S1: 5mL of graphene oxide aqueous solution with a mass density of 2mg/mL was taken, followed by addition of 20. Mu.L of H 2 O 2 、1mgCr(Ac) 3 1mg of vanadium chloride, 1mg of manganese chloride, 2mg of cobalt chloride, 1mg of nickel nitrate, 1mg of zinc chloride, 1mg of cadmium acetate, 1mg of stannous chloride, 1mg of chloroplatinic acid, 1mg of ammonium tungstate and 10mg of dicyandiamide, stirring for 24 hours to obtain uniformly dispersed liquid, freezing by adopting liquid nitrogen, and then putting the uniformly dispersed liquid into a freeze dryer for drying for 24 hours.
Step S2: self-propagating the precursor obtained in the step S1, igniting the precursor in air by adopting a lighter, wherein the ignition temperature is 400 ℃, and the reduced graphene oxide precursor pre-anchored with a plurality of metal atoms is obtained in 20 ms;
step S3: placing the material obtained in the step S2 into a high-temperature tube furnace, and placing the material in an inert atmosphere N 2 Heating to 900 ℃ at a heating rate of 6 ℃/min for 2 hours at constant temperature, and naturally cooling to room temperature to obtain the high-load polyatomic catalyst.
Structural characterization
The monoatomic catalyst prepared in example 1 was characterized by X-ray powder diffraction as shown in figure 1. As can be seen from fig. 1, there is no crystalline phase of the metal nanoparticles except for the characteristic peak of C.
The monoatomic catalyst prepared in example 1 was characterized by scanning electron microscopy, as shown in fig. 2. As can be seen from fig. 2, no metal atoms in the reduced graphene are agglomerated into particles.
The monoatomic catalyst prepared in example 1 was characterized by transmission electron microscopy, as shown in fig. 3. As can be seen from fig. 3, there are no metal nanoparticles on the surface of the reduced graphene.
The monoatomic catalyst prepared in example 1 was characterized by high angle annular dark field scanning transmission electron microscopy, as shown in fig. 4. As can be seen from fig. 4, a large number of metal monoatoms are uniformly dispersed on the surface of the reduced graphene.
The monoatomic catalyst prepared in example 1 was characterized by an X-ray absorbing fine structure, as shown in fig. 5. As can be seen from FIG. 5, characteristic peaks of Co-Co bonds appear inIn example 1, however, no corresponding characteristic peak was observed, further demonstrating the formation of a single atom.
Referring to fig. 1 to 5, it is proved that a large number of metal single atoms are uniformly dispersed on the surface of the reduced graphene oxide in the catalyst prepared in example 1, and metal nano particles are not formed by agglomeration, through the morphology, crystal phase, surface electronic structure characteristics and the like of the sample.
The monoatomic catalyst prepared in example 1 was characterized by X-ray photoelectron spectroscopy, as shown in fig. 6 and 7. As can be seen from fig. 6, the peak separation at high resolution Co XPS is not attributed to the peak of elemental cobalt metal. It can be seen from fig. 7 that there are no other elements than Co, N, C, O.
The monoatomic catalyst prepared in example 1 was quantitatively measured according to XPS full spectrum (FIG. 7), and the atomic ratios and mass ratios of the different elements are shown in Table 1.
TABLE 1
Element C N O Co
wt.％ 73.37 6.64 3.41 16.58
at.％ 88.55 5.61 2.52 3.32
As can be seen from Table 1, the metal Co content was 16.58wt%.
The monoatomic catalyst prepared in example 5 was characterized by high angle annular dark field scanning transmission electron microscopy, as shown in fig. 8. As can be seen from fig. 8, a large amount of metal monoatoms are supported on the surface of the reduced graphene.
The multimetal monoatomic catalyst prepared in example 5 was characterized by a profile of elements corresponding to a high angle annular dark field scanning transmission electron microscope, as shown in fig. 9. From fig. 9, it can be seen that V, cr, mn, co, ni, zn, cd, sn, W, and Pt ten elements are uniformly dispersed in the rGO high-entropy alloy, and the above results show that assembling the multi-metal composite SACs with the single-atom anchor site as a structural element is experimentally feasible.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (10)

1. A monatomic catalyst characterized by comprising a carrier and a metal monatom supported In the carrier, wherein the metal monatom comprises at least one of a Co atom, a Fe atom, a Ni atom, a Zn atom, a Cu atom, a Sn atom, a W atom, a Ga atom, an Ir atom, a Pt atom, a Bi atom, a Cd atom, a Mo atom, a Zr atom, a Cr atom, a Mn atom, a V atom, an In atom, a Pd atom, an Ag atom, a Lu atom, a Rh atom, and an Au atom.
2. The single-atom catalyst of claim 1 wherein the support comprises reduced graphene oxide.
3. The monoatomic catalyst according to claim 1 or 2, characterized in that the loading of the metal monoatoms is 2 to 25wt%.
4. A process for preparing a monoatomic catalyst according to any one of claims 1 to 3, characterised in that it comprises the following steps:
s1: dispersing a carrier raw material in a solvent, adding a pore-forming agent, an anchoring agent and metal salt, stirring, and freeze-drying to obtain a precursor;
s2: and (3) after the precursor is subjected to self-propagating combustion, annealing the product in a protective atmosphere to obtain the monoatomic catalyst.
5. The method of claim 4, wherein the pore-forming agent comprises H 2 O 2 。
6. The method of claim 4, wherein the anchor comprises at least one of urea, dicyandiamide, boric acid, ammonium thiocyanate, sodium hypophosphite, and phytic acid.
7. The method of claim 4, wherein the molar ratio of the anchor agent to the metal salt is 1-4:1.
8. The method of claim 4, wherein the self-propagating combustion has a pilot temperature of 200 ℃ to 600 ℃.
9. The method of claim 4, wherein the annealing process comprises: heating to 600-900 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 2-5 h.
10. Use of the monoatomic catalyst according to any of claims 1 to 3 for fuel cell reactions, waste water and air purification, organic synthesis and gas conversion.
CN202311375900.XA 2023-10-23 2023-10-23 Monoatomic catalyst and preparation method and application thereof Pending CN117654507A (en)

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