CN113258088A - Carbon-supported multi-element monoatomic metal catalyst - Google Patents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a carbon-supported multi-element monatomic metal catalyst, a preparation method thereof and application thereof in catalytic oxygen reduction reaction. The carbon-supported multi-element monatomic metal catalyst takes carbon as a carrier, and metal monatomics prepared by Pt, Pd, Au, Cu, Co, Ni, Fe and Mn precursors according to a regulated proportion through a transient Joule heating method are uniformly dispersed on the surface of the carbon carrier, so that the carbon-supported multi-element monatomic metal catalyst with excellent catalytic performance is obtained. The obtained catalyst has the characteristics of controllable components, stable structure, uniform distribution, more catalytic active sites, direct application to fuel cells and the like, and has good catalytic activity in the field of catalytic oxygen reduction reaction of the fuel cells. The obtained carbon-supported 8-membered single-atom metal catalyst is directly used as a cathode catalyst of a direct sodium borohydride fuel cell, 60oCan realize 523.13 mW.cm under C‑2The maximum output power density of.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a high-loading-capacity high-catalytic-performance multi-element monatomic metal catalyst, a preparation method thereof and application of the catalyst in catalytic oxygen reduction reaction.
Background
The current development of human society has the increasing consumption of fossil energy, the energy crisis and the environmental pollution problem are not negligible, the search for high-efficiency, green and renewable alternative energy is urgent, and the pursuit of renewable energy promotes the development of advanced catalytic materials applied to electrochemical reaction. The reduction of carbon dioxide, nitrogen and oxygen is an important chemical conversion process for the conversion of renewable energy sources, where the activity, selectivity and stability of the electrocatalyst play a crucial role in determining energy efficiency and system performance. The most advanced catalysts for these reactions rely extensively on noble metals such as platinum, palladium, rhodium, iridium, ruthenium and gold. However, the scarcity and high cost of noble metals have hindered the industrial development of corresponding electrochemical energy technologies. How to reduce the content of noble metals in electrocatalysts or find a substitute with high content in the earth poses great challenges for the development of renewable energy technology.
The concept of a monatomic metal catalyst, a catalyst composed of active centers containing only a single atom, was first introduced in 2011 by the billows researchers at the national laboratory martial steel institute and the central institute of continuations of the los alamos national laboratory. In principle, all metal atoms of the monatomic metal catalyst are exposed on the surface, and therefore 100% atomic utilization efficiency can be achieved, which is particularly attractive for reducing the cost of noble metal-based catalytic materials. The monatomic metal catalyst also has uniformly distributed under-coordinated active sites, providing a model system for the difference between heterogeneous catalysis and homogeneous catalysis. The initial study of monatomic catalysts began in order to perform an Oxygen Reduction Reaction (ORR)A substitute of platinum is found, rare earth-rich 3d transition metals, such as manganese (Mn), iron (Fe), cobalt (Co) and nickel (Ni), are dispersed on a carbon-based conductive substrate in a form of single atoms, and stably exist by combining with nitrogen-doped or other heteroatom substances, while covalently coordinated transition metal centers have good adsorption performance and stability, and obtain better ORR catalytic activity in an acidic electrolyte. But now its footprint has been extended to other areas of electrocatalysis, in Hydrogen Evolution Reactions (HER), oxygen reduction/evolution reactions (ORR/OER) and CO2And N2Reduction reactions (CO2RR and NRR) were used. It has been demonstrated that monatomic catalysts have attracted considerable attention since this concept was introduced into the catalytic field about ten years ago, and have been demonstrated to be superior in activity and/or selectivity to their cluster or nanoparticle counterparts in a wide range of catalytic reactions.
The synthesis of monatomic metal catalysts is a major area of research in this field, as achieving monatomic dispersion of metals presents a significant challenge to the preparation of monatomic metal catalysts. This usually means that thermodynamically unstable/metastable phases or structural motifs are produced, which require extrinsic control of the synthesis conditions to prevent metal atom aggregation, agglomeration and cluster/nanocrystal growth. Furthermore, instead of requiring thermal stability, monatomic metal catalysts are also required to be stable under the conditions of the catalyzed electrochemical reaction, which typically include acidic/alkaline electrolytes, oxidizing or reducing reactants (e.g., O2 and H2), and cathode/anode potentials. The synthesis of single atoms of all common metals is currently achieved mainly by various strategies such as coordination-calcination, surface and gold and atomic deposition. However, there is still a need to overcome the stability of the monatomic metal catalyst, apply the monatomic metal catalyst to commercial equipment, and develop the polyatomic metal catalyst in order to realize the industrialization of the monatomic metal catalyst.
Compared with the traditional wet chemical method, the transient Joule heating method can simply and quickly prepare the nano metal particles, and the high-energy electron current provided by the controllable circuit acts on a sample, the sample surface is converted into Joule heat, and the metal salt on the sample is instantly heated and quickly cooled to form the nano metal particles which are highly and uniformly dispersed on the surface of a matrix.
The carbon nanosphere loaded multi-element monoatomic metal catalyst developed by the invention has the advantages of simple preparation, controllable size, excellent performance, stable structure, low cost and the like, and the uniform dispersion of multi-element monoatomic metal on the carbon nanosphere substrate is realized by adjusting the parameters of transient joule heat and metal components. The synergistic effect between the multi-element monoatomic metal catalysts uniformly dispersed in the catalyst of the invention endows the material with excellent catalytic performance of oxygen reduction reaction.
Disclosure of Invention
The invention aims to provide a carbon-supported multi-element monatomic metal catalyst and a preparation method thereof, aiming at solving the problems that the existing monatomic metal catalyst is single in catalytic active site, low in blocking capacity, poor in stability, difficult to apply to commercial equipment and the like. The multi-component mixed precursor salt is loaded on the carbon nanospheres, and the carbon nanospheres can be graphitized after being electrified by Joule heat generated by instantaneous electrification in air or nitrogen atmosphere to form superfine intrinsic defects. Meanwhile, precursor salt loaded on the surface of the nano carbon sphere substrate is rapidly decomposed to form a multi-element single-atom catalyst and is instantly fixed by the nano defects. In the catalytic application, a plurality of adjacent metal monoatomic atoms of the multi-element monoatomic metal catalyst can accelerate a plurality of steps of the same reaction respectively, so that the overall reaction speed is accelerated, and the catalytic activity is improved. And in the preparation process, the type, the proportion and the concentration of the multi-element monoatomic atoms can be regulated and controlled according to the reaction type of specific application. Compared with the single atom metal catalyst in the prior art, the catalyst can reduce the cost, simplify the synthesis method and improve the catalytic performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon-supported multi-element monoatomic metal catalyst, wherein carrier carbon is a nano carbon sphere which is one of porous carbon or graphene; wherein the plurality of monoatomic atoms includes monoatomic atoms of one or more noble metals, and one or more non-noble metals. Wherein the noble metal is selected from Pt, Au or Pd, and the non-noble metal is selected from Co, Fe, Mn, Cu or Ni; wherein, each metal single atom is evenly dispersed on the surface of the carrier nano carbon sphere to obtain a very large specific surface area.
Wherein, in the carbon-supported multi-element monatomic metal catalyst, the molar ratio of the noble metal monatomic to the non-noble metal monatomic is preferably in the range of 1:3-3: 1; wherein when the molar ratio of each metal element is 1:1, the catalytic performance is better; particularly when the monoatomic metals include Pt, Au, Pd, Co, Fe, Mn, Cu and Ni, and the molar ratio of each metal is 1: when the ratio is 1:1:1:1:1:1:1, the catalyst is the optimal choice, and the catalyst with the ratio has the best catalytic performance.
The invention also provides a preparation method of the carbon-supported multi-element single-atom catalyst, which is characterized in that a carbon material is used as a carrier, proper components of the catalyst are regulated and controlled by designing the loading amount of metal precursor salt, precursor salt of noble metal and non-noble metal is loaded on the carbon material according to a certain loading amount, and the carbon-supported multi-element single-atom metal catalyst with excellent catalytic performance is prepared by a transient joule heating method. Specifically, the preparation method comprises the following steps:
1) one or more noble metal salts and one or more non-noble metal salts are mixed and then added into absolute ethyl alcohol, and metal precursor solution is obtained after stirring and dissolving; the concentration of the obtained metal precursor solution is preferably 0.005-0.05M; the molar ratio of the noble metal monoatomic atoms to the non-noble metal monoatomic atoms is preferably in the range of 1:3 to 3: 1; wherein the molar ratio of each metal element is 1: 1;
2) mixing the metal precursor solution obtained in the step 1) with carbon powder according to a mass ratio of 1:19-1:4, performing ultrasonic dispersion for 3-6 hours, and performing magnetic stirring for 12-24 hours to obtain mixed slurry; the carbon powder is graphene or nano carbon spheres of porous carbon;
3) uniformly coating the mixed slurry obtained in the step 2) on a carbon cloth, and drying the carbon cloth to obtain the carbon cloth loaded with the multi-element precursor salt;
4) applying instantaneous step current to the carbon cloth on a clamping fixture of the carbon cloth loaded with the multi-element precursor salt, and instantaneously electrifying the carbon cloth under the air atmosphere to generate Joule heat so that the nano carbon spheres are graphitized and form superfine intrinsic defects, meanwhile, the multi-element precursor salt loaded on the surfaces of the nano carbon spheres is quickly decomposed to form multi-element monatomic metal and is instantaneously fixed by the nano defects on the nano carbon spheres, namely the carbon-loaded multi-element monatomic catalyst is formed on the carbon cloth; scraping the carbon cloth from the carbon cloth.
Wherein the noble metal in the step 1) is selected from Pt, Au or Pd, and the non-noble metal is selected from Co, Fe, Mn, Cu or Ni; further, the noble metal salt refers to chloroplatinic acid, chloroauric acid or palladium chloride, and the non-noble metal salt is a chloride salt of Co, Fe, Mn, Cu or Ni.
And in the step 4), applying instantaneous step current to the carbon cloth for multiple times, wherein the current is 5-10A, the voltage is 17-20V, the instantaneous electrifying time is 60 mS each time, and the total electrifying time is not more than 600 mS.
The invention also provides application of the carbon-supported multi-element monatomic metal catalyst in catalyzing oxygen reduction reaction in a fuel cell.
Compared with the prior art, the inventor repeatedly tests and verifies the multi-element monatomic metal catalyst obtained by the technical scheme of the invention in exploration, and compared with the prior art according to the obtained actual technical effect data, the multi-element monatomic metal catalyst has the following remarkable effects:
(1) the kind of metal single atom elements in the catalyst prepared by the invention can reach 8 components at most, wherein the atom density is as high as 1.7 nm-2When the 8-membered single-atom metal catalyst is used for catalyzing ORR reaction, the mass activity at 0.8V reaches 1.2A mg-1Pt, 2.2 times that of the commercial Pt/C catalyst.
(2) The 8-element monatomic metal catalyst provided by the invention not only has high catalytic activity, but also shows good stability. The multi-element monoatomic metal catalyst is loaded on a glassy carbon electrode for accelerated life test (ADT). After 5000 cycles of accelerated cyclic voltammetry test, the half-wave potential difference of the linear sweep voltammetry curve of the catalyst is only 9mV, which is 70% lower than the corresponding value (-42 mV) of commercial Pt/C. This indicates that the stability of the 8-membered monatomic metal catalyst is far superior to commercial Pt/C and can be operated as an ORR catalyst in a fuel cell for a long period of time.
(3) The invention is madeThe prepared Pt loading amount is 0.0456 mg/cm2The carbon-supported 8-unit monatomic metal catalyst is directly used as a cathode of a direct sodium borohydride fuel cell and assembled into a single cell, and when a Nafion 212 membrane is selected as an electrolyte diaphragm, the maximum output power density of the single cell reaches 341.65 mW-2Is 0.4 mg/cm in commercial use21.7 times that of the fuel cell of the Pt/C catalyst. Further, a direct sodium borohydride fuel cell using a carbon supported 8-membered monatomic metal catalyst achieved 523.13 mw cm when a thinner Nafion 211 membrane was used as the electrolyte membrane-2The maximum output power density of.
(4) The carbon-supported 8-membered monatomic metal catalyst component developed by the invention greatly reduces the cost, the carbon-based carrier is cheap and easy to obtain, and the preparation method is simple and rapid, thereby providing an effective way for developing a green low-cost catalyst with low platinum content.
Drawings
Fig. 1 is a high-angle annular dark field image-spherical aberration correction scanning transmission electron microscope image of the PtNi binary monatomic catalyst prepared in example 1 of the present invention. Wherein (a) is a low magnification image, (b) is a high magnification image, and (c) is an element distribution diagram of Pt, and (d) is an element distribution diagram of Ni.
Fig. 2 is a high-angle annular dark field image-spherical aberration correction scanning transmission electron microscope (HAADF-STEM) image of the ptadppdco monatomic catalyst prepared in example 2 of the present invention.
Fig. 3 is a high-angle annular dark field image-spherical aberration corrected scanning transmission electron microscope (HAADF-STEM) image of the graphene-supported 8-membered monatomic catalyst prepared in example 3 of the present invention.
Fig. 4 is a high angle annular dark field image-spherical aberration corrected scanning transmission electron microscope (HAADF-STEM) image of a carbon-supported 8-membered monatomic catalyst prepared in example 4 of the present invention. (a) Results of HAADF-STEM images of prepared carbon-supported 8-membered monatomic catalysts and energy dispersive X-ray spectroscopy (EDS) images of their assembly: (b) carbon, (c 1) platinum, (c 2) gold, (c 3) palladium, (c 4) iron, (c 5) cobalt, (c 6) nickel, (c 7) manganese, (c 8) copper element distribution diagram. Scale bar, 5 nm.
FIG. 5 shows the linear voltammogram and Tafel curves of example 4 of the present invention measured with an RDE electrode rotating at 1600 rmp in an alkaline environment saturated with oxygen.
FIG. 6 is a comparison graph of linear voltammetric polarization curves before and after 5000 CV cycles of operation in an alkaline environment for example 4 of the present invention.
FIG. 7 is a graph showing the power generation performance of example 4 of the present invention as a direct sodium borohydride fuel cell.
FIG. 8 is a voltammogram of the catalytic ORR of example 4 of the present invention and comparative examples 1 and 2 in an oxygen-saturated basic environment.
Detailed Description
The present invention will now be described more clearly, in detail and completely with reference to the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention:
example 1:
preparation of carbon-supported PtNi monatomic catalyst
(1) 1gH is reacted with2PtCl6·6H2O was sufficiently dissolved in 193 ml of absolute ethanol to obtain a 0.01M chloroplatinic acid solution. Mixing NiCl2·6H2O was sufficiently dissolved in 200 ml of absolute ethanol to obtain a 0.01M nickel chloride solution. Taking 80mg BP2000 carbon powder, adding 4-10 ml chloroplatinic acid solution and nickel chloride solution into a 50ml beaker according to the molar ratio of metal elements of 1:1, adding 10 ml absolute ethyl alcohol diluted liquid, covering a preservative film and carrying out ultrasonic treatment for 120 min. The mixture was magnetically stirred for 12 hours with a magnetic rotor. To the resulting slurry was added 40 mg of nafion solution (5 wt.%), and the slurry was applied to a carbon cloth with a paintbrush, 50 wt.%oAnd C, drying for 1 h. Here, including the following examples and comparative example 1, Nafion was added to function as a binder to facilitate the operation of coating the slurry on the carbon cloth; so that no Nafion solution is used and any technical effect of the finally prepared catalyst is not influenced.
(2) The carbon cloth is cut into 1cm wide and fixed by a self-made clamp. And then applying instantaneous current to the carbon cloth for 3 times by a precise current source, wherein the current is 5-10A, the voltage is 19-20V, and the single electrifying time is 60 mS.
Example 2: preparation of carbon-supported PtAuPdCo single-atom catalyst
(1) Will be 1g H2PtCl6·6H2O was sufficiently dissolved in 193 ml of absolute ethanol to obtain a 0.01M chloroplatinic acid solution. 1g of HAuCl4·4H2O was sufficiently dissolved in 294.3ml of absolute ethanol to obtain a 0.01M chloroauric acid solution. Adding CoCl2·6H2O was sufficiently dissolved in 200 ml of absolute ethanol to obtain a 0.01M cobalt chloride solution. PdCl2Adding into 200 ml absolute ethyl alcohol, and magnetically stirring for 24h to obtain 0.01M palladium chloride ethanol solution. Taking 80mg BP2000 carbon powder, adding 2-5 ml chloroplatinic acid, chloroauric acid, palladium chloride and cobalt chloride solution into a 50ml beaker according to the molar ratio of each metal element of 1:1:1:1, adding 10 ml absolute ethyl alcohol diluted liquid, covering a preservative film and carrying out ultrasonic treatment for 120 min. The mixture was magnetically stirred for 12 hours with a magnetic rotor. To the resulting slurry was added 40 mg of 5wt.% Nafion solution, and the slurry was uniformly applied to a carbon cloth with a paintbrush, 50%oAnd C, drying for 1 h.
(2) The carbon cloth is cut into 1cm wide and fixed by a self-made clamp. And then applying instantaneous current to the carbon cloth for 5 times by a precise current source, wherein the current is 5-10A, the voltage is 19-20V, and the single electrifying time is 60 mS.
Example 3: preparation of graphene-supported PtAuPdFeCoNiMnCu single-atom catalyst
(1) Placing graphene in a magnetic boat in an ammonia environment 300 DEGoHeating for 1h to obtain a small amount of nitrogen-doped graphene substrate, wherein the heating rate is 10oC.min-1. Will be 1g H2PtCl6·6H2O was sufficiently dissolved in 193 ml of absolute ethanol to obtain a 0.01M chloroplatinic acid solution. 1g of HAuCl4·4H2O was sufficiently dissolved in 294.3ml of absolute ethanol to obtain a 0.01M chloroauric acid solution. 0.355 g of PdCl2Adding into 200 ml absolute ethyl alcohol, and magnetically stirring for 24h to obtain 0.01M palladium chloride ethanol solution. 0.397 g of FeCl3·4H2O、0.476 gCoCl2·6H2O、0.475 gNiCl2·6H2O、0.325gMnCl2·4H2O and 0.341gCuCl2·2H2O is fully dissolved to 200 mlObtaining 0.01M quinary non-noble metal precursor salt solution in water ethanol.
(2) Taking 100mg of graphene, adding 2-5 ml of chloroplatinic acid, chloroauric acid, palladium chloride and five-membered non-noble metal solution into a 50ml beaker according to the molar ratio of each metal element of 1:1, adding 10 ml of absolute ethyl alcohol diluted liquid, covering a preservative film and performing ultrasonic treatment for 120 min. The mixture was magnetically stirred for 12 hours with a magnetic rotor. To the resulting slurry was added 50mg of 5wt.% Nafion solution, and the slurry was uniformly applied to a carbon cloth with a paintbrush, 50%oAnd C, drying for 1 h.
(3) The carbon cloth was cut to 1cm width and fixed with a self-made aluminum jig. And then applying instantaneous current to the carbon cloth for no more than 10 times by a precise current source, wherein the current is 5-10A, the voltage is 17-18V, and the single-time electrifying time is 60 mS.
Example 4
Preparation of carbon-supported PtAuPdFeCoNiMnCu single-atom catalyst
(1) 1g of HAuCl4·4H2O was sufficiently dissolved in 294.3ml of absolute ethanol to obtain a 0.01M chloroauric acid solution. 0.355 g of PdCl2Adding into 200 ml absolute ethyl alcohol, and magnetically stirring for 24h to obtain 0.01M palladium chloride ethanol solution. 0.397 g of FeCl3·4H2O、0.476 gCoCl2·6H2O、0.475 gNiCl2·6H2O、0.325 gMnCl2·4H2O and 0.341gCuCl2·2H2And fully dissolving O into 200 ml of absolute ethanol to obtain 0.01M solution of five-membered non-noble metal precursor salt.
(2) Taking 80mg BP2000 pearl carbon powder, adding 1-2.5 ml chloroplatinic acid, chloroauric acid, palladium chloride and five-element non-noble metal precursor salt solution into a 50ml beaker according to the molar ratio of each metal element of 1:1, adding 10 ml absolute ethyl alcohol to dilute liquid, covering a preservative film and carrying out ultrasound treatment for 120 min. The mixture was put on a magnetic rotor and magnetic stirring was continued for 12 hours. To the resulting slurry was added 50mg of 5wt.% Nafion solution, and the slurry was uniformly applied to a carbon cloth with a paintbrush, 50%oAnd C, drying for 1 h.
(3) The carbon cloth was cut to 1cm width and fixed with a self-made aluminum jig. And then applying instantaneous current to the carbon cloth for no more than 10 times by a precise current source, wherein the current is 5-10A, the voltage is 17-18V, and the single-time electrifying time is 60 mS.
The above examples are only specific preferred examples of the present invention, and the technical effects of the above examples can be obtained by adjusting the above process parameters within a certain range during the preparation process of the catalyst of the present invention. For example, the molar ratio of the noble metal monoatomic atoms to the non-noble metal monoatomic atoms is adjusted within 1:3-3:1, and the catalytic performance of the obtained multi-element monoatomic catalyst meets the aim of the invention. The concentration of the prepared metal precursor solution can be adjusted within the range of 0.005-0.05M. The metal precursor solution and the carbon powder are mixed according to the mass ratio of 1:19-1:4, ultrasonic dispersion is carried out for 3-6 hours, and magnetic stirring is carried out for 12-24 hours, so that the mixed slurry meeting the requirements of the technical scheme of the invention can be prepared.
Comparative example 1
Preparation of Pt/C nanocatalyst (a carbon-supported nano Pt metal catalyst).
(1) Will be 1g H2PtCl6·6H2O was sufficiently dissolved in 193 ml of absolute ethanol to obtain a 0.01M chloroplatinic acid solution. Taking 80mg BP2000 carbon powder, adding 8-20 ml chloroplatinic acid solution into a 50ml beaker, adding 10 ml absolute ethyl alcohol diluted liquid, covering a preservative film and carrying out ultrasound for 120 min. The mixture was magnetically stirred for 12 hours with a magnetic rotor. To the resulting slurry was added 40 mg of nafion solution (5 wt.%), and the slurry was applied to a carbon cloth with a paintbrush, 50 wt.%oAnd C, drying for 1 h.
(2) The carbon cloth is cut into 1cm wide and fixed by a self-made clamp. And then applying instantaneous current to the carbon cloth for no more than 10 times by a precise current source, wherein the current is 5-10A, the voltage is 19-20V, and the single electrifying time is 60 mS, so as to prepare the carbon-supported nano platinum metal catalyst. The inventors found, through repeated experiments and analyses, that in the carbon-supported nano platinum metal catalyst prepared in the present comparative example, Pt supported on nano carbon spheres is nano particles rather than single atoms, compared to the examples. The inventor analyzes that the addition of the multi-component metal in the embodiment is beneficial to the dispersion of Pt atoms to obtain single atoms, and the Pt atoms are easy to agglomerate to form Pt nano-particles because of the mutual aggregation of the Pt atoms due to the use of the single-component Pt in the comparative example.
Comparative example 2
Preparation of Co/C catalyst (a carbon-loaded Co nanocluster catalyst)
Compared with the embodiment, the carbon-supported Co nanocluster catalyst is prepared by mixing non-noble metal salt and carbon nanospheres in the comparative example by adopting a transient Joule method under a protective atmosphere. The method comprises the following steps:
(1) 96.4mg of Co (NO)3)2·6H2O, 93.6mg of carbon powder and 50ml of ethanol are mixed and ultrasonically treated for 60min, and then the mixed suspension is magnetically stirred and reacts for 24h at room temperature.
(2) The evenly mixed slurry is stirred by open magnetic force to volatilize the ethanol until the slurry is sticky to be pasty, and then the sticky precursor slurry is coated on a layer of 30cm2The carbon cloth is coated and naturally dried for 12 hours.
(3) Cutting the dried carbon cloth into small pieces of 1 × 1.5cm, and fixing one piece of carbon cloth by using a self-made clamp. And then charging the capacitor by the voltage of 20V and the current of 2.5A, triggering carbon thermal impact on the carbon cloth loaded by the precursor by instantly discharging the charged capacitor to the carbon cloth under the argon atmosphere to obtain a product, and scraping black powder on the carbon cloth to obtain the carbon-loaded catalyst Co/C. The non-noble metal Co in the carbon-supported Co/C catalyst is represented by a conventional nanocluster and a non-monatomic form.
The catalysts prepared in the above examples and comparative examples are respectively tested and analyzed, and fig. 1 is a high-angle annular dark field image-spherical aberration correction scanning transmission electron microscope image of the PtNi binary monatomic catalyst prepared in example 1, wherein the PtNi binary monatomic catalyst has a small number of nanoclusters and a uniform atomic distribution. Wherein the surface density of the PtNi binary monatomic catalyst is 1.75 nm-2. It can also be seen from the HAADF diagram and EDS profile that the PtNi monatomic catalyst sample has a uniform atomic dispersion and forms a small number of large-size clusters. FIG. 2 is an image of a high-angle annular dark field image-spherical aberration correction scanning transmission electron microscope (HAADF-STEM) of the PtAuPdCo monatomic catalyst prepared in example 2, in which it can be seen that the carbon sphere substrate is instantaneously powered onThe long and thin stripes of graphitized carbon appear, which shows that the instantaneous energization process improves the graphitization degree of the carbon substrate, and the obtained catalyst is mainly of uniformly dispersed single atoms. FIG. 3 is an image of high-angle annular dark field image-spherical aberration corrected scanning transmission electron microscope (HAADF-STEM) of the graphene-supported 8-membered monatomic catalyst prepared in example 3, in which high-density monatomic (atomic density of about 1.7 nm) is instantaneously formed on carbon spheres after instantaneous energization in millisecond order-2). From the STEM graph, it can be seen that 8 metal elements are uniformly distributed in the form of single atoms in the carbon spheres. Fig. 4 is a high angle annular dark field image-spherical aberration correction scanning transmission electron microscope (HAADF-STEM) image of the carbon-supported 8-membered single-atom catalyst prepared in example 4, in which (a) is an EDS image and the others are elemental distribution maps, corresponding to (b) carbon, (c 1) platinum, (c 2) gold, (c 3) palladium, (c 4) iron, (c 5) cobalt, (c 6) nickel, (c 7) manganese, (c 8) copper, and 8 metal elements are uniformly distributed in the form of single atoms in the carbon sphere.
The catalytic performance tests of the catalysts prepared in the examples and comparative examples include a catalytic activity test of a catalytic Oxygen Reduction Reaction (ORR), a catalytic stability test of a catalytic oxygen reduction reaction, and an application performance test applied to a direct sodium borohydride fuel cell. Specific tests are as follows.
Catalytic activity test for catalytic oxygen reduction reaction
The electrochemical activity test of the catalyst mainly comprises an electrochemical workstation CHI 733e, a Rotating disk corollary instrument Gamry 710, different catalyst electrode Rotating Disk Electrodes (RDE) and (RRDE) and a three-electrode electrochemical cell. The electrochemical activity test of the catalyst can be carried out by a Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) characterization method, matching with a corresponding RDE or RRDE electrode and changing the parameter setting. The specific implementation method comprises the following steps:
(1) the carbon cloth that was energized was removed from the aluminum holder, and the carbon powder on the carbon cloth was gently scraped onto the weighing paper with a brush and collected in a 5 ml centrifuge tube. Adding ethanol into a centrifuge tube by using a suction tube,gently shaken to disperse uniformly. After standing for 1h, the supernatant liquid was removed. The steps are repeated for a plurality of times to obtain a clean monatomic catalyst sample. The catalyst in the centrifuge tube was placed at 70 deg.CoAnd C, drying in a vacuum drying oven for 10 hours to obtain the catalyst powder to be tested.
(2) A 4.0 mg home-made catalyst sample, 1.5 mL ethanol, and 0.1 mL of a 5wt.% Nafion solution were ultrasonically mixed for 2 min to form a uniform catalyst dispersion. And (4) pipetting the 5 microliter sample onto a clean 3 mm glassy carbon electrode by using a pipetting gun, drying, and then starting formal testing.
(3) RDE (RDE, BASi RDE 2) was selected as the working electrode at 10 mV. s-1The CV curve of the catalyst under oxygen saturation or nitrogen saturation was recorded at 0.2-1.2V. RDE testing Slow LSV scans (10 mV. s) were also performed using RDE electrodes at 400, 900, 1600 and 2500 rpm in the range of 0.2-1.2V-1) And analyzing the number of transfer electrons of the catalyst participating in the ORR reaction according to a Koutecky-Levich equation.
(4) Further analysis of the 1600 rpm RDE data allowed the Tafel slope of the catalyst to be calculated by first finding the onset reduction potential in the 1600 rpm RDE dataE onset Calculating the limiting diffusion current densityi d And limiting dynamic current densityi k According to the formula E = blogi+ a fittingEAnd logiData relationship between, to linear intervalE onset And (5) performing linear fitting on the +/-10 mV area, wherein the slope b of the linear part is the Tafel slope.
Catalytic stability testing of catalytic oxygen reduction reactions
(1) The carbon cloth that was energized was removed from the aluminum holder, and the carbon powder on the carbon cloth was gently scraped onto the weighing paper with a brush and collected in a 5 ml centrifuge tube. Add ethanol to the centrifuge tube with a pipette and shake gently to disperse evenly. After standing for 1h, the supernatant liquid was removed. The steps are repeated for a plurality of times to obtain a clean monatomic catalyst sample. The catalyst in the centrifuge tube was placed at 70 deg.CoAnd C, drying in a vacuum drying oven for 10 hours to obtain the catalyst powder to be tested.
(2) A 4.0 mg home-made catalyst sample, 1.5 mL ethanol, and 0.1 mL of a 5wt.% Nafion solution were ultrasonically mixed for 2 min to form a uniform catalyst dispersion. The 5 μ L sample was pipetted onto a clean 3 mm glassy carbon electrode with a pipette gun and dried before starting the test.
(3) A slow Linear sweep voltammetric scan (LSV) was performed at a rate of 10 mV ∙ s-1 in an oxygen saturated environment at 1600 rpm in the range of 0.2-1.2V, and the oxygen reduction curve was recorded at circle 1. A fast CV scan 5000-turn life test was then performed at a scan rate of 50 mV ∙ s-1, in the Faraday voltage range of ORR (0.2-1.2V). A slow LSV scan was then performed again and the oxygen reduction curve recorded after 5000 cycles.
(4) The process is repeated for many times, and LSV polarization curves of the catalyst after different cycles of life tests are recorded. CV turns were accumulated until the LSV curve of the catalyst had drifted significantly. The shift of the half-wave potential (Delta E) after 10000 LSV tests with 5000 CV cycles1/2) As a measure of the half-cell level electrochemical stability of the catalyst.
As shown in fig. 5, Δ E1/2 of the LSV polarization curve before and after 5000 CV runs of the eight-membered-unit-atom catalyst in an alkaline environment was only 9mV, demonstrating excellent stability of the eight-membered-unit-atom catalyst. Fig. 6 is a comparison graph of linear voltammetry polarization curves of example 4 before and after 5000 cycles of CV operation in an alkaline environment, and it can be seen that the half-wave potential of the linear voltammetry curve of example 4 is shifted by only 9mV after 5000 cycles of CV test, and the catalyst stability is excellent.
Performance test applied to direct sodium borohydride fuel cell
(1) The CoPPy-BP powder, 5wt.% Nafion solution and ethanol were mixed in a mass ratio of 1:7: 32, and coated on a nickel foam electrode to prepare a fuel cell anode.
(2) Dripping 1-10 wt.% of PTFE emulsion on a catalyst electrode (with the size of 1cm x 1 cm) after instantaneous electrification, and flattening the surface of the electrode by using a smooth convex surface (such as the bottom of a spoon) to enable the electrode to present a metallic luster.
(3) The treated carbon cloth is used as the cathode of the batteryThe middle was separated with commercial Nafion 117 membrane. Direct borohydride fuel cells were assembled by two rubber ring seals to evaluate the monatomic catalyst at 30 and 60oCell performance at C. Will contain 5wt.% NaBH4And 10 wt.% NaOH, by peristaltic pump at 50 ml.min-1The fuel was pumped into the anode at a flow rate of 100 ml.min humidified oxygen-1The cathode (oxygen pressure 0.25 MPa) was fed and the cell was tested for voltage at steady discharge at a range of current densities. The current density was gradually increased in each stage, and the discharge time was 60 s. The Maximum power density achieved by the fuel cell at different temperatures (Maximum power density,P max ) As an evaluation index of the fuel cell performance, the power density is obtained by multiplying the voltage by the current density. Eight-unit-atom catalyst in the case of using Co-PPY as an anode catalyst, an eight-unit-atom catalyst as a cathode catalyst, and a Nafion 212 membrane as a separator, DBFCP max Up to 512 mW.cm-2It can be seen that the monatomic catalysts prepared by this method have surprising membrane electrode properties, which are of great significance to the monatomic catalysis field.
Fig. 7 is a graph showing the power generation performance of the direct sodium borohydride fuel cell of example 4 according to the present invention. 523 mWcm was achieved for a direct sodium borohydride fuel cell using example 4 as the cathode catalyst and Nafion 211 membrane as the electrolyte membrane-2Fig. 8 is a graph showing the performance of the carbon-supported 8-membered single-atom metal catalyst prepared in example 4 in catalyzing the oxygen reduction reaction with the catalysts prepared in comparative examples 1 to 2, and it can be seen from comparison that the initial reduction potential of the carbon-supported 8-membered single-atom metal catalyst prepared in example 4 is superior to that of the Co/C catalyst prepared in comparative example 2 and is close to that of the pure noble metal Pt/C catalyst prepared in comparative example 1.
Claims (10)
1. A carbon-supported multi-element monoatomic metal catalyst is characterized in that: wherein the carrier carbon is a nano carbon sphere which is one of porous carbon or graphene; wherein the multi-element monoatomic comprises monoatomic atoms of one or more noble metals and one or more non-noble metals, wherein each metal monoatomic atom is uniformly dispersed on the surface of the carrier nano carbon sphere; wherein the noble metal is selected from Pt, Au or Pd, and the non-noble metal is selected from Co, Fe, Mn, Cu or Ni.
2. The carbon-supported multi-monoatomic metal catalyst according to claim 1, wherein: in the carbon-supported multi-element monatomic metal catalyst, the molar ratio of noble metal monatomic to non-noble metal monatomic is 1:3-3: 1.
3. The carbon-supported multi-monoatomic metal catalyst according to claim 2, wherein: in the carbon-supported multi-element monatomic metal catalyst, the molar ratio of each metal monatomic is 1: 1.
4. The carbon-supported multi-monoatomic metal catalyst according to claim 3, wherein: in the carbon-supported multi-element monatomic metal catalyst, the monatomic metal comprises Pt, Au, Pd, Co, Fe, Mn, Cu and Ni, and the molar ratio of each metal is 1: 1:1:1:1:1:1:1.
5. A method for preparing the carbon-supported multi-element monatomic metal catalyst according to any one of claims 1 to 4, which comprises the steps of:
one or more noble metal salts and one or more non-noble metal salts are mixed and then added into absolute ethyl alcohol, and metal precursor solution is obtained after stirring and dissolving;
2) mixing the metal precursor solution obtained in the step 1) with carbon powder, performing ultrasonic dispersion, and performing magnetic stirring to obtain mixed slurry; the carbon powder is graphene or nano carbon spheres of porous carbon;
uniformly coating the mixed slurry obtained in the step 2) on a carbon cloth, and drying the carbon cloth to obtain the carbon cloth loaded with the multi-element precursor salt;
4) applying instantaneous step current to the carbon cloth on a clamping fixture of the carbon cloth loaded with the multi-element precursor salt, and instantaneously electrifying the carbon cloth under the air atmosphere to generate Joule heat so that the nano carbon spheres are graphitized and form superfine intrinsic defects, meanwhile, the multi-element precursor salt loaded on the surfaces of the nano carbon spheres is quickly decomposed to form multi-element monatomic metal and is instantaneously fixed by the nano defects on the nano carbon spheres, namely the carbon-loaded multi-element monatomic catalyst is formed on the carbon cloth; scraping the carbon cloth from the carbon cloth.
6. The method for preparing a carbon-supported multi-element monatomic metal catalyst according to claim 5, wherein: wherein the noble metal in the step 1) is selected from Pt, Au or Pd, the non-noble metal is selected from Co, Fe, Mn, Cu or Ni, the noble metal salt refers to chloroplatinic acid, chloroauric acid or palladium chloride, and the non-noble metal salt refers to the chloride salt of Co, Fe, Mn, Cu or Ni.
7. The method for preparing a carbon-supported multi-element monatomic metal catalyst according to claim 5, wherein: the concentration of the metal precursor solution obtained in the step 1) is 0.005-0.05M; the molar ratio of the noble metal monoatomic atoms to the non-noble metal monoatomic atoms ranges from 1:3 to 3: 1.
8. The method for preparing a carbon-supported multi-element monatomic metal catalyst according to claim 5, wherein: and 2) mixing the metal precursor solution and carbon powder according to the mass ratio of 1:19-1:4, carrying out ultrasonic dispersion for 3-6 hours, and carrying out magnetic stirring for 12-24 hours to obtain mixed slurry.
9. The method for preparing a carbon-supported multi-element monatomic metal catalyst according to claim 5, wherein: in the step 4), the instantaneous step current is applied to the carbon cloth for no more than 10 times, the current is 5-10A, the voltage is 17-20V, and the single electrifying time is 60 mS.
10. Use of a carbon supported multi-unit metal catalyst according to any one of claims 1 to 4, wherein the catalyst is used to catalyze an oxygen reduction reaction in a fuel cell.
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