CN115259297B - Electrocatalytic hydrogen evolution catalyst and preparation method and application thereof - Google Patents
Electrocatalytic hydrogen evolution catalyst and preparation method and application thereof Download PDFInfo
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Abstract
An electrocatalytic hydrogen evolution catalyst and a preparation method and application thereof belong to the technical field of electrocatalytic. The catalyst comprises a porous carbon matrix and platinum group metals which are electrolessly deposited on the porous carbon matrix, wherein a precursor of the porous carbon matrix is cross-linked polyphosphazene, the cross-linked polyphosphazene is formed by polymerizing monomers hexachlorocyclotriphosphazene, 4' -sulfonyl diphenol and tannic acid, and the platinum group metals are a mixture of rhodium and palladium. The preparation method of the catalyst avoids the problem of high energy consumption of the traditional atomic vapor deposition, solvothermal reduction, electrodeposition reduction and other methods, can greatly reduce the cost of the catalyst, and simultaneously ensures that the electrocatalytic hydrogen evolution catalyst has good electrocatalytic activity in both acidic and alkaline environments by adopting the mixture of Rh and Pd as the active site of the catalyst.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to an electrocatalysis hydrogen evolution catalyst, a preparation method thereof and application thereof in an electrochemical circulating water treatment device.
Background
In recent years, the urban phenomenon is aggravated, and a great amount of domestic wastewater and industrial wastewater which are accompanied with the urban sewage treatment device provide challenges for the original water purification process. In industry, the discharge amount of industrial wastewater is reduced by adopting a circulating water mode, so that a stable and sustainable industrial circulating water treatment mode is needed to stabilize the quality of circulating water. The existing circulating water treatment process mostly adopts modes of adding medicines and the like to soften water, has high cost, and can greatly increase the content of metal ions in the water to bring secondary pollution. At present, the circulating water treatment process of electrochemical treatment is mainly developed to greatly reduce the treatment cost of industrial circulating water, and the method has the characteristics of high controllability, strong treatment capacity and thorough treatment effect.
In the electrochemical circulating water treatment device, water treatment is mainly carried out through oxidation-reduction reactions respectively occurring at two ends of an anode and a cathode. Oxygen evolution reactions mainly take place at the anode, and a number of catalysts such as IrO have been developed 2 Etc. for accelerating the progress of the anodic reaction. At present, development and application of an electrocatalytic hydrogen evolution catalyst with a high-activity cathode are more remarkable, the existing commercial Pt/C catalyst has high price due to the fact that the content of Pt element is up to 20wt percent, the preparation process is complex, the catalytic stability is obviously insufficient, and obvious performance attenuation can occur in the test of constant current and constant voltage.
Therefore, there is a need for a catalyst that is inexpensive and has good catalytic activity and catalytic stability in both acidic and basic media.
Disclosure of Invention
Object of the invention
The invention aims to provide a catalyst, a preparation method and application thereof in an electrochemical circulating water treatment device, the preparation method of the catalyst avoids the problem of high energy consumption of the traditional methods such as atomic vapor deposition, solvothermal reduction, electrodeposition reduction and the like, the cost of the catalyst can be greatly reduced, and meanwhile, the mixture of Rh and Pd is adopted as an active site of the catalyst, so that the electrocatalytic hydrogen evolution catalyst is ensured to have good electrocatalytic activity and catalytic stability in acidic and alkaline environments.
(II) technical scheme
In order to achieve the above object, in one aspect, the present invention provides an electrocatalytic hydrogen evolution catalyst, comprising a porous carbon substrate and a platinum group metal electroless deposited on the porous carbon substrate, wherein a precursor of the porous carbon substrate is a cross-linked polyphosphazene polymerized from monomers hexachlorocyclotriphosphazene, 4' -sulfonyl diphenol and tannic acid, and the platinum group metal is a mixture of rhodium and palladium.
Specifically, the mass content of rhodium in the catalyst is x, the mass content of palladium in the catalyst is y, x is more than or equal to 1.0wt% and less than or equal to 3.0wt%, y is more than or equal to 1.0wt% and less than or equal to 3.0wt%, wherein the mass of the catalyst is calculated by the mass of the porous carbon matrix, and the mass of the platinum group metal is calculated by the mass of the metal element.
In another aspect, the invention provides a method for preparing an electrocatalytic hydrogen evolution catalyst, comprising the following steps:
step 1: reacting a mixed solution containing an acid binding agent, tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol, centrifuging and drying to obtain cross-linked polyphosphazene;
step 2: crushing and carbonizing the obtained cross-linked polyphosphazene to obtain a porous carbon matrix, wherein the carbonization temperature is more than or equal to 950 ℃;
step 3: and (3) reacting, washing and drying an aqueous solution containing a porous carbon matrix, rhodium salt and palladium salt to obtain the electrocatalytic hydrogen evolution catalyst, wherein the reaction time is more than or equal to 8 hours.
Specifically, in the mixed solution in step 1:
the mass ratio of tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol is 0.8-1.4: 1:1, a step of;
the acid binding agent is at least one of triethylamine, pyridine and diisopropylethylamine;
the mass ratio of the acid binding agent to the tannic acid is 20-30: 1.
specifically, the solvent in the mixed solution in the step 1 is at least one selected from acetonitrile, acetone and ultrapure water;
the mass ratio of the solvent to the tannic acid is 150-300: 1.
specifically, specific conditions for carbonizing the cross-linked polyphosphazene in step 2 include:
under an inert atmosphere;
the carbonization temperature is 950-1100 ℃;
the carbonization time is 2-3 h.
Specifically, the heating rate during carbonization is 2-8 ℃/min.
Specifically, in step 3:
the rhodium salt is selected from RhCl 3 、Rh(NO 3 ) 3 、Rh 2 (SO 4 ) 3 At least one of (a) and (b);
the palladium salt is selected from Pd (OAc) 2 、PdCl 2 、Pd(NO 3 ) 2 At least one of (a) and (b);
the mass ratio of the rhodium salt to the palladium salt to the porous carbon matrix is 1:0.5 to 1.2:6 to 10.
Specifically, the specific conditions for the reaction described in step 3 include:
is carried out at room temperature under stirring;
the reaction time is 10-12 h.
The invention provides an electrocatalytic hydrogen evolution catalyst and application of any one of the electrocatalytic hydrogen evolution catalysts prepared by the preparation method in electrochemical circulating water treatment equipment.
(III) beneficial effects
The technical scheme of the invention has the following beneficial technical effects:
the embodiment of the invention providesAccording to the preparation method of the catalyst, cross-linked polyphosphazene PSTA is adopted as a precursor to obtain a porous carbon matrix NPSC, elements such as N, P, S introduced by polymerized monomer tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol are largely removed at a high temperature of more than or equal to 950 ℃ in the carbonization process of the precursor, the surface potential of the porous carbon matrix is reduced due to the massive volatilization of light components, the potential difference is formed between the low surface potential of the porous carbon matrix and metal ions, and Rh can be spontaneously generated at room temperature 3+ And Pd (Pd) 2+ The ionic reduction is carried out to Rh and Pd nano particles, so that the problem of high energy consumption of the traditional atomic vapor deposition, solvothermal reduction, electrodeposition reduction and other methods is avoided, the cost of the catalyst can be greatly reduced, and meanwhile, the problem of poor activity of Rh and Pd in an acidic medium and an alkaline medium respectively is solved by adopting a mixture of Rh and Pd as a catalytic active center; in addition, the inventor discovers that the mutual doping of Rh and Pd elements in the process of realizing the invention shows better catalytic activity and catalytic stability than those of single metal element in acidic and alkaline media, and ensures that the electrocatalytic hydrogen evolution catalyst has good electrocatalytic activity and catalytic stability in acidic and alkaline environments.
The noble metal content in the catalyst provided by the embodiment of the invention is less than or equal to 3.0wt%, which is reduced by more than 14wt% compared with the current commercial Pt/C catalyst, and the use amount of noble metal in the catalyst is greatly reduced, so that the catalyst cost is further reduced; meanwhile, when the catalyst is used in an electrocatalytic hydrogen evolution process, the catalyst can simultaneously ensure high catalytic activity in alkaline and acidic media and has good universality; compared with the commercial Pt/C catalyst, the catalyst has greatly improved catalytic stability (about 63% for 24h stability in alkaline medium and about 74% for 24h stability in acid medium).
Drawings
FIG. 1 is a scanning electron micrograph of a Precursor (PSTA) of a porous carbon matrix of the catalyst provided in example 1 of the present invention;
FIG. 2 is a single batch mass weighing plot of the precursor cross-linked polyphosphazenes for porous carbon substrates provided in example 1 and comparative example 4 of the present invention, where a is the PSTA single batch yield result in example 1 and b is the single batch yield result provided in comparative example 4;
FIG. 3 is a scanning electron micrograph of a porous carbon substrate (NPSC) provided in example 1 of this invention, wherein a is a NPSC topography at 300nm scale and b is a NPSC topography at 5.00um scale;
FIG. 4 is a graph of ultraviolet electron energy spectrum of porous carbon substrate (NPSC) provided in example 1 and comparative example 5, wherein a is the secondary electron cutoff result of NPSC in ultraviolet electron test in comparative example 5, b is the Fermi side result of NPSC in ultraviolet electron test in comparative example 5, c is the secondary electron cutoff result of NPSC in ultraviolet electron test in example 1, and d is the Fermi side result of NPSC in ultraviolet electron test in example 1;
FIG. 5 is an ultraviolet electron energy spectrum of a porous carbon substrate (NPSC) provided in comparative example 4, wherein a is a secondary electron cutoff edge result of NPSC in ultraviolet electron test in comparative example 4, and b is a Fermi edge result of NPSC in ultraviolet electron test in comparative example 4;
FIG. 6 is a transmission electron micrograph (RhPd/NPSC) of the catalyst provided in example 1 and the elemental distribution, wherein a is the RhPd/NPSC catalyst observed in the high angle annular dark field scanning transmission mode, b is the elemental distribution of carbon (C), C is the elemental distribution of rhodium (Rh), and d is the elemental distribution of palladium (Pd);
FIG. 7 is an X-ray photoelectron spectrum of a catalyst (RhPd/NPSC) provided in example 1 of the present invention, wherein a is a high resolution spectrum of the 3d track of Rh element in the RhPd/NPSC catalyst, and b is a high resolution spectrum of the 3d track of Pd element in the RhPd/NPSC catalyst;
FIG. 8 is an electrocatalytic hydrogen LSV graph of the catalysts provided in example 1, comparative example 2 and commercial Pt/C catalysts in alkaline environment;
FIG. 9 is an electrocatalytic hydrogen LSV graph of the catalysts provided in example 1, comparative example 2 and commercial Pt/C catalysts in an acidic environment;
FIG. 10 is a graph showing the constant current density stability test of the catalyst provided in example 1 and a commercially available Pt/C catalyst under alkaline conditions;
FIG. 11 is a graph showing the constant current density stability test of the catalyst provided in example 1 and a commercially available Pt/C catalyst under acidic conditions;
FIG. 12 is a graph of the electrocatalytic hydrogen LSV of the catalyst provided in example 1, comparative example 5 and a commercially available Pt/C catalyst in an alkaline environment;
FIG. 13 is a graph of the electrocatalytic hydrogen LSV of the catalyst provided in example 1, comparative example 5 and a commercially available Pt/C catalyst in an acidic environment;
FIG. 14 is an electrocatalytic hydrogen LSV graph of the catalysts provided in example 1, comparative example 6, comparative example 7 and commercially available Pt/C catalysts in alkaline environments;
FIG. 15 is an electrocatalytic hydrogen LSV graph of the catalysts provided in example 1, comparative example 6, comparative example 7 and commercial Pt/C catalysts in an acidic environment;
FIG. 16 is a graph of the electrocatalytic hydrogen LSV of the catalyst provided in example 1, comparative example 3 and a commercially available Pt/C catalyst in an alkaline environment;
FIG. 17 is a graph of the electrocatalytic hydrogen LSV of the catalyst provided in example 1, comparative example 3 and a commercially available Pt/C catalyst in an acidic environment;
FIG. 18 is a graph showing the electrocatalytic hydrogen evolution LSV of the catalyst provided in example 1 before and after accelerated durability testing (10000 cycle voltammetry) under alkaline conditions;
FIG. 19 is a graph showing the LSV of electrocatalytic hydrogen evolution of the catalyst provided in example 1 before and after accelerated durability test (10000 cycle voltammetry) under acidic conditions;
FIG. 20 is a graph of the electrocatalytic hydrogen evolution LSV of the catalyst provided in comparative example 3 before and after accelerated durability testing (10000 cycle voltammetry) under alkaline conditions;
fig. 21 is a graph of the electrocatalytic hydrogen evolution LSV of the catalyst provided in comparative example 3 before and after accelerated durability test (10000 cyclic voltammetry test) under acidic conditions.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings and examples.
The embodiment of the invention provides a preparation method of an electrocatalytic hydrogen evolution catalyst, which comprises the following steps:
step 1: reacting a mixed solution containing an acid binding agent, tannic acid, hexachlorocyclotriphosphazene and 4,4 '-sulfonyl diphenol, centrifuging and drying to obtain cross-linked polyphosphazene PSTA (cross-linked poly HCCP-BPS-TA phosphazene), wherein HCCP is hexachlorocyclotriphosphazene, BPS is 4,4' -sulfonyl diphenol, and TA is tannic acid;
step 2: crushing and carbonizing the obtained cross-linked polyphosphazene PSTA to obtain a porous carbon matrix, wherein the carbonization temperature is more than or equal to 950 ℃;
step 3: and (3) reacting, washing and drying an aqueous solution containing a porous carbon matrix, rhodium salt and palladium salt to obtain the electrocatalytic hydrogen evolution catalyst, wherein the reaction time is more than or equal to 8 hours.
According to the preparation method of the catalyst provided by the embodiment of the invention, the cross-linked polyphosphazene PSTA is used as the precursor to obtain the porous carbon matrix NPSC, and the precursor volatilizes a large amount of light components in the carbonization process, so that the surface potential of the porous carbon matrix is reduced, the potential difference is formed between the low surface potential of the porous carbon matrix and metal ions, and Rh can be spontaneously reacted at room temperature 3+ And Pd (Pd) 2+ The ionic reduction is carried out to Rh and Pd nano particles, so that the problem of high energy consumption of the traditional atomic vapor deposition, solvothermal reduction, electrodeposition reduction and other methods is avoided, the cost of the catalyst can be greatly reduced, and meanwhile, the problem of poor activity of Rh and Pd in an acidic medium and an alkaline medium respectively is solved by adopting a mixture of Rh and Pd as active sites of the catalyst; in addition, the inventor discovers that the mutual doping of Rh and Pd elements in the process of realizing the invention shows better catalytic activity and catalytic stability than those of single metal elements in acidic and alkaline media, and ensures that the electrocatalytic hydrogen evolution catalyst has good electrocatalytic activity in acidic and alkaline environments.
The mass ratio of tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol in the mixed solution is 0.8-1.4: 1:1, a step of;
the acid binding agent is at least one of triethylamine, pyridine and diisopropylethylamine;
the mass ratio of the acid binding agent to the tannic acid is 20-30: 1, a step of;
the solvent in the mixed solution is at least one selected from acetonitrile, acetone and ultrapure water;
the mass ratio of the solvent to the tannic acid is 150-300: 1.
in an alternative embodiment, the reacting a mixed solution containing an acid binding agent, tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol specifically comprises:
dissolving tannic acid in part of solvent to obtain mixed solution I;
dissolving an acid binding agent in the mixed solution I to obtain a mixed solution II;
dissolving hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol in another part of solvent to obtain a mixed solution III;
under the ultrasonic condition, dropwise adding the mixed solution III into the mixed solution II to obtain a mixed solution containing an acid binding agent, tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol, wherein the dropwise adding time is 10-120 min;
after the dripping is finished, stirring and reacting for 2-6 hours at 25-45 ℃, and then reacting for 0.5-1.5 hours under the condition that the ultrasonic power is 20-160 w.
Specific conditions for the centrifugation include: the rotating speed is 500-1500 rpm, and the centrifugation time is 6-20 min;
the specific conditions for the drying include: the drying is carried out under the vacuum condition, the drying temperature is 30-60 ℃ and the drying time is 6-24 h.
In the step 2, the precursor is crushed in a grinding mode to obtain powdery precursor cross-linked polyphosphazene PSTA, and specific conditions for carbonizing the crushed cross-linked polyphosphazene PSTA include:
the method is carried out under an inactive atmosphere, wherein the inactive atmosphere comprises an inactive gas atmosphere such as nitrogen, argon and the like;
the carbonization temperature is 950-1100 ℃, preferably 1000 ℃ to ensure that a carrier with a negative surface potential is obtained and that the deposition reaction is effectively carried out;
the carbonization time is 2-3 h.
Further, the heating rate during carbonization is 2-8 ℃/min.
Specifically, in step 3:
the rhodium salt is selected from RhCl 3 、Rh(NO 3 ) 3 、Rh 2 (SO 4 ) 3 At least one of (a) and (b);
the palladium salt is selected from Pd (OAc) 2 、PdCl 2 、Pd(NO 3 ) 2 At least one of (a) and (b);
the mass ratio of the rhodium salt to the palladium salt to the porous carbon matrix is 1:0.5 to 1.2:6 to 10.
Specifically, the specific conditions for the reaction described in step 3 include:
the method is carried out under the conditions of room temperature and stirring, wherein the room temperature is 15-35 ℃, and the stirring speed is 500-1500 rpm;
the reaction time is optionally 8 to 12 hours, preferably 10 to 12 hours.
In an alternative embodiment, a porous carbon-based electrocatalytic material (RhPd/NPSC) loaded with Rh, pd nanoparticles prepared based on an electroless deposition method, comprising the steps of:
and (1) dissolving a certain amount of tannic acid and triethylamine in acetonitrile, and placing in an oil bath atmosphere at 35 ℃ and fully stirring until the tannic acid and the triethylamine are fully dissolved.
And (2) dissolving a certain amount of hexachlorocyclotriphosphazene and 4,4 '-sulfonyl diphenol in acetonitrile, uniformly mixing with an acetonitrile solution containing tannic acid and triethylamine after the hexachlorocyclotriphosphazene and the 4,4' -sulfonyl diphenol are uniformly dissolved, centrifuging, drying to obtain polymer cross-linked polyphosphazene PSTA, and carbonizing to obtain the porous carbon NPSC of the substrate.
And (3) fully mixing porous carbon with an aqueous solution containing rhodium salt and palladium salt, fully stirring for 12 hours at room temperature, and carrying out suction filtration, deionized water washing and freeze drying to obtain the high-activity hydrogen evolution catalyst (RhPd/NPSC) for acid and alkali medium.
Further, in the step (1), the mass ratio of tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol is 1.2:1:1.
in the step (2), inert gas is used as protective gas in the carbonization process, the protective gas is firstly introduced for 0.5 to 1 hour, then the temperature is raised to 800 to 1000 ℃ at the speed of 2 to 8.0 ℃/min, and the temperature is naturally cooled to the room temperature after the temperature is kept for 2 to 3 hours. Preferably, the temperature rising rate is set to be 5.0 ℃/min, the temperature is raised to 1000 ℃, and the temperature is kept for 2 hours.
The rhodium salt and the palladium salt in the step (3) are RhCl 3 The palladium salt was Pd (OAc) 2 The mass ratio of the metal salt to the porous carbon is 1:1:10.
in another embodiment, the invention provides an electrocatalytic hydrogen evolution catalyst, which comprises a porous carbon matrix and platinum group metals deposited on the porous carbon matrix in an electroless manner, wherein a precursor of the porous carbon matrix is cross-linked polyphosphazene PSTA (HCCP-BPS-TA phosphazene, HCCP is hexachlorocyclotriphosphazene, BPS is 4,4 '-sulfonyl diphenol, TA is tannic acid), the cross-linked polyphosphazene PSTA is polymerized by monomer hexachlorocyclotriphosphazene, 4' -sulfonyl diphenol and tannic acid, and the platinum group metals are mixtures of rhodium and palladium.
The noble metal content in the catalyst provided by the embodiment of the invention is less than or equal to 3.0wt%, and is reduced by 14wt% compared with the current commercial Pt/C catalyst, so that the consumption of noble metal in the catalyst is greatly reduced, and the cost of the catalyst is reduced; meanwhile, when the catalyst is used in an electrocatalytic hydrogen evolution process, the catalyst can simultaneously ensure high catalytic activity in alkaline and acidic media and has good universality; compared with the commercial Pt/C catalyst, the catalyst has greatly improved catalytic stability (about 63% for 24h stability in alkaline medium and about 74% for 24h stability in acid medium).
Specifically, the mass content of rhodium in the catalyst is x, the mass content of palladium in the catalyst is y, x is more than or equal to 1.0wt% and less than or equal to 3.0wt%, y is more than or equal to 1.0wt% and less than or equal to 3.0wt%, wherein the mass of the catalyst is calculated by the mass of the porous carbon matrix, and the mass of the platinum group metal is calculated by the mass of the metal element.
The catalyst of the embodiment of the present invention is prepared by the above method embodiment, and specific effects and descriptions thereof are referred to the above method embodiment and are not described herein.
In still another embodiment of the present invention, an electrochemical circulating water treatment apparatus is provided, where a cathode catalyst of the apparatus is provided by the foregoing catalyst and preparation method embodiments, and specific description and effects are referred to the foregoing catalyst and preparation method embodiments, and are not described herein again.
The following are several embodiments of the present invention:
the raw materials and the reagents used in each example are all conventional commercial products;
example 1
Step (1) preparation of porous carbon precursor cross-linked polyphosphazene PSTA:
weighing tannic acid 0.48g and dissolving in 40mL of acetonitrile to obtain a mixed solution I;
transferring 16mL of triethylamine into the mixed solution I, and placing the mixed solution I in an oil bath atmosphere at 35 ℃ to be fully stirred for 3 hours to obtain a mixed solution II;
hexachlorocyclotriphosphazene and 4,4' -sulfonyldiphenol were weighed 0.4g each and dissolved in 60mL acetonitrile to obtain a mixed solution III.
And (3) placing the mixed solution III in an ultrasonic atmosphere for fully dispersing and dropwise adding the mixed solution II, and controlling the dropwise adding time to be 20min. The mixture obtained after the completion of the dropwise addition was stirred sufficiently at 35℃for 4 hours, followed by ultrasonic treatment in an ultrasonic cleaner for 1 hour (ultrasonic power was controlled to 40W). Finally, the precipitate was collected by centrifugation (speed: 1100rpm,10 min) and transferred to a vacuum oven at 40 ℃ for drying overnight to give the cross-linked polyphosphazene PSTA.
Step (2) preparation of porous carbon matrix NPSC:
the porous carbon precursor cross-linked polyphosphazene PSTA was ground sufficiently to a powder and transferred to a porcelain boat equipped with a lid. Placing the porcelain boat in a quartz tube of a tube furnace, setting the heating rate to 5 ℃ for min -1 Carbonizing for 3h at 1000 ℃, and grinding uniformly to obtain the porous carbon matrix NPSC.
Preparation of catalyst RhPd/NPSC in step (3):
weighing RhCl 3 、Pd(OAc) 2 Each 5mg was dissolved in 60mL deionized water and sonicated in an ultrasonic cleaner until uniformly dispersed. NPSC was fully ground to a powder and 40mg was weighed and transferred into the above solution. The mixed solution is stirred for 12 hours at the normal temperature with the rotating speed of 1200rpm, and the electroless deposition of the metal nano particles occurs in the vigorous stirring process. The mixed solution was separated by suction filtration, and the cake was washed with deionized water (for washingDeionized water was used in an amount of 600 mL). The filter cake was collected and transferred to a-40 ℃ environment for lyophilization. And fully grinding the dried filter cake to obtain the catalyst RhPd/NPSC.
Example 2
Substantially the same as in example 1 was conducted, except that the carbonization temperature in step 2 was 950℃and the carbonization time was 3 hours.
Example 3
Substantially the same as in example 1, except that in step (3), the porous carbon matrix NPSC contains RhCl 3 、Pd(OAc) 2 The deposition time (stirring time) in the mixed solution was 480min.
Example 4
Substantially the same as in example 1, except that in step (3), metal salt RhCl was used 3 、Pd(OAc) 2 The amounts of (3) and (3.6) were 3mg and 30mg, respectively.
Comparative example 1
The same preparation as in example 1, except that only 5mg of RhCl was used in step (3) 3 。
Comparative example 2
The same preparation as in example 1, except that only 5mg Pd (OAc) was used in step (3) 2 。
Comparative example 3
The same preparation as in example 1, except that only 5mg of RuCl was used in step (3) 3 Replace RhCl 3 。
Comparative example 4
The same procedure as in example 1 was followed except that 0.4g of 4,4 '-diaminodiphenyl ether was used in place of 4,4' -sulfonyldiphenol in step (1).
Comparative example 5
Substantially the same as in example 1 was found, except that the carbonization temperature in step 2 was 800℃and the carbonization time was 3 hours. The catalyst prepared by the method is named as RhPd/NPSC-800.
Comparative example 6
Preparation method as in example 1Substantially identical, except that in step (3) the porous carbon matrix NPSC comprises RhCl 3 、Pd(OAc) 2 The deposition time (stirring time) in the mixed solution was 60min. The catalyst prepared by the method is named as RhPd-60/NPSC.
Comparative example 7
Substantially the same as in example 1, except that in step (3), the porous carbon matrix NPSC contains RhCl 3 、Pd(OAc) 2 The deposition time (stirring time) in the mixed solution was 180min. The catalyst prepared by the method is named as RhPd-180/NPSC.
Characterization of the catalysts provided in the examples:
the materials prepared in each embodiment are proved to be general high-activity electrocatalytic hydrogen evolution catalytic materials with metal nano particles and acid base mediums through a series of characterizations such as scanning electron microscope, transmission electron microscope, X-ray photoelectron spectroscopy, X-ray spectroscopy, inductively coupled plasma mass spectrum, BET and the like, and the porous carbon precursor, porous carbon and the morphology of the catalyst are described below by taking the example 1 as typical representation:
as can be seen from SEM in FIG. 1, the prepared catalyst carrier carbonized precursor cross-linked polyphosphazene PSTA has a spherical structure with a diameter of about 500nm, and PSTAs provided in other examples have spherical structures with diameters of about 500 nm;
in FIG. 2, the catalyst support prepared in example 1 was carbonized to give a single yield of 1456.65mg and 96.56% for the cross-linked polyphosphazene PSTA, and similar yields were obtained for the PSTA prepared in the other examples; the catalyst support carbonized precursor prepared in comparative example 4 was cross-linked polyphosphazene PSTA with a single yield of 106.39mg and a yield of 28.20%, and the lower PSTA yield in comparative example 4 was not suitable as carbonized precursor for porous carbon NPSC;
SEM images of the porous carbon matrix (NPSC) of the catalyst in fig. 3 show that the porous carbon surface exhibits a distinct porous structure, and that the porous carbon provided by the other examples all have the same or similar characteristics;
the ultraviolet light electron spectrum (UPS) of fig. 4 shows the surface potential of porous carbon substrates (NPSC) prepared at different carbonization temperatures in example 1 and comparative example 5. The surface potential of NPSC obtained by carbonization at 800 ℃ prepared in comparative example 5 is +0.47V, and the surface potential of NPSC obtained by carbonization at 1000 ℃ prepared in example 1 is-0.1V, which shows that the increase of carbonization temperature can promote the reduction of the surface potential of NPSC, and the NPSC with lower surface potential is more favorable for reaction when being used as an electroless deposition carrier, and has better performance; the NPSC surface potential provided by other examples is about-0.1V;
the ultraviolet light electron spectrum (UPS) of fig. 5 shows the surface potential of the porous carbon substrate (NPSC) provided in comparative example 4, which has a surface potential of +0.26V, and is unsuitable as an electroless deposition carrier due to its higher surface potential (undesirable negative surface potential);
in a STEM mode observation of TEM in fig. 6, the catalyst (RhPd/NPSC) prepared in example 1 contains obvious metal nanoparticle bright spots, and in EDS-mapping, it is proved that the metal nanoparticle bright spots have obvious responses to Rh and Pd elements, and it is proved that the synthesized catalyst contains Rh and Pd nanoparticles, and the mass fractions of Rh and Pd elements in the catalyst RhPd/NPSC are respectively 1.02wt% and 2.36wt% as determined by ICP-MS, and the porous carbon provided in other examples all have the same or similar characteristics;
in fig. 7, the X-ray photoelectron spectrum of the catalyst RhPd/NPSC shows that the results of the fine orbit patterns of the Rh 3d orbit and the Pd3d orbit prove that the Rh and the Pd which are mainly in metal states in the Rh and Pd nano particles have the same or similar characteristics as those of the porous carbon provided by other examples.
The catalysts provided in the examples and comparative examples were subjected to performance tests:
the method for testing the electrocatalytic hydrogen evolution performance of the catalyst specifically comprises the following steps:
preparing a working electrode:
the catalyst was ground to a powder, and 3mg was weighed and transferred to a centrifuge tube. Mu.l of isopropanol, 300. Mu.l of deionized water were added to the centrifuge tube by a pipette, followed by 30. Mu.l of 5% Nafion solution. And (3) ultrasonically dispersing the centrifuge tube filled with the mixed solution in an ultrasonic cleaner for 1.5 hours until the catalyst mixed solution is in a uniform ink state and has no particle wall hanging phenomenon.
And taking 10 mu l of the dispersed catalyst mixed solution, and dropwise adding the solution onto the mirror surface of the polished and smooth glassy carbon electrode. When the solution is added dropwise, the solution is added dropwise after the last time the solution is completely dried. The electrochemical test should be carried out after the completion of the dropwise addition of 10. Mu.l of the mixed solution and complete drying.
Electrochemical performance testing method:
electrochemical testing of the catalyst was performed in a standard three-electrode system on a universal electrochemical standard test workstation (equipment model CHI760e, shanghai). In the three-electrode system, a commercial carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a working electrode is a glassy carbon rotary disc electrode with the diameter of 5 mm. The solutions for testing the electrochemical hydrogen evolution performance of the catalysts included two, one acidic (0.5M H 2 SO 4 Solution) and the other alkaline (1M KOH solution) (for use on the same day as the electrochemical test).
In the electrochemical performance test process, the temperature of the electrolyte is kept at 25 ℃, and the rotating speed of the working electrode is set at 1600r min -1 . Before electrochemical hydrogen evolution test, the test section is scanned for multiple times by Cyclic Voltammetry (CV) at a scanning rate of 5mV s -1 . After a stable CV curve was obtained, the catalyst was subjected to an electrochemical hydrogen evolution test. Catalytic stability test of catalyst with constant current of 10mA cm -2 Is set to 24 hours.
As is typical of the catalyst provided in example 1, FIG. 8 shows from the LSV curve that the catalyst provided in example 1, rhPd/NPSC, in alkaline medium (1M KOH solution), has a current density of 10mA cm for hydrogen evolution reactions -2 The overpotential value is 40mV, and the catalytic performance can be equivalent to that of the current commercial Pt/C catalyst (34 mV). In FIG. 9, in an acidic medium (0.5. 0.5M H 2 SO 4 In solution), the current density of the catalyst RhPd/NPSC catalytic hydrogen evolution reaction reaches 10mA cm -2 The overpotential value is 38mV, and the catalytic performance can be equivalent to that of the current commercial Pt/C catalyst (34 mV). RhPd/N provided by each embodiment of the inventionPSC catalysts have excellent electrocatalytic hydrogen evolution activity in alkaline and acidic media. In contrast, the catalyst RhPd/NPSC-800 provided in comparative example 5 had a current density of 10mA cm in various media -2 The overpotential values at this time were 225mV (alkaline) and 393mV (acidic), respectively, as shown in FIGS. 12 and 13. The catalyst RhPd-60/NPSC provided in comparative example 6 and the catalyst RhPd-180/NPSC provided in comparative example 7 have a current density of 10mA cm in different media -2 The overpotential values at this time were 107mV (alkaline) and 224mV (acidic), 74mV (alkaline) and 158mV (acidic), respectively, as shown in FIGS. 14 and 15. The catalysts Rh/NPSC and Pd/NPSC provided in comparative example 2 and comparative example 3 only have obvious electrocatalytic hydrogen evolution activity in alkaline or acid respectively, and the current density is 10mA cm -2 The overpotential values were 99mV (basic) and 59mV (acidic), 156mV (basic) and 80mV (acidic), respectively, but the catalytic activity could not be compared with the commercial catalyst. The catalyst RuPd/NPSC provided in comparative example 3 (as shown in FIGS. 16, 17) had good catalytic activity in alkaline medium (current density of 10mA cm) -2 The time overpotential value is 15 mV), but the catalytic activity in an acidic medium is not comparable with that of the current commercial Pt/C catalyst (the current density is 10mA cm) -2 The time overpotential value was 67 mV). Therefore, none of the catalysts provided in the comparative examples are suitable as a general hydrogen evolution catalyst in a pH range, and cannot replace the currently marketed Pt/C catalysts.
In FIG. 10, the constant current density in an alkaline medium (1M KOH solution) at 24 hours is 10mA cm -2 In the electrocatalytic hydrogen evolution stability test, the catalyst RhPd/NPSC prepared in example 1 shows smaller overpotential increase compared with the commercial Pt/C catalyst, which shows that the catalyst RhPd/NPSC prepared in example 1 has more excellent electrocatalytic stability in alkaline medium.
In FIG. 11, in an acidic medium (0.5. 0.5M H 2 SO 4 Solution) at a constant current density of 10mA cm for 24 hours -2 In the electrocatalytic hydrogen evolution stability test, the catalyst RhPd/NPSC prepared in example 1 shows smaller overpotential increase compared with the commercial Pt/C catalyst, which shows that the prepared catalyst RhPd/NPSC has more excellent electrocatalytic stability in an acidic medium.
In FIG. 18, the catalyst RhPd/NPSC provided in example 1 shows very low potential decay at 10mA cm after 10000 cycle voltammetry acceleration durability test in alkaline medium (1M KOH solution) -2 The overpotential at the current density increases by only 3mV, indicating that it has excellent cycling stability in alkaline media. Comparative example 3 shows similar cycle durability at 10mA cm under the same test conditions -2 The overpotential increases by 3mV at the current density as shown in fig. 20.
FIG. 19 (0.5. 0.5M H in acid Medium 2 SO 4 Solution) after 10000 cyclic voltammetry acceleration durability test, the catalyst RhPd/NPSC provided in example 1 shows very low potential decay at 10mA cm -2 The overpotential at the current density increases by only 2mV, indicating that it also has excellent cycling stability in acidic media. The catalyst provided in comparative example 3 was subjected to 10000 cyclic voltammetry acceleration durability test at 10mA cm -2 The overpotential increases by 42mV at the current density, as shown in fig. 21, indicating that it is not suitable as a stable electrocatalytic hydrogen evolution catalyst for general use in a pH range.
It will be apparent to those skilled in the art that a number of variations and modifications of the method of the invention are possible based on the above teachings, and such variations and modifications are intended to be included within the scope of the invention.
Claims (10)
1. The electrocatalytic hydrogen evolution catalyst is characterized by comprising a porous carbon matrix and platinum group metals which are electrolessly deposited on the porous carbon matrix, wherein a precursor of the porous carbon matrix is cross-linked polyphosphazene, the cross-linked polyphosphazene is polymerized by monomer hexachlorocyclotriphosphazene, 4' -sulfonyl diphenol and tannic acid, and the platinum group metals are a mixture of rhodium and palladium.
2. The catalyst according to claim 1, wherein the mass content of rhodium in the catalyst is x, the mass content of palladium in the catalyst is y,1.0wt% or more x is or less than 3.0wt%, and 1.0wt% or less y is or less than 3.0wt%, wherein the mass of the catalyst is based on the mass of the porous carbon substrate, and the mass of the platinum group metal is based on the mass of the metal element.
3. The preparation method of the electrocatalytic hydrogen evolution catalyst is characterized by comprising the following steps of:
step 1: reacting a mixed solution containing an acid binding agent, tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol, centrifuging and drying to obtain cross-linked polyphosphazene;
step 2: crushing and carbonizing the obtained cross-linked polyphosphazene to obtain a porous carbon matrix, wherein the carbonization temperature is more than or equal to 950 ℃;
step 3: and (3) reacting, washing and drying an aqueous solution containing a porous carbon matrix, rhodium salt and palladium salt to obtain the electrocatalytic hydrogen evolution catalyst, wherein the reaction time is more than or equal to 8 hours.
4. A method according to claim 3, wherein in the mixture of step 1:
the mass ratio of tannic acid, hexachlorocyclotriphosphazene and 4,4' -sulfonyl diphenol is 0.8-1.4: 1:1, a step of;
the acid binding agent is at least one of triethylamine, pyridine and diisopropylethylamine;
the mass ratio of the acid binding agent to the tannic acid is 20-30: 1.
5. a method of preparation according to claim 3, characterized in that:
the solvent in the mixed solution in the step 1 is at least one selected from acetonitrile, acetone and ultrapure water;
the mass ratio of the solvent to the tannic acid is 150-300: 1.
6. a method according to claim 3, wherein the specific conditions for carbonizing the cross-linked polyphosphazene in step 2 include:
under an inert atmosphere;
the carbonization temperature is 950-1100 ℃;
the carbonization time is 2-3 h.
7. The method according to claim 6, wherein the temperature rise rate at the time of carbonization is 2 to 8 ℃/min.
8. A method according to claim 3, wherein in step 3:
the rhodium salt is selected from RhCl 3 、Rh(NO 3 ) 3 、Rh 2 (SO 4 ) 3 At least one of (a) and (b);
the palladium salt is selected from Pd (OAc) 2 、PdCl 2 、Pd(NO 3 ) 2 At least one of (a) and (b);
the mass ratio of the rhodium salt to the palladium salt to the porous carbon matrix is 1:0.5 to 1.2:6 to 10.
9. A method according to claim 3, wherein the specific conditions of the reaction of step 3 include:
is carried out at room temperature under stirring;
the reaction time is 10-12 h.
10. Use of any one of the electrocatalytic hydrogen evolution catalyst according to claim 1 or 2 and the electrocatalytic hydrogen evolution catalyst prepared by the preparation method according to any one of claims 3-9 in electrochemical circulating water treatment equipment.
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