CN115125579A - Preparation method and application of platinum monoatomic coordination cobalt-platinum alloy in limitation of nitrogen-doped porous carbon - Google Patents
Preparation method and application of platinum monoatomic coordination cobalt-platinum alloy in limitation of nitrogen-doped porous carbon Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 187
- GUBSQCSIIDQXLB-UHFFFAOYSA-N cobalt platinum Chemical compound [Co].[Pt].[Pt].[Pt] GUBSQCSIIDQXLB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000000670 limiting effect Effects 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 123
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 230000015572 biosynthetic process Effects 0.000 claims description 34
- 238000003786 synthesis reaction Methods 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 230000002195 synergetic effect Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 10
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 150000004687 hexahydrates Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- 230000000694 effects Effects 0.000 abstract description 25
- 239000003054 catalyst Substances 0.000 abstract description 24
- 239000002159 nanocrystal Substances 0.000 abstract description 14
- 229910045601 alloy Inorganic materials 0.000 abstract description 10
- 239000000956 alloy Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 230000002378 acidificating effect Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010200 validation analysis Methods 0.000 description 2
- 229910002514 Co–Co Inorganic materials 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 229910020707 Co—Pt Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of limiting a platinum monatomic (Pt) in nitrogen-doped porous carbon in cooperation with cobalt-platinum alloy SA ) And cobalt platinum alloy (CoPt) nanocrystals confined to nitrogen-doped porousCarbon Frameworks (NDPCF) derived from platinum nanoparticles (PtNPs) encapsulated in amino-functionalized ZIF-67. Under alkaline and acidic conditions, CoPt-Pt SA the/NDPCF shows excellent electrocatalytic hydrogen evolution performance, including lower overpotential, smaller Tafel slope, higher current density, higher switching frequency and better cycle stability. CoPt-Pt SA The excellent electrocatalytic hydrogen evolution performance of/NDPCF is attributed to Pt protected by nitrogen-doped porous carbon skeleton SA Strong synergy with CoPt alloy nanocrystals. The method not only improves the electro-catalytic hydrogen evolution activity of the catalyst, but also solves the problems of dissolution, corrosion, agglomeration and the like of the monatomic material and the platinum alloy nanocrystal in the long-term circulation process, and fundamentally improves the catalytic activity and the long-circulation durability of the catalyst.
Description
Technical Field
The invention relates to the technical field of electrocatalytic hydrogen evolution materials, in particular to a preparation method and application of a platinum monoatomic synergetic cobalt-platinum alloy in nitrogen-doped porous carbon.
Background
Single Atom Catalysts (SAC) with ultra-high atomic utilization and rich active sites can significantly improve the electrocatalytic performance of the catalyst and are considered as potential candidates for most catalytic reactions. Currently, much research is mainly focused on improving the electrocatalytic activity of SAC by inhibiting the agglomeration of Single Atoms (SA) during synthesis or electrocatalytic reaction. Recently, many studies have been reported to support SA on a surface of a support having a specific coordination to explore its electrocatalytic activity and cycle stability. Although the formation of strong chemical bonds with the support can modulate the intrinsic catalytic properties of SA, the long-cycle performance of SA is easily adversely affected due to its exposure on the surface of the support. Therefore, it is important to improve the cycle stability of SAC by confining SA to the inside of the carrier. Metal Organic Frameworks (MOFs) have periodic pores and unique structures, are considered to be ideal carriers for realizing cycle stability of SA, and can be designed into various functional hybrid complexes according to the selection of different kinds of coordination metals. In addition, MOFs are also considered as a new generation of ideal carriers for encapsulating Nanoparticles (NPs), and the interaction of NPs with conventional porous materials can also facilitate the transfer of protons and charges. Derivatives of MOFs are also considered to be excellent supports because their derivatives porous carbon have many advantages such as high conductivity and environmental stability.
Electrocatalytic hydrogen evolution is a promising approach to obtain chemical fuels for energy sustainability and effective reduction of carbon dioxide emissions. Of the various metals of the electrocatalytic Hydrogen Evolution (HER) catalyst, platinum (Pt) adsorbs the gibbs free energy (| Δ G) due to its inherent ultra-low H H* 0.0071eV) with low overpotential and rapid kinetic response, is the most effective active metal for HER performance improvement. However, the high cost, ultra-low utilization and poor cycle stability of Pt metal severely limit its further large-scale applications. Monoatomic Pt (Pt) SA ) The efficiency of atom utilization can be maximized, thereby reducing catalyst cost and maintaining its superior HER activity. Related studies have found that monodisperse metal atoms such as Fe, Co, Ni, Pd and Pt, and some Pt alloy nanocrystals that enhance HER activity by modulating the d-band of Pt, exhibit high electrocatalytic activity and cycling durability on various supports. However, such SA materials and Pt alloy nanocrystals still suffer from dissolution, corrosion, and agglomeration during long-term cycling, resulting in rapid degradation of catalytic activity and cycling durability. The current research has not elucidated in detail by adjusting Pt SA The ambient conditions adjust the relationship between the metal alloy and the SA.
Disclosure of Invention
The invention aims to provide a preparation method and application of a platinum monatomic synergistic cobalt platinum alloy in nitrogen-doped porous carbon, which solve the problems of dissolution, corrosion and agglomeration of an SA material and a Pt alloy nanocrystal in a long-term circulation process and increase the electrocatalytic HER activity and the circulation durability of the SA material and the Pt alloy nanocrystal.
In order to achieve the purpose, the invention provides a preparation method for limiting a platinum monatomic synergetic cobalt-platinum alloy in nitrogen-doped porous carbon, which comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving chloroplatinic acid hexahydrate powder in deionized water to form a uniform solution, namely a solution A;
secondly, adding polyvinylpyrrolidone into the solvent to form a uniform solution, namely a solution B;
thirdly, dropwise adding the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then washing with anhydrous acetone and chloroform for three times respectively to collect final PtNPs, and uniformly dispersing in the solvent, wherein the concentration is controlled at 3mg/mL to obtain a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving cobalt salt in a solvent to obtain a solution A;
secondly, dispersing 2-methylimidazole and the PtNPs solution in a solvent to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and then aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、Co n Pt-Pt SA synthesis of/NDPCF: heating Pt/ZIF-67 containing Co with different proportions to 500-900 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere in a tube furnace, and calcining for 2h to obtain Co n Pt-Pt SA /NDPCF, wherein n is 0.5 or 1 or 2.
Preferably, Pt/ZIF-67 containing Co in various proportions is obtained by adjusting the contents of cobalt salt and PtNPs.
Preferably, the cobalt salt is one of cobalt sulfate heptahydrate, cobalt nitrate hexahydrate and cobalt chloride hexahydrate.
Preferably, the solvent is one of methanol, ethanol, acetone and water.
Preferably, the purity of the Ar atmosphere in step S3 is 99.999%.
Preferably, the preparation method of limiting the platinum monoatomic synergetic cobalt-platinum alloy in the nitrogen-doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of chloroplatinic acid hexahydrate powder in 20mL of deionized water to form a uniform solution, namely solution A;
secondly, 0.015mmol of polyvinylpyrrolidone is added into 60mL of ethanol to form a uniform solution, namely a solution B;
thirdly, dripping 20mL of the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then washing with anhydrous acetone and chloroform for three times respectively to collect final PtNPs, uniformly dispersing the PtNPs in ethanol, and controlling the concentration to be 3mg/mL to obtain a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving 12mmol of cobalt sulfate heptahydrate in 120mL of ethanol to obtain a solution A;
secondly, dispersing 48mmol of 2-methylimidazole and 8.8mL of the PtNPs solution in 40mL of ethanol to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、CoPt-Pt SA synthesis of/NDPCF: heating Pt/ZIF-67 to 900 ℃ at a heating rate of 2 ℃/min in Ar atmosphere in a tubular furnace, and calcining for 2h to obtain CoPt-Pt SA /NDPCF。
An application of a platinum monoatomic synergetic cobalt-platinum alloy in electrocatalytic hydrogen evolution limited in nitrogen-doped porous carbon.
Mixing Pt SA And cobalt platinum (CoPt) alloy nanocrystals confined to a nitrogen-doped porous carbon framework (CoPt-Pt) SA NDPCF), the framework is derived fromPtNPs encapsulated in amino-functionalized ZIF-67. CoPt-Pt in comparison to commercial 10% Pt/C catalysts under basic and acidic conditions SA the/NDPCF all showed excellent electrocatalytic HER performance including lower overpotential, smaller Tafel slope, higher current density, higher switching frequency (TOF) and better cycling stability. CoPt-Pt SA The excellent performance of/NDPCF is attributed to Pt SA Strong synergy with CoPt alloy nanocrystals protected by nitrogen-doped porous carbon backbone (NDPCF). The theoretical calculation of density functional shows that Pt SA With ultra-low | Δ G in combination with CoPt alloy nanocrystals in NDPCF H* L (-0.059 eV), which is a key factor that enhances the reaction kinetics affecting HER activity. In addition, the synergistic effect of SAs and the metal alloy nanocrystalline electrocatalyst coated by the porous carbon material provides a new strategy for constructing high-efficiency SACs.
Therefore, the preparation method and the application of the platinum monoatomic and cobalt platinum alloy in the nitrogen-doped porous carbon limit are adopted, the problems of dissolution, corrosion and agglomeration of the SA material and the Pt alloy nanocrystal in the long-term circulation process are solved, and the electrocatalytic HER activity and the circulation durability are improved.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is CoPt-Pt SA A synthetic schematic diagram of/NDPCF;
FIG. 2 is CoPt-Pt SA TEM picture of/NDPCF;
FIG. 3 shows CoPt-Pt SA EDX element distribution map of/NDPCF;
FIG. 4 shows CoPt-Pt SA HAADF-STEM diagram of/NDPCF;
FIG. 5 is an XRD pattern of Pt-ZIF-67 through different sintering temperatures;
FIG. 6 is CoPt-Pt SA EXAFS and a corresponding fitting curve of the NDPCF in the R space of the Co K-edge;
FIG. 7 is CoPt-Pt SA NDPCF on Pt L 3 -EXAFS and corresponding fitted curve in R-space of the edge;
FIG. 8 shows Co/NDPCF and CoPt-Pt SA N of/NDPCF 2 Adsorption-desorption isotherms;
FIG. 9 is CoPt-Pt SA Polarization curves of/NDPCF and other catalysts in 1M KOH solution;
FIG. 10 is a graph of commercial 10% Pt/C and 5% Pt/C catalysts, CoPt-Pt SA Activity of the/NDPCF catalyst per unit mass of Pt;
FIG. 11 shows CoPt-Pt SA The current density of the/NDPCF catalyst is-10 mA cm -2 And-50 mA cm -2 I-t cycle performance under conditions;
FIG. 12 shows different catalysts in acid (0.5 MH) 2 SO 4 ) iR compensated Linear Sweep Voltammetry (LSV) curve under conditions;
FIG. 13 is CoPt-Pt SA Activity plot of Pt per unit mass of/NDPCF catalyst under 0.5M acidic conditions.
Detailed Description
The invention provides a preparation method for limiting a platinum monatomic synergetic cobalt-platinum alloy in nitrogen-doped porous carbon, which comprises the following steps of:
s1, synthesis of PtNPs:
firstly, dissolving cobalt salt in deionized water to form a uniform solution, namely solution A;
secondly, adding polyvinylpyrrolidone into a solvent to form a uniform solution, namely a solution B;
thirdly, dropwise adding the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing excessive solvent by a rotary evaporation method to obtain PtNPs, then washing with anhydrous acetone and chloroform for three times respectively to collect final PtNPs, and uniformly dispersing in the solvent, wherein the concentration is controlled at 3mg/mL to obtain the PtNPs solution.
S2, synthesis of Pt/ZIF-67:
firstly, dissolving cobalt salt in a solvent to obtain a solution A;
secondly, dispersing 2-methylimidazole and the PtNPs solution in a solvent to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and then aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67; Pt/ZIF-67 containing Co in different proportions was obtained by adjusting the contents of cobalt salt and PtNPs.
S3、Co n Pt-Pt SA Synthesis of/NDPCF: heating Pt/ZIF-67 containing Co with different proportions to 500-900 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere (with the purity of 99.999%) in a tubular furnace, and calcining for 2h to obtain Co n Pt-Pt SA /NDPCF, wherein n is 0.5 or 1 or 2.
The cobalt salt used is one of cobalt sulfate heptahydrate, cobalt nitrate hexahydrate and cobalt chloride hexahydrate. The solvent is one of methanol, ethanol, acetone and water.
The technical scheme of the invention is further explained by the attached drawings and the embodiment.
Example 1
As shown in fig. 1, a preparation method of limiting a platinum monoatomic coordination cobalt platinum alloy in nitrogen-doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of chloroplatinic acid hexahydrate powder in 20mL of deionized water to form a uniform solution, namely solution A;
secondly, 0.015mmol of polyvinylpyrrolidone is added into 60mL of ethanol to form a uniform solution, which is solution B;
thirdly, dropwise adding 20mL of the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then washing with anhydrous acetone and chloroform for three times respectively to collect final PtNPs, and uniformly dispersing in ethanol, wherein the concentration is controlled at 3mg/mL to obtain a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving 12mmol of cobalt sulfate heptahydrate in 120mL of ethanol to obtain a solution A;
secondly, dispersing 48mmol of 2-methylimidazole and 8.8mL of the PtNPs solution in 40mL of ethanol to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and then aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、CoPt-Pt SA synthesis of/NDPCF: heating Pt/ZIF-67 to 500 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere in a tubular furnace, and calcining for 2h to obtain CoPt-Pt SA /NDPCF。
Example 2
As shown in fig. 1, a preparation method of limiting a platinum monoatomic coordination cobalt platinum alloy in nitrogen-doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of chloroplatinic acid hexahydrate powder in 20mL of deionized water to form a uniform solution, namely solution A;
secondly, 0.015mmol of polyvinylpyrrolidone is added into 60mL of ethanol to form a uniform solution, namely a solution B;
thirdly, dripping 20mL of the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then washing with anhydrous acetone and chloroform for three times respectively to collect final PtNPs, and uniformly dispersing in ethanol, wherein the concentration is controlled at 3mg/mL to obtain a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving 12mmol of cobalt sulfate heptahydrate in 120mL of ethanol to obtain a solution A;
secondly, dispersing 48mmol of 2-methylimidazole and 8.8mL of the PtNPs solution in 40mL of ethanol to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and then aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、CoPt-Pt SA synthesis of/NDPCF: heating Pt/ZIF-67 to 750 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere in a tubular furnace, and calcining for 2h to obtain CoPt-Pt SA /NDPCF。
Example 3
As shown in fig. 1, a preparation method of limiting a platinum monoatomic coordination cobalt platinum alloy in nitrogen-doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of chloroplatinic acid hexahydrate powder in 20mL of deionized water to form a uniform solution, namely solution A;
secondly, 0.015mmol of polyvinylpyrrolidone is added into 60mL of ethanol to form a uniform solution, namely a solution B;
thirdly, dripping 20mL of the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then washing with anhydrous acetone and chloroform for three times respectively to collect final PtNPs, and uniformly dispersing in ethanol, wherein the concentration is controlled at 3mg/mL to obtain a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving 12mmol of cobalt sulfate heptahydrate in 120mL of ethanol to obtain a solution A;
secondly, dispersing 48mmol of 2-methylimidazole and 8.8mL of the PtNPs solution in 40mL of ethanol to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and then aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、CoPt-Pt SA synthesis of/NDPCF: Pt/ZIF-67 was placed in a tube furnace at 2 deg.C/mi in an Ar atmospheren, raising the temperature to 900 ℃ at the temperature rise rate, and calcining for 2h to obtain CoPt-Pt SA /NDPCF。
Example 4
As shown in fig. 1, a preparation method of limiting a platinum monatomic synergetic cobalt-platinum alloy in nitrogen-doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of chloroplatinic acid hexahydrate powder in 20mL of deionized water to form a uniform solution, namely solution A;
secondly, 0.015mmol of polyvinylpyrrolidone is added into 60mL of ethanol to form a uniform solution, namely a solution B;
thirdly, dripping 20mL of the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then washing with anhydrous acetone and chloroform for three times respectively to collect final PtNPs, uniformly dispersing in ethanol, and controlling the concentration at 3mg/mL to obtain a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving 0.5M cobalt sulfate heptahydrate in 120mL of ethanol to obtain a solution A;
secondly, dispersing 48mmol of 2-methylimidazole and 10mL of PtNPs solution in 40mL of ethanol to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and then aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、CoPt-Pt SA synthesis of/NDPCF: heating Pt/ZIF-67 to 900 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere in a tubular furnace, and calcining for 2h to obtain Co 0.5 Pt-Pt SA /NDPCF。
Example 5
As shown in fig. 1, a preparation method of limiting a platinum monatomic synergetic cobalt-platinum alloy in nitrogen-doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of chloroplatinic acid hexahydrate powder in 20mL of deionized water to form a uniform solution, namely solution A;
secondly, 0.015mmol of polyvinylpyrrolidone is added into 60mL of ethanol to form a uniform solution, which is solution B;
thirdly, dropwise adding 20mL of the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then washing with anhydrous acetone and chloroform for three times respectively to collect the final PtNPs, uniformly dispersing in ethanol, and controlling the concentration at 3mg/mL to obtain a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving 2M cobalt sulfate heptahydrate in 120mL of ethanol to obtain a solution A;
secondly, dispersing 48mmol of 2-methylimidazole and 15mL of PtNPs solution in 40mL of ethanol to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and then aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、CoPt-Pt SA synthesis of/NDPCF: heating Pt/ZIF-67 to 900 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere in a tubular furnace, and calcining for 2h to obtain Co 2 Pt-Pt SA /NDPCF。
FIG. 1 shows CoPt-Pt SA The synthesis process of the/NDPCF is shown schematically.
Comparative example 1
Commercial 10% Pt/C catalyst.
Comparative example 2
Commercial 5% Pt/C catalyst.
The performance of CoPt-PtSA/NDPCF is characterized as follows:
the TEM image of FIG. 2 shows CoPt-Pt SA the/NDPCF has a typical regular dodecahedron structure, the diameter is about 700nm, and CoPt-Pt subjected to high-temperature sintering SA the/NDPCF structure did not collapse.
FIG. 3 shows elemental mapping of energy dispersive X-ray spectroscopy (EDX) to indicate that Co, Pt, N and C elements are uniformly distributed in ordered CoPt-Pt SA In the/NDPCF structure.
FIG. 4 shows CoPt-Pt SA the/NDPCF contains CoPt alloy and Pt SA In which Pt is supported on CoPt-Pt in two forms SA the/NDPCF surface, one was CoPt alloyed with Co, as shown in FIG. 4 a. In addition, Pt is supported on the surface of the carrier in a single atom form, as shown in FIG. 4c
FIG. 5 is an XRD pattern showing that Pt-ZIF-67 does not significantly carbonize at 500 ℃ for 2 h. In addition, a small amount of Co is formed at 500 deg.C 3 O 4 (PDF #43-1003), which further demonstrates that Pt-ZIF-67 does not carbonize completely at 500 ℃ for 2 h. As the sintering temperature was gradually increased to 750 ℃ and 900 ℃, the carbon (C) and Co peaks of the composite increased significantly. As a result of the formation of the CoPt alloy, a small amount of Pt was replaced by Co, and the XRD peak of the CoPt alloy disappeared.
FIG. 6 is a graph of CoPt-Pt SA R-space of/NDPCF and corresponding fitted extended X-ray absorption fine structure spectral curve in
There is a peak from the Co-Co cluster. In addition to this, the present invention is,
and
the small peaks at (A) correspond to Co-N and Co-Pt, respectively, which further confirms that Co forms coordination with N and Pt.
In FIG. 7, CoPt-Pt SA Extended X-ray absorption fine structure spectral curve of/NDPCF confirms Pt SA In that
Is coordinated to about 2N atoms. In that
It is shown that it forms mainly alloyed nanocrystals with Co.
FIG. 8 shows Co/NDPCF and CoPt-Pt SA N of/NDPCF 2 The adsorption-desorption isotherms showed that their specific surface areas were 297.72 and 254.04m, respectively 2 /g。
FIG. 9 is an iR compensated Linear Sweep Voltammetry (LSV) curve under basic (1MKOH) conditions for different catalysts. The results show that the catalyst, CoPt-Pt SA NDPCF at a current density of-10 mA cm -2 It exhibited the highest HER activity, with an overpotential as low as 31mV compared to the Reversible Hydrogen Electrode (RHE), much lower than pure Co/NDPCF (309mV), approaching commercial 10% Pt/C (38 mV). Due to Co content to Pt SA The distribution of (a) has a great influence, and we focus on the influence of the Co content on the electrocatalytic HER activity of the composite material. Co 0.25 Pt-Pt SA NDPCF and Co 2 Pt-Pt SA The overpotentials for/NDPCF were 47 and 38mV, respectively, indicating that Co content has a significant effect on HER activity. The main reason is Co 0.25 Pt-Pt SA The Co content in the/NDPCF composite material is too low to form the active site of the CoPt alloy. When Co is present 2 Pt-Pt SA When the Co content in the/NDPCF is too high, the Co occupies too many sites, which is not beneficial to Pt SA Is uniformly dispersed. Furthermore, CoPt-Pt SA The current density of the/NDPCF in 1M KOH reaches-1000 mA cm at 474mV -2 And is far better than the current density of 10% Pt/C.
FIG. 10 is CoPt-Pt SA The activity of the/NDPCF catalyst on the unit mass Pt under the alkaline condition of 1MKOH is as high as 19.3A mg -1 Further validation of Pt was achieved by 33.9 and 77.2 times (test conditions: overpotential. eta. 50mV) that of commercial 10% Pt/C and 5% Pt/C catalysts, respectively SA And CoPt alloys are limited to CoPt-Pt SA The electrocatalytic HER activity of the material can be enhanced in the structure of the/NDPCF.
FIG. 11 is a diagram of CoPt-Pt SA The current density of the/NDPCF catalyst is-10 mA cm -2 And-50 mA cm -2 I-t cycle performance under conditions. The results show that CoPt-Pt SA NDPCF at-10 mA cm -2 Current density lower cycle 100The h current has substantially no decay. And at-50 mA cm -2 Can be stabilized for 50 hours under the condition of high current, and shows excellent cycling stability.
FIG. 12 shows different catalysts in acidic (0.5 MH) 2 SO 4 ) Under the condition, an iR compensated Linear Sweep Voltammetry (LSV) curve is obtained. The results show that CoPt-Pt SA NDPCF at a current density of-10 mA cm -2 It exhibited the highest HER activity, with an overpotential as low as 20mV compared to Reversible Hydrogen Electrode (RHE), much lower than pure Co/NDPCF (285mV), better than commercial 10% Pt/C (37 mV). Due to Co content versus Pt SA The distribution of (a) has a great influence, and we focus on the influence of the Co content on the electrocatalytic HER activity of the composite material. Co 0.25 Pt-Pt SA NDPCF and Co 2 Pt-Pt SA The overpotentials for/NDPCF were 32 and 27mV, respectively, indicating that Co content has a significant effect on HER activity. Moreover, CoPt-Pt SA NDPCF at 0.5M H 2 SO 4 The current density in the medium reaches-1000 mA cm at 258mV -2 And is far better than the current density of 10% Pt/C.
FIG. 13 shows CoPt-Pt SA The activity of the/NDPCF catalyst on the unit mass Pt under the 0.5M acidic condition is as high as 74.31A mg -1 Further validation of Pt was achieved with 130.3 and 285.8 times the commercial 10% Pt/C and 5% Pt/C catalysts, respectively (test conditions: overpotential η ═ 50mV) SA And CoPt alloys are limited to CoPt-Pt SA The electrocatalytic hydrogen evolution activity of the material can be enhanced in the structure of the/NDPCF.
Therefore, the preparation method and application of the platinum monoatomic synergetic cobalt-platinum alloy limited in the nitrogen-doped porous carbon have superior alkaline and acidic electrocatalytic HER reaction activity compared with a commercial 10% Pt/C catalyst, simultaneously solve the problems of dissolution, corrosion and agglomeration of SA materials and Pt alloy nanocrystals in a long-term circulation process, and increase the electrocatalytic HER activity and the circulation durability of the SA materials and the Pt alloy nanocrystals.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method for limiting a platinum monatomic synergetic cobalt-platinum alloy in nitrogen-doped porous carbon is characterized by comprising the following steps of:
s1, synthesis of PtNPs:
firstly, dissolving chloroplatinic acid hexahydrate powder in deionized water to form a uniform solution, namely a solution A;
secondly, adding polyvinylpyrrolidone into a solvent to form a uniform solution, namely a solution B;
thirdly, dropwise adding the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under the atmosphere, removing redundant solvent by a rotary evaporation method, washing with anhydrous acetone and chloroform for three times respectively to collect the final PtNPs, and uniformly dispersing in the solvent, wherein the concentration is controlled at 3mg/mL to obtain a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving cobalt salt in a solvent to obtain a solution A;
secondly, dispersing 2-methylimidazole and the PtNPs solution in a solvent to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and then aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、Co n Pt-Pt SA synthesis of/NDPCF: heating Pt/ZIF-67 containing Co with different proportions to 500-900 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere in a tube furnace, and calcining for 2h to obtain Co n Pt-Pt SA a/NDPCF in which n is 0.5 or 1 or 2.
2. The method for preparing the nitrogen-doped porous carbon limited by the platinum monoatomic synergetic cobalt-platinum alloy according to claim 1, wherein the method comprises the following steps: Pt/ZIF-67 containing Co in different proportions was obtained by adjusting the contents of cobalt salt and PtNPs.
3. The method for preparing the nitrogen-doped porous carbon limited by the platinum monoatomic synergetic cobalt-platinum alloy according to claim 2, wherein the method comprises the following steps: the cobalt salt is one of cobalt sulfate heptahydrate, cobalt nitrate hexahydrate and cobalt chloride hexahydrate.
4. The method for preparing the porous carbon doped with nitrogen by limiting the platinum monoatomic cooperated with the cobalt platinum alloy according to the claim 3, wherein the method comprises the following steps: the solvent is one of methanol, ethanol, acetone and water.
5. The method for preparing the porous carbon doped with nitrogen by limiting the platinum monoatomic cooperated with the cobalt platinum alloy according to the claim 4, wherein the method comprises the following steps: the purity of the Ar atmosphere in step S3 was 99.999%.
6. The method for preparing the nitrogen-doped porous carbon limited by the platinum monoatomic synergetic cobalt platinum alloy according to claim 5, wherein the method comprises the following steps of:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of chloroplatinic acid hexahydrate powder in 20mL of deionized water to form a uniform solution, namely solution A;
secondly, 0.015mmol of polyvinylpyrrolidone is added into 60mL of ethanol to form a uniform solution, which is solution B;
thirdly, dripping 20mL of the solution A into the solution B, and stirring for 0.5h to obtain a mixed solution;
finally, the above mixed solution was heated to 73 ℃ and heated to N 2 Refluxing for 3h under atmosphere, removing excessive solvent by rotary evaporation to obtain PtNPs, washing with anhydrous acetone and chloroform for three times respectively to collect final PtNPs, uniformly dispersing PtNPs in ethanol with concentration of 3mg/mL,obtaining a PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, dissolving 12mmol of cobalt sulfate heptahydrate in 120mL of ethanol to obtain a solution A;
secondly, dispersing 48mmol of 2-methylimidazole and 8.8mL of the PtNPs solution in 40mL of ethanol to obtain a solution B;
thirdly, dropwise adding the solution A into the solution B, stirring for 2 hours, and aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67;
S3、CoPt-Pt SA synthesis of/NDPCF: heating Pt/ZIF-67 to 900 ℃ at a heating rate of 2 ℃/min in an Ar atmosphere in a tubular furnace, and calcining for 2h to obtain CoPt-Pt SA /NDPCF。
7. An application of a platinum monoatomic synergetic cobalt-platinum alloy in electrocatalytic hydrogen evolution limited in nitrogen-doped porous carbon.
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