CN115125579B - Preparation method and application of platinum monoatomic synergistic cobalt-platinum alloy limited in nitrogen-doped porous carbon - Google Patents
Preparation method and application of platinum monoatomic synergistic cobalt-platinum alloy limited in nitrogen-doped porous carbon Download PDFInfo
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Abstract
The invention discloses a preparation method of platinum monoatoms and cobalt-platinum alloy limited in nitrogen doped porous carbon, which comprises the steps of preparing platinum monoatoms (Pt SA ) And cobalt-platinum alloy (CoPt) nanocrystals are confined in a Nitrogen Doped Porous Carbon Framework (NDPCF) derived from platinum nanoparticles (PtNPs) encapsulated in an amino-functionalized ZIF-67. Under alkaline and acidic conditions, coPt-Pt SA NDPCF exhibits excellent electrocatalytic hydrogen evolution performance, including lower overpotential, smaller Tafel slope, higher currentDensity, higher switching frequency and better cycling stability. CoPt-Pt SA The excellent electrocatalytic hydrogen evolution performance of/NDPCF is due to Pt protected by nitrogen doped porous carbon skeleton SA Strong synergy with CoPt alloy nanocrystals. The method not only improves the electrocatalytic hydrogen evolution activity of the catalyst, but also solves the problems of dissolution, corrosion, agglomeration and the like of single-atom materials and platinum alloy nanocrystals in the long-term circulation process, thereby fundamentally increasing the catalytic activity and long-term 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 platinum single-atom synergized cobalt-platinum alloy in nitrogen doped porous carbon.
Background
Single-atom catalysts (SAC) with ultra-high atom utilization and rich active sites can significantly improve the electrocatalytic performance of the catalyst, and are considered as potential candidate materials for most catalytic reactions. Currently, many studies are focused on improving the electrocatalytic activity of SAC by inhibiting agglomeration of Single Atoms (SA) during synthesis or electrocatalytic reaction. Recently, many studies have been reported to support SA on a support surface having specific coordination to explore electrocatalytic activity and cycle stability thereof. Although strong chemical bonds with the support can modulate the inherent catalytic properties of SA, SA tends to adversely affect its long-cycling performance due to its exposure to the support surface. Therefore, it is important to limit SA to the inside of the carrier and to improve the cycling stability of SAC. Metal Organic Frameworks (MOFs) have periodic pores and unique structures, are considered ideal carriers for achieving cycling stability for SA, and can be designed into various functional hybrid complexes depending on the choice of different types of coordinating metals. In addition, MOFs are also considered to be a new generation of ideal carriers for encapsulated Nanoparticles (NPs), and interactions with conventional porous materials NPs and MOFs can also promote proton and charge transfer. Derivatives of MOFs are also considered to be excellent carriers because their derivative porous carbons 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. Among the various metals of electrocatalytic Hydrogen Evolution (HER) catalysts, platinum (Pt) has its inherent ultra-low H-adsorption gibbs free energy (|Δg) H* 0.0071 eV) with low overpotential and fast kinetics, is the most effective active metal to improve HER performance. However, the high cost, ultra low availability and poor cycling stability of Pt metals severely limit their further large scale applications. Monoatomic Pt (Pt) SA ) The atomic utilization efficiency can be maximized, thereby reducing the 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 higher electrocatalytic activity and cycle durability on a variety of supports. However, such SA materials and Pt alloy nanocrystals still have problems of dissolution, corrosion and agglomeration during long-term cycling, resulting in rapid decline of catalytic activity and cycling durability. Current research does not detail the modulation of Pt by SA The surrounding environment adjusts the interrelation between the metal alloy and the SA.
Disclosure of Invention
The invention aims to provide a preparation method and application of platinum single-atom synergic cobalt-platinum alloy in nitrogen-doped porous carbon, which solve the problems of dissolution, corrosion and agglomeration of SA material and Pt alloy nanocrystals in a long-term circulation process and increase the electrocatalytic HER activity and circulation durability of the SA material and Pt alloy nanocrystals.
In order to achieve the above object, the present invention provides a preparation method of platinum monoatomic co-cobalt platinum alloy limited in nitrogen doped porous carbon, comprising the following steps:
s1, synthesis of PtNPs:
firstly, dissolving hexahydrated chloroplatinic acid powder in deionized water to form a uniform solution which is solution A;
secondly, polyvinylpyrrolidone is added into a solvent to form a uniform solution which is 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then respectively washing three times by using anhydrous acetone and chloroform to collect final PtNPs, uniformly dispersing the PtNPs in the solvent, and controlling the concentration to be 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, cobalt salt is dissolved in a solvent to obtain solution A;
secondly, dispersing the 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 aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying the purple precipitate 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 in different proportions to 500-900 ℃ in a tubular furnace at a heating rate of 2 ℃/min in Ar atmosphere, and calcining for 2h to obtain Co n Pt-Pt SA NDPCF, where n is 0.5 or 1 or 2.
Preferably, pt/ZIF-67 containing Co in different proportions is obtained by adjusting the content 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 Ar atmosphere purity in the step S3 is 99.999%.
Preferably, a method for preparing a platinum monoatomic synergistic cobalt platinum alloy limited in nitrogen doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of hexa-hydrated chloroplatinic acid powder in 20mL of deionized water to form a uniform solution, wherein the uniform solution is solution A;
next, 0.015mmol of polyvinylpyrrolidone was added to 60mL of ethanol to form a homogeneous solution as 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, and then respectively washing three times by using anhydrous acetone and chloroform to collect final PtNPs, wherein the PtNPs are uniformly dispersed in ethanol, and the concentration is controlled at 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
first, 12mmol of cobalt sulfate heptahydrate was dissolved in 120mL of ethanol to obtain solution a;
secondly, 48mmol of 2-methylimidazole and 8.8mL of PtNPs solution are dispersed 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 the purple precipitate 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 a tubular furnace in Ar atmosphere, and calcining for 2 hours to obtain CoPt-Pt SA /NDPCF。
The use of platinum monoatoms in combination with cobalt platinum alloys in the electrocatalytic hydrogen evolution is limited to nitrogen doped porous carbon.
Pt is combined with SA And cobalt-platinum (CoPt) alloy nanocrystals are confined to a nitrogen-doped porous carbon framework (CoPt-Pt) SA NDPCF), the frameDerived from PtNPs encapsulated in amino-functionalized ZIF-67. CoPt-Pt under basic and acidic conditions compared to commercial 10% Pt/C catalysts SA NDPCF all exhibit 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 due to Pt SA Strong synergy with CoPt alloy nanocrystals protected by Nitrogen Doped Porous Carbon Frameworks (NDPCFs). Theoretical calculation of Density functional shows Pt SA Has ultra-low |ΔG in combination with CoPt alloy nanocrystals in NDPCF H* I (-0.059 eV), which is a key factor in enhancing the kinetics of the reaction 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 efficient SACs.
Therefore, the preparation method and the application of the platinum single-atom synergistic cobalt-platinum alloy in the nitrogen-doped porous carbon are adopted, so that the problems of dissolution, corrosion and agglomeration of SA materials and Pt alloy nanocrystals in a long-term circulation process are solved, and the electrocatalytic HER activity and circulation durability are improved.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a CoPt-Pt diagram SA Synthetic schematic of NDPCF;
FIG. 2 is a CoPt-Pt diagram SA TEM pictures of NDPCF;
FIG. 3 is a CoPt-Pt diagram SA EDX element distribution map of NDPCF;
FIG. 4 is a CoPt-Pt diagram SA HAADF-STEM diagram of NDPCF;
FIG. 5 is an XRD pattern of Pt-ZIF-67 over different sintering temperatures;
FIG. 6 is a CoPt-Pt diagram SA NDPCF (non-linear transformation) generates EXAFS and a corresponding fitting curve in the R space of the Co K-side;
FIG. 7 is a CoPt-Pt diagram SA NDPCF at Pt L 3 -EXAFS and corresponding fitted curves in the R space of the edges;
FIG. 8 is Co/NDPCF and CoPt-Pt SA N of NDPCF 2 Adsorption-desorption isotherms;
FIG. 9 is a CoPt-Pt diagram SA Polarization curves of NDPCF and other catalysts in 1M KOH solution;
FIG. 10 is a commercial 10% Pt/C and 5% Pt/C catalyst, coPt-Pt SA Activity per mass Pt of NDPCF catalyst;
FIG. 11 is a CoPt-Pt diagram SA NDPCF catalyst with current density of-10 mA cm -2 And-50 mA cm -2 I-t cycle performance under conditions;
FIG. 12 shows the acidity of the various catalysts (0.5 MH 2 SO 4 ) An iR compensated Linear Sweep Voltammetric (LSV) curve under conditions;
FIG. 13 is a CoPt-Pt diagram SA Activity pattern per unit mass Pt of NDPCF catalyst under 0.5M acidic conditions.
Detailed Description
The invention provides a preparation method of platinum monoatomic synergetic cobalt-platinum alloy limited in nitrogen-doped porous carbon, which comprises the following steps:
s1, synthesis of PtNPs:
firstly, cobalt salt is dissolved in deionized water to form a uniform solution which is solution A;
secondly, polyvinylpyrrolidone is added into a solvent to form a uniform solution which is 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, and then washing with anhydrous acetone and chloroform three times respectively to collect final PtNPs, uniformly dispersing in the solvent, wherein the concentration is controlled at 3mg/mL, thus obtaining PtNPs solution.
S2, synthesis of Pt/ZIF-67:
firstly, cobalt salt is dissolved in a solvent to obtain solution A;
secondly, dispersing the 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 aging for 24 hours to obtain a purple precipitate;
finally, washing the obtained purple precipitate with methanol for 3 times, and drying the purple precipitate in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt/ZIF-67; by adjusting the content of cobalt salt and PtNPs, pt/ZIF-67 containing Co in different proportions is obtained.
S3、Co n Pt-Pt SA Synthesis of NDPCF: heating Pt/ZIF-67 containing Co at different proportions to 500-900 ℃ in a tubular furnace at a heating rate of 2 ℃/min in Ar atmosphere (purity is 99.999%), calcining for 2h to obtain Co n Pt-Pt SA NDPCF, where n is 0.5 or 1 or 2.
The cobalt salt used was 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 described below through the attached drawings and the embodiments.
Example 1
As shown in fig. 1, a preparation method of platinum monoatomic co-cobalt platinum alloy limited in nitrogen doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of hexa-hydrated chloroplatinic acid powder in 20mL of deionized water to form a uniform solution, wherein the uniform solution is solution A;
next, 0.015mmol of polyvinylpyrrolidone was added to 60mL of ethanol to form a homogeneous solution as 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then respectively washing three times by using anhydrous acetone and chloroform to collect final PtNPs, uniformly dispersing the final PtNPs in ethanol, and controlling the concentration to be 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
first, 12mmol of cobalt sulfate heptahydrate was dissolved in 120mL of ethanol to obtain solution a;
secondly, 48mmol of 2-methylimidazole and 8.8mL of PtNPs solution are dispersed 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 the purple precipitate 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 a tubular furnace in Ar atmosphere, and calcining for 2 hours to obtain CoPt-Pt SA /NDPCF。
Example 2
As shown in fig. 1, a preparation method of platinum monoatomic co-cobalt platinum alloy limited in nitrogen doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of hexa-hydrated chloroplatinic acid powder in 20mL of deionized water to form a uniform solution, wherein the uniform solution is solution A;
next, 0.015mmol of polyvinylpyrrolidone was added to 60mL of ethanol to form a homogeneous solution as 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then respectively washing three times by using anhydrous acetone and chloroform to collect final PtNPs, uniformly dispersing the final PtNPs in ethanol, and controlling the concentration to be 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
first, 12mmol of cobalt sulfate heptahydrate was dissolved in 120mL of ethanol to obtain solution a;
secondly, 48mmol of 2-methylimidazole and 8.8mL of PtNPs solution are dispersed 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 the purple precipitate 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 a tubular furnace in Ar atmosphere, and calcining for 2 hours to obtain CoPt-Pt SA /NDPCF。
Example 3
As shown in fig. 1, a preparation method of platinum monoatomic co-cobalt platinum alloy limited in nitrogen doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of hexa-hydrated chloroplatinic acid powder in 20mL of deionized water to form a uniform solution, wherein the uniform solution is solution A;
next, 0.015mmol of polyvinylpyrrolidone was added to 60mL of ethanol to form a homogeneous solution as 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, then respectively washing three times by using anhydrous acetone and chloroform to collect final PtNPs, uniformly dispersing the final PtNPs in ethanol, and controlling the concentration to be 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
first, 12mmol of cobalt sulfate heptahydrate was dissolved in 120mL of ethanol to obtain solution a;
secondly, 48mmol of 2-methylimidazole and 8.8mL of PtNPs solution are dispersed 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 the purple precipitate 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 heated in a tube furnace at 2 in Ar atmosphereHeating to 900 ℃ at the heating rate of DEG C/min, and calcining for 2h to obtain CoPt-Pt SA /NDPCF。
Example 4
As shown in fig. 1, a preparation method of platinum monoatomic co-cobalt platinum alloy limited in nitrogen doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of hexa-hydrated chloroplatinic acid powder in 20mL of deionized water to form a uniform solution, wherein the uniform solution is solution A;
next, 0.015mmol of polyvinylpyrrolidone was added to 60mL of ethanol to form a homogeneous solution as 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, and then respectively washing three times by using anhydrous acetone and chloroform to collect final PtNPs, uniformly dispersing the final PtNPs in ethanol, and controlling the concentration to be 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
first, 0.5M cobalt sulfate heptahydrate was dissolved in 120mL ethanol to be solution a;
secondly, 48mmol of 2-methylimidazole and 10mL of PtNPs solution are dispersed 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 the purple precipitate 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 ℃ in a tubular furnace at a heating rate of 2 ℃/min in Ar atmosphere, and calcining for 2 hours to obtain Co 0.5 Pt-Pt SA /NDPCF。
Example 5
As shown in fig. 1, a preparation method of platinum monoatomic co-cobalt platinum alloy limited in nitrogen doped porous carbon comprises the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of hexa-hydrated chloroplatinic acid powder in 20mL of deionized water to form a uniform solution, wherein the uniform solution is solution A;
next, 0.015mmol of polyvinylpyrrolidone was added to 60mL of ethanol to form a homogeneous solution as 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, and then respectively washing three times by using anhydrous acetone and chloroform to collect final PtNPs, uniformly dispersing the final PtNPs in ethanol, and controlling the concentration to be 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
firstly, 2M cobalt sulfate heptahydrate is dissolved in 120mL of ethanol to obtain solution A;
secondly, 48mmol of 2-methylimidazole and 15mL of PtNPs solution are dispersed 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 the purple precipitate 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 ℃ in a tubular furnace at a heating rate of 2 ℃/min in Ar atmosphere, and calcining for 2 hours to obtain Co 2 Pt-Pt SA /NDPCF。
FIG. 1 is a CoPt-Pt diagram SA Schematic diagram of NDPCF synthesis process.
Comparative example 1
10% Pt/C catalyst was commercialized.
Comparative example 2
A 5% pt/C catalyst was commercialized.
The CoPt-PtSA/NDPCF was characterized as follows:
TEM image of FIG. 2 shows CoPt-Pt SA NDPCF has a typical regular dodecahedron structure, a diameter of about 700nm, and is sintered at high temperature to form CoPt-Pt SA The NDPCF structure does not collapse.
FIG. 3 shows that energy dispersive X-ray spectroscopy (EDX) elemental mapping indicates 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 Wherein Pt is supported on CoPt-Pt in two forms SA On the surface of the NDPCF, one is to form a CoPt alloy with Co, as shown in fig. 4a. In addition, pt is also supported on the surface of the carrier in the form of monoatoms, as shown in FIG. 4c
FIG. 5 is an XRD pattern showing that Pt-ZIF-67 has no significant carbonization for 2 hours at 500 ℃. In addition, a small amount of Co was formed at 500℃ 3 O 4 (PDF # 43-1003), which further demonstrates that Pt-ZIF-67 is not fully carbonized at 500℃for 2 h. As the sintering temperature is gradually increased to 750 ℃ and 900 ℃, the carbon (C) and Co peaks of the composite material are significantly increased. Due to 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 CoPt-Pt SA R space of NDPCF and corresponding fitted extended X-ray absorption fine structure spectrum curve, in
There is a peak from the Co-Co cluster. Furthermore, the->
And->
The small peaks at these correspond to Co-N and Co-Pt, respectively, which further confirm that Co coordinates with N and Pt.
FIG. 7 CoPt-Pt SA Extended X-ray absorption fine structure spectrum curve of NDPCF confirms Pt SA At the position of
Is coordinated to about 2N atoms at a distance. At->
It is shown here that it forms alloy nanocrystals mainly with Co.
FIG. 8 is a Co/NDPCF and CoPt-Pt SA N of NDPCF 2 Adsorption-desorption isotherms showed specific surface areas of 297.72 and 254.04m, respectively 2 /g。
FIG. 9 is an iR compensated Linear Sweep Voltammetry (LSV) curve for different catalysts under alkaline (1 MKOH) conditions. The results indicate that the catalyst, coPt-Pt SA NDPCF at a current density of-10 mA cm -2 Exhibits the highest HER activity, with overpotential as low as 31mV, much lower than pure Co/NDPCF (309 mV), approaching commercial 10% Pt/C (38 mV), compared to Reversible Hydrogen Electrode (RHE). Due to Co content to Pt SA The distribution of (2) has a great influence, and we have focused on the influence of Co content on the electrocatalytic HER activity of the composite material. Co (Co) 0.25 Pt-Pt SA NDPCF and Co 2 Pt-Pt SA The overpotential of the/NDPCF was 47 and 38mV, respectively, indicating that the Co content had a significant effect on HER activity. The main reason is Co 0.25 Pt-Pt SA The Co content in the/NDPCF composite is too low to form the active sites of the CoPt alloy. When Co is 2 Pt-Pt SA When the Co content in the NDPCF is too high, the Co occupies too many sites, which is unfavorable for Pt SA Is uniformly dispersed. Furthermore, coPt-Pt SA The current density of the NDPCF in 1M KOH reaches 1000mA cm at 474mV -2 Far better than the current density of 10% pt/C.
FIG. 10 is a CoPt-Pt diagram SA The activity of the NDPCF catalyst per unit mass Pt under the alkaline condition of 1MKOH is as high as 19.3A mg -1 Pt was further verified at 33.9 and 77.2 times (test conditions: overpotential η=50 mV) for commercial 10% Pt/C and 5% Pt/C catalysts, respectively SA And CoPt alloys limited to CoPt-Pt SA The electrocatalytic HER activity of the material can be enhanced in the NDPCF structure.
FIG. 11 is a CoPt-Pt diagram SA NDPCF catalyst with current density of-10 mA cm -2 And-50 mA cm -2 I-t cycle performance under conditions. The results indicate CoPt-Pt SA NDPCF at-10 mA cm -2 The current is not basically attenuated after 100h of circulation under the current density. And at-50 mA cm -2 Can be stabilized for 50 hours under the condition of high current, and shows excellent cycle stability.
FIG. 12 shows the acidity of the various catalysts (0.5 MH 2 SO 4 ) An iR compensated Linear Sweep Voltammetric (LSV) curve under conditions. The results indicate CoPt-Pt SA NDPCF at a current density of-10 mA cm -2 Exhibits the highest HER activity, with overpotential as low as 20mV, much lower than pure Co/NDPCF (285 mV), better than commercial 10% Pt/C (37 mV) compared to Reversible Hydrogen Electrode (RHE). Due to Co content to Pt SA The distribution of (2) has a great influence, and we have focused on the influence of Co content on the electrocatalytic HER activity of the composite material. Co (Co) 0.25 Pt-Pt SA NDPCF and Co 2 Pt-Pt SA The overpotential of the/NDPCF was 32 and 27mV, respectively, indicating that the Co content had a significant effect on HER activity. Furthermore, coPt-Pt SA NDPCF at 0.5M H 2 SO 4 The current density in (a) reaches-1000 mA cm at 258mV -2 Far better than the current density of 10% pt/C.
FIG. 13 is a CoPt-Pt diagram SA The activity of the NDPCF catalyst per unit mass Pt under the acidic condition of 0.5M is up to 74.31A mg -1 Pt was further verified by 130.3 and 285.8 times (test conditions: overpotential η=50 mV) for commercial 10% Pt/C and 5% Pt/C catalysts, respectively SA And CoPt alloys limited to CoPt-Pt SA The electro-catalytic hydrogen evolution activity of the material can be enhanced in the NDPCF structure.
Therefore, compared with a commercial 10% Pt/C catalyst, the preparation method and application of the platinum single-atom synergistic cobalt-platinum alloy in nitrogen-doped porous carbon have excellent alkaline and acidic electrocatalytic HER reaction activity, 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 circulation durability of the SA materials and Pt alloy nanocrystals.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (6)
1. A method for preparing a platinum monoatomic co-cobalt platinum alloy limited in nitrogen-doped porous carbon, comprising the steps of:
s1, synthesis of PtNPs:
firstly, dissolving hexahydrated chloroplatinic acid powder in deionized water to form a uniform solution which is solution A;
secondly, polyvinylpyrrolidone is added into a solvent to form a uniform solution which is 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method, then respectively washing with anhydrous acetone and chloroform for three times to collect final PtNPs, uniformly dispersing in the solvent, and controlling the concentration at 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
first, 12mmol of cobalt salt was dissolved in 120mL of solvent to be solution a;
secondly, 48mmol of 2-methylimidazole and 8.8mL of PtNPs solution are dispersed in 40mL of solvent 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 the purple precipitate 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 750-900 ℃ in a tube furnace at a heating rate of 2 ℃/min in Ar atmosphere, and calcining for 2 hours to obtain CoPt-Pt SA /NDPCF。
2. The method for preparing the platinum monoatomic synergistic cobalt-platinum alloy limited in the nitrogen-doped porous carbon according to claim 1, wherein the method comprises the following steps: the cobalt salt is one of cobalt sulfate heptahydrate, cobalt nitrate hexahydrate and cobalt chloride hexahydrate.
3. The method for preparing the platinum monoatomic synergistic cobalt-platinum alloy limited in the nitrogen-doped porous carbon according to claim 2, wherein the method comprises the following steps: the solvent is one of methanol, ethanol, acetone and water.
4. A method of preparing a platinum monoatomic co-cobalt platinum alloy limited to nitrogen doped porous carbon according to claim 3, wherein: the Ar atmosphere purity in the step S3 was 99.999%.
5. The method for preparing the platinum monoatomic synergistic cobalt platinum alloy limited in the nitrogen doped porous carbon according to claim 4, comprising the following steps:
s1, synthesis of PtNPs:
firstly, dissolving 0.120mmol of hexa-hydrated chloroplatinic acid powder in 20mL of deionized water to form a uniform solution, wherein the uniform solution is solution A;
next, 0.015mmol of polyvinylpyrrolidone was added to 60mL of ethanol to form a homogeneous solution as 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 mixed solution is heated to 73 ℃ and is subjected to N 2 Refluxing for 3 hours under the atmosphere, removing redundant solvent by a rotary evaporation method to obtain PtNPs, and then respectively washing three times by using anhydrous acetone and chloroform to collect final PtNPs, wherein the PtNPs are uniformly dispersed in ethanol, and the concentration is controlled at 3mg/mL to obtain PtNPs solution;
s2, synthesis of Pt/ZIF-67:
first, 12mmol of cobalt sulfate heptahydrate was dissolved in 120mL of ethanol to obtain solution a;
secondly, 48mmol of 2-methylimidazole and 8.8mL of PtNPs solution are dispersed 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 the purple precipitate 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 a tubular furnace in Ar atmosphere, and calcining for 2 hours to obtain CoPt-Pt SA /NDPCF。
6. Use of a platinum monoatomic co-cobalt platinum alloy prepared by the method of any one of claims 1 to 5 for limiting electrocatalytic hydrogen evolution in nitrogen doped porous carbon.
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