Sulfur-modified carbon materials and their preparation methods and uses

Abstract

The sulfur-modified carbon material includes conductive carbon black and sulfur element dispersed therein, and the total sulfur content in the sulfur-modified carbon material is 1.2 times or more the surface sulfur content. The sulfur-modified carbon material is prepared by A) an impregnation step: impregnating the conductive carbon black with a solution containing sulfur at 10 to 80°C for 1 to 5 hours, and B) a drying step: drying the impregnated product obtained in step A). ​​The sulfur-modified carbon material is used as a support for preparing a platinum-carbon catalyst.

Description

[Technical field]

[0001] The present invention discloses a sulfur modified carbon material, its preparation method and application. [Background technology]

[0002] In recent years, major countries around the world have put forward the goals of "peak carbon emissions" and "carbon neutrality," and the development of hydrogen energy and fuel cell technology has become an important means. Pt / C catalysts are practical catalysts in the fields of fuel cells and water electrolysis, and cost, activity, and stability are also important factors limiting the development of fuel cells and water electrolysis. Unlike sulfur-containing platinum-carbon catalysts used in chemical catalysis, Pt / C catalysts required in the field of electrochemistry usually require high Pt loading, uniform particle size, excellent dispersion, and strong bonding with the carbon support. However, it is very difficult to prepare high-loading Pt / C catalysts on a large scale while maintaining high dispersion of Pt particles and strong bonding with the support.

[0003] In China Patent Publication No. 109904474, sulfur-doped carbon materials are prepared using sulfur-containing organic small molecules, which are mixed with platinum precursors and then heat-treated in a reducing atmosphere to obtain sulfur-doped platinum-carbon catalysts and carbon. The catalyst has good stability due to the anchoring effect of sulfur on platinum. However, because transition metal salts are used to catalyze the condensation and carbonization of sulfur-containing small molecules, only the surface of the conductive carbon black is coated with sulfur-containing substances, on the one hand, the coating is uneven, so the platinum particles on the catalyst are not uniformly distributed, and especially when the loading rate is high, the particle size distribution is wide and the electrochemically active area (ECSA) of the catalyst is small; on the other hand, the abundant pore structure of the carbon support cannot be fully utilized, making it difficult to effectively utilize platinum.

[0004] Nature Communications, (2019) 10: 4977 used silica as a template to prepare mesoporous carbon supports doped with thiophene sulfur and sulfur oxide by cobalt-assisted pyrolysis, and after wet impregnation of the mesoporous carbon support, a Pt / C single-atom catalyst with a loading rate of 6.24% was obtained. However, the loading rate and catalytic activity of the Pt / C single-atom catalyst are both low, making it difficult to meet the needs of practical applications.

[0005] Furthermore, in the case of Pt / C catalysts, especially when used in fuel cells, the impurities CO in H2, trace impurities H2S, and the impurity SO in air are x Since is strongly adsorbed on the surface of the precious metal Pt, Pt-based catalysts are easily poisoned, causing a problem of reduced catalytic activity. The general solution is to start with controlling the purity of hydrogen or to introduce other metal components, but such alloy catalysts have problems such as complicated preparation methods and poor stability.

[0006] Therefore, it is crucial to develop Pt / C catalysts with high loading, high uniformity, high activity, and high stability, and preparation methods for Pt / C catalysts that are easy to scale up industrially. Carbon materials have a wide range of sources and abundant properties, and are widely used in various technical fields. In the field of electrocatalysis, conductive carbon black is a practical support for electrocatalysts. By appropriately modifying conductive carbon black, it is expected that the use of suitable modified carbon materials as supports will break through the limitations of catalytic performance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] China Patent Application Publication No. 109904474 [Non-patent literature]

[0008] [Non-Patent Document 1] Nature Communications,(2019)10:4977 Summary of the Invention [Problem to be solved by the invention]

[0009] One object of the present invention is to provide a sulfur-modified carbon material that is particularly suitable as a support for platinum-carbon electrocatalysts and can significantly improve the catalytic performance of the platinum-carbon electrocatalysts. Another object of the present invention is to provide a sulfur-containing platinum-carbon catalyst obtained by using the sulfur-modified carbon material, which has a catalytic activity and stability significantly superior to existing commercial catalysts. Another object of the present invention is to provide a use of the sulfur-containing platinum-carbon catalyst in a fuel cell or water electrolysis. Another object of the present invention is to provide a use of the sulfur-containing platinum-carbon catalyst for improving the resistance of the platinum-carbon catalyst to catalytic poisoning, the poisoning being caused by SO. x The poisoning is selected from poisoning, CO poisoning, and H2S poisoning.

[0010] In order to achieve one or more of the above objectives, the present invention provides technical solutions in the following exemplary embodiments.

[0011] 1. A sulfur modified carbon material comprising conductive carbon black and elemental sulfur dispersed therein, characterized in that the total sulfur content in the sulfur modified carbon material is at least 1.2 times, preferably at least 1.5 times, the surface sulfur content.

[0012] 2. The sulfur modified carbon material according to exemplary embodiment 1, wherein the total sulfur content in the sulfur modified carbon material is from 0.1 to 10 wt.%, preferably from 1 to 8 wt.%, and more preferably from 1 to 4 wt.%, based on the total weight of the sulfur modified carbon material.

[0013] 3. The sulfur modified carbon material according to exemplary embodiment 1, wherein the surface sulfur content in the sulfur modified carbon material is 0.1-6 wt. %, preferably 0.5-3 wt. %, based on the total weight of the surface layer of the sulfur modified carbon material.

[0014] 4. The sulfur-modified carbon material according to exemplary embodiment 1, wherein the specific surface area of ​​the sulfur-modified carbon material is 200 to 2000 m 2 / g of sulfur modified carbon material.

[0015] 5. The sulfur modified carbon material according to exemplary embodiment 1, wherein the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0016] 6. The sulfur modified carbon material according to exemplary embodiment 1, wherein the sulfur modified carbon material is prepared by an impregnation method, in which the conductive carbon black is impregnated with a solution comprising a sulfur source.

[0017] 7. The sulfur modified carbon material according to exemplary embodiment 1, wherein elemental sulfur is introduced into the conductive carbon black in the form of elemental sulfur.

[0018] Thus, in combination with embodiments 6 and 7, it is preferred that the sulfur source used in the impregnation is elemental sulfur, whereby elemental sulfur is introduced into the conductive carbon black in the form of elemental sulfur. Further, it is preferred that after elemental sulfur is introduced into the conductive carbon black in the form of elemental sulfur, the elemental sulfur in the sulfur modified carbon material is present in the conductive carbon black in the form of elemental sulfur or substantially in the form of elemental sulfur.

[0019] 8. A method for preparing the sulfur-modified carbon material according to any one of the exemplary embodiments 1-7, comprising: A) impregnation step: a step of impregnating conductive carbon black with a solution containing sulfur at 10 to 80° C. for 1 to 5 hours; and B) Drying step: drying the impregnated product obtained in step A), The method includes:

[0020] 9. The method of exemplary embodiment 8, wherein the solvent in the sulfur-containing solution is one or more of CCl4, CS2, cyclohexane, and n-hexane.

[0021] 10. The method of exemplary embodiment 8, wherein the concentration of sulfur in the sulfur-containing solution is 0.0004 to 0.02 g / mL.

[0022] 11. The method of exemplary embodiment 8, wherein the amount of sulfur used is 0.005 to 0.06 g per gram of conductive carbon black.

[0023] 12. The method according to exemplary embodiment 8, wherein the impregnation temperature is 10 to 40° C., preferably 20 to 30° C., particularly preferably room temperature (25° C.), and the impregnation time is preferably 2 to 4 hours.

[0024] 13. The method of exemplary embodiment 8, wherein the drying conditions include a temperature of 20 to 100° C. and a time of 5 to 10 hours.

[0025] 14. Use of the sulfur-modified carbon material according to exemplary embodiment 1 as a support for preparing a catalyst.

[0026] 15. The use of exemplary embodiment 14, wherein the catalyst is a platinum-carbon catalyst for electrocatalysis.

[0027] Alternatively, or in combination with the above technical solutions, the present invention also provides the following alternative technical solutions.

[0028] 1. A sulfur-containing platinum-carbon catalyst comprising a sulfur-containing conductive carbon black as a support and platinum metal supported on the sulfur-containing conductive carbon black, characterized in that at least 70% by weight of the platinum metal particles are supported within the sulfur-containing conductive carbon black and the characteristic peak of Pt 4f 7 / 2 in the XPS spectrum is increased by at least 0.3 eV compared to a benchmark platinum-carbon catalyst supported on conductive carbon black that does not contain sulfur.

[0029] 2. The sulfur-containing platinum-carbon catalyst according to alternative embodiment 1, wherein the Pt 4f 7 / 2 characteristic peak of the benchmark platinum-carbon catalyst is located at about 71.3 eV in the XPS spectrum, and the Pt 4f 7 / 2 characteristic peak of the sulfur-containing platinum-carbon catalyst is located at about 71.6 eV or higher, about 71.7 eV or higher, or about 71.9 eV or higher in the XPS spectrum, and preferably the Pt 4f 7 / 2 characteristic peak of the sulfur-containing platinum-carbon catalyst is located at about 72.2 eV or lower in the XPS spectrum.

[0030] 3. The sulfur-containing platinum-carbon catalyst has no Pt-characteristic peak in the XRD spectrum, or the ratio of the unit weight platinum normalized peak intensity to the full width at half maximum of the Pt(111) characteristic peak is 0.8 or less, and the ratio of the unit weight platinum normalized peak intensity to the full width at half maximum of the Pt(200) characteristic peak is 0.5 or less; Preferably, when the platinum content of the sulfur-containing platinum-carbon catalyst is 10 wt. % or less, the sulfur-containing platinum-carbon catalyst has no Pt characteristic peak in the XRD spectrum, or the ratio of the unit weight platinum normalized peak intensity to the full width at half maximum of the Pt(111) characteristic peak is 0.6 or less and the ratio of the unit weight platinum normalized peak intensity to the full width at half maximum of the Pt(200) characteristic peak is 0.4 or less.

[0031] 4. The sulfur-containing platinum-carbon catalyst according to alternative embodiment 1, wherein the total average sulfur content of the sulfur-containing conductive carbon black is equal to or greater than the surface sulfur content, and preferably the total sulfur content is equal to or greater than 1.2 times, preferably equal to or greater than 1.5 times, the surface sulfur content.

[0032] 5. The sulfur-containing platinum-carbon catalyst according to alternative embodiment 1, wherein the sulfur-containing conductive carbon black has a total sulfur content of 0.1 to 10% by weight, preferably 1 to 8% by weight, and more preferably 1 to 4% by weight.

[0033] 6. The sulfur-containing platinum-carbon catalyst according to alternative embodiment 1, wherein the platinum content is from 1 to 20% by weight, preferably from 5 to 20% by weight, preferably from 5 to 15% by weight, and more preferably from 7 to 10% by weight, based on the total weight of the sulfur-containing platinum-carbon catalyst.

[0034] 7. The sulfur-containing platinum-carbon catalyst according to alternative embodiment 1, wherein the platinum content is 20-70 wt.%, preferably 20-60 wt.%, more preferably 40-60 wt.%, based on the total weight of the sulfur-containing platinum-carbon catalyst.

[0035] 8. The sulfur-containing platinum-carbon catalyst according to alternative embodiment 1, wherein not more than 60%, preferably not more than 40% by weight, and more preferably not more than 10% by weight, of the platinum metal particles have regular lattice fringes.

[0036] 9. A method for preparing the sulfur-containing platinum-carbon catalyst according to alternative embodiment 1, comprising: (1) a step of impregnating a conductive carbon black with a solution containing sulfur at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-containing conductive carbon black; (2) removing the solvent from the homogeneous mixture containing the sulfur-containing conductive carbon black, the platinum source and the solvent obtained in step (1) to obtain a precursor material; and (3) heat treating the precursor material in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst; The method according to claim 1, further comprising:

[0037] 10. The method of alternative embodiment 9, wherein the concentration of sulfur in the sulfur-containing solution is 0.0004 to 0.02 g / mL.

[0038] 11. The method of alternative embodiment 9, wherein the amount of sulfur used is 0.005 to 0.06 g per gram of conductive carbon black.

[0039] 12. The method according to alternative embodiment 9, wherein the heat treatment in step (3) is carried out at 80 to 200°C.

[0040] 13. The method according to alternative embodiment 9, wherein the drying conditions in step (1) comprise a temperature of 20 to 100° C. and a time of 5 to 10 hours.

[0041] 14. Use of the sulfur-containing platinum-carbon catalyst according to any one of alternative embodiments 1 to 8 in a fuel cell or water electrolysis, preferably in a proton exchange membrane fuel cell or proton exchange membrane water electrolysis.

[0042] 15. Use of a sulfur-containing platinum-carbon catalyst according to any one of alternative embodiments 1 to 8 to improve the resistance of a platinum-carbon catalyst to catalyst poisoning, wherein the poisoning is SO x The use is selected from poisoning, CO poisoning, and H2S poisoning.

[0043] 16. A sulfur-containing platinum-carbon catalyst is used in the cathode reaction of a fuel cell, where O2 in the feed gas comes into contact with the sulfur-containing platinum-carbon catalyst and SO2 in the feed gas is removed. x The use according to alternative embodiment 15, wherein the content of is not more than 120 ppm, preferably not more than 100 ppm, and more preferably not more than 50 ppm.

[0044] 17. The use according to alternative embodiment 15, wherein the sulfur-containing platinum-carbon catalyst is used in the anode reaction of a hydrogen fuel cell, in which H2 in a feed gas contacts the sulfur-containing platinum-carbon catalyst, and the CO content in the feed gas is 1500 ppm or less, preferably 1200 ppm or less, and more preferably 1000 ppm or less.

[0045] 18. The use according to alternative embodiment 15, wherein the sulfur-containing platinum-carbon catalyst is used in the anode reaction of a hydrogen fuel cell, H2 in a feed gas contacts the sulfur-containing platinum-carbon catalyst, and the content of H2S in the feed gas is 15 ppm or less, preferably 10 ppm or less, and more preferably 5 ppm or less. [Means for solving the problem]

[0046] Therefore, the present invention provides the following solution:

[0047] Solution (I): Sulfur-modified carbon materials and their preparation methods and applications The purpose of one aspect of the present invention is to overcome the above-mentioned technical problems existing in the prior art and provide a sulfur-modified carbon material and a preparation method thereof, a sulfur-containing platinum-carbon catalyst, and a fuel cell. The sulfur-modified carbon material is suitable as a support for the sulfur-containing platinum-carbon catalyst, and can significantly improve the catalytic performance and poisoning resistance of the sulfur-containing platinum-carbon catalyst.

[0048] In order to achieve the above object, another aspect of the present invention is to provide a sulfur-modified carbon material comprising conductive carbon black and elemental sulfur incorporated therein, wherein the total sulfur content in the sulfur-modified carbon material is equal to or greater than the surface sulfur content, preferably, the total sulfur content in the sulfur-modified carbon material is equal to or greater than 1.2 times, more preferably, equal to or greater than 1.5 times, the surface sulfur content.

[0049] Preferably, the total sulfur content in the sulfur modified carbon material is from 0.1 to 10% by weight, preferably from 1 to 8% by weight, more preferably from 1 to 4% by weight.

[0050] Preferably, the surface sulfur content in the sulfur modified carbon material is between 0.1 and 6% by weight, preferably between 0.5 and 3% by weight.

[0051] Preferably, the oxygen content in the sulfur modified carbon material is between 4 and 15% by weight.

[0052] Preferably, the specific surface area of ​​the sulfur-modified carbon material is 200 to 2000 m 2 / g.

[0053] Preferably, the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0054] Another aspect of the present invention is to provide a method for preparing a sulfur modified carbon material, the method comprising impregnating a conductive carbon black with a solution containing sulfur at 10-80° C. for 1-5 hours and drying the impregnated product to obtain the sulfur modified carbon material.

[0055] Preferably, the solvent in the sulfur-containing solution is one or more of CCl4, CS2, cyclohexane, and n-hexane.

[0056] Preferably, the concentration of sulfur in the sulfur-containing solution is 0.0004 to 0.02 g / mL.

[0057] Preferably, the amount of sulfur used is 0.005 to 0.06 g per 1 g of conductive carbon black.

[0058] Preferably, the drying conditions include: a temperature of 20-100° C., and a time of 5-10 hours.

[0059] Preferably, the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0060] Another aspect of the present invention provides a sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon material and platinum metal supported thereon, wherein the sulfur-modified carbon material is the sulfur-modified carbon material of the present invention or is obtained by the preparation method of the present invention.

[0061] Preferably, the weight fraction of platinum is 0.1-70 wt%, based on the total weight of the sulfur-containing platinum-carbon catalyst, and depending on the application, the weight fraction of platinum can be 0.1-1 wt%, 1-4 wt%, 1-8 wt%, 4-20 wt%, 20-40 wt%, or 40-70 wt%.

[0062] Preferably, the sulfur-containing platinum-on-carbon catalyst contains no more than 60% by weight of platinum particles having regular lattice stripes.

[0063] Another aspect of the present invention provides the use of the sulfur-modified carbon material of the present invention, the sulfur-modified carbon material obtainable by the preparation method of the present invention, or the sulfur-containing platinum-carbon catalyst of the present invention as an electrode material.

[0064] Another aspect of the present invention is to provide a fuel cell, which uses the sulfur-modified carbon material of the present invention, the sulfur-modified carbon material obtained by the preparation method of the present invention, or the sulfur-containing platinum-carbon catalyst of the present invention.

[0065] Preferably, the fuel cell is a hydrogen fuel cell.

[0066] Another aspect of the present invention is to provide a PEM electrolyser, characterized in that the cathode of the PEM electrolyser uses the sulfur modified carbon material of the present invention, the sulfur modified carbon material obtained by the preparation method of the present invention, or the sulfur-containing platinum-carbon catalyst of the present invention.

[0067] With the above technical solutions, compared with the prior art, the present invention can achieve the following beneficial technical effects:

[0068] 1. The present invention provides a novel sulfur-modified carbon material through a simple process, and the sulfur in the sulfur-modified carbon material is more distributed inside the sulfur-modified carbon material.

[0069] 2. The sulfur-modified carbon material produced by the present invention is particularly suitable as a support for platinum-carbon electrocatalysts, and can significantly improve the catalytic performance of platinum-carbon electrocatalysts.

[0070] 3. The sulfur modified carbon material produced by the present invention can be used to fabricate platinum-carbon electrocatalysts with excellent anti-poisoning performance, high activity and high stability.

[0071] Solution (II): Sulfur-containing platinum-carbon catalyst with high Pt content and its preparation method and application The purpose of one aspect of the present invention is to solve the problems that the Pt / C catalyst synthesized by the conventional technology is difficult to achieve both high Pt loading and high dispersion, and the problem that the interaction between the carrier and Pt is weak. By utilizing the strong interaction between sulfur and Pt to prepare sulfur-containing conductive carbon black, a strong interaction is formed between the carrier and platinum, the dispersion of platinum is improved, and a Pt / C catalyst with high loading, high uniformity, high activity, and high stability is developed with a simple preparation method. Secondly, in view of the problems that the current thermal reduction method requires high temperature, the liquid phase reduction method is complicated, and the wastewater volume is large, a new catalyst preparation method that is more green and environmentally friendly is provided.

[0072] In order to achieve the above-mentioned object, the present invention provides a sulfur-containing platinum-carbon catalyst comprising a sulfur-containing conductive carbon black and platinum metal supported thereon, in which the total sulfur content in the sulfur-containing conductive carbon black is 1.2 times or more, preferably 1.5 times or more, of the surface sulfur content, and the weight fraction of platinum is 20 to 70% by weight based on the total weight of the catalyst.

[0073] For the purposes of the present invention, the sulfur-modified carbon material of the present invention can be used as a sulfur-containing conductive carbon black. Therefore, the "sulfur-containing conductive carbon black" is also referred to as a "sulfur-modified conductive carbon black."

[0074] Preferably, the sulfur-containing platinum-on-carbon catalyst contains no more than 60% by weight of platinum metal particles having regular lattice stripes.

[0075] Preferably, at least 90% by weight of the platinum metal particles are supported within the sulfur-containing conductive carbon black.

[0076] According to the present invention, based on the total weight of the catalyst, the weight fraction of platinum is 20-70 wt%, and can also be 20-40 wt% or 40-70 wt%. Therefore, the sulfur-containing platinum-carbon catalyst with a high Pt content provided by the solution (II) of the present invention can be called a high platinum content (sulfur-containing platinum-carbon) catalyst.

[0077] Preferably, the total sulfur content in the sulfur-containing conductive carbon black is 0.4 to 8% by weight, preferably 1 to 6% by weight.

[0078] Preferably, the surface sulfur content of the sulfur-containing conductive carbon black is 0.1 to 6% by weight, preferably 0.5 to 4% by weight.

[0079] Preferably, the sulfur-containing platinum-on-carbon catalyst has a Pt 4f 7 / 2 characteristic peak located above 71.6 eV in the XPS spectrum.

[0080] Preferably, the conductive carbon black in the sulfur-containing conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0081] Another aspect of the present invention is to provide a sulfur-containing platinum-carbon catalyst comprising a sulfur-containing conductive carbon black and platinum metal supported thereon, in which the total sulfur content in the sulfur-containing platinum-carbon catalyst is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum is 20-70 wt % based on the total weight of the catalyst.

[0082] Preferably, the sulfur-containing platinum-on-carbon catalyst contains no more than 60% by weight of platinum metal particles having regular lattice stripes.

[0083] Preferably, at least 90% by weight of the platinum metal particles are supported within the sulfur-containing conductive carbon black.

[0084] According to the present invention, the weight fraction of platinum is 20-70% by weight, and can be 20-40% by weight or 40-70% by weight, based on the total weight of the catalyst.

[0085] Preferably, the total sulfur content is between 0.4 and 8% by weight, preferably between 1 and 6% by weight.

[0086] Preferably, the surface sulfur content is between 0.1 and 6% by weight, preferably between 0.5 and 4% by weight.

[0087] Preferably, the sulfur-containing platinum-on-carbon catalyst has a Pt 4f 7 / 2 characteristic peak located above 71.6 eV in the XPS spectrum.

[0088] Preferably, the conductive carbon black in the sulfur-containing conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0089] Another aspect of the present invention is to provide a method for preparing a sulfur-containing platinum-on-carbon catalyst, the method comprising: (1) a step of impregnating a conductive carbon black with a solution containing sulfur at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-containing conductive carbon black; (2) removing the solvent from the homogeneous mixture containing the sulfur-containing conductive carbon black, the platinum source and the solvent obtained in step (1) to obtain a precursor material; and (3) heat-treating the precursor material obtained in step (2) at 80-200° C. for 1-4 hours in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst; In the step (2), the amount of the platinum source used is 0.25 to 2.4 g in terms of platinum element per 1 g of the sulfur-containing conductive carbon black.

[0090] Preferably, in step (1), the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0091] Preferably, in step (1), XPS analysis of the conductive carbon black shows an oxygen content of greater than 4% by weight.

[0092] Preferably, in step (1), the specific surface area of ​​the conductive carbon black is 200 to 2000 m 2 / g.

[0093] Preferably, in step (1), the solvent in the sulfur-containing solution is one or more of CCl4, CS2, cyclohexane, and n-hexane.

[0094] Preferably, in the step (1), the amount of sulfur used is 0.005 to 0.06 g per 1 g of the carbon support.

[0095] Preferably, in step (1), the drying conditions include a temperature of 20 to 100° C. and a time of 5 to 10 hours.

[0096] Preferably, in step (2), the platinum source is one or more of chloroplatinic acid, chloroplatinate, tetraammineplatinum acetate, and platinum acetylacetonate.

[0097] Preferably, in step (2), the solvent is one or more of water, an alcohol solvent, or a ketone solvent. Also, preferably, the solvent is water and / or ethanol, and preferably a mixed solvent of water and ethanol.

[0098] Preferably, in step (2), the homogeneous mixture is allowed to stand for at least 4 hours, preferably for 16 to 30 hours, before removing the solvent.

[0099] Preferably, in step (2), the drying temperature for removing the solvent is 100° C. or lower.

[0100] Preferably, in step (3), the reducing atmosphere contains hydrogen, preferably a mixed atmosphere of hydrogen and an inert gas, more preferably a mixed atmosphere of hydrogen and nitrogen, and preferably hydrogen accounts for 5 to 30% by volume of the total gas.

[0101] Another aspect of the present invention is to provide a sulfur-containing platinum-on-carbon catalyst prepared by the preparation method of the present invention.

[0102] Another aspect of the present invention provides the use of the sulfur-containing platinum-carbon catalyst of the present invention in fuel cells or water electrolysis.

[0103] The sulfur-containing platinum-carbon catalyst of the present invention is suitable as an anode catalyst for a fuel cell. The fuel cell is not particularly limited, and may be, for example, a hydrogen fuel cell (proton exchange membrane hydrogen fuel cell), a direct alcohol fuel cell (e.g., a direct alcohol fuel cell using methanol or ethanol as the anode fuel), etc.

[0104] Another aspect of the present invention is to provide a PEM electrolyser using the sulfur-containing platinum-on-carbon catalyst of the present invention in the cathode of the PEM electrolyser.

[0105] Due to the above technical solutions, compared with the prior art, the present invention has the following beneficial technical effects:

[0106] 1. The total sulfur content in the carbon support of the present invention is greater than the surface sulfur content, so that the abundant pore structure can be fully utilized, and as a result, Pt is not only supported on the surface of the support, but also forms a better dispersion state. 2. The preparation method of the present invention has a low reduction temperature and low energy consumption. 3. Compared with the sulfur-modified sulfur-containing platinum-carbon catalyst prepared by liquid-phase reduction method, the preparation method of the sulfur-containing platinum-carbon catalyst of the present invention is simple and easy to scale up industrially, and there is obvious interaction between Pt and the support, and the XPS spectrum peak of Pt is shifted to high electron volts, but there is no such shift in the catalyst obtained by the liquid-phase reduction method, and this interaction is believed to be very beneficial to the improvement of catalytic performance. 4. The sulfur-containing platinum-carbon catalyst prepared by the method of the present invention has significantly better ORR and HER catalytic activity and stability than commercial catalysts. 5. The sulfur-containing platinum-carbon catalyst prepared by the method of the present invention has a large electrochemically active area (ECSA) because the platinum particles are small, uniformly distributed, and form a special structure with imperfect order.

[0107] Solution (III): Sulfur-containing platinum-carbon catalyst with low Pt content and its preparation method and application In view of the problem of low catalytic activity of sulfur-containing platinum-carbon catalysts in the prior art, one of the objectives of the present invention is to provide a sulfur-containing platinum-carbon catalyst, its preparation method and application, in which Pt in the sulfur-containing platinum-carbon catalyst exists in the form of atomic clusters, has high dispersion, and its weight specific activity and overvoltage are far superior to those of commercial catalysts. The present invention also improves the wet impregnation method for preparing the sulfur-containing platinum-carbon catalyst, realizing the preparation of the catalyst with lower energy consumption.

[0108] In order to achieve the above-mentioned object, one aspect of the present invention provides a sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon support and 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 equal to or greater than the surface sulfur content, the total sulfur content being 1-8 wt%, preferably equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum being 1-20 wt%, based on the total weight of the sulfur-containing platinum-carbon catalyst.

[0109] Preferably, the sulfur-containing platinum-carbon catalyst has no Pt-characteristic peak in the XRD spectrum, or the ratio of the platinum-normalized peak intensity per unit weight to the full width at half maximum of the Pt(111)-characteristic peak is 0.8 or less, and the ratio of the platinum-normalized peak intensity per unit weight to the full width at half maximum of the Pt(200)-characteristic peak is 0.5 or less.

[0110] Preferably, when the platinum content of the sulfur-containing platinum-carbon catalyst is 10% by weight or less, the sulfur-containing platinum-carbon catalyst does not have a Pt characteristic peak in the XRD spectrum, or the ratio of the platinum normalized peak intensity per unit weight to the full width at half maximum of the Pt(111) characteristic peak is 0.6 or less, and the ratio of the platinum normalized peak intensity per unit weight to the full width at half maximum of the Pt(200) characteristic peak is 0.4 or less.

[0111] Preferably, the weight fraction of platinum is 5-20% by weight, preferably 5-15% by weight, more preferably 7-10% by weight, based on the total weight of the sulfur-containing platinum-carbon catalyst. Therefore, the low Pt content sulfur-containing platinum-carbon catalyst provided by the solution (III) of the present invention can be called a low platinum content (sulfur-containing platinum-carbon) catalyst.

[0112] Preferably, the total sulfur content in the sulfur modified carbon support is from 1 to 8 wt%, preferably from 3 to 6 wt%.

[0113] Preferably, the surface sulfur content in the sulfur modified carbon support is between 0.1 and 6% by weight, preferably between 0.5 and 3% by weight.

[0114] Preferably, the sulfur-containing platinum-on-carbon catalyst has a Pt 4f 7 / 2 characteristic peak located above 71.7 eV in the XPS spectrum.

[0115] Preferably, the conductive carbon black in the sulfur modified conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0116] Preferably, XPS analysis of the conductive carbon black shows an oxygen content of greater than 4% by weight.

[0117] Preferably, the conductive carbon black has a specific surface area of ​​200 to 2000 m 2 / g.

[0118] Another aspect of the present invention provides a sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon support and platinum metal supported thereon, wherein the sulfur-modified carbon support is a sulfur-modified conductive carbon black, and wherein the total sulfur content in the sulfur-containing platinum-carbon catalyst is equal to or greater than the surface sulfur content, the total sulfur content being 1-8 wt.%, preferably the total sulfur content being equal to or greater than 1.2 times, and more preferably equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum being 1-20 wt.%, based on the total weight of the sulfur-containing platinum-carbon catalyst.

[0119] Preferably, the sulfur-containing platinum-carbon catalyst has no Pt characteristic peak in the XRD spectrum, or the ratio of the platinum normalized peak intensity per unit weight to the full width at half maximum of the Pt(111) characteristic peak is 0.8 or less, and the ratio of the platinum normalized peak intensity per unit weight to the full width at half maximum of the Pt(200) characteristic peak is 0.5 or less.

[0120] Preferably, when the platinum content of the sulfur-containing platinum-carbon catalyst is 10% by weight or less, the sulfur-containing platinum-carbon catalyst does not have a Pt characteristic peak in the XRD spectrum, or the ratio of the platinum normalized peak intensity per unit weight to the full width at half maximum of the Pt(111) characteristic peak is 0.6 or less, and the ratio of the platinum normalized peak intensity per unit weight to the full width at half maximum of the Pt(200) characteristic peak is 0.4 or less.

[0121] Preferably, the weight fraction of platinum is 5-20% by weight, preferably 5-15% by weight, more preferably 7-10% by weight, based on the total weight of the sulfur-containing platinum-on-carbon catalyst.

[0122] Preferably, the total sulfur content is between 1 and 8% by weight, preferably between 3 and 6% by weight.

[0123] Preferably, the surface sulfur content is between 0.1 and 6% by weight, preferably between 0.5 and 3% by weight.

[0124] Preferably, the sulfur-containing platinum-on-carbon catalyst has a Pt 4f 7 / 2 characteristic peak located above 71.7 eV in the XPS spectrum.

[0125] Preferably, the conductive carbon black in the sulfur modified conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0126] Preferably, XPS analysis of the conductive carbon black shows an oxygen content of greater than 4% by weight.

[0127] Preferably, the conductive carbon black has a specific surface area of ​​200 to 2000 m 2 / g.

[0128] Another aspect of the present invention is to provide a method for preparing a sulfur-containing platinum-on-carbon catalyst, the method comprising: (1) impregnating a carbon support with a sulfur-containing solution at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-modified carbon support; (2) removing the solvent from the homogeneous mixture comprising the sulfur-modified carbon support, the platinum source, and the solvent obtained in step (1) to obtain a precursor material; and (3) heat-treating the precursor material obtained in step (2) at 80-200° C. for 1-4 hours in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst; In step (1), the carbon support is conductive carbon black; In step (2), the amount of the platinum source used is 0.01 to 0.25 g in terms of platinum element per 1 g of the sulfur-modified carbon support.

[0129] Preferably, in step (1), the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0130] Preferably, in step (1), XPS analysis of the conductive carbon black shows an oxygen content of greater than 4% by weight.

[0131] Preferably, in step (1), the specific surface area of ​​the conductive carbon black is 200 to 2000 m 2 / g.

[0132] Preferably, in step (1), the solvent in the sulfur-containing solution is one or more of CCl4, CS2, cyclohexane, and n-hexane.

[0133] Preferably, in the step (1), the sulfur-containing solution has a sulfur concentration of 0.0004 to 0.02 g / mL.

[0134] Preferably, in the step (1), the amount of sulfur used is 0.005 to 0.06 g per 1 g of the carbon support.

[0135] Preferably, in step (1), the drying conditions include a temperature of 20 to 100° C. and a time of 5 to 10 hours.

[0136] Preferably, in step (2), the platinum source is one or more of chloroplatinic acid, chloroplatinate, tetraammineplatinum acetate, and platinum acetylacetonate.

[0137] Preferably, in step (2), the solvent is one or more of water, an alcohol solvent, or a ketone solvent. Also, preferably, the solvent is water and / or ethanol, and also preferably, a mixed solvent of water and ethanol.

[0138] Preferably, in step (2), the homogeneous mixture is allowed to stand for at least 10 hours, preferably 15 to 24 hours, before removing the solvent.

[0139] Preferably, in step (2), the drying temperature for removing the solvent is 100° C. or lower.

[0140] Preferably, in step (3), the reducing atmosphere contains hydrogen, preferably a mixed atmosphere of hydrogen and an inert gas, more preferably a mixed atmosphere of hydrogen and nitrogen, with hydrogen preferably occupying 5 to 30% by volume of the total gas.

[0141] Another aspect of the present invention is to provide a sulfur-containing platinum-on-carbon catalyst prepared by the preparation method of the present invention.

[0142] Another aspect of the present invention provides the use of the sulfur-containing platinum-carbon catalyst of the present invention in fuel cells or water electrolysis.

[0143] Another aspect of the present invention is to provide a PEM electrolyser, which uses the sulfur-containing platinum-carbon catalyst of the present invention in the cathode of the PEM electrolyser.

[0144] Due to the above technical solutions, compared with the prior art, the present invention has the following beneficial technical effects:

[0145] 1. The present invention provides a novel carbon carrier by modifying conductive carbon black with elemental sulfur, and the sulfur-containing platinum-carbon catalyst prepared using the carbon carrier can greatly improve the weight-specific activity of the catalyst and reduce the overvoltage.

[0146] 2. In the preferred embodiment of the present invention, the sulfur-modified carbon support is prepared by simple solution impregnation without the need for high-temperature calcination treatment. The preparation method is simple and has low energy consumption. The overall sulfur content in the prepared carbon support structure is much higher than the surface sulfur content. This novel structure can maximize the dispersion of Pt, so that Pt atom cluster catalyst can be obtained even at higher Pt loading rates.

[0147] 3. When the commonly used wet impregnation method is used to prepare Pt-based catalysts, the reduction temperature is high and the energy consumption is large. However, the improved method of the present application has a low reduction temperature and can reduce the energy consumption of catalyst preparation.

[0148] Solution (IV): SO x Use of sulfur-containing platinum-carbon catalysts in resistance to poisons. The sulfur-containing platinum-carbon catalyst of the present invention is a platinum-carbon catalyst having a sulfur-containing x The sulfur-containing platinum-carbon catalyst of the present invention utilizes the strong interaction between sulfur and Pt, and the sulfur-modified carbon support is prepared by simply modifying the carbon support, so that a strong interaction is formed between the support and platinum, and the sulfur-containing platinum-carbon catalyst of the present invention can be used to improve the resistance to SO x The adsorption of Pt on the catalyst is weakened, and the SO x Improved resistance to.

[0149] Accordingly, the present invention provides a method for the cathodic reaction of a fuel cell, the method comprising contacting O2 in a feed gas with a sulfur-containing platinum-carbon catalyst of the present invention under cathodic reaction conditions, and x The content is 120 ppm or less, preferably 100 ppm or less, and preferably 50 ppm or less.

[0150] Preferably, the sulfur-containing platinum-carbon catalyst of the present invention is used as a cathode catalyst in a fuel cell.

[0151] Preferably, the fuel cell is a hydrogen fuel cell.

[0152] Preferably, the cathodic reaction conditions include a voltage of 0V or more, preferably 0 to 1.1V.

[0153] Due to the above technical solutions, compared with the prior art, the sulfur-containing platinum-carbon catalyst of the present invention has the following advantages: First, the preparation method is simple, it is easy to scale up industrially, and the SO x The improvement of the poisoning resistance can only be achieved by the modification of the support; secondly, the Pt particles of the catalyst obtained by this method are uniformly dispersed, and there is obvious interaction between Pt and the support, which not only helps to improve the poisoning resistance of the catalyst, but also improves the catalytic activity and stability.

[0154] Solution (V): Use of sulfur-containing platinum-carbon catalysts in resistance to CO poisoning The sulfur-containing platinum-carbon catalyst of the present invention can be used to improve the resistance of platinum-carbon catalysts to CO poisoning. The sulfur-containing platinum-carbon catalyst of the present invention utilizes the strong interaction between sulfur and Pt, and the sulfur-modified carbon support is prepared by simply modifying the carbon support, so that a strong interaction is formed between the support and platinum, which promotes the transfer of electrons from Pt to the support, weakens the adsorption of Pt to CO, and improves the resistance of the catalyst to CO poisoning.

[0155] Thus, the present invention provides an anode reaction method for a fuel cell, the method comprising contacting H2 in a feed gas with the sulfur-containing platinum-carbon catalyst of the present invention under anode reaction conditions, wherein the CO content in the feed gas is 1500 ppm or less, preferably 1200 ppm or less, preferably 1000 ppm or less.

[0156] Preferably, the sulfur-containing platinum-carbon catalyst of the present invention is used as an anode catalyst in a fuel cell.

[0157] Preferably, the fuel cell is a hydrogen fuel cell.

[0158] Preferably, the anode reaction conditions include a voltage of 0V or more, preferably 0 to 0.4V.

[0159] Thus, the present invention also provides a method for electrolyzing water comprising contacting water with a sulfur-containing platinum-carbon catalyst of the present invention under conditions for electrolyzing water, wherein at least a portion of the contacting is carried out in the presence of CO.

[0160] Preferably, the conditions for electrolyzing water include a voltage of -0.4V or higher, preferably -0.4 to 1.0V.

[0161] With the above technical solution, the sulfur-containing platinum-carbon catalyst of the present invention has the following advantages compared with the prior art: first, the preparation method is simple, easy to scale up industrially, and the resistance of the catalyst to CO poisoning can be improved only by the modification of the support. In-situ infrared characterization of CO shows that there is no obvious CO chemisorption on the catalyst; second, the Pt particles of the catalyst obtained by this method are uniformly dispersed, and there is obvious interaction between Pt and the support, which not only improves the resistance of the catalyst to poisoning, but also shifts the XPS spectrum peak of Pt to high electron volts, which can also improve the catalytic activity and stability.

[0162] Solution (VI): Use of sulfur-containing platinum-carbon catalysts in resisting H2S poisoning The sulfur-containing platinum-carbon catalyst of the present invention can be used to improve the resistance of platinum-carbon catalysts to H2S poisoning. The sulfur-containing platinum-carbon catalyst of the present invention utilizes the strong interaction between sulfur and Pt, and the sulfur-modified carbon support is prepared by simply modifying the carbon support, so that a strong interaction is formed between the support and platinum, which promotes the transfer of electrons from Pt to the support, weakens the adsorption of H2S on Pt, and improves the resistance of the catalyst to H2S poisoning.

[0163] Thus, the present invention provides a method for the anode reaction of a fuel cell comprising contacting the sulfur-containing platinum-carbon catalyst of the present invention with H in a feed gas under anode reaction conditions, wherein the H2S content in the feed gas is 15 ppm or less, preferably 10 ppm or less, preferably 5 ppm or less.

[0164] Preferably, the sulfur-containing platinum-carbon catalyst of the present invention is used as an anode catalyst in a fuel cell.

[0165] Preferably, the fuel cell is a hydrogen fuel cell.

[0166] Preferably, the anode reaction conditions include a voltage of 0V or more, preferably 0.01 to 0.4V.

[0167] Due to the above technical solutions, compared with the prior art, the sulfur-containing platinum-carbon catalyst of the present invention has the following advantages: firstly, the preparation method is simple, easy to be industrially scaled up, and the resistance of the catalyst to H2S poisoning can be improved only by the modification of the support; secondly, the Pt particles of the catalyst obtained by this method are uniformly dispersed, and there is obvious interaction between Pt and the support, so that the resistance of the catalyst to poisoning is improved, and the XPS spectrum peak of Pt is shifted to high electron volts, which can also improve the catalytic activity and stability.

[0168] By way of example, the present invention provides the following exemplary embodiments, or combinations thereof:

[0169] A first series of exemplary embodiments of the present invention are as follows: 1. A sulfur modified carbon material comprising conductive carbon black and elemental sulfur incorporated therein, characterized in that the total sulfur content in the sulfur modified carbon material is equal to or greater than the surface sulfur content, preferably the total sulfur content in the sulfur modified carbon material is equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times.

[0170] 2. The total sulfur content in the sulfur-modified carbon material is 0.1 to 10% by weight, preferably 1 to 8% by weight, more preferably 1 to 4% by weight; Preferably, the surface sulfur content in the sulfur-modified carbon material is 0.1 to 6% by mass, preferably 0.5 to 3% by mass; Preferably, the sulfur modified carbon material according to exemplary embodiment 1, wherein the oxygen content in the sulfur modified carbon material is 4-15% by mass.

[0171] 3. The specific surface area of ​​the sulfur-modified carbon material is 200-2000 m 2 / g, Preferably, the sulfur modified carbon material according to exemplary embodiment 1 or 2 has a resistivity of less than 10.0 Ω·m.

[0172] 4. The sulfur modified carbon material of any one of exemplary embodiments 1-3, wherein the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0173] 5. A platinum-carbon catalyst comprising a sulfur-modified carbon material and platinum metal supported thereon; A platinum-carbon catalyst, wherein the sulfur-modified carbon material is a sulfur-modified carbon material according to any one of the exemplary embodiments 1 to 4.

[0174] 6. The mass fraction of platinum is 0.1 to 70 mass% based on the total mass of the platinum-carbon catalyst; Preferably, the platinum-carbon catalyst according to Exemplary embodiment 5, wherein no more than 60% of the platinum particles in the platinum-carbon catalyst have regular lattice fringes.

[0175] 7. Use of the sulfur-modified carbon material according to any one of exemplary embodiments 1 to 4 or the platinum-carbon catalyst according to exemplary embodiment 5 or 6 as an electrode material.

[0176] 8. A fuel cell, wherein the sulfur-modified carbon material according to any one of exemplary embodiments 1 to 4 or the platinum-carbon catalyst according to exemplary embodiment 5 or 6 is used in the fuel cell; A fuel cell, preferably a hydrogen fuel cell.

[0177] 9. A PEM electrolyser, characterized in that the sulfur modified carbon material according to any one of exemplary embodiments 1 to 4 or the platinum-carbon catalyst according to exemplary embodiment 5 or 6 is used in the cathode of the PEM electrolyser.

[0178] A second series of exemplary embodiments of the present invention include: 1. A platinum-carbon catalyst comprising sulfur-containing conductive carbon black and platinum metal supported thereon; The total sulfur content in the sulfur-containing conductive carbon black is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content; A platinum-carbon catalyst, characterized in that the mass fraction of platinum is 20-70% based on the total mass of the catalyst.

[0179] 2. The platinum metal particles in the platinum-carbon catalyst do not exceed 60% with regular lattice fringes; Preferably, at least 90% of the platinum metal particles are supported within the sulfur-containing conductive carbon black; Preferably, the platinum-carbon catalyst according to Exemplary embodiment 1 has a mass fraction of platinum of 20-60%, more preferably 20-40%, based on the total mass of the catalyst.

[0180] 3. The total sulfur content in the sulfur-containing conductive carbon black is 0.4 to 8 mass%, preferably 1 to 6 mass%, Preferably, the platinum-carbon catalyst according to exemplary embodiment 1 or 2 is characterized in that the surface sulfur content of the sulfur-containing conductive carbon black is 0.1-6% by weight, preferably 0.5-4% by weight.

[0181] 4. The platinum-carbon catalyst according to any one of exemplary embodiments 1 to 3, wherein the platinum-carbon catalyst has a Pt 4f 7 / 2 characteristic peak at 71.6 eV or higher in the XPS spectrum.

[0182] 5. The platinum-carbon catalyst according to any one of exemplary embodiments 1 to 4, wherein the conductive carbon black in the sulfur-containing conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0183] 6. A platinum-carbon catalyst comprising sulfur-containing conductive carbon black and platinum metal supported thereon; The total sulfur content in the platinum-carbon catalyst is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content; A platinum-carbon catalyst, characterized in that the mass fraction of platinum is 20 to 70% based on the total mass of the catalyst.

[0184] 7. A method for preparing a platinum-carbon catalyst comprising the steps of: (1) a step of impregnating a conductive carbon black with a solution containing sulfur at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-containing conductive carbon black; (2) removing the solvent from the homogeneous mixture containing the sulfur-containing conductive carbon black, the platinum source and the solvent obtained in step (1) to obtain a precursor material; and (3) heat-treating the precursor material obtained in step (2) at 80 to 200° C. for 1 to 4 hours in a reducing atmosphere to obtain a platinum-carbon catalyst; The preparation method, wherein in the step (2), the amount of the platinum source is 0.25 to 2.4 g in terms of platinum element per 1 g of the sulfur-containing conductive carbon black.

[0185] 8. In the step (1), the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2; Preferably, XPS analysis of the conductive carbon black shows an oxygen content of greater than 4% by weight; Preferably, the conductive carbon black has a resistivity of less than 10 Ω·m; Preferably, the specific surface area of ​​the conductive carbon black is 200 to 2000 m 2 The method of preparing the method of exemplary embodiment 7, wherein the hydroxyl group is 0.1 to 0.25 g.

[0186] 9. In step (1), the solvent in the sulfur-containing solution is one or more of CCl4, CS2, cyclohexane, and n-hexane; Preferably, the amount of sulfur is 0.005 to 0.06 g per 1 g of conductive carbon black, Preferably, the preparation method according to exemplary embodiment 7 or 8, wherein the drying conditions include a temperature of 20 to 100° C. and a time of 5 to 10 hours.

[0187] 10. The preparation method according to any one of exemplary embodiments 7 to 9, wherein in step (2), the platinum source is one or more of chloroplatinic acid, chloroplatinic acid salt, tetraamineplatinum acetate, and platinum acetylacetonate.

[0188] 11. In step (2), the solvent is one or more of water, an alcohol solvent, or a ketone solvent; The preparation method according to any one of exemplary embodiments 7 to 10, wherein the solvent is preferably water and / or ethanol, more preferably a mixed solvent of water and ethanol.

[0189] 12. In step (2), the homogeneous mixture is allowed to stand for 4 hours or more, preferably 16 to 30 hours, and then the solvent is removed; The preparation method according to any one of Exemplary Embodiments 7 to 11, wherein the drying temperature in removing the solvent in step (2) is 100° C. or lower.

[0190] 13. The preparation method according to any one of exemplary embodiments 7 to 12, wherein in step (3), the reducing atmosphere contains hydrogen, preferably a mixed atmosphere of hydrogen and an inert gas, more preferably a mixed atmosphere of hydrogen and nitrogen, and preferably hydrogen accounts for 5 to 30 volume % of the total gas.

[0191] 14. A platinum-carbon catalyst, characterized in that the platinum-carbon catalyst is prepared by the preparation method described in any one of exemplary embodiments 7 to 13.

[0192] 15. Use of the platinum-carbon catalyst according to any one of exemplary embodiments 1-6 and 14 in a fuel cell or water electrolysis.

[0193] 16. A PEM electrolyser, characterized in that a platinum-carbon catalyst according to any one of exemplary embodiments 1 to 6 and 14 is used in the cathode of the PEM electrolyser.

[0194] A third series of exemplary embodiments of the present invention include: 1. A platinum-carbon catalyst, comprising a sulfur-modified carbon support and platinum metal supported thereon; The sulfur-modified carbon support is a sulfur-modified conductive carbon black, and the total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content, the total sulfur content being 1 to 8 mass%, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times; A platinum-carbon catalyst, characterized in that the mass fraction of platinum is 1 to 20% based on the total mass of the platinum-carbon catalyst.

[0195] 2. The platinum-carbon catalyst has no Pt characteristic peak in an XRD spectrum, or the ratio of the platinum-normalized peak intensity of the Pt(111) characteristic peak to the full width at half maximum of the Pt(111) characteristic peak per unit mass is 0.8 or less, and the ratio of the platinum-normalized peak intensity of the Pt(200) characteristic peak to the full width at half maximum of the Pt(200) characteristic peak per unit mass is 0.5 or less; Preferably, when the platinum content of the platinum-carbon catalyst is 10% by mass or less, the platinum-carbon catalyst does not have a Pt characteristic peak in an XRD spectrum, or the ratio of the platinum-normalized peak intensity of the Pt(111) characteristic peak to the full width at half maximum of the Pt(111) characteristic peak per unit mass is 0.6 or less, and the ratio of the platinum-normalized peak intensity of the Pt(200) characteristic peak to the full width at half maximum of the Pt(200) characteristic peak per unit mass is 0.4 or less; Preferably, the platinum-carbon catalyst according to Exemplary embodiment 1 has a mass fraction of platinum of 5-20%, preferably 5-15%, more preferably 7-10%, based on the total mass of the platinum-carbon catalyst.

[0196] 3. The total sulfur content in the sulfur-modified carbon support is 3 to 6% by mass; Preferably, the platinum-carbon catalyst according to exemplary embodiment 1, wherein the surface sulfur content in the sulfur-modified carbon support is 0.1-6 wt%, preferably 0.5-3 wt%.

[0197] 4. The platinum-carbon catalyst according to any one of exemplary embodiments 1 to 3, wherein the Pt 4f 7 / 2 characteristic peak of the platinum-carbon catalyst in the XPS spectrum is located at 71.7 eV or higher.

[0198] 5. The conductive carbon black in the sulfur modified conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2; Preferably, XPS analysis of the conductive carbon black shows an oxygen content of greater than 4% by weight; Preferably, the conductive carbon black has a resistivity of less than 10 Ω·m; Preferably, the conductive carbon black has a specific surface area of ​​200 to 2000 m 2 / g of the platinum-carbon catalyst of any one of Exemplary Embodiments 1-4.

[0199] 6. A platinum-carbon catalyst, comprising a sulfur-modified carbon support and platinum metal supported thereon; the sulfur-modified carbon support is a sulfur-modified conductive carbon black, the total sulfur content in the platinum-carbon catalyst is equal to or greater than the surface sulfur content, the total sulfur content being 1-8% by mass, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times; A platinum-carbon catalyst, characterized in that the mass fraction of platinum is 1 to 20% based on the total mass of the platinum-carbon catalyst.

[0200] 7. A method for preparing a platinum-carbon catalyst comprising the steps of: (1) impregnating a carbon support with a sulfur-containing solution at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-modified carbon support; (2) removing the solvent from the homogeneous mixture comprising the sulfur-modified carbon support, the platinum source, and the solvent obtained in step (1) to obtain a precursor material; and (3) heat-treating the precursor material obtained in step (2) at 80 to 200° C. for 1 to 4 hours in a reducing atmosphere to obtain a platinum-carbon catalyst; In step (1), the carbon support is conductive carbon black; The method according to claim 1, wherein the amount of the platinum source used in step (2) is 0.01 to 0.25 g of elemental platinum per 1 g of the sulfur-modified carbon support.

[0201] 8. In the step (1), the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2; Preferably, XPS analysis of the conductive carbon black shows an oxygen content of greater than 4% by weight; Preferably, the conductive carbon black has a resistivity of less than 10 Ω·m; Preferably, the conductive carbon black has a specific surface area of ​​200 to 2000 m 2 The method of preparing the method of exemplary embodiment 7, wherein the hydroxyl group is 0.1 to 0.25 g.

[0202] 9. In step (1), the solvent in the sulfur-containing solution is one or more of CCl4, CS2, cyclohexane, and n-hexane; Preferably, the sulfur concentration in the sulfur-containing solution is 0.0004 to 0.02 g / mL; Preferably, the amount of sulfur is 0.005 to 0.06 g per 1 g of the carbon carrier; Preferably, the preparation method according to exemplary embodiment 7 or 8, wherein the drying conditions include a temperature of 20 to 100° C. and a time of 5 to 10 hours.

[0203] 10. The preparation method according to any one of exemplary embodiments 7 to 9, wherein in step (2), the platinum source is one or more of chloroplatinic acid, chloroplatinic acid salt, tetraamineplatinum acetate, and platinum acetylacetonate.

[0204] 11. In step (2), the solvent is one or more of water, an alcohol solvent, or a ketone solvent; The preparation method according to any one of exemplary embodiments 7 to 10, wherein the solvent is preferably water and / or ethanol, more preferably a mixed solvent of water and ethanol.

[0205] 12. In step (2), the homogeneous mixture is allowed to stand for at least 10 hours, preferably 15 to 24 hours, before removing the solvent; The preparation method according to any one of Exemplary Embodiments 7 to 11, wherein the drying temperature in removing the solvent in step (2) is 100° C. or lower.

[0206] 13. The preparation method according to any one of exemplary embodiments 7 to 12, wherein in step (3), the reducing atmosphere contains hydrogen, preferably a mixed atmosphere of hydrogen and an inert gas, more preferably a mixed atmosphere of hydrogen and nitrogen, and preferably hydrogen accounts for 5 to 30 volume % of the total gas.

[0207] 14. A platinum-carbon catalyst, wherein the platinum-carbon catalyst is prepared by the preparation method described in any one of exemplary embodiments 7 to 13.

[0208] 15. Use of the platinum-carbon catalyst according to any one of exemplary embodiments 1-6 and 14 in a fuel cell or water electrolysis.

[0209] 16. A PEM electrolyser, characterized in that a platinum-carbon catalyst according to any one of exemplary embodiments 1-6 and 14 is used at the cathode of the PEM electrolyser.

[0210] Exemplary embodiments of the fourth series of the present invention include: 1.SO x 1. Use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to poisoning, characterized in that the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and platinum metal supported thereon, the total sulfur content in the sulfur-modified carbon support being equal to or greater than the surface sulfur content, preferably the total sulfur content being equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times, and the mass fraction of platinum being 20-70% based on the total mass of the catalyst.

[0211] 2. The mass fraction of platinum is 20-60%, preferably 40-60%, based on the total mass of the catalyst; Preferably, the total sulfur content in the sulfur-modified carbon support is 0.4 to 8% by mass, preferably 1 to 6% by mass; Preferably, the use according to exemplary embodiment 1, wherein the surface sulfur content in the sulfur-modified carbon support is between 0.1 and 6% by weight, preferably between 0.5 and 4% by weight.

[0212] 3. 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 The use according to exemplary embodiment 1 or 2, wherein the gel is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0213] 4. A method for the cathodic reaction of a fuel cell, the method comprising: contacting O2 in a feed gas with a sulfur-containing platinum-carbon catalyst under cathodic reaction conditions; SO in the feed gas x The content is 120 ppm or less, 1. The method of claim 1, wherein the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and 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 equal to or greater than the surface sulfur content, preferably the total sulfur content being equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content, and the mass fraction of platinum being 20-70% based on the total mass of the catalyst.

[0214] 5.SO in the feed gas x The content is 100 ppm or less, preferably 50 ppm or less, Preferably, the method according to exemplary embodiment 4, wherein the cathodic reaction conditions include a voltage of 0V or more, preferably 0 to 1.1V.

[0215] 6. The mass fraction of platinum is 20-60%, preferably 40-60%, based on the total mass of the catalyst; Preferably, the total sulfur content in the sulfur-modified carbon support is 0.4 to 8% by mass, preferably 1 to 6% by mass; The method according to Exemplary embodiment 4 or 5, wherein the surface sulfur content in the sulfur-modified carbon support is preferably 0.1-6 wt%, preferably 0.5-4 wt%.

[0216] 7. The method of any one of exemplary embodiments 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, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0217] 8. 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 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 equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content, the mass fraction of platinum being 20-70% based on the total mass of the catalyst, SO in fuel cell feed gas x The method according to claim 1, wherein the content is 120 ppm or less.

[0218] 9.SO in the feed gas x The content is 100 ppm or less, preferably 50 ppm or less, The use according to exemplary embodiment 8, wherein the sulfur-containing platinum-carbon catalyst is used as a cathode catalyst in a fuel cell.

[0219] 10. The mass fraction of platinum is 20-60%, preferably 40-60%, based on the total mass of the catalyst; Preferably, the total sulfur content in the sulfur-modified carbon support is 0.4 to 8% by mass, preferably 1 to 6% by mass; The use according to exemplary embodiment 8 or 9, wherein the surface sulfur content in the sulfur-modified carbon support is preferably 0.1 to 6% by mass, preferably 0.5 to 4% by mass.

[0220] 11.SO x 1. Use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to poisoning, the sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon support and platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, the total sulfur content in the sulfur-containing platinum-carbon catalyst being equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content, and the mass fraction of platinum being 20-70% by mass, based on the total mass of the catalyst.

[0221] Exemplary embodiments of the fifth series of the present invention include:

[0222] 1. Use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to CO poisoning, characterized in that the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and platinum metal supported thereon, the total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content, preferably the total sulfur content is equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times, and the mass fraction of platinum is 20-70% based on the total mass of the catalyst.

[0223] 2. The mass fraction of platinum is 20 to 60%, more preferably 20 to 40%, based on the total mass of the catalyst; Preferably, the total sulfur content in the sulfur-modified carbon support is 0.4 to 8% by mass, preferably 1 to 6% by mass; Preferably, the use according to exemplary embodiment 1, wherein the surface sulfur content in the sulfur-modified carbon support is between 0.1 and 6% by weight, preferably between 0.5 and 4% by weight.

[0224] 3. The sulfur-modified carbon support is a sulfur-modified conductive carbon black; The use according to exemplary embodiment 1 or 2, wherein the conductive carbon black in the sulfur modified conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0225] 4. A hydrogen fuel cell anode reaction method, the method comprising contacting H2 in a feed gas with a sulfur-containing platinum-carbon catalyst under anode reaction conditions; The CO content in the feed gas is less than 1500 ppm, 1. A method for producing a sulfur-containing platinum-carbon catalyst comprising: a sulfur-modified carbon support and platinum metal supported thereon; the sulfur-modified carbon support being a sulfur-modified conductive carbon black; a total sulfur content in the sulfur-modified carbon support being equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content; and a mass fraction of platinum being 20-70% based on the total mass of the catalyst.

[0226] 5. The CO content in the raw material gas is 1200 ppm or less, preferably 1000 ppm or less; Preferably, the anode reaction condition includes a voltage of 0V or more, preferably 0 to 0.4V.

[0227] 6. The mass fraction of platinum is 20-60%, more preferably 20-40%, based on the total mass of the catalyst; Preferably, the total sulfur content in the sulfur-modified carbon support is 0.4 to 8% by mass, preferably 1 to 6% by mass; Preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1-6 mass%, preferably 0.5-4 mass%.

[0228] 7. The anode reaction method according to any one of exemplary embodiments 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, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0229] 8. Use of a sulfur-containing platinum-carbon catalyst in a fuel cell, comprising: the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and 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 equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content, and the mass fraction of platinum being 20-70% based on the total mass of the catalyst; 2. Use of the fuel cell, characterized in that the CO content in the feed gas of the fuel cell is 1500 ppm or less.

[0230] 9. The CO content in the raw material gas is 1200 ppm or less, preferably 1000 ppm or less; Preferably, the fuel cell is a hydrogen fuel cell; The use according to exemplary embodiment 8, wherein the sulfur-containing platinum-carbon catalyst is used as an anode catalyst in a fuel cell.

[0231] 10. The mass fraction of platinum is 20 to 60%, more preferably 20 to 40%, based on the total mass of the catalyst; Preferably, the total sulfur content in the sulfur-modified carbon support is 0.4 to 8% by mass, preferably 1 to 6% by mass; The use according to exemplary embodiment 8 or 9, wherein the surface sulfur content in the sulfur-modified carbon support is preferably 0.1 to 6% by mass, preferably 0.5 to 4% by mass.

[0232] 11. A method for electrolyzing water, the method comprising contacting the water with a sulfur-containing platinum-carbon catalyst under conditions to electrolyze the water; At least a portion of the contacting occurs in the presence of CO; 1. A method for producing a sulfur-containing platinum-carbon catalyst comprising: a sulfur-modified carbon support and platinum metal supported thereon; the sulfur-modified carbon support being a sulfur-modified conductive carbon black; a total sulfur content in the sulfur-modified carbon support being equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content; and a mass fraction of platinum being 20-70% based on the total mass of the catalyst.

[0233] 12. The conditions for electrolyzing water include a voltage of -0.4 V or more, preferably -0.4 to 1.0 V; The method according to exemplary embodiment 11, wherein the method for electrolyzing water is proton exchange membrane electrolysis of water.

[0234] 13. The mass fraction of platinum is 20 to 60%, more preferably 20 to 40%, based on the total mass of the catalyst; Preferably, the total sulfur content in the sulfur-modified carbon support is 0.4 to 8% by mass, preferably 1 to 6% by mass; The method according to exemplary embodiment 11 or 12, wherein the surface sulfur content in the sulfur-modified carbon support is preferably 0.1-6 wt%, preferably 0.5-4 wt%.

[0235] 14. Use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to CO poisoning, characterized in that the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, the total sulfur content in the sulfur-containing platinum-carbon catalyst is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content, and the mass fraction of platinum is 20-70% based on the total mass of the catalyst.

[0236] Exemplary embodiments of the sixth series of the present invention include:

[0237] 1. Use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to H2S poisoning, characterized in that the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and platinum metal supported thereon, the total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content, preferably the total sulfur content is equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times, and the mass fraction of platinum is 20-70% based on the total mass of the catalyst.

[0238] 2. 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 support is 0.4 to 8% by mass, preferably 1 to 6% by mass; Preferably, the use according to exemplary embodiment 1, wherein the surface sulfur content in the sulfur-modified carbon support is between 0.1 and 6% by weight, preferably between 0.5 and 4% by weight.

[0239] 3. The sulfur-modified carbon support is a sulfur-modified conductive carbon black; The use according to exemplary embodiment 1 or 2, wherein the conductive carbon black in the sulfur modified conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0240] 4. A hydrogen fuel cell anode reaction method, the method comprising contacting H2 in a feed gas with a sulfur-containing platinum-carbon catalyst under anode reaction conditions; The H2S content in the raw gas is 15 ppm or less. 1. A method for producing a sulfur-containing platinum-carbon catalyst comprising: a sulfur-modified carbon support and platinum metal supported thereon; the sulfur-modified carbon support being a sulfur-modified conductive carbon black; a total sulfur content in the sulfur-modified carbon support being equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content; and a mass fraction of platinum being 20-70% based on the total mass of the catalyst.

[0241] 5. The H2S content in the raw material gas is 10 ppm or less, preferably 5 ppm or less; Preferably, the anode reaction condition includes a voltage of 0V or more, preferably 0.01 to 0.4V.

[0242] 6. 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 support is 0.4 to 8% by mass, preferably 1 to 6% by mass; Preferably, the surface sulfur content in the sulfur-modified carbon support is 0.1-6 mass%, preferably 0.5-4 mass%.

[0243] 7. The anode reaction method according to any one of exemplary embodiments 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, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0244] 8. Use of a sulfur-containing platinum-carbon catalyst in a fuel cell, comprising: the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and 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 equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content, and the mass fraction of platinum being 20-70% based on the total mass of the catalyst; 2. Use of the fuel cell, characterized in that the H2S content in the feed gas of the fuel cell is 15 ppm or less.

[0245] 9. The H2S content in the raw material gas is 10 ppm or less, preferably 0.4 to 10 ppm; Preferably, the fuel cell is a hydrogen fuel cell; The use according to exemplary embodiment 8, wherein the sulfur-containing platinum-carbon catalyst is used as an anode catalyst in a fuel cell.

[0246] 10. 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 support is 0.4 to 8% by mass, preferably 1 to 6% by mass; The use according to exemplary embodiment 8 or 9, wherein the surface sulfur content in the sulfur-modified carbon support is preferably 0.1 to 6% by mass, preferably 0.5 to 4% by mass.

[0247] 11. Use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to H2S poisoning, the sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon support and platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, the total sulfur content in the sulfur-containing platinum-carbon catalyst being equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content, and the mass fraction of platinum being 20-70% based on the total mass of the catalyst. [Brief description of the drawings]

[0248] [Figure 1] FIG. I.1 shows the polarization curves of the ORR reaction catalyzed by sulfur-containing platinum-carbon catalysts prepared by the sulfur-modified carbon materials of Example I.1 and Comparative Example I.2 and the commercial platinum-carbon catalyst of Comparative Example I.1. [Diagram 2] Figure I.2 shows the polarization curves before and after stabilization of the HER reaction catalyzed by the sulfur-containing platinum-carbon catalyst prepared by the sulfur-modified carbon material of Example I.1. [Diagram 3] Figure I.3 shows the polarization curves before and after stabilization of the HER reaction catalyzed by the commercial platinum-carbon catalyst of Comparative Example I.1. [Figure 4] FIG. I.4 shows a STEM image of a platinum-carbon catalyst prepared using a carbon material without the incorporated elements of Comparative Example I.2. [Diagram 5] Figure I.5 shows the bond length information of the sample of test example I.5. [Figure 6] Figure I.6 shows the valence information for the sample of test example I.5. [Figure 7] FIG. II.1 shows the XPS spectra of the sulfur-containing platinum-on-carbon catalysts of Example II.2 and Comparative Example II.3. [Figure 8] Figure II.2 shows a STEM image of the sulfur-containing platinum-carbon catalyst of Example II.2. [Figure 9] Figure II.3 shows a STEM image of the sulfur-containing platinum-carbon catalyst of Example II.3. [Figure 10] Figure II.4 shows a TEM photograph of the sulfur-containing platinum-carbon catalyst of Comparative Example II.1. [Figure 11] Figure II.5 shows a TEM photograph of the sulfur-containing platinum-carbon catalyst of Comparative Example II.2. [Figure 12] Figure II.6 shows a STEM image of the sulfur-containing platinum-carbon catalyst of Comparative Example II.4. [Figure 13] Figure II.7 is a STEM photograph showing platinum particles with regular lattice fringes. [Figure 14] Figure II.8 shows a TEM image of the sulfur-containing platinum-carbon catalyst of Example II.2. [Figure 15]Figure II.9 shows a TEM photograph of the sulfur-containing platinum-carbon catalyst of Comparative Example II.4. [Figure 16] FIG. III.1 shows the XRD spectra of the sulfur-containing platinum-carbon catalysts of Examples III.1, 3-5 and Comparative Examples III.1-2. [Figure 17] FIG. III.2 shows the XPS spectra of the sulfur-containing platinum-on-carbon catalysts of Example III.1 and Comparative Examples III.1-3. [Figure 18] Figure III.3 shows the LSV curves of the sulfur-containing platinum-on-carbon catalysts of Example III.1 and Comparative Examples III.1-3. [Figure 19] FIG. IV.1 shows the LSV curves of the ORR of the platinum-carbon catalysts of Example 1 and Comparative Example 2 before and after the SOx poisoning treatment. [Figure 20] FIG. V.1 shows the XPS spectra of the platinum-carbon catalysts of Example V.1 and Comparative Example V.1. [Figure 21] Figure V.2 shows the LSV curves of the HER of the platinum-carbon catalysts of Example V.1 and Comparative Example V.1 before and after the CO poisoning treatment. [Figure 22] Figure V.3 shows the LSV curves of HOR of the platinum-carbon catalysts of Example V.1 and Comparative Example V.2 before and after CO poisoning treatment. [Figure 23] Figure V.4 shows the CO in-situ infrared curves of the platinum-carbon catalysts of Example V.1 and Comparative Example V.1. [Figure 24] Figure V.5 shows the LSV curves of HOR of the platinum-carbon catalysts of Example V.2 and Comparative Example V.4 before and after CO poisoning treatment. [Diagram 25] Figure VI.1 shows the LSV curves of the platinum-carbon catalyst of Example VI.2 before and after poisoning with H2S. [Figure 26] Figure VI.2 shows the CV curves of the platinum-carbon catalyst of Example VI.2 before and after poisoning with H2S. [Figure 27] FIG. VI.3 shows the LSV curves of the platinum-carbon catalysts of Example VI.1 and Comparative Example VI.1 before and after poisoning with H2S. [Figure 28]FIG. VI.4 shows the CV curves of the platinum-carbon catalysts of Example VI.1 and Comparative Example VI.1 before and after poisoning with H2S. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0249] Hereinafter, the present invention will be described in detail in conjunction with specific embodiments. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments and principle descriptions, but is determined by the exemplary embodiments.

[0250] The range endpoints and values ​​disclosed herein are not limited to the exact ranges or values, and should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, and the individual point values ​​of each range, can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0251] In the present invention, except for the contents explicitly described, any undescribed items or items can be directly applied to items or items known in the technical field without modification. In addition, any embodiment described in this specification can be freely combined with one or more other embodiments described in this specification, and the technical solutions or technical ideas formed thereby are considered to be part of the original disclosure or record of the present invention, and should not be considered as new contents not disclosed or anticipated in this specification unless a person skilled in the art judges that the combination is obviously unreasonable.

[0252] All features disclosed in the present invention can be arbitrarily combined, and these combinations are understood as being disclosed or recorded in the present invention, and are considered to be specifically disclosed and recorded in the present invention, unless a person skilled in the art judges that the combination is obviously unreasonable. The numerical points disclosed in this specification include not only the numerical points specifically disclosed in the examples, but also the end points of each numerical range in the specification, and the range formed by any combination of these numerical points is considered to be a range disclosed or recorded in the present invention.

[0253] Numerical ranges defined in the present invention include the endpoints of the numerical range. A "range" disclosed herein is given in the form of a lower limit and an upper limit, e.g., one or more lower limits and one or more upper limits. A given range can be defined by selecting lower and upper limits, with the selected lower and upper limits defining the boundaries of the given range. All ranges defined in this manner are inclusive and combinable. That is, any lower limit can be combined with any upper limit to form a range. For example, for a particular parameter, ranges of 60-110 and 80-120 are recited, but it is understood that ranges of 60-120 and 80-110 are also contemplated. Furthermore, if the recited lower limits are 1 and 2 and the recited upper limits are 3, 4 and 5, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0254] In the present invention, unless otherwise specified, terms such as "comprise", "comprise", "contain", "have" and the like are to be understood as expressly disclosing open-ended situations, but at the same time expressly disclosing closed-ended situations. For example, "comprise" means that other elements not listed may be included, but at the same time expressly disclosing situations including only the listed elements. Furthermore, as used herein, "comprise" is to be interpreted as expressly reciting the presence of the mentioned features, integers, steps, or components, but does not exclude the presence or addition of one or more other features, integers, steps, components, or groups thereof. Furthermore, the term "comprise" is intended to include embodiments encompassed by the terms "consisting essentially of" and "consisting of". Similarly, the term "consisting essentially of" is intended to include embodiments encompassed by the term "consisting of".

[0255] In the present invention, "charcoal black" and "carbon black" are interchangeable terms of art.

[0256] The "inert gas" in the present invention refers to a gas that does not significantly affect the performance of the sulfur-containing conductive carbon black / sulfur-modified carbon material in the preparation method of the present invention.

[0257] In the present invention, "surface sulfur content" refers to the sulfur weight fraction measured by XPS analysis of the test object. Those skilled in the art will understand that according to the principles and test methods of XPS analysis, it can be used to characterize the sulfur concentration of the surface of the test object based on the total weight of the surface layer of the test object.

[0258] In the present invention, the "total sulfur content" refers to the sulfur weight fraction measured by a sulfur-carbon analyzer for the test object. Those skilled in the art will understand that according to the principles and test methods of the sulfur-carbon analyzer, it can be used to characterize the sulfur concentration of the entire test based on the total weight of the test object.

[0259] For the purposes of the present invention, the sulfur-modified carbon material is generally used as a support for preparing a catalyst, etc., and therefore, unless otherwise specified, the terms "sulfur-modified carbon material" and "sulfur-modified carbon support" are used interchangeably in the present invention. For the purposes of the present invention, the sulfur-modified carbon material is generally used as a sulfur-containing conductive carbon black, and therefore, unless otherwise specified, the terms "sulfur-modified carbon material" and "sulfur-containing conductive carbon black" are used interchangeably in the present invention. Thus, "sulfur-containing conductive carbon black" is also referred to as "sulfur-modified conductive carbon black".

[0260] According to the technical solution of the present invention, the platinum-carbon catalyst provided by the present invention can be prepared using a sulfur-modified carbon material as a support. Therefore, the platinum-carbon catalyst provided by the present invention contains sulfur, and is therefore called a sulfur-containing platinum-carbon catalyst, in contrast to the conventional platinum-carbon catalyst that does not contain sulfur. Therefore, in describing the technical solution of the present invention, the terms "sulfur-containing platinum-carbon catalyst" and "platinum-carbon catalyst" may be used interchangeably, unless a person skilled in the art can determine that they have a specific and clearly different meaning. For example, when the term "platinum-carbon catalyst" is specifically used to describe the prior art and / or a sulfur-free platinum-carbon catalyst for comparison.

[0261] In the present invention, unless otherwise specified, all solutions, embodiments, series, exemplary embodiments, and preferred embodiments mentioned in this specification, as well as their respective features, can be combined with each other to form new technical solutions. Specifically, for example, for the embodiments I to VI covered by the present invention, the technical features and technical solutions mentioned therein can be combined with each other internally and with each other, as long as the combination is not contrary to the object of the present invention; for another example, for the exemplary embodiments of the first to sixth series covered by the present invention, the technical features and technical solutions mentioned therein can be combined with each other internally and with each other, as long as the combination is not contrary to the object of the present invention, and can also be combined with each other with the embodiments I to VI.

[0262] At the same time, the designations "first", "second", etc., and numbers such as I-VI, given to the solutions, embodiments, series, exemplary embodiments and preferred embodiments of the present invention are for ease of description, reading and understanding, and do not imply any sequence or primary and secondary relationship between them, and consecutive numbering is not necessary. At the same time, unless otherwise specified, references to terms, features, numbers, etc. preferably refer to objects within the same solutions, embodiments, series, exemplary embodiments and preferred embodiments.

[0263] Embodiment 1: Sulfur-modified carbon material and its preparation method and application The first embodiment of the present invention provides a sulfur-modified carbon material, which is formulated with conductive carbon black and elemental sulfur, and the total sulfur content in the sulfur-modified carbon material is equal to or greater than the surface sulfur content. According to the sulfur-modified carbon material of the present invention, preferably, the total sulfur content in the sulfur-modified carbon material is at least 1.2 times, at least 1.5 times, at least 1.7 times, at least 2 times, at least 3 times, etc., the surface sulfur content, which may be, for example, 1.2 to 10 times, the surface sulfur content being the sulfur weight fraction measured by XPS analysis, and the total sulfur content being the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0264] According to the present invention, on the one hand, the inventors have found that the incorporation of more elemental sulfur in the carbon material is suitable for preparing a catalyst that better promotes the loading of platinum in the conductive carbon black and provides better electrocatalytic performance, and on the other hand, the inventors have found that the introduction of elemental sulfur into the conductive carbon black by impregnation and drying can produce a sulfur-containing platinum-carbon catalyst with better performance.

[0265] Preferably, the elemental sulfur is introduced into the conductive carbon black in the form of elemental sulfur. Thus, in the method for preparing the sulfur-modified carbon material, it is preferred that the sulfur source used for impregnation is elemental sulfur, so that the elemental sulfur is introduced into the conductive carbon black in the form of elemental sulfur. Furthermore, it is preferred that after the elemental sulfur is introduced into the conductive carbon black in the form of elemental sulfur, the elemental sulfur in the sulfur-modified carbon material is present in the conductive carbon black in the form of elemental sulfur or substantially in the form of elemental sulfur.

[0266] Preferably, the total sulfur content in the sulfur-modified carbon material is 0.1-10% by weight, more preferably 1-8% by weight, and even more preferably 1-4% by weight, and the surface sulfur content in the sulfur-modified carbon material is preferably 0.1-6% by weight, and even more preferably 0.5-3% by weight.

[0267] According to the present invention, the sulfur-modified carbon material is preferably a sulfur-containing conductive carbon black, and preferably contains conductive carbon black and sulfur and oxygen elements blended therein. The oxygen content in the sulfur-modified carbon material of the present invention is 4-15% by weight, preferably 6-10% by weight. It is also preferable that the sulfur-modified carbon material of the present invention does not contain blended elements other than sulfur. Here, the "blended elements" in the present invention refer to nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine. It is also preferable that the sulfur-modified carbon material contains conductive carbon black and sulfur and oxygen elements blended therein.

[0268] The conductive carbon black that can be used in the present invention may be one or more of ordinary conductive carbon blacks, super conductive carbon blacks, or extra conductive carbon blacks, such as Ketjen black, Cabot conductive carbon blacks (Cabot, Black pearls, etc.), Orilon conductive carbon blacks (HIBLACK, PRINTEX, etc.), and more specifically, may be one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0269] The present invention is not limited to the preparation method and source of the conductive carbon black, which may be acetylene black, furnace carbon black, etc.

[0270] The specific surface area of ​​the conductive carbon black is preferably 200 to 2000 m2 / g, more preferably 220 to 1500 m 2 The specific surface area can be measured by the BET method.

[0271] Preferably, the resistivity of the conductive carbon black is less than 10 Ω·m, preferably less than 5 Ω·m, more preferably less than 3 Ω·m, and even more preferably from 0.01 to 1 Ω·m.

[0272] Another aspect of the present invention is to provide a method for preparing a sulfur-modified carbon material, comprising impregnating a conductive carbon black with a solution containing sulfur at 10-80° C. for 1-5 hours and drying the impregnated product to obtain the sulfur-modified carbon material.

[0273] The preparation method of the sulfur-modified carbon material of the present invention can be used to prepare the sulfur-containing platinum-carbon catalyst of the present invention, and the conductive carbon black is the same as above, and will not be described in detail here.

[0274] In the above preparation method, the solvent in the sulfur-containing solution can dissolve sulfur. Preferably, from the viewpoint of better preparing the sulfur-modified carbon material, for example, the solvent can be one or more of CCl4, CS2, cyclohexane, and n-hexane, and is preferably cyclohexane, n-hexane, CCl4, etc. The concentration of sulfur in the sulfur-containing solution is 0.0004 to 0.02 g / mL, preferably 0.0005 to 0.01 g / mL. The amount of the sulfur-containing solution used can be, for example, 5 to 15 mL per 1 g of conductive carbon black.

[0275] In order to obtain an appropriate sulfur loading rate and sulfur distribution, the amount of sulfur used is preferably 0.005 to 0.06 g, more preferably 0.01 to 0.055 g, per 1 g of conductive carbon black. The impregnation temperature is preferably 10 to 40° C., more preferably 20 to 30° C., and particularly preferably room temperature (25° C.), and the impregnation time is preferably 2 to 4 hours.

[0276] The drying method is not particularly limited as long as it can remove the solvent in the sulfur-containing solution, and vacuum drying is preferably used. Drying conditions include a temperature of 20 to 100° C. and a time of 5 to 10 hours.

[0277] By preparing the sulfur-modified carbon material under the above conditions, it is possible to obtain a sulfur-modified carbon material having the desired sulfur distribution of the present invention. The sulfur-modified carbon material prepared by the preparation method of the present invention can be more easily dispersed in an aqueous phase.

[0278] Another aspect of the present invention provides a sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon material and platinum metal supported thereon, the sulfur-modified carbon material being the sulfur-modified carbon material of the present invention or obtained by the preparation method of the present invention.

[0279] According to the present invention, the weight fraction of platinum can be 0.1-70% by weight based on the total weight of the sulfur-containing platinum-carbon catalyst. Depending on different applications, the weight fraction of platinum can be 0.1-1% by weight, 1-4% by weight, 1-8% by weight, 4-20% by weight, 1-70% by weight, 5-60% by weight, 10-55% by weight, 20-40% by weight, or 40-70% by weight. In addition, it is preferable that the sulfur-containing platinum-carbon catalyst of the present invention does not contain any metal element other than platinum.

[0280] According to the present invention, the proportion of platinum particles having regular lattice fringes in the sulfur-containing platinum-carbon catalyst is 60% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less, more preferably 20% by weight or less, or 10% by weight or less. Here, the presence of lattice fringes indicates that the Pt particles are present in the form of nanocrystals, and the absence of lattice fringes indicates that the Pt particles are present in the form of atoms or atomic clusters. Specifically, the lattice fringes can be confirmed by observation with TEM or STEM (preferably AC-TEM or AC-STEM).

[0281] In the sulfur-containing platinum-carbon catalyst of the present invention, preferably, 70% by weight or more (preferably 80% by weight or more, 90% by weight or more, more preferably 95% by weight or more) of the platinum metal particles are supported inside the carbon material. The distribution position of the platinum metal particles can be determined by the following method: in the TEM image, the relative positions of 200 metallic platinum particles along the edge of the carbon support and the carbon material are randomly counted, the percentage A% of the metallic platinum particles protruding from the carbon material is calculated, and (100-A)% is used to represent the percentage of the platinum metal particles supported inside the carbon material. In the TEM image, "protruding from the carbon material" can be understood to mean that the metallic platinum particles are located on the surface of the carbon material, and "not protruding from the carbon material" can be understood to mean that the metallic platinum particles are located inside the carbon material.

[0282] According to some preferred embodiments of the present invention, the sulfur-containing platinum-carbon catalyst has a Pt 4f 7 / 2 characteristic peak located at 71.6 eV or more, for example, 71.6 to 72.2 eV, in the XPS spectrum. The XPS spectrum refers to an XPS spectrum corrected with the C1s peak located at 284.3 eV. In a normal situation, such as when platinum is supported on a carbon support that does not contain any compounding elements, the Pt 4f 7 / 2 characteristic peak is located near 71.3 eV, which indicates that the sulfur-containing platinum-carbon catalyst of the present invention has a Pt 4f 7 / 2 characteristic peak shifted to the high electron volt side by 0.3 eV or more in the XPS spectrum.

[0283] The sulfur-containing platinum-carbon catalyst of the present invention can be obtained by supporting platinum on the sulfur-modified carbon material of the present invention. The method for preparing the sulfur-containing platinum-carbon catalyst can, for example, include the following steps:

[0284] (1) removing a solvent from a homogeneous mixture comprising a sulfur modified carbon material, a platinum source, and a solvent to obtain a precursor material; (2) A step of heat treating the precursor material obtained in step (1) at 80-200° C. for 1-4 hours in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0285] According to the present invention, in step (1), the platinum source can be one or more of chloroplatinic acid, chloroplatinate, tetraammineplatinum acetate, and platinum acetylacetonate, where the chloroplatinate can be potassium chloroplatinate or sodium chloroplatinate.

[0286] Preferably, the amount of platinum source used is 0.01 to 2.4 g, preferably 0.05 to 1.5 g, calculated as elemental platinum, per gram of sulfur-modified carbon material.

[0287] According to the present invention, in step (2), the precursor material is obtained by dissolving the sulfur-modified carbon material and the platinum source in a solvent to form a homogeneous mixture, and then removing the solvent in the homogeneous mixture. The type of the solvent is not particularly limited. The solvent may be one or more of water, an alcohol solvent, or a ketone solvent, and the alcohol solvent may be, for example, ethanol, and the ketone solvent may be, for example, acetone. The solvent is preferably water, ethanol, or a mixture of ethanol and water (the volume ratio of ethanol to water can be selected arbitrarily, and may be, for example, 0.1 to 10:1, preferably 1 to 5:1). The present invention is also not particularly limited by the amount of the solvent, and may be, for example, 3 to 20 mL per 1 g of the sulfur-modified carbon material.

[0288] The present invention can obtain a homogeneous mixture by mixing the sulfur-modified carbon material, the platinum source and the solvent, preferably with stirring. The present invention is not particularly limited on the stirring speed and time as long as the homogeneous mixture can be formed. Heating can also be used to further promote dissolution in order to form a homogeneous mixture.

[0289] As a method for removing the solvent in the homogeneous mixture, the solvent in the homogeneous mixture can be removed by evaporation, and the temperature and method of evaporation can be any existing technology known to those skilled in the art. According to the present invention, in step (1), the drying temperature for removing the solvent is 100°C or lower, and for example, the solvent in the homogeneous mixture can be removed by drying in an oven at 60 to 95°C for 12 to 24 hours.

[0290] According to a preferred embodiment of the present invention, in step (1), the homogeneous mixture is allowed to stand for at least 4 hours, preferably 16 to 30 hours, before removing the solvent.

[0291] According to the present invention, in step (2), the heat treatment temperature is preferably 100 to 180° C., and the heat treatment time is preferably 2 to 3 hours. The heating rate of the heat treatment is 4 to 15° C. / min, and generally 5° C. / min.

[0292] According to the present invention, in step (2), the heat treatment is carried out in a reducing atmosphere. The reducing atmosphere preferably contains hydrogen, and is preferably a mixed atmosphere of hydrogen and an inert gas, and the inert atmosphere is nitrogen and / or argon, etc., specifically, a mixed atmosphere of hydrogen and nitrogen. Preferably, hydrogen occupies 5 to 30 volume % of the total gas. The heat treatment can be carried out in any apparatus that provides the above heat treatment conditions, for example, in a tubular furnace.

[0293] By carrying out the platinum loading under the above conditions, a sulfur-containing platinum-carbon catalyst in which platinum is loaded in the form desired by the present invention can be obtained.

[0294] Another aspect of the present invention is to provide a use of the sulfur modified carbon material, the sulfur modified carbon material obtained by the preparation method, or the sulfur-containing platinum-carbon catalyst as an electrode material.

[0295] The sulfur-containing platinum-carbon catalyst of the present invention is suitable as an anode catalyst for a fuel cell. The fuel cell is not particularly limited, and examples thereof include a hydrogen fuel cell (e.g., a proton exchange membrane hydrogen fuel cell) and a direct alcohol fuel cell (e.g., a direct alcohol fuel cell using methanol or ethanol as the anode fuel).

[0296] Another aspect of the present invention is to provide a fuel cell using the sulfur modified carbon material according to the present invention, or obtained by the preparation method according to the present invention, or using the sulfur-containing platinum-carbon catalyst according to the present invention.

[0297] Preferably, the fuel cell is a hydrogen fuel cell.

[0298] Another aspect of the present invention is to provide a PEM electrolyser, the cathode of which is made of the sulfur modified carbon material of the present invention, the sulfur modified carbon material obtained by the preparation method of the present invention, or the sulfur-containing platinum-carbon catalyst of the present invention.

[0299] The sulfur-modified carbon material and sulfur-containing platinum-carbon catalyst of the present invention can be applied to the anode hydrogen oxidation reaction, the cathode oxygen reduction reaction of hydrogen fuel cells, and the cathode hydrogen evolution reaction of PEM water electrolysis, and have excellent catalytic activity and stability.

[0300] Embodiment II: Sulfur-containing platinum-carbon catalyst with high Pt content and its preparation method and application The embodiment II of the present invention provides a sulfur-containing platinum-carbon catalyst comprising the sulfur-containing conductive carbon black of the present invention and platinum metal supported thereon, in which the total sulfur content in the sulfur-containing conductive carbon black is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times. Based on the total weight of the catalyst, the weight fraction of platinum is 20-70% by weight.

[0301] In the present invention, sulfur-containing conductive carbon black is used as the sulfur-containing carbon support.

[0302] In the sulfur-containing platinum-carbon catalyst of the present invention, the sulfur element inside the carbon support further promotes platinum loading inside the carbon support, so that the sulfur-containing platinum-carbon catalyst has better electrocatalytic performance. Preferably, the total sulfur content in the sulfur-containing conductive carbon black is 1.7 times or more, 2 times or more, 3 times or more, such as 1.2 to 10 times, of the surface sulfur content. Here, the surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and the total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0303] According to the present invention, the total sulfur content of the sulfur-containing conductive carbon black is preferably 0.4 to 8% by weight, and more preferably 1 to 6% by weight, and the surface sulfur content of the sulfur-containing conductive carbon black is preferably 0.1 to 6% by weight, and more preferably 0.5 to 4% by weight.

[0304] Preferably, the elemental sulfur in the sulfur-containing conductive carbon black is present in the form of elemental sulfur.

[0305] According to the present invention, preferably, at least 90% by weight, preferably 95% by weight 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 metallic platinum particles along the edge of the carbon support and the carbon support are randomly counted, the percentage A% of the metallic platinum particles protruding from the carbon support is calculated, and (100-A)% is used to represent the percentage of the platinum metal particles supported inside the carbon support. In the TEM image, "protruding from the carbon support" is understood to mean that the metallic platinum particles are located on the surface of the carbon support, and "not protruding from the carbon support" means that the metallic platinum particles are located inside the carbon support.

[0306] 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 do not exceed 60% by weight, preferably 50% by weight or less, more preferably 40% by weight or less, more preferably 20% by weight or less or 10% by weight or less. The presence of lattice fringes indicates that the Pt particles are present in the form of nanocrystals, and the absence of lattice fringes indicates that the Pt particles are present in the form of atoms or atomic clusters. Specifically, the lattice fringes can be confirmed by observation with TEM or STEM (preferably AC-TEM or AC-STEM).

[0307] In the sulfur-containing platinum-carbon catalyst of the present invention, the sulfur-containing platinum-carbon catalyst has a Pt 4f 7 / 2 characteristic peak located at 71.6 eV or more, for example, 71.6 to 72.2 eV, for example, 71.7 eV in the XPS spectrum. The XPS spectrum refers to an XPS spectrum corrected with the C1s peak located at 284.3 eV. Usually, for example, when platinum is supported on a carbon support that does not contain a compounding element, the Pt 4f 7 / 2 characteristic peak is located near 71.3 eV, so the sulfur-containing platinum-carbon catalyst of the present invention shows that it has a Pt 4f 7 / 2 characteristic peak shifted to the high electron volt side by 0.3 eV or more in the XPS spectrum.

[0308] In the sulfur-containing platinum-carbon catalyst of the present invention, the weight fraction of platinum is 20 to 70% by weight, preferably 20 to 60% by weight, 20 to 40% by weight, or 40 to 70% by weight, based on the total weight of the catalyst. Preferably, the sulfur-containing platinum-carbon catalyst of the present invention does not contain any other metal element than platinum.

[0309] According to the present invention, the sulfur-containing conductive carbon black preferably contains conductive carbon black and sulfur and oxygen elements blended therein. The sulfur-containing conductive carbon black of the present invention preferably does not contain blended elements other than sulfur. Here, the "blended elements" in the present invention means nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine. The sulfur-containing conductive carbon black preferably consists of conductive carbon black and sulfur and oxygen elements blended therein.

[0310] The conductive carbon black that can be used in the present invention may be one or more of ordinary conductive carbon blacks, super conductive carbon blacks, or extra conductive carbon blacks, such as Ketjen Black, Cabot conductive carbon blacks (Cabot, Black Pearls, etc.), Orilon conductive carbon blacks (HIBLACK, PRINTEX, etc.), and more specifically, may be one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

[0311] The present invention is not limited to the preparation method and source of the conductive carbon black, which may be acetylene black, furnace carbon black, etc.

[0312] Preferably, XPS analysis of the conductive carbon black shows an oxygen content of at least 4% by weight, for example 5-12% by weight.

[0313] Preferably, the specific surface area of ​​the conductive carbon black is 200 to 2000 m 2 / g, preferably 220 to 1500m 2 / g.

[0314] This embodiment II also provides a sulfur-containing platinum-carbon catalyst comprising a sulfur-containing conductive carbon black and platinum metal supported thereon, wherein the total sulfur content in the sulfur-containing platinum-carbon catalyst is equal to or greater than the surface sulfur content, preferably the total sulfur content is equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum is 20 to 70 wt %, based on the total weight of the catalyst.

[0315] This embodiment II also provides a method for preparing a sulfur-containing platinum-on-carbon catalyst, the method comprising: (1) a step of impregnating a carbon support (conductive carbon black) with a solution containing sulfur at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-containing carbon support (also called sulfur-containing conductive carbon black); (2) removing the solvent from the homogeneous mixture of the sulfur-containing carbon support, the platinum source and the solvent obtained in step (1) to obtain a precursor material; and (3) heat-treating the precursor material obtained in step (2) at 80-200° C. for 1-4 hours in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst; In the step (2), the amount of the platinum source used is 0.25 to 2.4 g in terms of platinum element per 1 g of the sulfur-containing conductive carbon black.

[0316] Preferably, in step (1), the solvent in the sulfur-containing solution can dissolve sulfur. From the viewpoint of better preparation of the sulfur-containing carbon support, for example, it may be one or more of CCl4, CS2, cyclohexane, and n-hexane, and is preferably cyclohexane and n-hexane. The sulfur concentration in the sulfur-containing solution is 0.0004 to 0.02 g / mL, preferably 0.0005 to 0.01 g / mL. The amount of the sulfur-containing solution used is 5 to 15 mL per 1 g of the carbon support.

[0317] To obtain an appropriate sulfur loading amount and sulfur distribution, the amount of sulfur used is preferably 0.005 to 0.06 g, more preferably 0.01 to 0.055 g, per 1 g of carbon support. The impregnation temperature is preferably 10 to 40° C., more preferably 20 to 30° C., and particularly preferably room temperature (25° C.), and the impregnation time is preferably 2 to 4 hours.

[0318] The drying method is not particularly limited as long as it can remove the solvent in the sulfur-containing solution, but vacuum drying is preferably used.

[0319] By preparing the sulfur-containing carbon support under the above conditions, a carbon support having the sulfur distribution desired by the present invention can be obtained. The sulfur-containing carbon support obtained in step (1) can be easily dispersed in the aqueous phase. However, it is difficult to directly disperse a carbon support that has not been treated in step (1), such as Ketjen Black, in the aqueous phase, and it is usually necessary to add ethanol or the like to facilitate dispersion.

[0320] According to the present invention, in step (2), the platinum source is one or more of chloroplatinic acid, chloroplatinate, tetraamineplatinum acetate, and platinum acetylacetonate, and the chloroplatinate can be potassium chloroplatinate or sodium chloroplatinate.

[0321] The amount of the platinum source used is preferably 0.25 to 2.4 g, and more preferably 0.25 to 0.67 g, in terms of platinum element per gram of the sulfur-containing carbon support.

[0322] According to the present invention, in step (2), the sulfur-containing carbon support and the platinum source are dissolved in a solvent to form a homogeneous mixture, and then the solvent in the homogeneous mixture is removed to obtain a precursor material. The type of the solvent is not particularly limited. The solvent may be one or more of water, an alcohol solvent, or a ketone solvent, and the alcohol solvent may be, for example, ethanol, and the ketone solvent may be, for example, acetone. The solvent is preferably water, ethanol, or a mixture of ethanol and water (the volume ratio of ethanol to water can be selected arbitrarily, for example, 0.1 to 10:1, preferably 1 to 5:1). The present invention also does not particularly limit the amount of the solvent, and for example, the amount of the solvent may be 3 to 20 mL per 1 g of the sulfur-containing carbon support.

[0323] In the present invention, the sulfur-containing carbon support, the platinum source and the solvent are mixed, preferably with stirring, to obtain a homogeneous mixture. In the present invention, there is no particular limitation on the stirring speed and time as long as the homogeneous mixture can be formed. In addition, in order to form a homogeneous mixture, heating can be performed to promote dissolution.

[0324] As a method for removing the solvent in the homogeneous mixture, an evaporation method can be used to remove the solvent in the homogeneous mixture, and the evaporation temperature and evaporation method can be any existing technology known to those skilled in the art. According to the present invention, in step (2), the drying temperature for removing the solvent is 100°C or less, and for example, the solvent in the homogeneous mixture can be removed by drying in an oven at 60 to 95°C for 12 to 24 hours.

[0325] According to a preferred embodiment of the present invention, in step (2), the homogeneous mixture is allowed to stand for at least 4 hours, preferably 16 to 30 hours, before removing the solvent.

[0326] According to the present invention, in step (3), the heat treatment temperature is preferably 100 to 180° C., and the heat treatment time is preferably 2 to 3 hours. The heating rate of the heat treatment is 4 to 15° C. / min, and generally 5° C. / min.

[0327] According to the present invention, in step (3), the heat treatment is carried out in a reducing atmosphere. The reducing atmosphere preferably contains hydrogen, and is preferably a mixed atmosphere of hydrogen and an inert gas, and the inert atmosphere is nitrogen and / or argon, etc., specifically, a mixed atmosphere of hydrogen and nitrogen. Preferably, hydrogen occupies 5 to 30 volume % of the total gas. The heat treatment can be carried out in any apparatus that provides the above heat treatment conditions, for example, in a tubular furnace.

[0328] By carrying out the platinum loading under the above conditions, it is possible to obtain a sulfur-containing platinum-on-carbon catalyst having platinum loaded in the form desired in the present invention.

[0329] In any embodiment, the resistivity of the conductive carbon black or sulfur modified carbon material of the present invention is less than 10 Ω·m, such as less than 5 Ω·m, such as less than 3 Ω·m, for example 0.01-1 Ω·m.

[0330] This embodiment II provides a sulfur-containing platinum-on-carbon catalyst prepared by the preparation method of the present invention.

[0331] This embodiment II provides the use of the sulfur-containing platinum-carbon catalyst described above in the present invention in fuel cells or water electrolysis.

[0332] The sulfur-containing platinum-carbon catalyst of the present invention is suitable as an anode catalyst for a fuel cell. The fuel cell is not particularly limited, and examples thereof include a hydrogen fuel cell (e.g., a proton exchange membrane hydrogen fuel cell) and a direct alcohol fuel cell (e.g., a direct alcohol fuel cell using methanol or ethanol as the anode fuel).

[0333] This embodiment II provides a PEM electrolyser, the cathode of which employs a sulfur-containing platinum-carbon catalyst according to the present invention.

[0334] The sulfur-containing platinum-carbon catalyst of the present invention is applicable to the anode hydrogen oxidation reaction, cathode oxygen reduction reaction, and cathode hydrogen evolution reaction of PEM water electrolysis in hydrogen fuel cells, and has excellent catalytic activity and stability.

[0335] Embodiment III: Sulfur-containing platinum-carbon catalyst with low Pt content and its preparation method and use Embodiment III of the present invention provides a sulfur-containing platinum-carbon catalyst comprising the sulfur-modified carbon support of the present invention and platinum metal supported thereon, wherein the sulfur-modified carbon support is a sulfur-modified conductive carbon black, the total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content, the total sulfur content being 1-8 wt%, preferably the total sulfur content being equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum being 1-20 wt%, based on the total weight of the sulfur-containing platinum-carbon catalyst.

[0336] In the sulfur-containing platinum-carbon catalyst of the present invention, a new carbon support structure modified by elemental sulfur is constructed, which makes it easier to support platinum inside the carbon support, thereby improving the electrocatalytic performance of the sulfur-containing platinum-carbon catalyst. In addition, the total sulfur content in the sulfur-modified carbon support is preferably 1.7 times or more, 2 times or more, or 3 times or more, for example, 1.5 to 10 times, of the surface sulfur content. Here, the surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and the total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0337] Preferably, the total sulfur content in the sulfur modified carbon support is 0.1-8 wt%, preferably 0.5-6 wt%. Preferably, the surface sulfur content in the sulfur modified carbon support is 0.1-6 wt%, preferably 0.5-3 wt%.

[0338] 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, or 10 times the surface sulfur content. The total sulfur content may be 0.4% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, or 8% by weight, and the surface sulfur content may be 0.1% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, or 6% by weight, etc.

[0339] Preferably, the modified sulfur element in the sulfur-modified carbon support is present in the form of elemental sulfur. By employing the sulfur-modified carbon support of the present invention, the platinum in the synthesized sulfur-containing platinum-carbon catalyst is supported in the carbon support in the form of atomic clusters, thereby improving the catalytic activity. Preferably, at least 70% by weight, preferably 70-80% by weight, of the platinum metal particles is supported in the carbon support.

[0340] In the sulfur-containing platinum-carbon catalyst of the present invention, the sulfur-containing platinum-carbon catalyst does not have a Pt characteristic peak in the XRD spectrum, or the ratio of the unit weight platinum normalized peak intensity to the full width at half maximum of the Pt(111) characteristic peak is 0.8 or less, and the ratio of the unit weight platinum normalized peak intensity to the full width at half maximum of the Pt(200) characteristic peak is 0.5 or less. Preferably, when the platinum content of the sulfur-containing platinum-carbon catalyst is 10% by weight or less, the sulfur-containing platinum-carbon catalyst does not have a Pt characteristic peak in the XRD spectrum, or the ratio of the unit weight platinum normalized peak intensity to the full width at half maximum of the Pt(111) characteristic peak is 0.6 or less, and the ratio of the unit weight platinum normalized peak intensity to the full width at half maximum of the Pt(200) characteristic peak is 0.4 or less.

[0341] Specifically, "having no Pt characteristic peak in the XRD spectrum, or having a ratio of the platinum normalized peak intensity per unit weight to the full width at half maximum of the Pt(111) characteristic peak of 0.8 or less, and a ratio of the platinum normalized peak intensity per unit weight to the full width at half maximum of the Pt(200) characteristic peak of 0.5 or less" means that at least most of the platinum in the sulfur-containing platinum-carbon catalyst of the present invention is present in an amorphous phase, excluding any small amount of crystalline phase. As described above, the presence of a small amount of crystalline phase does not affect the performance of the sulfur-containing platinum-carbon catalyst. According to spherical aberration electron microscopy analysis, most of the platinum in the sulfur-containing platinum-carbon catalyst of the present invention is present in the form of atomic clusters.

[0342] The ratio of normalized peak intensity to full width at half maximum per unit weight of platinum represents the ratio of normalized peak intensity (normalized intensity, NI) to full width at half maximum (FWHM) and the weight content of platinum in the catalyst, i.e., normalized peak intensity / (full width at half maximum) * platinum weight content), and in the following, NI / (FWHM * m Pt). The calculation procedure is as follows: (1) Under the operating conditions of the powder X-ray diffractometer (tube voltage 40 kV, tube current 40 mA, Cu target Kα radiation), collect the X-ray diffraction spectrum of the test catalyst in the range of 2θ = 20 to 70 °. After subtracting the background signal and Kα2, perform normalization processing by setting the maximum value of the intensity data in the range of 2θ = 22 to 28 ° as 1 and the minimum value of the intensity data in the range of 65 to 70 ° as 0, and obtain the normalized peak intensities of the Pt (111) characteristic peak and the Pt (200) characteristic peak of the test catalyst, respectively. (2) Perform peak fitting on the normalized X-ray diffraction spectrum to obtain the full width at half maximum (°) of the Pt (111) characteristic peak and the Pt (200) characteristic peak. The above-mentioned Pt(111) characteristic peak and Pt(200) characteristic peak were usually characteristic peaks at 2θ: 39.8±0.2° and 46.2±0.2°, respectively. (3) The normalized peak intensities of the Pt(111) characteristic peak and the Pt(200) characteristic peak were divided by the corresponding full width at half maximum and the weight content of platinum in the catalyst to obtain the ratio of the unit weight platinum normalized peak intensity and full width at half maximum of the Pt(111) characteristic peak and the Pt(200) characteristic peak of the catalyst.

[0343] In the sulfur-containing platinum-carbon catalyst of the present invention, the sulfur-containing platinum-carbon catalyst has a Pt 4f 7 / 2 characteristic peak located at 71.7 eV or more, preferably 71.9 eV or more in the XPS spectrum. The XPS spectrum refers to the XPS spectrum corrected with the C1s peak located at 284.3 eV. In a normal environment, for example, when platinum is supported on a carbon support that does not have any compounding elements, the Pt 4f 7 / 2 characteristic peak is located at about 71.4 eV, so the sulfur-containing platinum-carbon catalyst of the present invention shows that the Pt 4f 7 / 2 characteristic peak is shifted to the high electron volt side by 0.3 eV or more, preferably 0.5 eV or more in the XPS spectrum.

[0344] In the sulfur-containing platinum-carbon catalyst of the present invention, the weight fraction of platinum is preferably 5 to 20% by weight, more preferably 5 to 15% by weight, and further preferably 7 to 10% by weight, based on the total weight of the catalyst. It is preferable that the sulfur-containing platinum-carbon catalyst of the present invention does not contain any metal element other than platinum.

[0345] According to the present invention, the sulfur-modified carbon support preferably comprises conductive carbon black and elemental sulfur and elemental oxygen blended therein. Also, the sulfur-modified carbon support of the present invention preferably does not comprise blended elements other than sulfur. Here, the "blended elements" in the present invention refer to nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine. Also, the sulfur-modified carbon support preferably comprises conductive carbon black and elemental sulfur and elemental oxygen blended therein.

[0346] According to the present invention, the sulfur modified carbon support may be a sulfur modified conductive carbon black.

[0347] This embodiment III also provides a method for preparing a sulfur-containing platinum-on-carbon catalyst, the method comprising: (1) impregnating a carbon support with a sulfur-containing solution at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-modified carbon support; (2) removing the solvent from the homogeneous mixture comprising the sulfur-modified carbon support, the platinum source, and the solvent obtained in step (1) to obtain a precursor material; and (3) heat-treating the precursor material obtained in step (2) at 80-200° C. for 1-4 hours in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst; In step (1), the carbon support is conductive carbon black; In step (2), the amount of the platinum source used is 0.01 to 0.25 g in terms of platinum element per 1 g of the sulfur-modified carbon support.

[0348] Preferably, the amount of the platinum source used is 0.01 to 0.25 g, preferably 0.05 to 0.18 g, calculated as platinum element, per gram of the sulfur-modified carbon support.

[0349] According to a preferred embodiment of the present invention, in step (2), the homogeneous mixture is allowed to stand for at least 10 hours, preferably for 12 to 72 hours, more preferably for 15 to 24 hours, before removing the solvent.

[0350] By carrying out the platinum loading under the above conditions, it is possible to obtain a sulfur-containing platinum-carbon catalyst in which platinum is loaded in the form desired in the present invention.

[0351] The features and technical solutions relating to various components, carbon materials, catalysts, preparation methods, applications, etc. not specifically mentioned in this embodiment III may refer to other embodiments, particularly to embodiments I and II, unless they contradict the specific disclosure of this embodiment.

[0352] Embodiment IV: SO x Use of sulfur-containing platinum-carbon catalysts in resistance to poisons. Embodiment IV of the present invention relates to a platinum-carbon catalyzed SO x The present invention provides a use of a sulfur-containing platinum-carbon catalyst for improving resistance to poisoning. The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support of the present invention and platinum metal supported thereon. The total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content. Based on the total weight of the catalyst, the weight fraction of platinum is 20-70% by weight.

[0353] In other words, the sulfur-containing platinum-on-carbon catalyst used in this embodiment IV of the invention is preferably the sulfur-containing platinum-on-carbon catalyst described in embodiment II of the invention.

[0354] According to the present invention, by using the above-mentioned sulfur-containing platinum-carbon catalyst of the present invention, it is possible to obtain a more excellent anti-SO 2 catalyst than the existing platinum-carbon catalyst. x The sulfur-containing platinum-carbon catalyst is particularly suitable as a cathode catalyst for fuel cells.

[0355] SO x Toxic SO x The oxidant currently used in fuel cells is generally O2 from the air, and there is also SO x The main source of these emissions is automobile exhaust gases, and the amount of SO2, SO3, etc. is high in these congested road environments. x Concentrations can exceed 15 ppm.

[0356] In the sulfur-containing platinum-carbon catalyst of the present invention, the incorporation of sulfur element into the carbon support can promote the loading of platinum into the carbon support, so that the electrocatalytic performance of the sulfur-containing platinum-carbon catalyst is better. Preferably, the total sulfur content in the sulfur-modified carbon support is greater than the surface sulfur content. Here, the surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and the total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0357] According to the present invention, the total sulfur content in the sulfur-modified carbon support is preferably 0.4-8 wt%, and more preferably 1-6 wt%, and the surface sulfur content in the sulfur-modified carbon support is preferably 0.1-6 wt%, and more preferably 0.5-4 wt%.

[0358] According to the present invention, preferably, at least 90% by weight of platinum metal particles, preferably 95% or more, are supported in the carbon support. The distribution position of platinum metal particles can be determined by the following method: in the TEM image, the relative positions of 200 metallic platinum particles along the edge of the carbon support and the carbon support are randomly counted, the percentage A% of metallic platinum particles protruding from the carbon support is calculated, and the percentage of metallic platinum particles supported inside the carbon support is expressed as (100-A)%. It can be seen that in the TEM image, "protruding from the carbon support" means that the metallic platinum particles are present on the surface of the carbon support, and "not protruding from the carbon support" means that the metallic platinum particles are present inside the carbon support.

[0359] In the sulfur-containing platinum-carbon catalyst of the present invention, the weight fraction of platinum is 20 to 70% by weight, preferably 20 to 60% by weight, and more preferably 40 to 60% by weight, based on the total weight of the catalyst. It is preferable that the sulfur-containing platinum-carbon catalyst of the present invention does not contain any metal element other than platinum.

[0360] The method for preparing the sulfur-containing platinum-carbon catalyst of the present invention may be such that the catalyst has the desired properties. Specifically, the method for preparing the sulfur-containing platinum-carbon catalyst may be, for example, as follows: (1) impregnating a carbon support with a sulfur-containing solution at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-modified carbon support; (2) removing the solvent from the homogeneous mixture comprising the sulfur-modified carbon support, the platinum source, and the solvent obtained in step (1) to obtain a precursor material; and (3) A step of heat treating the precursor material obtained in step (2) at 80 to 200° C. for 1 to 4 hours in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst. Preferably, the amount of the platinum source used in step (2) is 0.25 to 2.4 g, preferably 0.67 to 1.5 g, in terms of platinum element, per gram of the sulfur-modified carbon support.

[0361] This embodiment IV also provides a method for a cathode reaction of a fuel cell, the method comprising contacting O2 in a feed gas with a sulfur-containing platinum-carbon catalyst under cathode reaction conditions, and x the sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and platinum metal supported thereon, the sulfur-modified carbon support being sulfur-modified conductive carbon black, the total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times, and more preferably equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum is 20 to 70 wt % based on the total weight of the catalyst.

[0362] The raw material gas in the present invention may be an oxygen-containing gas such as pure oxygen or air. Usually, air is used as the raw material gas in the present invention.

[0363] By using the sulfur-containing platinum-carbon catalyst of the present invention, the amount of SO in the raw gas is reduced. x Even if the catalyst contains any of the above elements, so long as the content is equal to or less than a predetermined amount, the catalyst activity is maintained and the cathode reaction can proceed for a long period of time.

[0364] Preferably, the SO in the feed gas x The content may be preferably 100 ppm or less, more preferably 50 ppm or less, for example, 5 to 50 ppm. x The content is 10, 20, 30, 40, or 50 ppm.

[0365] According to the present invention, the cathode reaction conditions are sufficient as long as they allow the cathode reaction to occur. Specifically, the cathode reaction conditions are a voltage of 0 V or more, preferably 0 to 1.5 V, and more preferably 0 to 1.1 V. The cathode reaction can be carried out in, for example, an acidic electrolyte, and various organic and / or inorganic acid solutions such as a perchloric acid solution or a sulfuric acid solution can be used. When the cathode reaction is carried out in an electrolyte, the cathode reaction conditions may be a hydrogen ion concentration in the electrolyte of 0.0001 M or more, preferably 0.001 to 1.0 M.

[0366] This embodiment IV also provides a 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 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 equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content, the weight fraction of platinum being 20-70 wt% based on the total weight of the catalyst, and wherein the SO in the feed gas of the fuel cell is 0.01 to 0.01 wt. x The content is 120 ppm or less.

[0367] According to the present invention, the fuel cell can 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 using methanol or ethanol as the anode fuel), etc. Preferably, the fuel cell is a hydrogen fuel cell. Specifically, the sulfur-containing platinum-carbon catalyst can be used as the anode catalyst and / or the cathode catalyst of the fuel cell, preferably as the cathode catalyst.

[0368] According to the present invention, the cathode reaction conditions are sufficient as long as they allow the cathode reaction to occur. Specifically, the cathode reaction conditions include a voltage of 0 V or more, preferably 0 to 1.5 V, and more preferably 0 to 1.1 V. The cathode reaction can be performed in an acidic electrolyte, and various organic and / or inorganic acid solutions such as a perchloric acid solution or a sulfuric acid solution can be used. In addition, when the cathode reaction is performed in an electrolyte, the cathode reaction conditions can include a hydrogen ion concentration in the electrolyte of 0.01 M or more, preferably 0.05 to 1.0 M.

[0369] This embodiment IV is a SO x Also provided is a use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to poisoning, the sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon support and platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, the total sulfur content in the sulfur-containing platinum-carbon catalyst being equal to or greater than the surface sulfur content, preferably the total sulfur content being equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum being 20 to 70 wt % based on the total weight of the catalyst.

[0370] The features and technical solutions relating to various components, carbon materials, catalysts, preparation methods and applications thereof, etc., not specifically described in this embodiment IV, may refer to other embodiments, particularly embodiments I and II, unless they are inconsistent with the specific disclosure of this embodiment.

[0371] Embodiment V: Use of sulfur-containing platinum-carbon catalysts in CO poisoning resistance Embodiment V of the present invention provides the use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to CO poisoning. The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support of the present invention and platinum metal supported thereon. The total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content. Preferably, the total sulfur content is equal to or greater than 1.2 times, more preferably equal to or greater than the surface sulfur content. Based on the total weight of the catalyst, the weight fraction of platinum is 20-70% by weight.

[0372] In other words, it is preferred that the sulfur-containing platinum-carbon catalyst used in embodiment V of the present invention is the sulfur-containing platinum-carbon catalyst described in embodiment II of the present invention.

[0373] According to the present invention, by using the sulfur-containing platinum-carbon catalyst of the present invention, a better anti-CO poisoning effect can be obtained based on the existing platinum-carbon catalyst, and the effect of extending the life of the platinum-carbon catalyst can be obtained. Specifically, the sulfur-containing platinum-carbon catalyst can be used as an anode catalyst for fuel cells, a cathode catalyst for water electrolysis, etc.

[0374] Sources of CO that cause CO toxicity include, for example, CO impurities that are mixed into the raw gas and are difficult to remove (considering the preparation method and cost), and CO generated during the reaction, such as CO generated by oxidation of the carbon support or carbon paper.

[0375] In the sulfur-containing platinum-carbon catalyst of the present invention, by blending sulfur element inside the carbon support, the loading of platinum inside the carbon support is further promoted, and the electrocatalytic performance of the sulfur-containing platinum-carbon catalyst is further improved. Preferably, the total sulfur content in the sulfur-modified carbon support is 1.7 times or more, 2 times or more, 3 times or more, etc., of the surface sulfur content, for example, 1.5 to 10 times. Here, the surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and the total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0376] In the sulfur-containing platinum-carbon catalyst of the present invention, the sulfur-containing platinum-carbon catalyst has a Pt 4f 7 / 2 characteristic peak located at 71.6 eV or more, for example, 71.6 to 72.2 eV, for example, 71.7 eV, in the XPS spectrum. The XPS spectrum refers to an XPS spectrum corrected with the C1s peak located at 284.3 eV. Usually, for example, when platinum is supported on a carbon support that does not contain a compounding element, the Pt 4f 7 / 2 characteristic peak is located near 71.3 eV, so the sulfur-containing platinum-carbon catalyst of the present invention shows that the Pt 4f 7 / 2 characteristic peak is shifted to the high electron volt side by 0.3 eV or more in the XPS spectrum.

[0377] In the sulfur-containing platinum-carbon catalyst of the present invention, the weight fraction of platinum is preferably 20 to 70% by weight, based on the total weight of the catalyst, and may be, for example, 20 to 60% by weight, 20 to 40% by weight, or 40 to 70% by weight, etc. Preferably, the sulfur-containing platinum-carbon catalyst of the present invention does not contain any other metal element than platinum.

[0378] The method for preparing the sulfur-containing platinum-carbon catalyst of the present invention may be such that the catalyst has the above-mentioned properties. Specifically, the method for preparing the sulfur-containing platinum-carbon catalyst includes: (1) impregnating a carbon support with a sulfur-containing solution at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-modified carbon support; (2) removing the solvent from the homogeneous mixture comprising the sulfur-modified carbon support, the platinum source, and the solvent obtained in step (1) to obtain a precursor material; and (3) heat-treating the precursor material obtained in step (2) at 80 to 200° C. for 1 to 4 hours in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst; In step (2), the amount of the platinum source used is 0.25 to 2.4 g in terms of platinum element per 1 g of the sulfur-modified carbon support.

[0379] Preferably, the amount of platinum source used is 0.25 to 2.4 g, preferably 0.25 to 0.67 g, in terms of elemental platinum, per gram of sulfur-modified carbon support.

[0380]

[0023] Embodiment V also provides a method for the anode reaction of a hydrogen fuel cell, the method comprising contacting H2 in a feed gas with a sulfur-containing platinum-carbon catalyst under anode reaction conditions; The CO content in the raw gas is 1500 ppm or less, The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, and the total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content. Based on the total weight of the catalyst, the weight fraction of platinum is 20-70 wt%.

[0381] The raw material gas in the present invention may have a hydrogen content of, for example, 99.5% by weight (preferably 99.85% by weight or more). For example, hydrogen produced by a method such as a methane steam reforming method, a coal hydrogen preparation method, a methanol hydrogen preparation method, an ammonia decomposition hydrogen preparation method, a hydrogen recovery and purification method, or a biomass hydrogen preparation method may be used. Alternatively, hydrogen produced as a by-product of a reaction device, such as hydrogen-containing gas produced by a catalytic cracking unit in an oil refinery, may be used.

[0382] By using the sulfur-containing platinum-carbon catalyst of the present invention, even if the raw material gas contains CO, as long as the CO content is below a predetermined amount, the catalytic activity is maintained and the anode reaction can be carried out for a long period of time.

[0383] The CO content in the raw material gas is preferably 1200 ppm or less, more preferably 1000 ppm or less, for example, 100 to 800 ppm. Specifically, the CO content in the raw material gas may be 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, or 1200 ppm.

[0384] According to the present invention, the anode reaction conditions are sufficient as long as they allow the anode reaction to occur. Specifically, the anode reaction conditions include a voltage of 0 V or more, preferably 0 to 0.4 V, and more preferably 0 to 0.2 V. The anode reaction can be performed, for example, in an acidic electrolyte, and various organic and / or inorganic acid solutions such as a perchloric acid solution or a sulfuric acid solution can be used. When the anode reaction is performed in an electrolyte, the anode reaction conditions include a hydrogen ion concentration in the electrolyte of 0.0001 M or more, preferably 0.001 to 1.0 M.

[0385] This embodiment V also provides a 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 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 equal to or greater than the surface sulfur content, preferably the total sulfur content being equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content, the weight fraction of platinum being 20-70 wt% based on the total weight of the catalyst, and the CO content in the feed gas of the fuel cell being equal to or less than 1500 ppm.

[0386] 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 using methanol or ethanol as the anode fuel), etc. Preferably, the fuel cell is a hydrogen fuel cell. Specifically, the sulfur-containing platinum-carbon catalyst is used as an anode catalyst or a cathode catalyst of the fuel cell, and is preferably used as an anode catalyst.

[0387] Preferably, the CO content in the raw material gas is 1200 ppm or less, more preferably 1000 ppm or less, for example, 100 to 1000 ppm. Specifically, the CO content in the raw material gas can be 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, or 1200 ppm. In addition, in the application of the third aspect of the present invention, the raw material gas used and its characteristics can be the same as those in the second aspect, so they will not be repeated here.

[0388] According to the present invention, the anode reaction conditions are sufficient as long as the anode reaction can be performed. Specifically, the anode reaction conditions include a voltage of 0 V or more, preferably 0 to 0.4 V. The anode reaction can be performed in an acidic electrolyte, and various organic and / or inorganic acid solutions such as a perchloric acid solution or a sulfuric acid solution can be used. When the anode reaction is performed in an electrolyte, the anode reaction conditions include a hydrogen ion concentration in the electrolyte of 0.01 M or more, preferably 0.05 to 1.0 M.

[0389] This embodiment V also provides a method of electrolyzing water, the method comprising contacting water with a sulfur-containing platinum-carbon catalyst under conditions for electrolyzing water, wherein at least a portion of the contacting is in the presence of CO, the sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon support and 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 equal to or greater than the surface sulfur content, preferably the total sulfur content being equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum being 20 to 70 wt. %, based on the total weight of the catalyst.

[0390] The conditions for electrolyzing water are not particularly limited, and may preferably include a voltage of −0.4V or higher, preferably −0.4 to 1.0V, and more preferably −0.4 to 0V.

[0391] Preferably, the method for electrolyzing water is proton exchange membrane electrolysis of water.

[0392] This embodiment V also provides a use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to CO poisoning, the sulfur-containing platinum-carbon catalyst comprising a sulfur-modified carbon support and platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, the total sulfur content in the sulfur-containing platinum-carbon catalyst is equal to or greater than the surface sulfur content, preferably, the total sulfur content is equal to or greater than 1.2 times, more preferably, equal to or greater than 1.5 times, the surface sulfur content, and the weight fraction of platinum is 20 to 70 wt.% based on the total weight of the catalyst.

[0393] The features and technical solutions relating to various components, carbon materials, catalysts, preparation methods, applications, etc. not specifically mentioned in this embodiment V can refer to other embodiments, particularly embodiments I and II, unless they contradict the specific disclosure of this embodiment.

[0394] Use of sulfur-containing platinum-carbon catalysts in resistance to H2S poisoning Embodiment VI of the present invention provides the use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to H2S poisoning. The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and platinum metal supported thereon. The total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content. Preferably, the total sulfur content is equal to or greater than 1.2 times, more preferably equal to or greater than the surface sulfur content. The weight fraction of platinum is 20-70 wt% based on the total weight of the catalyst.

[0395] In other words, the sulfur-containing platinum-on-carbon catalyst used in embodiment V of the present invention is preferably the sulfur-containing platinum-on-carbon catalyst described in embodiment II of the present invention.

[0396] According to the present invention, the sulfur-containing platinum-carbon catalyst of the present invention can provide a better anti-H2S poisoning effect based on the existing platinum-carbon catalyst, thereby extending the life of the platinum-carbon catalyst. Specifically, the sulfur-containing platinum-carbon catalyst can be used as an anode catalyst in a fuel cell.

[0397] Sources of H2S that cause H2S toxicity include, for example, H2S impurity mixed into the raw material gas due to the preparation method or ingredients, and H2S that is difficult to remove from the raw material gas.

[0398] The method for preparing the sulfur-containing platinum-carbon catalyst of the present invention may be such that the catalyst has the above-mentioned properties. Specifically, the method for preparing the sulfur-containing platinum-carbon catalyst includes the following steps: (1) impregnating a carbon support with a sulfur-containing solution at 10 to 80° C. for 1 to 5 hours and drying the impregnated product to obtain a sulfur-modified carbon support; (2) removing the solvent from the homogeneous mixture comprising the sulfur-modified carbon support, the platinum source, and the solvent obtained in step (1) to obtain a precursor material; and (3) heat-treating the precursor material obtained in step (2) at 80 to 200° C. for 1 to 4 hours in a reducing atmosphere to obtain a sulfur-containing platinum-carbon catalyst; In step (2), the amount of the platinum source used is 0.25 to 2.4 g in terms of platinum element per 1 g of the sulfur-modified carbon support.

[0399] This embodiment VI also provides an anode reaction method for a hydrogen fuel cell, the method comprising contacting H2 in a feed gas with a sulfur-containing platinum-carbon catalyst under anode reaction conditions; The H2S content in the raw material gas is 15 ppm or less.

[0400] The sulfur-containing platinum-carbon catalyst comprises a sulfur-modified carbon support and platinum metal supported thereon, the sulfur-modified carbon support being a sulfur-modified conductive carbon black, and the total sulfur content in the sulfur-modified carbon support is equal to or greater than the surface sulfur content, preferably equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content. Based on the total weight of the catalyst, the weight fraction of platinum is 20-70 wt%.

[0401] The raw material gas in the present invention may, for example, have a hydrogen content of 99.5% by weight (99.98% by weight or more). For example, hydrogen prepared by a method such as methane steam reforming hydrogen preparation, coal hydrogen preparation, methanol hydrogen preparation, ammonia decomposition hydrogen preparation, hydrogen recovery and purification, or biomass hydrogen preparation may be used. Alternatively, hydrogen produced as a by-product of other reactions, such as hydrogen-containing gas produced by a catalytic cracking unit in an oil refinery, may be used.

[0402] By using the sulfur-containing platinum-carbon catalyst of the present invention, even if the raw material gas contains H2S, as long as the content is below a predetermined amount, the catalytic activity is maintained and the anode reaction can be carried out for a long period of time.

[0403] Preferably, the H2S content in the raw material gas is 15 ppm or less, more preferably 10 ppm or less, for example, 0.4 to 5 ppm. Specifically, the H2S content in the raw material gas can 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 15 ppm, etc.

[0404] According to the present invention, the anode reaction conditions are sufficient as long as they allow the anode reaction to occur. Specifically, the anode reaction conditions include a voltage of 0 V or more, preferably 0.01 to 0.4 V. For example, the anode reaction can be performed in an acid electrolyte, and various organic and / or inorganic acid solutions such as a perchloric acid solution or a sulfuric acid solution can be used. In addition, when the anode reaction is performed in an electrolyte, the anode reaction conditions may be: a hydrogen ion concentration in the electrolyte of 0.01 M or more, preferably 0.05 to 1.0 M.

[0405] This embodiment VI also provides a 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 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 equal to or greater than the surface sulfur content, preferably the total sulfur content being equal to or greater than 1.2 times the surface sulfur content, more preferably equal to or greater than 1.5 times the surface sulfur content, the weight fraction of platinum being 20-70 wt% based on the total weight of the catalyst, and the content of H2S in the feed gas of the fuel cell being equal to or less than 15 ppm, preferably 0.4-5 ppm.

[0406] Examples of the fuel cell include hydrogen fuel cells (e.g., proton exchange membrane hydrogen fuel cells), direct alcohol fuel cells (e.g., direct alcohol fuel cells using methanol or ethanol as the anode fuel), etc. Preferably, the fuel cell is a hydrogen fuel cell. Specifically, the sulfur-containing platinum-carbon catalyst may be used as an anode catalyst or a cathode catalyst of the fuel cell, and preferably as an anode catalyst.

[0407] Preferably, the content of H2S in the raw gas is 10 ppm or less, preferably 5 ppm or less. Specifically, the content of H2S in the raw gas can 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, 15 ppm, etc. In addition, in the use of the third embodiment of the present invention, the raw gas used and its characteristics can be the same as in the second embodiment, so they will not be repeated here.

[0408] This embodiment VI also provides a use of a sulfur-containing platinum-carbon catalyst for improving the resistance of a platinum-carbon catalyst to H2S poisoning. The sulfur-containing platinum-carbon catalyst includes a sulfur-modified carbon support and platinum metal supported thereon. The sulfur-modified carbon support is a sulfur-modified conductive carbon black. The total sulfur content in the sulfur-containing platinum-carbon catalyst is equal to or greater than the surface sulfur content. Preferably, the total sulfur content is equal to or greater than 1.2 times, more preferably equal to or greater than 1.5 times, the surface sulfur content. Based on the total weight of the catalyst, the weight fraction of platinum is 20-70% by weight.

[0409] The features and technical solutions relating to various components, carbon materials, catalysts and their preparation methods, uses, etc. not specifically described in this embodiment VI can refer to other embodiments, particularly embodiment V, and can also refer to embodiments I and II and other embodiments, as long as they do not contradict the specific disclosure content of this embodiment.

[0410] Working Example The present invention will be described in detail below in conjunction with specific examples. The following examples will be helpful for those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any way.

[0411] Unless otherwise specified, all reagents used in the present invention are analytically pure and commercially available.

[0412] Reagents, Equipment, and Tests The model of high-resolution transmission electron microscope (HRTEM) was JEM-2100 (HRTEM) (JEOL Ltd.), and the test conditions were an accelerating voltage of 200 kV.

[0413] The X-ray photoelectron spectrometer was an ESCALab220i-XL type X-ray photoelectron spectrometer equipped with Avantage V5.926 software manufactured by VG Scientific. The analytical test conditions of the X-ray photoelectron spectrometer were as follows: the excitation source was monochromatic A1Kα X-ray, the power was 330 W, and the base vacuum during the analytical test was 3 × 10 -9 The electron binding energies were calibrated using the C1s peak of elemental carbon (284.3 eV) and the post-peak processing software was XPSPEAK.

[0414] The specific method for detecting the surface sulfur content by XPS analysis is as follows: the scan range of the full spectrum scan was 0-1200 eV, the band pass energy (pass energy) was 100 eV, the analysis energy step was 1.0 eV, the number of channels was 1211, and the number of scans was 1. The pass energy of the narrow band spectrum scan was 30.0 eV, the analysis energy step was 0.05 eV, the number of channels was 401, and the number of scan cycles was 16.

[0415] The sulfur-carbon analyzer was a CS-844 model manufactured by LECO, USA.

[0416] The spherical aberration corrected transmission electron microscope (AC-STEM) was a JEOL Ltd. ARM200F model.

[0417] Apparatus, method and conditions for testing the weight fraction of platinum in sulfur-containing platinum-carbon catalyst: 30 mg of the prepared Pt / C catalyst was taken, 30 mL of aqua regia was added, and the catalyst was condensed and refluxed at 120°C for 12 hours, cooled to room temperature, and the supernatant was collected and diluted, and the Pt content was examined using ICP-AES.

[0418] ORR electrochemical performance test: The equipment model was Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), Method and test conditions: The polarization curve LSV of the catalyst was tested in 0.1M HClO4 saturated with O2 at a speed of 1600 rpm, and the electrochemically active area ECSA was tested in 0.1M HClO4 saturated with Ar. During the stability test, the LSV and ECSA were tested according to the above method after 5000 cycles of scanning in the range of 0.6V-0.95V (vs. RHE) in 0.1M HClO4 saturated with O2. In the above test, the catalyst was prepared into a uniformly dispersed slurry and applied to a glassy carbon electrode with a diameter of 5 mm. The amount of platinum in the catalyst on the electrode was controlled in the range of 1-4 μg, and no iR correction was performed during the calculation.

[0419] HER electrochemical performance test: Equipment model Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), Method and test conditions: The polarization curve LSV of the catalyst was tested in 0.5M H2SO4 saturated with N2 at a speed of 2500 rpm, and the electrochemical active area ECSA was tested in 0.5M H2SO4 saturated with N2. During the stability test, the range of -0.1V to 0.2V (vs. RHE) was scanned in 0.5M H2SO4 saturated with N2 at a speed of 2500 rpm. After a certain number of scan cycles, the LSV and ECSA were tested according to the above method. In the above test, the catalyst was prepared into a uniformly dispersed slurry and applied to a glassy carbon electrode with a diameter of 5 mm. The amount of platinum in the catalyst on the electrode was controlled in the range of 1-4 μg, and no iR correction was performed during the calculation.

[0420] When Ketjenblack ECP600JD (Ketjenblack, manufactured by Lion Corporation) was tested using the above-mentioned device and method, the specific surface area was found to be 1362 m 2 / g, pore volume 2.29mL / g, oxygen weight fraction 6.9%, I D / I Gwas 1.25.

[0421] A commercially available platinum-carbon catalyst 1 (brand name: HISPEC4000, manufactured by Johnson Matthey) was tested using the aforementioned apparatus and the results showed that the weight fraction of platinum was 40.2%.

[0422] A commercially available platinum-on-carbon catalyst 2 (brand number TEC10F50E, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) was tested using the above apparatus method and showed a platinum loading of 46 wt %.

[0423] VXC72 (VulcanXC72, manufactured by Cabot Corporation, USA) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tests using the aforementioned equipment and method showed that the specific surface area was 258 m 2 / g, pore volume 0.388mL / g, oxygen weight fraction 8.72%, I D / I G was 1.02.

[0424] XRD analysis apparatus, method, and conditions: X-ray diffraction analysis (XRD) was performed on a Shimadzu XRD-6000 X-ray diffractometer. The test conditions were: tube voltage 40 kV, tube current 40 mA, Cu target Kα radiation, 2θ scan range 10°-70°.

[0425] NI / (FWHM * m PtThe calculation method of is as follows: (1) Under the operating conditions of the powder X-ray diffractometer (tube voltage 40 kV, tube current 40 mA, Cu target Kα radiation), the X-ray diffraction spectrum of the tested catalyst was collected in the range of 2θ 20-70°. After subtracting the background signal and Kα2, the maximum value of the intensity data in the range of 2θ 22-28° was 1, and the minimum value of the intensity data in the range of 65-70° was 0. The normalized peak intensities of the Pt(111) characteristic peak at 39.8 ± 0.2° and the Pt(200) characteristic peak at 46.2 ± 0.2° of the tested catalyst were obtained. (2) The normalized X-ray diffraction spectrum was peak-fitted to obtain the full width at half maximum (in degrees) of the Pt(111) characteristic peak and the Pt(200) characteristic peak. (3) The normalized peak intensities of the Pt(111) characteristic peak and the Pt(200) characteristic peak were divided by the corresponding full width at half maximum and the weight content of platinum in the catalyst to obtain the NI / (FWHM * m Pt ) was sought.

[0426] Equipment and method for testing the in-situ infrared curve of CO: Infrared spectrometer: Thermo Fisher 50. During the test, the sample was first purged with nitrogen at room temperature, then reduced in H2 atmosphere at 250°C for 1 hour and depressurized. 5% CO / He was introduced and CO was adsorbed at room temperature for 1 hour. After removing the physically adsorbed CO by vacuum desorption, the above test was performed at 25°C.

[0427] Characterization method of elemental sulfur: Synchrotron radiation X-ray microspectroscopy was used to characterize sulfur in carbon supports. The equipment is Beijing Electron-Positron Collider 4B7A-Medium Energy X-ray Experimental Station. Elemental sulfur and 2,2'-bithiophene are used as standards.

[0428] Embodiment I Example I.1 0.1 g of sulfur was dissolved in 70 ml of cyclohexane to form a homogeneous solution, 9.9 g of Ketjen Black ECP600JD was dispersed therein, and after uniform stirring, the mixture was immersed for 5 hours and dried in vacuum at 50° C. to obtain a sulfur-modified carbon material A.

[0429] Example I.2 0.40 g of sulfur was dissolved in 70 ml of cyclohexane to form a homogeneous solution, and 9.60 g of Ketjen Black ECP600JD was dispersed therein and stirred uniformly. The solution was then immersed for 5 hours and dried in vacuum at 50° C. to obtain sulfur-modified carbon material C.

[0430] Example I.3 0.55 g of sulfur was dissolved in 70 ml of cyclohexane to form a homogeneous solution, and 9.45 g of Ketjen Black ECP600JD was dispersed therein and stirred uniformly. The solution was then immersed for 5 hours and dried in vacuum at 50° C. to obtain a sulfur-modified carbon material D.

[0431] Comparative example I.1 A commercially available platinum-carbon catalyst of the HISPEC4000 brand was used.

[0432] Comparative example I.2 A carbon material was prepared according to the method of Example I.1, except that no sulfur was used, i.e., a carbon material containing no incorporated elements was used.

[0433] Comparative example I.3 The sulfur-doped carbon material was prepared according to the method in Nature Communications, 2019, 10:4977.

[0434] Test Example I.1 The surface sulfur content and total sulfur content in the sulfur-modified carbon materials obtained in Examples I.1 to I.3 and Comparative Example I.3 were measured, and the results are shown in Table I.1.

[0435] [Table 1]

[0436] In Table I.1, surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0437] Test Example 1.2 The carbon materials of Examples I.1 to I.3 and Comparative Example I.2 were used to support platinum, and sulfur-containing platinum-carbon catalysts with a platinum loading rate of 40 wt % were prepared. The method for supporting platinum was as follows.

[0438] 0.40 g of chloroplatinic acid (calculated as platinum) was dissolved in 20 mL of a solution with a volume ratio of water to ethanol of 10:1, and 0.6 g of each of the above carbon materials was dispersed in the chloroplatinic acid solution and stirred to disperse uniformly. After leaving it for 24 hours, the mixture was placed in a vacuum drying oven and dried. The dried precursor was placed in a tubular furnace, heated to 140 °C at a rate of 5 °C / min, reduced in an atmosphere of N2:H2 = 5:1 for 2 hours, and the temperature was lowered in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0439] The performance of the sulfur-containing platinum-carbon catalyst prepared as above and the commercial platinum-carbon catalyst of Comparative Example I.1 were measured. The obtained ORR performance is shown in Table I.2 below. Figure I.1 shows the polarization curves of the ORR reaction catalyzed by the sulfur-containing platinum-carbon catalyst prepared from the carbon materials of Example I.1 and Comparative Example I.2 and the commercial platinum-carbon catalyst of Comparative Example I.1.

[0440] [Table 2]

[0441] From the results in Table I.2, it can be seen that the use of the sulfur-modified carbon material of the present invention can have the effect of improving the weight specific activity of the prepared sulfur-containing platinum-carbon catalyst.

[0442] Test Example I.3 Using the carbon supports of Example I.1 and Comparative Example I.3, sulfur-containing platinum-carbon catalysts were prepared according to the method of Test Example 2-2, and the platinum loadings used were shown in Table 1.3. The performance of the sulfur-containing platinum-carbon catalysts prepared as above and the commercial catalyst of Comparative Example I.1 were measured, and the obtained HER performances were shown in Table 3 below.

[0443] Figure I.2 shows the polarization curves before and after stabilization of the HER reaction catalyzed by the sulfur-containing platinum-carbon catalyst prepared by the sulfur-modified carbon material of Example I.1, and Figure I.3 shows the polarization curves before and after stabilization of the HER reaction catalyzed by the commercial platinum-carbon catalyst of Comparative Example I.1.

[0444] [Table 3]

[0445] From the results in Table I.3, it can be seen that the sulfur-containing platinum-carbon catalyst of the sulfur-modified carbon material of Example I.1 of the present invention has a lower overpotential, a higher weight specific activity, and a smaller performance degradation of overpotential and weight specific activity after stabilization for 12,000 cycles than the commercial catalyst of Comparative Example I.1.

[0446] Test Example I.4 A sulfur-containing platinum-carbon catalyst having a platinum loading of 40% by weight, which was prepared using the carbon material of Comparative Example I.2 of Test Example I.2, was observed using a STEM to obtain the STEM photograph shown in Figure I.4.

[0447] The statistics of the STEM photograph in Figure 1.4 show that the platinum particles with regular lattice fringes in the sulfur-containing platinum-carbon catalyst account for approximately 100% by weight.

[0448] Using the same method, it was observed that the sulfur-containing platinum-carbon catalyst with 40 wt. % platinum loading prepared using the carbon material of Example I.3 did not have more than 40 wt. % platinum particles with regular lattice fringes.

[0449] Test Example I.5 The sulfur-modified carbon material of Example I.3 was characterized by synchrotron radiation X-ray fine spectrum, the equipment was Beijing Electron-Positron Collider 4B7A-Medium Energy X-ray Experiment Station. Elemental sulfur and 2,2'-dithiophene were used as standards. Figure I.5 reflects the bond length information of the two standards and three samples of sulfur-modified carbon material. By comparison, it can be seen that S of carbon carrier D is bonded at about 0.93 Å and 1.62 Å, which is completely overlapped with elemental sulfur, proving that it is elemental sulfur. Figure I.6 reflects the valence information of the three samples. Similarly, the sulfur in carbon carrier D is overlapped with elemental sulfur, which is completely different from thiophene sulfur, further proving that it is elemental sulfur.

[0450] Embodiment II Example II.1 0.1g of sulfur was dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.9g of Ketjen Black ECP600JD was dispersed therein, stirred uniformly, and soaked for 5 hours, and then vacuum dried at 50℃ to obtain sulfur-containing conductive carbon black as a sulfur-containing carbon carrier; 1.4g of platinum-equivalent chloroplatinic acid was dissolved in 100ml of a solution in which the volume ratio of water to ethanol was 10:1; 0.6g of sulfur-containing carbon carrier was dispersed in the chloroplatinic acid solution, stirred to disperse uniformly, and left for 24 hours, after which the unadsorbed chloroplatinic acid solution was filtered, and the obtained solid was placed in a vacuum drying oven to dry; the dried precursor was placed in a tubular furnace, heated to 180℃ at a rate of 8℃ / min, reduced in an atmosphere of N2:H2=5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0451] Example II.2 0.25g of sulfur was dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.75g of Ketjen Black ECP600JD was dispersed therein, and after uniform stirring, it was immersed for 5 hours and dried in vacuum at 50℃ to obtain sulfur-containing conductive carbon black as a sulfur-containing carbon carrier; 0.52g of chloroplatinic acid (calculated as platinum) was dissolved in 20ml of a solution with a volume ratio of water to ethanol of 10:1; 0.6g of sulfur-containing carbon carrier was dispersed in the chloroplatinic acid solution, and stirred to uniformly disperse. After standing for 24 hours, the dispersion was placed in a vacuum drying oven to dry; the dried precursor was placed in a tubular furnace, heated to 160℃ at a rate of 6℃ / min, reduced in an atmosphere of N2:H2=5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0452] Example II.3 0.40g of sulfur was dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.60g of Ketjen Black ECP600JD was dispersed therein, stirred uniformly, and soaked for 5 hours, and then vacuum dried at 50℃ to obtain sulfur-containing conductive carbon black as a sulfur-containing carbon carrier; 0.15g of platinum-equivalent chloroplatinic acid was dissolved in 20mL of a solution with a volume ratio of water to ethanol of 10:1; 0.6g of sulfur-containing carbon carrier was dispersed in the chloroplatinic acid solution, stirred to disperse uniformly, and left for 24 hours, after which the dispersion was placed in a vacuum drying oven to dry; the dried precursor was placed in a tubular furnace, heated to 100℃ at a rate of 4℃ / min, reduced in an atmosphere of N2:H2=5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0453] Example II.4 0.55g of sulfur was dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.45g of Ketjen Black ECP600JD was dispersed therein, stirred uniformly, and soaked for 5 hours, and then vacuum dried at 50℃ to obtain sulfur-containing conductive carbon black as a sulfur-containing carbon carrier; 0.40g of chloroplatinic acid, calculated as platinum, was dissolved in 20ml of a solution in which the volume ratio of water to ethanol was 10:1; 0.6g of sulfur-containing carbon carrier was dispersed in the chloroplatinic acid solution, stirred to disperse uniformly, and left for 24 hours, after which the dispersion was placed in a vacuum drying oven to dry; the dried precursor was placed in a tubular furnace, heated to 140℃ at a rate of 5℃ / min, reduced in an atmosphere of N2:H2=5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0454] Comparative Example II.1 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example II.1, except that the heat treatment temperature was 240°C.

[0455] Comparative Example II.2 A platinum-carbon catalyst was prepared according to the method of Example II.1, except that the carbon support used was Ketjenblack ECP600JD without any loading elements.

[0456] Comparative Example II.3 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example II.3, except that the carbon support used was Ketjenblack ECP600JD without any loading elements.

[0457] Comparative Example II.4 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example II.4, except that the carbon support used was a sulfur-doped carbon material prepared according to the method of Nature Communications, 2019, 10:4977.

[0458] Test Example II.1 The surface sulfur content and total sulfur content of the carbon supports prepared in Examples II.1-II.4 and Comparative Example II.4 were measured, and the results are shown in Table II.1.

[0459] [Table 4]

[0460] In Table II.1, surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0461] Test Example 1-2 The XPS spectra of the sulfur-containing platinum-carbon catalysts of Example II.2 and Comparative Example II.3 are shown in Figure II.1. As shown in Figure II.1, the Pt 4f 7 / 2 characteristic peak of the sulfur-containing platinum-carbon catalyst of Example II.2 is located at 71.72 eV, which is shifted to about 0.4 eV higher electron volts than that of Comparative Example II.3.

[0462] The XPS spectra of Examples II.1, II.3, and II.4 were measured as described above, and all of their Pt 4f 7 / 2 characteristic peaks were located above 71.6 eV.

[0463] Test Example 1-3 The sulfur-containing platinum-carbon catalysts of Examples II.2 and II.3 and Comparative Examples II.1, II.2, and II.4 were observed by TEM and STEM. Here, Figure II.2 shows a STEM photograph of the sulfur-containing platinum-carbon catalyst of Example II.2. Figure II.3 shows a STEM photograph of the sulfur-containing platinum-carbon catalyst of Example II.3. Figure II.4 shows a TEM photograph of the sulfur-containing platinum-carbon catalyst of Comparative Example II.1. Figure II.5 shows a TEM photograph of the sulfur-containing platinum-carbon catalyst of Comparative Example II.2. Figure II.6 shows a STEM photograph of the sulfur-containing platinum-carbon catalyst of Comparative Example II.4. Figure II.7 shows a STEM photograph of platinum particles with regular lattice fringes. Figure II.8 shows a TEM photograph of the sulfur-containing platinum-carbon catalyst of Example II.2. Figure II.9 shows a TEM photograph of the sulfur-containing platinum-carbon catalyst of Comparative Example II.4.

[0464] If platinum particles have a lattice and the lattice fringes are parallel, as shown by the black parallel lines in Figure II.7, they are considered to contain regular lattice fringes. For each sulfur-containing platinum-carbon catalyst, the number of platinum metal particles with regular lattice fringes out of 100 platinum metal particles was randomly counted and their percentage was calculated.

[0465] The results are as follows: the platinum metal particles with regular lattice fringes in the sulfur-containing platinum-carbon catalysts of Examples II.2 and II.3 account for 6% and 9%, respectively, while the platinum metal particles with regular lattice fringes in the sulfur-containing platinum-carbon catalysts of Comparative Examples II.1 and 1-4 account for 70% by weight and more than 99%, respectively. In Comparative Example II.2, the Pt content is low, so the count number is insufficient and statistically insignificant.

[0466] Using the same method, the sulfur-containing platinum-on-carbon catalysts of Examples II.1 and II.4 were observed and counted, and it was found that platinum metal particles with regular lattice fringes did not exceed 20% by weight.

[0467] In the TEM image, the relative positions of 200 metallic platinum particles along the edge of the carbon support and the carbon support are randomly counted, the percentage of metallic platinum particles protruding from the carbon support is calculated, and (100-A)% is used to represent the percentage of platinum metal particles supported inside the carbon support. The statistics are taken for the samples in Figures II.8 and II.9. In Example II.2, more than 98% of the platinum particles are located inside the carbon support, while in Comparative Example II.4, only about 70% by weight of the platinum particles are located inside the carbon support.

[0468] Using the same method, the sulfur-containing platinum-carbon catalysts of Examples II.1, II.3, and II.4 were observed and counted, revealing that at least 94% of the platinum metal particles were supported inside the carbon support.

[0469] Test Example II.4 The performance of the sulfur-containing platinum-on-carbon catalysts prepared in Examples II.1-II.4 and Comparative Examples II.1-II.4 was measured and the results are shown in Tables II.2 and II.3.

[0470] [Table 5]

[0471] [Table 6]

[0472] From the results in Tables II.2 and II.3, it can be seen that in Examples II.1 to II.4, the use of the sulfur-containing carbon support of the present invention provides superior electrochemical performance to Comparative Examples II.2 to II.3, which used a carbon support without any compounding element.

[0473] Comparing Example II.1 and Comparative Example II.1, it can be seen that the sulfur-containing carbon support prepared by the method of the present invention can achieve better electrochemical performance by heat-treating at a lower temperature.

[0474] EMBODIMENT III Preparation example III.1 0.55 g of sulfur was dissolved in 70 ml of cyclohexane to form a homogeneous solution, and 9.45 g of Ketjen Black ECP600JD was dispersed therein, stirred uniformly, soaked for 5 hours, and dried in vacuum at 50° C. to obtain sulfur-modified carbon support A.

[0475] Preparation example III.2 0.1 g of sulfur was dissolved in 40 ml of cyclohexane to form a homogeneous solution, in which Vulcan XC72 (9.9 g) was dispersed, stirred uniformly, soaked for 5 hours, and dried at 50° C. under vacuum to obtain sulfur-modified carbon support B.

[0476] Comparative Preparation Example III.1 Sulfur-doped carbon material D1 was prepared according to the method in Nature Communications, 2019, 10:4977.

[0477] Comparative Preparation Example III.2 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Preparation Example III.1, except that the amount of sulfur used was 0.9 g and the amount of Ketjen Black ECP600JD used was 9.1 g. A sulfur-modified carbon support D2 was obtained.

[0478] Test Example III.1 The surface sulfur content and total sulfur content of the carbon supports prepared in Preparation Example III and Comparative Preparation Example III were measured, and the results are shown in Table III.1.

[0479] [Table 7]

[0480] In Table III.1, surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0481] Example III.1 According to the ratio of 0.57 mmol of chloroplatinic acid per 1 g of carbon support, chloroplatinic acid was first dissolved in 15 ml of a 1:1 volumetric water-ethanol solution, 1 g of carbon support A was dispersed in the chloroplatinic acid solution, uniformly dispersed, left for 16 hours, and then dried in an oven at 60 °C to obtain a catalyst precursor. The precursor was crushed, placed in a tubular furnace, heated to 160 °C, heat-treated in an N2:H2=4:1 atmosphere for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst with a loading rate of 10 wt%.

[0482] Example III.2 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example III.1, except that the carbon support A prepared in Preparation Example III.1 was used, 1.28 mmol of chloroplatinic acid was added per gram of carbon support, and the reduction temperature was 140° C. to obtain a sulfur-containing platinum-carbon catalyst with a loading rate of 20 wt.%.

[0483] Example III.3 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example III.1, except that the carbon support B prepared in Preparation Example III.2 was used and the reduction temperature was 160° C. to obtain a sulfur-containing platinum-carbon catalyst with a loading rate of 10 wt.%.

[0484] Example III.4 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example III.1, except that the carbon support B prepared in Preparation Example III.2 was used, 0.27 mmol of chloroplatinic acid was added per 1 g of carbon support, and the reduction temperature was 100 °C to obtain a sulfur-containing platinum-carbon catalyst with a loading rate of 5 wt.%.

[0485] Example III.5 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example III.2, except that 0.27 mmol of chloroplatinic acid was added per gram of carbon support and the heat treatment temperature was 100° C. to obtain a sulfur-containing platinum-carbon catalyst with a loading of 5 wt %.

[0486] Example III.6 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example III.2, except that 0.27 mmol of chloroplatinic acid was added per gram of carbon support and the heat treatment temperature was 180° C. to obtain a sulfur-containing platinum-carbon catalyst with a loading of 5 wt %.

[0487] Comparative example III.1 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example III.2, except that the support was Ketjenblack ECP600JD and 0.57 mmol of chloroplatinic acid was added per gram of carbon support to obtain a sulfur-containing platinum-carbon catalyst with a loading of 10 wt%.

[0488] Comparative example III.2 The platinum-carbon catalyst is a commercially available catalyst under the brand name HISPEC4000.

[0489] Comparative example III.3 A sulfur-containing platinum-carbon catalyst was prepared according to the method of Example III.1, except that the sulfur-doped carbon material D1 of Comparative Preparation Example III.1 was used as the support to obtain a platinum carbon atom cluster catalyst with a loading of 6.24 wt.%.

[0490] Test Example III.2 As shown in Figure III.1, the XRD spectra of the sulfur-containing platinum-carbon catalysts of Examples III.1, 3 to 5 and Comparative Examples III.1 to 2 were measured. From the XRD spectra in Figure III.1, the NI / (FWHM * m Pt ) and the results are shown in Table III.2.

[0491] [Table 8]

[0492] In the above table, "absent" means that the sulfur-containing platinum-on-carbon catalyst does not have a corresponding Pt characteristic peak.

[0493] From the results in Table III.2, all of the sulfur-containing platinum-carbon catalysts of the present invention: no Pt characteristic peak or no Pt(111) characteristic peak NI / (FWHM * m Pt ) is less than 0.8, and the NI / (FWHM * m Pt ) is 0.5 or less and the platinum content of the sulfur-containing platinum-carbon catalyst is less than 10 wt %, the sulfur-containing platinum-carbon catalyst of the present invention has no Pt characteristic peak in the XRD spectrum, or the NI / (FWHM of the Pt(111) characteristic peak is * m Pt) is 0.6 or less, and the NI / (FWHM * m Pt ) is less than or equal to 0.4.

[0494] The XRD spectrum of Example III.2 was measured in the same manner as above, and the results were the same as those of Example III.1. * m Pt ) was calculated, which also satisfied the above relationship.

[0495] Test Example III.3 As shown in Figure III.2, the XPS spectra of the sulfur-containing platinum-carbon catalysts of Example III.1 and Comparative Examples III.1 to III.3 were measured. As shown in Figure III.2, the characteristic peak of Pt 4f 7 / 2 of the sulfur-containing platinum-carbon catalyst of Example III.2 is located at 72.2 eV, which is shifted to the high electron volt side by about 0.8 eV compared to Comparative Example III.1.

[0496] The XPS spectra of Examples III.2 to III.6 were measured by the same method as above, and all of the characteristic peaks of Pt 4f 7 / 2 were located above 71.9 eV.

[0497] Test Example III.4 The performance of the sulfur-containing platinum-carbon catalysts prepared in the above examples and comparative examples was measured, and the results are shown in Table III.3 and Figure III.3. Figure III.3 shows the LSV curves of the sulfur-containing platinum-carbon catalysts of Example III.1 and Comparative Examples III.1-3.

[0498] [Table 9]

[0499] The results in Table III.3 show that Examples III.1 to 6, which use the sulfur-containing platinum-carbon catalyst of the present invention, have lower overpotentials and higher weight specific activities than the commercial catalyst of Comparative Example III.2.

[0500] Comparing Examples III.1-6 with Comparative Example III.3, it can be seen that the sulfur-containing platinum-carbon catalyst of the present invention can significantly reduce the overvoltage while improving the weight specific activity by using the sulfur-modified carbon support of the present invention.

[0501] Comparing Examples III.2 with 5 to 6, it can be seen that the heat treatment temperature is 100 to 140° C., which can further reduce the overpotential and improve the weight specific activity.

[0502] Embodiment IV Example IV.1 0.1g of sulfur is dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.9g of Ketjen Black ECP600JD is dispersed therein, stirred uniformly, and soaked for 5 hours, then dried in vacuum at 50°C to obtain a sulfur-modified carbon support; 0.4g of chloroplatinic acid, calculated as platinum, is dissolved in 20mL of a solution with a volume ratio of water and ethanol of 10:1; 0.6g of sulfur-modified carbon support is dispersed in the chloroplatinic acid solution, stirred to disperse uniformly, and left for 24 hours, then placed in a vacuum drying oven to dry; the dried precursor is placed in a tubular furnace, heated to 140°C at a rate of 8°C / min, reduced in an atmosphere of N2:H2=5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0503] Example IV.2 0.55g of sulfur is dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.45g of Ketjen Black ECP600JD is dispersed therein, stirred uniformly, and soaked for 5 hours, then vacuum dried at 50℃ to obtain a sulfur-modified carbon support; 0.4g of chloroplatinic acid in terms of platinum is dissolved in 20mL of a solution with a volume ratio of water and ethanol of 10:1; 0.6g of sulfur-modified carbon support is dispersed in the chloroplatinic acid solution, stirred to disperse uniformly, and left for 24 hours, then placed in a vacuum drying oven to dry; the dried precursor is placed in a tubular furnace, heated to 160℃ at a rate of 6℃ / min, reduced in an atmosphere of N2:H2=5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0504] Comparative example IV.1 The carbon support used was unmodified Ketjen Black ECP600JD, and the Pt loading method and loading amount were the same as in Example IV.1 to obtain a platinum-carbon catalyst.

[0505] Comparative example IV.2 The platinum on carbon catalyst was commercially available TEC10F50E and had a platinum content of 46 wt %.

[0506] Test Example IV.1 The surface sulfur content and total sulfur content of the carbon support prepared in Example IV above were measured, and the results are shown in Table 1.

[0507] [Table 10]

[0508] In Table IV.1, surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0509] Test Example IV.2 SO x The ORR activity of each of the platinum-carbon catalysts prepared in Example IV and Comparative Example IV before and after the poisoning treatment was tested according to the following method. The test method is as follows: For electrochemical performance testing, the equipment model was Solartron analytical EnergyLab and Princeton Applied Research (Model 636A).

[0510] ORR activity test method: (i) In 0.1 M HClO4 saturated with N2, the catalyst was subjected to 50 mV s in the potential range of 0 to 1.1 V. -1 (ii) The catalyst was electrochemically pretreated by triangular wave scanning at a rate of 50 mV s−1 in 0.1 M HClO4 saturated with N2 for 10 cycles. -1(iii) In 0.1 M HClO4 saturated with O2, the polarization curves of the catalysts were measured in the potential range of 0–1.1 V at 10 mV s−1 with a rotating disk speed of 1600 rpm. -1 The catalyst was tested by periodically scanning at a speed of 0.01 μm for 10 cycles. The kinetic current was calculated using the KL equation, and the area-specific activity or weight-specific activity of the catalyst was calculated by dividing the kinetic current by the electrochemically active area or Pt content of the electrode surface.

[0511] SO in ORR x Resistance test method: The catalytic electrode is placed in a N2 gas flow for electrochemical pretreatment, and then placed in an O2 gas flow to record the initial ORR polarization curve. After the scan is completed, the electrode is placed in a 0.1 mol / L HClO4 solution containing 0.1 mmol / L Na2SO3 (6.4 ppm SO2 equivalent). x The catalyst was then inserted into a gas-saturated 0.1 M HClO4 solution and poisoned for 120 s at a constant voltage of 0.65 V (vs. RHE) under N2 saturation. The electrode was then removed and placed in a poison-free 0.1 M HClO4 solution to test the ORR activity of the poisoned catalyst according to the activity test method. Gas saturation was maintained for each test, and the scan rate for the polarization curve was 10 mV s -1 It is.

[0512] The test results are shown in Figure IV.1 and Table IV.2. Figure IV.1 shows the SO x 4 shows the LSV curves of ORR of platinum-carbon catalysts synthesized in Example IV.1 and Comparative Example IV.2 before and after poisoning treatment.

[0513] [Table 11]

[0514] From the results in Table IV.2, Example IV.1-2 shows that the use of the sulfur-containing platinum-carbon catalyst of the present invention reduced the amount of SO x Higher weight specific activity and SO than Comparative Example IV.2 under poisoning conditions. x It can be seen that the material has remarkably excellent electrochemical performance such as durability.

[0515] From the results, it can be seen that the sulfur-containing platinum-carbon catalyst of the present invention is x It is clear that this has the effect of improving the resistance of the platinum-carbon catalyst to toxicity.

[0516] Embodiment V Example V.1 0.1g of sulfur was dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.9g of Ketjen Black ECP600JD was dispersed therein, uniformly stirred, and soaked for 5 hours, and then dried in vacuum at 50 ° C to obtain a sulfur-modified carbon support; 0.4g of chloroplatinic acid in terms of platinum was dissolved in 20mL of a solution with a volume ratio of water to ethanol of 10:1; 0.6g of sulfur-modified carbon support was dispersed in the chloroplatinic acid solution, stirred to uniformly disperse, and left for 24 hours, then placed in a vacuum drying oven to dry; the dried precursor was placed in a tubular furnace, heated to 140 ° C at a rate of 8 ° C / min, reduced in an atmosphere of N2:H2 = 5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0517] Example V.2 0.55g of sulfur was dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.45g of Ketjen Black ECP600JD was dispersed therein, uniformly stirred, and soaked for 5 hours, and then vacuum dried at 50℃ to obtain a sulfur-modified carbon support. 0.35g of chloroplatinic acid in terms of platinum was dissolved in 20mL of a solution with a volume ratio of water to ethanol of 10:1, 0.6g of sulfur-modified carbon support was dispersed in the chloroplatinic acid solution, stirred to uniformly disperse, and left for 24 hours, then placed in a vacuum drying oven to dry. The dried precursor was placed in a tubular furnace, heated to 160℃ at a rate of 6℃ / min, reduced in an atmosphere of N2:H2=5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0518] Comparative example V.1 The carbon support used was unmodified Ketjen Black ECP600JD, and the Pt supporting method and supporting ratio were the same as in Example V.1 to obtain a platinum-carbon catalyst.

[0519] Comparative example V.2 A commercially available platinum-carbon catalyst, TEC10F50E grade, with a platinum loading of 46 wt % was used.

[0520] Comparative example V.3 A sulfur-doped carbon material was prepared according to the method in Nature Communications, 2019, 10:4977, and platinum was supported according to the method in Example V.1 to prepare a sulfur-containing platinum-carbon catalyst.

[0521] Comparative example V.4 A commercially available platinum-carbon catalyst, HISPEC 4000 grade, with a platinum loading of 40 wt % was used.

[0522] Test Example V.1 The surface sulfur content and total sulfur content of the carbon supports prepared in the above Example and Comparative Example V.3 were measured, and the results are shown in Table 1.

[0523] [Table 12]

[0524] In Table V.1, surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0525] Test Example V.2 The HOR and HER activities of the platinum-carbon catalysts of Example V and Comparative Example V before and after the CO poisoning treatment were tested by the following methods. The test methods are as follows: For electrochemical performance testing, the equipment model was Solartron analytical EnergyLab and Princeton Applied Research (Model 636A).

[0526] HOR activity test method: (i) In 0.1 M HClO4 or 0.5 M H2SO4 saturated with N2, the catalyst was subjected to 50 mV s in the potential range of 0.05 to 1.0 V. -1 (ii) the catalyst was electrochemically pretreated by triangular wave scanning at a rate of 50 mV s in 0.1 M HClO4 saturated with N2 in the potential range of 0.05–1.1 V. -1 The cyclic voltammetry curves of the catalysts were examined by periodically scanning at a rate of 10 mV s−1 for 10 cycles, and (iii) the catalysts were subjected to cyclic voltammetry in HClO4 saturated with H2 at a rotating disk speed of 1600 rpm in the potential range of 0–0.2 V at a rate of 10 mV s−1. -1 The polarization curves of the catalysts were tested by periodically scanning at a rate of 10 cycles. The HOR activity of the catalysts was evaluated by calculating the overpotential at a specified current density (j) in the polarization curve, the apparent current value at a specified electrode potential (i) divided by the Pt content (mPt) on the electrode surface (apparent gravimetric activity (MA, calculated as Pt weight), etc.

[0527] CO tolerance test method in HOR: The catalytic electrode is placed in a N2 gas flow for electrochemical pretreatment, and then in a H2 gas flow to record the initial HOR polarization curve. The catalytic electrode is then placed in a H2 gas flow mixed with 1000 ppm CO to record the HOR polarization curve when high concentration CO is mixed into the system. Each test is maintained in a gas saturated state, and the scan rate of the polarization curve is 10 mV s -1 It is.

[0528] HER Test Method: The polarization curves LSV of the catalysts were tested in the potential range of -0.2~0.2V in 0.1M HClO4 saturated with N2 at a speed of 2500 rpm, and the electrochemically active areas ECSA were tested in 0.1M HClO4 saturated with N2. In the above tests, the catalysts were prepared into a uniformly dispersed slurry and applied on a glassy carbon electrode with a diameter of 5 mm. The amount of platinum in the catalysts on the electrode was controlled in the range of 1~4 μg.

[0529] The CO tolerance test method in HER is the same as that in HOR.

[0530] The test results are shown in Figures V.1 to V.5 and Tables V.2 to V.3. Figure V.1 is an XPS spectrum of the platinum-carbon catalyst of Example V.1 and Comparative Example V.1. Figure V.2 is an LSV curve of the HER of the platinum-carbon catalyst of Example V.1 and Comparative Example V.1 before and after the CO poisoning treatment. Figure V.3 is an LSV curve of the HOR of the platinum-carbon catalyst of Example V.1 and Comparative Example V.2 before and after the CO poisoning treatment. Figure V.4 is an in-situ infrared curve of CO of the platinum-carbon catalyst of Example V.1 and Comparative Example V.1. Figure V.5 is an LSV curve of the HOR of the platinum-carbon catalyst of Example V.2 and Comparative Example V.4 before and after the CO poisoning treatment. Here, when Example V.1 and Comparative Examples V.1 to V.3 were tested, the raw gas flow rate was 200 mL / min, and when Example V.2 and Comparative Example V.4 were tested, the raw gas flow rate was 100 mL / min.

[0531] [Table 13] [a] "Not reached" means that the current density of the sample is less than 2 mA / cm within the measured potential range. 2 This means that it has never been reached.

[0532] [Table 14]

[0533] From the results in Tables V.2 and V.3, it can be seen that Examples V.1-2 have superior electrochemical performance, such as higher weight specific activity and higher CO tolerance, under CO poisoning conditions than Comparative Examples V.1-4, by using the sulfur-containing platinum-carbon catalyst of the present invention.

[0534] From Figure V.4, it can be seen that by using the sulfur modified carbon support of the present invention, the resulting sulfur-containing platinum-on-carbon catalyst has substantially no CO chemisorption to CO and is therefore CO tolerant.

[0535] From the above results, it is apparent that the sulfur-containing platinum-carbon catalyst of the present invention has the effect of improving the resistance of the platinum-carbon catalyst to CO poisoning.

[0536] EMBODIMENT VI Example VI.1 0.1g of sulfur was dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.9g of Ketjen Black ECP600JD was dispersed therein, stirred uniformly, soaked for 5 hours, and dried in vacuum at 50°C to obtain a sulfur-modified carbon support; 0.4g of chloroplatinic acid in terms of platinum was dissolved in 20mL of a solution with a volume ratio of water and ethanol of 10:1; 0.6g of sulfur-modified carbon support was dispersed in the chloroplatinic acid solution, stirred to disperse uniformly, and left for 24 hours, then placed in a vacuum drying oven to dry; the dried precursor was placed in a tubular furnace, heated to 140°C at a rate of 8°C / min, reduced in an atmosphere of N2:H2=5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0537] Example VI.2 0.25g of sulfur was dissolved in 70ml of cyclohexane to form a homogeneous solution, 9.75g of Ketjen Black ECP600JD was dispersed therein, uniformly stirred, and soaked for 5 hours, and then dried in vacuum at 50 ° C to obtain a sulfur-modified carbon support; 0.52g of chloroplatinic acid in terms of platinum was dissolved in 20mL of a solution with a volume ratio of water to ethanol of 10:1; 0.6g of sulfur-modified carbon support was dispersed in the chloroplatinic acid solution, stirred to uniformly disperse, and left for 24 hours, then placed in a vacuum drying oven to dry; the dried precursor was placed in a tubular furnace, heated to 160 ° C at a rate of 6 ° C / min, reduced in an atmosphere of N2:H2 = 5:1 for 2 hours, and cooled in an N2 atmosphere to obtain a sulfur-containing platinum-carbon catalyst.

[0538] Comparative example VI.1 A commercially available catalyst with the brand name HISPEC4000, with a platinum loading of 40% by weight.

[0539] Comparative example VI.2 A sulfur-doped carbon material was prepared according to the method in Nature Communications, 2019, 10:4977, and platinum was supported according to the method in Example VI.1 to prepare a platinum-carbon catalyst.

[0540] Test Example VI.1 The surface sulfur content and total sulfur content of the carbon supports prepared in the above examples and comparative examples were measured, and the results are shown in Table VI.1.

[0541] [Table 15]

[0542] In Table VI.1, surface sulfur content represents the sulfur weight fraction measured by XPS analysis, and total sulfur content represents the sulfur weight fraction measured by a sulfur-carbon analyzer.

[0543] Test Example VI.2 HOR electrochemical performance test: Equipment model: Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), Method and test conditions: The polarization curve LSV of the catalyst was tested in 0.1M HClO4 saturated with H2 at a speed of 2500 rpm and a scan rate of 10 mV / s, and the electrochemical active area ECSA was tested in 0.1M HClO4 saturated with N2 at a scan rate of 50 mV / s. In the above test, the catalyst was prepared into a uniformly dispersed slurry, and 10 μl was taken and applied to a glassy carbon electrode with a diameter of 5 mm. H2S poison resistance test method 1: 0.4 ppm H2S was mixed into H2, and the HOR activity was tested again in 0.1M HClO4 saturated with H2+0.4 ppm H2S, and the activity change before and after the introduction of H2S was compared. H2S poisoning resistance test method 2: 10 μmol / L Na2S was added to 0.5M H2SO4, and poisoning was carried out at a constant voltage of 0.1 V for 5 hours, and the change in catalyst performance before and after poisoning was tested.

[0544] Method 1 was used to test the HOR activity of the platinum-carbon catalyst of Example VI.2 before and after H2S poisoning, and Method 2 was used to test the HOR activity of the platinum-carbon catalysts of Example VI.1 and Comparative Examples VI.1-2 before and after H2S poisoning. The results are shown in Table VI.2. Figures VI.1 and VI.2 show the LSV and CV curves of the platinum-carbon catalyst of Example VI.2 before and after H2S poisoning, respectively. Figures VI.3 and VI.4 show the LSV and CV curves of the platinum-carbon catalysts of Example VI.1 and Comparative Example VI.1 after H2S poisoning, respectively.

[0545] [Table 16]

[0546] From the results in Table VI.2, it can be seen that Examples VI.1-2 have better electrochemical performance and resistance to sulfide poisoning under H2S poisoning conditions than Comparative Examples VI.1-2 by using the sulfur-modified carbon support of the present invention.

[0547] From the above results, it can be seen that the sulfur-containing platinum-carbon support of the present invention has the effect of improving the resistance of the platinum-carbon catalyst to H2S poisoning.

Claims

1. 1. A sulfur modified carbon material comprising conductive carbon black and elemental sulfur dispersed therein, characterized in that the total sulfur content in the sulfur modified carbon material is at least 1.2 times, preferably at least 1.5 times, the surface sulfur content.

2. 2. The sulfur modified carbon material of claim 1, wherein the total sulfur content in the sulfur modified carbon material is 0.1 to 10 wt.%, preferably 1 to 8 wt.%, more preferably 1 to 4 wt.%, based on the total weight of the sulfur modified carbon material.

3. 2. The sulfur modified carbon material according to claim 1, wherein the surface sulfur content in the sulfur modified carbon material is 0.1-6 wt.%, preferably 0.5-3 wt.%, based on the total weight of the surface layer of the sulfur modified carbon material.

4. The specific surface area of ​​the sulfur-modified carbon material is 200 to 2000 m ２ 2. The sulfur modified carbon material of claim 1, wherein the sulfur modified carbon material has a molecular weight of 1.0 to 1.0 g.

5. 2. The sulfur modified carbon material of claim 1, wherein the conductive carbon black is one or more of EC-300J, EC-600JD, ECP600JD, VXC72, VXC72R, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2.

6. 10. The sulfur modified carbon material of claim 1, wherein the sulfur modified carbon material is prepared by an impregnation method, in which the conductive carbon black is impregnated with a solution containing a sulfur source.

7. 2. The sulfur modified carbon material of claim 1, wherein the elemental sulfur is introduced into the conductive carbon black in the form of elemental sulfur.

8. A method for preparing the sulfur modified carbon material according to any one of claims 1 to 7, comprising the steps of: A) an impregnation step: a step of impregnating the conductive carbon black with a solution containing sulfur at 10 to 80° C. for 1 to 5 hours; and B) Drying step: drying the impregnated product obtained in step A). A method comprising:

9. The solvent in the sulfur-containing solution is CCl ４ , C.S. ２ 9. The method of claim 8, wherein the hexane is one or more of cyclohexane, cyclohexane, and n-hexane.

10. 9. The method of claim 8, wherein the concentration of sulfur in the sulfur-containing solution is 0.0004 to 0.02 g / mL.

11. The method according to claim 8, wherein the amount of sulfur used is 0.005 to 0.06 g per 1 g of conductive carbon black.

12. 9. The method according to claim 8, wherein the temperature of the impregnation is between 10 and 40° C., preferably between 20 and 30° C., particularly preferably at room temperature (25° C.), and the time of the impregnation is preferably between 2 and 4 hours.

13. 9. The method of claim 8, wherein the drying conditions include a temperature of 20 to 100° C. and a time of 5 to 10 hours.

14. 2. Use of the sulfur-modified carbon material according to claim 1 as a support for the preparation of a catalyst.

15. The use according to claim 14, wherein the catalyst is a platinum-carbon catalyst for electrocatalysis.

Images