CN116646545A - Sulfur-containing platinum-carbon catalyst for improving H resistance of platinum-carbon catalyst 2 Application in S toxicity - Google Patents
Sulfur-containing platinum-carbon catalyst for improving H resistance of platinum-carbon catalyst 2 Application in S toxicity Download PDFInfo
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- 239000011593 sulfur Substances 0.000 title claims abstract description 166
- 239000003054 catalyst Substances 0.000 title claims abstract description 132
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- 230000001988 toxicity Effects 0.000 title claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 119
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- 239000011865 Pt-based catalyst Substances 0.000 description 1
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- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of electrochemistry, and discloses a sulfur-containing platinum-carbon catalyst for improving H resistance of the platinum-carbon catalyst 2 Application in S toxicity. The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the total sulfur content in the sulfur-modified carbon carrier is greater than or equal to the surface sulfur content, and the mass fraction of the platinum is 20-70% based on the total mass of the catalyst. By using the platinum carbon catalyst of the present invention, the catalyst can be made resistant to H 2 And (5) improving S toxicity.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a sulfur-containing platinum-carbon catalyst for improving H resistance of the platinum-carbon catalyst 2 The application of S toxicity also relates to an anode reaction method of a hydrogen fuel cell and the application of a platinum carbon catalyst in the fuel cell.
Background
The platinum-carbon catalyst is a common catalyst in the field of electrocatalysis, and is a cathode-anode catalyst in a proton exchange membrane hydrogen fuel cell. When Pt/C catalyst is used as anode catalyst, the activity is high, but the toxicity resistance is poor, H 2 Trace impurity H in (a) 2 S generates strong adsorption on the surface of noble metal Pt, and causes accumulative irreversible poisoning of the catalyst. This results in national standards for H in hydrogen gas used in hydrogen fuel cells 2 The S requirement is extremely high, requiring less than 4ppb, resulting in a dramatic increase in the cost of hydrogen purification. Thus, H-resistance 2 S toxicity is critical for use in proton exchange membrane fuel cell anode catalysts.
Due to H 2 S has too strong poisoning effect on Pt and is currently resistant to H 2 Few S-toxic catalysts have been studied, starting only from controlling the purity of hydrogen. Energy environ. Sci.,2018,11,166, by adding 2, 6-diacetylpyridine to an external solution, uses the covering effect of the compound on the Pt surface to block Pt and H 2 S contact effect, thereby improving H resistance of the catalyst 2 S toxicity. However, in practical application, it is difficult to add other molecules to hydrogen fuel cells, and therefore it is critical to develop a hydrogen fuel cell having H resistance itself 2 S toxic catalyst.
Disclosure of Invention
The object of the present invention is to prepare a composition which is tolerant to H 2 S toxic sulfur-containing platinum-carbon catalyst for solving the problem that no effective H tolerance exists at present 2 Pt-based catalysts of S toxicityProblems. The invention utilizes the strong interaction between sulfur and Pt to prepare the sulfur modified carbon carrier by simply modifying the carbon carrier, so that the strong interaction is formed between the carrier and platinum, electrons are transferred from Pt to the carrier, and the H of Pt is weakened 2 S is adsorbed, and the catalyst is promoted to H 2 Tolerance of S.
To achieve the above object, one aspect of the present invention provides a sulfur-containing platinum-carbon catalyst for improving the H-resistance of the platinum-carbon catalyst 2 The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the total sulfur content in the sulfur-modified carbon carrier is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times, more preferably more than 1.5 times, of the surface sulfur content, and the mass fraction of the platinum is 20-70 percent based on the total mass of the catalyst.
Preferably, the mass fraction of platinum is 20-60%, more preferably 40-60%, based on the total mass of the catalyst.
Preferably, the total sulfur content in the sulfur-modified carbon carrier is 0.4 to 8 mass%, preferably 1 to 6 mass%.
Preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1 to 6 mass%, preferably 0.5 to 4 mass%.
Preferably, the sulfur-modified carbon support is a sulfur-modified conductive carbon black.
Preferably, the conductive carbon Black in the sulfur-modified conductive carbon Black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72R, black pears 2000, PRINTEX XE2-B, PRINTEX L6 and HIBLASXK 40B 2.
In a second aspect, the present invention provides a method of anode reaction for a hydrogen fuel cell, the method comprising: under the anode reaction condition, H in the raw material gas 2 Contacting with a sulfur-containing platinum carbon catalyst; wherein H in the raw material gas 2 The S content is below 15 ppm; the sulfur-containing platinum carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the sulfur-modified carbon carrier is sulfur-modified conductive carbon black, the total sulfur content in the sulfur-modified carbon carrier is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times of the surface sulfur content, and more preferablyPreferably 1.5 times or more, the mass fraction of platinum is 20 to 70% based on the total mass of the catalyst.
Preferably, H in the feed gas 2 The S content is 10ppm or less, more preferably 5ppm or less.
Preferably, the anode reaction conditions include: the voltage is 0V or more, preferably 0.01-0.4V.
Preferably, the mass fraction of platinum is 20-60%, more preferably 40-60%, based on the total mass of the catalyst.
Preferably, the total sulfur content in the sulfur-modified carbon carrier is 0.4 to 8 mass%, preferably 1 to 6 mass%.
Preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1 to 6 mass%, preferably 0.5 to 4 mass%.
Preferably, the conductive carbon Black in the sulfur-modified conductive carbon Black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72R, black pears 2000, PRINTEX XE2-B, PRINTEX L6 and HIBLASXK 40B 2.
The third aspect of the present invention provides the use of a platinum carbon catalyst in a fuel cell, the platinum carbon catalyst comprising a sulfur-modified carbon support and a platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, the total sulfur content in the sulfur-modified carbon support being greater than or equal to the surface sulfur content, preferably the total sulfur content being greater than or equal to 1.2 times the surface sulfur content, more preferably greater than or equal to 1.5 times the surface sulfur content, the mass fraction of platinum being from 20 to 70% based on the total mass of the catalyst; wherein, H in the feed gas of the fuel cell 2 The S content is 15ppm or less.
Preferably, the fuel cell is a hydrogen fuel cell.
Preferably, the sulfur-containing platinum carbon catalyst acts as an anode catalyst in a fuel cell.
Preferably, H in the feed gas 2 The S content is 10ppm or less, preferably 0.4 to 10ppm.
Preferably, the mass fraction of platinum is 20-60%, more preferably 40-60%, based on the total mass of the catalyst.
Preferably, the total sulfur content in the sulfur-modified carbon carrier is 0.4 to 8 mass%, preferably 1 to 6 mass%.
Preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1 to 6 mass%, preferably 0.5 to 4 mass%.
Preferably, the conductive carbon Black in the sulfur-modified conductive carbon Black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72R, black pears 2000, PRINTEX XE2-B, PRINTEX L6 and HIBLASXK 40B 2.
In a fourth aspect, the present invention provides a sulfur-containing platinum carbon catalyst for improving the H resistance of the platinum carbon catalyst 2 The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the sulfur-modified carbon carrier is sulfur-modified conductive carbon black, the total sulfur content in the sulfur-containing platinum-carbon catalyst is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times of the surface sulfur content, more preferably more than 1.5 times of the surface sulfur content, and the mass fraction of platinum is 20-70 percent based on the total mass of the catalyst.
Through the technical scheme, the sulfur-containing platinum-carbon catalyst has the following advantages: firstly, the preparation method is simple, the industrial amplification is easy, and the H resistance of the catalyst can be realized only by modifying the carrier 2 S toxicity elevation; secondly, the catalyst obtained by the method has extremely strong H 2 S tolerance performance, and no other substances are required to be additionally added in the using process.
Drawings
FIG. 1 is a platinum carbon catalyst of example 2 over H 2 LSV curves before and after S poisoning.
FIG. 2 is a platinum carbon catalyst of example 2 over H 2 CV curves before and after S poisoning.
FIG. 3 is a graph of the platinum carbon catalyst of example 1 and comparative example 1 over H 2 LSV curves before and after S poisoning.
FIG. 4 is a graph of the platinum carbon catalyst of example 1 and comparative example 1 over H 2 CV curves before and after S poisoning.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a sulfur-containing platinum carbon catalyst for improving the H resistance of the platinum carbon catalyst 2 The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the total sulfur content in the sulfur-modified carbon carrier is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times, more preferably more than 1.5 times, of the surface sulfur content, and the mass fraction of the platinum is 20-70 percent based on the total mass of the catalyst.
According to the present invention, by using the sulfur-containing platinum carbon catalyst of the present invention, it is possible to provide a better H-resistance based on the existing platinum carbon catalyst 2 S toxicity effect, thereby achieving the effect of prolonging the service life of the platinum-carbon catalyst. Specifically, the sulfur-containing platinum carbon catalyst may be used as an anode catalyst or the like in a fuel cell.
As a cause of H 2 S toxic H 2 The source of S may be, for example, impurity H which is mixed into the raw material gas or hardly removed from the viewpoint of the production process, the components, and the like 2 S, etc.
In the sulfur-containing platinum-carbon catalyst, the sulfur element is compounded in the carbon carrier, so that the platinum is more favorably loaded in the carbon carrier, and the sulfur-containing platinum-carbon catalyst has better electrocatalytic performance. Preferably, the total sulfur content in the sulfur-modified carbon carrier is 1.7 times or more, 2 times or more, 3 times or more, etc., for example, 1.5 to 10 times the surface sulfur content. Wherein the surface sulfur content represents the mass fraction of sulfur measured by XPS analysis, and the total sulfur content represents the mass fraction of sulfur measured by a sulfur carbon analyzer.
According to the present invention, the total sulfur content in the sulfur-modified carbon carrier is preferably 0.4 to 8 mass%, and preferably 1 to 6 mass%. Preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1 to 6 mass%, preferably 0.5 to 4 mass%.
The sulfur-containing platinum carbon catalyst of the present invention may have a total sulfur content of, for example, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, or the like, as the surface sulfur content. The total sulfur content may be 0.4 mass%, 0.5 mass%, 1 mass%, 1.5 mass%, 2 mass%, 3 mass%, 4 mass%, 5 mass%, 6 mass%, 7 mass%, 8 mass%, or the like; the surface sulfur content may be 0.1 mass%, 0.5 mass%, 1 mass%, 1.5 mass%, 2 mass%, 3 mass%, 4 mass%, 5 mass%, 6 mass%, or the like.
Preferably, the elemental sulfur in the sulfur-modified carbon support is present as elemental sulfur.
According to the present invention, preferably, at least 90%, preferably 95% or more of the platinum metal particles are supported inside the carbon support. The distribution position of the platinum metal particles can be determined by the following method: in the TEM image, the relative positions of 200 metal platinum particles along the edge of the carbon support and the carbon support were randomly counted, and the proportion A of the metal platinum particles protruding from the carbon support was calculated and the proportion of the platinum metal particles supported inside the carbon support was expressed as (100-A)%. It will be appreciated that in the TEM images, "protruding from the carbon support" means that the metal platinum particles are located on the surface of the carbon support, and "not protruding from the carbon support" means that the metal platinum particles are located inside the carbon support.
In the sulfur-containing platinum-carbon catalyst of the present invention, the platinum metal particles having regular lattice fringes in the sulfur-containing platinum-carbon catalyst are not more than 60%, preferably 50% or less, more preferably 40% or less, still more preferably 20% or less, or 10% or less. Having lattice fringes indicates that the Pt particles exist in a nano-crystalline form, while not having lattice fringes indicates that the Pt particles exist in an atomic or cluster form. Specifically, the lattice fringes can be confirmed by observation under a TEM or STEM (preferably AC-TEM or AC-STEM).
In the sulfur-containing platinum carbon catalyst, the characteristic peak of Pt 4f7/2 in the XPS spectrum is above 71.6eV, for example, between 71.6 and 72.2eV, such as 71.7eV. The XPS spectrum is corrected by using the C1s peak at 284.3 eV. In general, for example, when platinum is supported by a carbon carrier without composite elements, the characteristic peak of Pt 4f7/2 is located near 71.3eV, which indicates that the characteristic peak of Pt 4f7/2 in the sulfur-containing platinum carbon catalyst of the invention deviates more than 0.3eV from high electron volts in an XPS spectrum.
In the sulfur-containing platinum-carbon catalyst of the present invention, the mass fraction of platinum may be 20 to 70%, specifically 20 to 60%, 20 to 40%, 40 to 60% or 40 to 70%, based on the total mass of the catalyst. Preferably, the sulfur-containing platinum carbon catalyst of the present invention does not contain other metal elements other than platinum.
According to the present invention, preferably, the sulfur-modified carbon carrier includes conductive carbon black and elemental sulfur and elemental oxygen compounded therein. The sulfur-modified carbon support of the present invention preferably contains no complex elements other than sulfur. Herein, the "complex element" in the present invention means nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine. More preferably, the sulfur-modified carbon carrier is composed of conductive carbon black and elemental sulfur and elemental oxygen compounded therein.
According to the invention, the sulfur-modified carbon support is a sulfur-modified conductive carbon black.
As the conductive carbon Black usable in the present invention, one or more of ordinary conductive carbon Black (Conductive Blacks), super conductive carbon Black (Super Conductive Blacks) or special conductive carbon Black (Extra Conductive Blacks) may be used, for example, one or more of Ketjen Black (Ketjen Black), cabot conductive carbon Black (Black pears, etc.), eurolone conductive carbon Black (HIBLACK, PRINTEX, etc.), etc., and specifically EC-300J, EC-600JD, ECP600JD, VXC72R, black pears 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK40B2 may be used.
The invention has no limitation on the preparation method and the source of the conductive carbon black. The conductive carbon black can be acetylene black, furnace black and the like.
Preferably, the oxygen content in XPS analysis of the conductive carbon black is greater than 4 mass%, for example, 5 to 12 mass%.
Preferably, the resistivity of the conductive carbon black is less than 10Ω·m, preferably less than 5Ω·m, more preferably less than 3Ω·m, and even more preferably 0.01 to 1Ω·m.
Preferably, the specific surface area of the conductive carbon black is 200-2000m 2 Preferably 220-1500m 2 /g。
The preparation method of the sulfur-containing platinum carbon catalyst of the present invention is only required to have the above-described properties. Specifically, as the preparation method of the sulfur-containing platinum carbon catalyst, the method can comprise the following steps:
(1) Impregnating the carbon carrier with a solution containing sulfur at 10-80 ℃ for 1-5h, and drying the impregnated product to obtain a sulfur modified carbon carrier;
(2) Removing the solvent in the uniform mixed solution containing the sulfur-modified carbon carrier, the platinum source and the solvent obtained in the step (1) to obtain a precursor material;
(3) Carrying out heat treatment on the precursor material obtained in the step (2) for 1-4 hours at 80-200 ℃ in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst;
wherein in the step (2), the amount of the platinum source is 0.25 to 2.4g in terms of platinum element relative to 1g of the sulfur-modified carbon carrier.
According to the present invention, in the step (1), the carbon carrier is the same as the corresponding part described above, and the description thereof will be omitted.
Preferably, in the step (1), the solvent in the solution containing sulfur is capable of dissolving sulfur, and from the viewpoint of better preparation of the sulfur-modified carbon carrier, may be, for example, cci 4 、CS 2 One or more of cyclohexane and n-hexane, more preferably cyclohexane, n-hexane and the like. The concentration of sulfur in the sulfur-containing solution is 0.0004 to 0.02g/mL, preferably 0.0005 to 0.01g/mL. The amount of the sulfur-containing solution is 5 to 15mL relative to 1g of the carbon support.
In order to obtain a suitable sulfur loading and sulfur distribution, the amount of sulfur is preferably 0.005 to 0.06g, more preferably 0.01 to 0.055g, relative to 1g of the carbon support. And, the temperature of the impregnation is preferably 20 to 30 ℃, more preferably at room temperature (25 ℃) for a time of preferably 2 to 4 hours.
The drying method is not particularly limited as long as the solvent in the sulfur-containing solution can be removed, and vacuum drying is preferably employed.
By preparing the sulfur-modified carbon support under the above conditions, the carbon support in the case of sulfur distribution required for the present invention can be obtained. The sulfur-modified carbon carrier produced by the step (1) can be more easily dispersed in the aqueous phase.
According to the present invention, in the step (2), the platinum source may be one or more of chloroplatinic acid, chloroplatinate, tetraamineplatinum acetate and platinum acetylacetonate. Wherein the chloroplatinic acid salt can be potassium chloroplatinate or sodium chloroplatinate, etc.
Preferably, the platinum source is used in an amount of 0.25 to 2.4g, preferably 0.25 to 0.67g, in terms of elemental platinum, relative to 1g of the sulfur-modified carbon carrier.
According to the present invention, in the step (2), the precursor material is obtained by dissolving the sulfur-modified carbon support and the platinum source in a solvent to form a uniform mixed solution, and then removing the solvent from the uniform mixed solution. The kind of the solvent is not particularly limited. The solvent can be one or more of water, alcohol solvents or ketone solvents; the alcohol solvent may be ethanol, for example, and the ketone solvent may be acetone, for example. The solvent is more preferably water, ethanol or a homogeneous mixture of ethanol and water (the volume ratio of ethanol to water may be arbitrarily selected, and may be, for example, 0.1 to 10:1, preferably 1 to 5:1). The amount of the solvent used in the present invention is not particularly limited, and may be, for example, 3 to 20mL relative to 1g of the sulfur-modified carbon support.
The present invention can mix the sulfur-modified carbon support, the platinum source and the solvent to obtain the above-mentioned homogeneous mixed solution, preferably with stirring. The stirring rate and time are not particularly limited in the present invention, and the uniform mixed solution may be formed. In order to form the homogeneous mixture, the dissolution may be further accelerated by heating.
As a method for removing the solvent in the homogeneous mixed solution, the solvent in the homogeneous mixed solution may be removed by evaporation, and the temperature and process of evaporation may be the conventional techniques known to those skilled in the art. According to the present invention, in the step (2), the drying temperature at the time of removing the solvent is 100℃or lower, and for example, the solvent in the homogeneous mixed solution may be removed by drying in an oven at 60 to 95℃for 12 to 24 hours.
According to a preferred embodiment of the present invention, in step (2), the solvent is removed after the homogeneous mixture is allowed to stand for a period of 4 hours or more, preferably 16 to 30 hours.
According to the invention, in step (3), the temperature of the heat treatment is preferably 100-180 ℃, and the time is preferably 2-3 hours. And the heating rate of the heat treatment may be 4 to 15℃per minute, generally 5℃per minute.
According to the invention, in step (3), the heat treatment is performed in a reducing atmosphere. The reducing atmosphere preferably comprises hydrogen, preferably a mixed atmosphere of hydrogen and an inert gas, wherein the inert atmosphere can be nitrogen and/or argon and the like, and particularly can be a mixed atmosphere of hydrogen and nitrogen. Preferably, the hydrogen comprises 5-30% by volume of the total gas. The heat treatment may be carried out in any apparatus that provides the above heat treatment conditions, for example, in a tube furnace.
The sulfur-containing platinum carbon catalyst used in other aspects of the present invention and the preparation method thereof are the same as those of the first aspect.
In a second aspect, the present invention provides a method of anode reaction for a hydrogen fuel cell, the method comprising: under the anode reaction condition, H in the raw material gas 2 Contacting with a sulfur-containing platinum carbon catalyst;
wherein H in the raw material gas 2 The S content is below 15 ppm;
the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the sulfur-modified carbon carrier is sulfur-modified conductive carbon black, the total sulfur content in the sulfur-modified carbon carrier is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times, more preferably more than 1.5 times, of the surface sulfur content, and the mass fraction of platinum is 20-70% based on the total mass of the catalyst.
The raw material gas used in the present invention may be, for example, a raw material gas having a hydrogen content of 99.5 mass% (99.98 mass%) or more, and may be, for example, hydrogen produced by a method such as methane steam reforming hydrogen production, coal hydrogen production, methanol hydrogen production, ammonia decomposition hydrogen production, hydrogen recovery and purification, biomass hydrogen production, or hydrogen produced as a by-product of other reactions, for example, a hydrogen-containing gas produced by a catalytic cracker in a refinery.
By using the sulfur-containing platinum carbon catalyst of the present invention, even if the raw material gas contains H 2 The content of S may be a predetermined amount or less, and the anode reaction may be performed for a long period of time while maintaining the catalyst activity.
Preferably, H in the feed gas 2 The S content is preferably 15ppm or less, more preferably 10ppm or less, and may be, for example, 0.4 to 5ppm. Specifically, H in the raw material gas 2 The S content may be 0.4, 0.6, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, or 15ppm, etc.
According to the present invention, the anode reaction conditions are such that the anode reaction can proceed. Specifically, the anode reaction conditions further include: the voltage is 0V or more, preferably 0.01-0.4V. The anodic reaction may be carried out, for example, in an acidic electrolyte solution, and various organic and/or inorganic acid solutions, such as a perchloric acid solution or sulfuric acid solution, may be used. In addition, in performing the anode reaction in the electrolyte solution, the anode reaction conditions may include: the concentration of hydrogen ions in the electrolyte is 0.01M or more, preferably 0.05 to 1.0M.
The third aspect of the present invention provides the use of a sulfur-containing platinum-carbon catalyst in a fuel cell, the sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon support and a platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, the total sulfur content in the sulfur-modified carbon support being greater than or equal to the surface sulfur content, preferably the total sulfur content being 1.2 times or more, more preferably 1.5 times or more the surface sulfur content, the mass fraction of platinum being 20 to 70% based on the total mass of the catalyst; wherein, H in the feed gas of the fuel cell 2 The S content is 15ppm or less, preferably 0.4 to 5ppm.
The fuel cell may be, for example, a hydrogen fuel cell (e.g., a proton exchange membrane hydrogen fuel cell), a direct alcohol fuel cell (e.g., a direct alcohol fuel cell in which methanol or ethanol is the anode fuel), or the like. Preferably, the fuel cell is a hydrogen fuel cell. In particular, the sulfur-containing platinum carbon catalyst may be used as an anode catalyst or a cathode catalyst in a fuel cell, preferably as an anode catalyst.
Preferably, H in the feed gas 2 The S content is 10ppm or less, preferably 5ppm or less. Specifically, H in the raw material gas 2 The S content may be 0.4, 0.6, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, or 15ppm, etc. In addition, in the application of the third aspect of the present invention, the raw material gas and its properties may be the same as those of the second aspect, and are not described herein.
According to the present invention, the anode reaction conditions are such that the anode reaction can proceed. Specifically, the anode reaction conditions further include: the voltage is 0V or more, preferably 0.01-0.4V. The anodic reaction may be carried out, for example, in an acidic electrolyte solution, and various organic and/or inorganic acid solutions, such as a perchloric acid solution or sulfuric acid solution, may be used. In addition, in performing the anode reaction in the electrolyte solution, the anode reaction conditions may include: the concentration of hydrogen ions in the electrolyte is 0.001M or more, preferably 0.05 to 1.0M.
In a fourth aspect, the present invention provides a sulfur-containing platinum carbon catalyst for improving the H resistance of the platinum carbon catalyst 2 The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the sulfur-modified carbon carrier is sulfur-modified conductive carbon black, the total sulfur content in the sulfur-containing platinum-carbon catalyst is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times of the surface sulfur content, more preferably more than 1.5 times of the surface sulfur content, and the mass fraction of platinum is 20-70 mass percent based on the total mass of the catalyst.
In the application of the fourth aspect of the present invention, the sulfur-containing platinum-carbon catalyst has the same properties as those of the first aspect in sulfur content and distribution, platinum content and distribution, pt characteristic peaks in XRD pattern, pt 4f7/2 characteristic peaks in XPS pattern, and the like. The sulfur-containing platinum carbon catalyst can be obtained by the same sulfur-modified carbon support and platinum supporting method as in the first aspect. In addition, in the second and third aspects of the present invention, the sulfur-containing platinum carbon catalyst of the fourth aspect of the present invention may also be used.
In the present invention, other references to "carbon support" refer to carbon support that does not contain a composite element, except that it may be determined to be "carbon support that contains a composite element" depending on the context or definition itself; the same applies to the underlying concept of carbon supports, such as conductive carbon blacks.
In the present invention, "carbon black" and "carbon black" are interchangeable terms of art.
The "inert gas" in the present invention refers to a gas that does not have any appreciable effect on the performance of the sulfur-modified carbon support in the production process of the present invention.
The present invention will be described in detail by examples. In the examples and comparative examples of the present invention, if used, the apparatus and test methods thereof are as follows:
the model of High Resolution Transmission Electron Microscope (HRTEM) was JEM-2100 (HRTEM) (Japanese electronics Co., ltd.) under the following test conditions: the acceleration voltage was 200kV.
The X-ray photoelectron spectroscopy analyzer is an ESCALab220i-XL type ray electron spectroscopy manufactured by VG Scientific company and provided with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions are as follows: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar. In addition, the electron binding energy was corrected by the C1s peak (284.3 eV) of elemental carbon, and the post-peak splitting treatment software was XPSPEAK.
The specific method for detecting the surface sulfur content by XPS analysis is as follows: the scanning range of the full spectrum scanning is 0-1200eV, the band-pass energy (pass energy) is 100eV, the analysis energy step length is 1.0eV, the channel number is 1211, and the scanning circle number is 1. The narrow-spectrum scanning energy is 30.0eV, the analysis energy step length is 0.05eV, the channel number is 401, and the scanning turns are 16.
The sulfur carbon analyzer is model CS-844 of the company America force Coke (LECO).
The spherical aberration correcting transmission electron microscope (AC-STEM) is model ARM200F of JEOL company.
The resistivity test is carried out by using a four-probe resistivity tester, the model KDY-1 of the tester, the method and the test conditions are as follows: the applied pressure was 3.9.+ -. 0.03MPa and the current was 500.+ -. 0.1mA.
Apparatus, method, conditions for testing mass fraction of platinum in platinum carbon catalyst: 30mg of the prepared platinum-carbon catalyst was taken, 30mL of aqua regia was added, the mixture was refluxed at 120℃for 12 hours, cooled to room temperature, and the supernatant was diluted and tested for Pt content by ICP-AES.
Ketjenback ECP600JD (Ketjen Black, manufactured by Lion corporation, japan). The test by the instrument method shows that: specific surface area 1362m 2 Per gram, pore volume 2.29mL/g, oxygen mass fraction 6.9%, I D /I G 1.25, and the resistivity was 1.31. Omega. M.
Commercial platinum carbon catalyst (trade name HISPEC4000, manufactured by Johnson Matthey Co.) has a mass fraction of platinum of 40.2%.
Example 1
Dissolving 0.1g of sulfur in 70ml of cyclohexane to form a homogeneous solution, dispersing 9.9g Ketjenblack ECP600JD in the solution, uniformly stirring, soaking for 5 hours, and carrying out vacuum drying at 50 ℃ to obtain a sulfur modified carbon carrier; 0.4g of chloroplatinic acid, calculated as platinum, was dissolved in 20mL of water: dispersing 0.6g of the sulfur-modified carbon carrier in a chloroplatinic acid solution in a solution with the volume ratio of ethanol being 10:1, stirring and dispersing uniformly, standing for 24 hours, and then placing in a vacuum drying oven for drying; placing the dried precursor into a tube furnace, heating to 140 ℃ at a speed of 8 ℃/min, and heating to N 2 ：H 2 Reduction for 2h in an atmosphere of =5:1, n 2 Cooling in the atmosphere to obtain the sulfur-containing platinum-carbon catalyst.
Example 2
Dissolving 0.25g of sulfur in 70ml of cyclohexane to form a homogeneous solution, dispersing 9.75g Ketjenblack ECP600JD in the solution, uniformly stirring, soaking for 5 hours, and carrying out vacuum drying at 50 ℃ to obtain a sulfur modified carbon carrier; 0.52g of chloroplatinic acid, calculated as platinum, was dissolved in 20mL of water: dispersing 0.6g of the sulfur-modified carbon carrier in a chloroplatinic acid solution in a solution with ethanol volume ratio of 10:1, stirring and dispersing uniformly, standing for 24h, and then placing in vacuum for dryingDrying in a box; placing the dried precursor into a tube furnace, heating to 160deg.C at a speed of 6deg.C/min, and heating to N 2 ：H 2 Reduction for 2h in an atmosphere of =5:1, n 2 Cooling in the atmosphere to obtain the sulfur-containing platinum-carbon catalyst.
Comparative example 1
Commercial catalyst, brand HISPEC4000, platinum loading 40 mass%.
Comparative example 2
The sulfur-doped carbon material was prepared according to the method of document "Nature Communications,2019,10:4977" and platinum was carried in accordance with the method of example 1 to prepare a platinum-carbon catalyst.
Test example 1
The surface sulfur content and the total sulfur content of the carbon carriers prepared in the above examples and comparative examples were measured, and the results are shown in table 1.
TABLE 1
| Numbering device | Surface sulfur content | Total sulfur content | Total sulfur content/surface sulfur content |
| Example 1 | 0.52％ | 1.0％ | 1.9 |
| Example 2 | 1.76％ | 2.5％ | 1.4 |
| Comparative example 2 | 10.74％ | 4.61％ | 0.4 |
In table 1, the surface sulfur content represents the sulfur mass fraction measured by XPS analysis, and the total sulfur content represents the sulfur mass fraction measured by a sulfur carbon analyzer.
Test example 2
HOR electrochemical performance test, instrument models Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), method and test conditions: polarization curve LSV of catalyst at 2500rpm, H 2 Saturated 0.1M HClO 4 In the test, the scanning speed is 10mV/s, and the electrochemical active area ECSA is N 2 Saturated 0.1M HClO 4 The scan speed was 50mV/s. In the above test, the catalyst was prepared as a uniformly dispersed slurry, and 10. Mu.l of the slurry was applied to a glassy carbon electrode having a diameter of 5 mm. H 2 S toxicity resistance test method I: will H 2 Mixing 0.4ppm H 2 S, at H 2 +0.4ppmH 2 S saturated 0.1M HClO 4 In (2) re-testing HOR activity, comparative H 2 Changes in activity before and after S-in. H 2 S toxicity resistance test method II: at 0.5M H 2 SO 4 Adding 10 mu mol/L Na 2 S, poisoning for 5 hours under a constant voltage of 0.1V, and testing the performance change of the catalyst before and after poisoning.
Platinum carbon catalyst H of example 2 was tested using method one 2 HOR activity before and after S poisoning treatment, platinum carbon catalyst H of example 1 and comparative examples 1-2 was tested by method II 2 HOR activity before and after S poisoning treatment. The results are shown in Table 2. FIGS. 1 and 2 show the platinum carbon catalyst of example 2, respectively, over H 2 LSV curve and CV curve before and after S poisoning; FIGS. 3 and 4 show the platinum carbon catalyst of example 1 and comparative example 1, respectively, over H 2 LSV curves and CV curves before and after S poisoning.
TABLE 2
As can be seen from the results of Table 2, examples 1-2 were prepared by using the sulfur-modified carbon support of the present invention in H 2 Under S poisoning conditions, the catalyst has better electrochemical performance and sulfide toxicity resistance than comparative examples 1-2.
From the above results, it can be seen that the sulfur-containing platinum carbon catalyst of the present invention has an improved resistance to H of the platinum carbon catalyst 2 S toxic effects.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. Sulfur-containing platinum-carbon catalyst for improving H resistance of platinum-carbon catalyst 2 Use in S toxicity, characterized in that the sulfur-containing platinum carbon catalyst comprises a sulfur-modified carbon support and a platinum metal supported thereon, the total sulfur content in the sulfur-modified carbon support being greater than or equal to the surface sulfur content, preferably the total sulfur content being 1.2 times or more, more preferably 1.5 times or more the surface sulfur content, the mass fraction of platinum being 20-70% based on the total mass of the catalyst.
2. Use according to claim 1, wherein the mass fraction of platinum is 20-60%, more preferably 40-60%, based on the total mass of the catalyst;
preferably, the total sulfur content in the sulfur-modified carbon carrier is 0.4 to 8 mass%, preferably 1 to 6 mass%;
preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1 to 6 mass%, preferably 0.5 to 4 mass%.
3. The use according to claim 1 or 2, wherein the sulfur-modified carbon support is a sulfur-modified conductive carbon black;
preferably, the conductive carbon Black in the sulfur-modified conductive carbon Black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72R, black pears 2000, PRINTEX XE2-B, PRINTEX L6 and HIBLASXK 40B 2.
4. An anode reaction method of a hydrogen fuel cell, comprising: under the anode reaction condition, H in the raw material gas 2 Contacting with a sulfur-containing platinum carbon catalyst;
wherein H in the raw material gas 2 The S content is below 15 ppm;
the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the sulfur-modified carbon carrier is sulfur-modified conductive carbon black, the total sulfur content in the sulfur-modified carbon carrier is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times, more preferably more than 1.5 times, of the surface sulfur content, and the mass fraction of platinum is 20-70% based on the total mass of the catalyst.
5. The anode reaction method according to claim 4, wherein H in the raw material gas 2 The S content is 10ppm or less, preferably 5ppm or less;
preferably, the anode reaction conditions include: the voltage is 0V or more, preferably 0.01-0.4V.
6. The anodic reaction method according to claim 4 or 5, wherein the mass fraction of platinum is 20 to 60%, more preferably 40 to 60%, based on the total mass of the catalyst;
preferably, the total sulfur content in the sulfur-modified carbon carrier is 0.4 to 8 mass%, preferably 1 to 6 mass%;
preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1 to 6 mass%, preferably 0.5 to 4 mass%.
7. The anode reaction method according to any one of claims 4 to 6, wherein the conductive carbon Black in the sulfur-modified conductive carbon Black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72R, black pears 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK40B 2.
8. The use of a sulfur-containing platinum carbon catalyst in a fuel cell, characterized in that,
the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the sulfur-modified carbon carrier is sulfur-modified conductive carbon black, the total sulfur content in the sulfur-modified carbon carrier is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times, more preferably more than 1.5 times, and the mass fraction of platinum is 20-70% based on the total mass of the catalyst;
wherein, H in the feed gas of the fuel cell 2 The S content is 15ppm or less.
9. The use according to claim 8, wherein H in the feed gas 2 The S content is 10ppm or less, preferably 0.4 to 10ppm;
preferably, the fuel cell is a hydrogen fuel cell;
preferably, the sulfur-containing platinum carbon catalyst acts as an anode catalyst in a fuel cell.
10. Use according to claim 8 or 9, wherein the mass fraction of platinum is 20-60%, more preferably 40-60%, based on the total mass of the catalyst;
preferably, the total sulfur content in the sulfur-modified carbon carrier is 0.4 to 8 mass%, preferably 1 to 6 mass%;
preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1 to 6 mass%, preferably 0.5 to 4 mass%.
11. Sulfur-containing platinum-carbon catalyst for improving H resistance of platinum-carbon catalyst 2 Use of S-toxicity, characterized in that the sulfur-containing platinumThe carbon catalyst comprises a sulfur-modified carbon carrier and platinum metal loaded on the sulfur-modified carbon carrier, wherein the sulfur-modified carbon carrier is sulfur-modified conductive carbon black, the total sulfur content in the sulfur-containing platinum carbon catalyst is greater than or equal to the surface sulfur content, preferably the total sulfur content is more than 1.2 times, more preferably more than 1.5 times, of the surface sulfur content, and the mass fraction of platinum is 20-70 percent based on the total mass of the catalyst.
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