CN112981452A - Water oxidation electrocatalyst and preparation method thereof, and water oxidation electrode and preparation method thereof - Google Patents
Water oxidation electrocatalyst and preparation method thereof, and water oxidation electrode and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a water oxidation electrocatalyst and a preparation method thereof, and a water oxidation electrode and a preparation method thereof. Wherein the water oxidation electrocatalyst is a self-supporting water oxidation electrocatalyst synthesized by electrochemical reaction of an electrochemical reaction system; the water oxidation electrocatalyst is a composite metal hydroxide deposited on the surface of a metal substrate; wherein one metal element contained in the composite metal hydroxide is derived from the metal substrate connected with the electrode of the electrochemical reaction system and obtained through electrochemical oxidation, and the other metal element is derived from the metal salt electrolyte in the electrochemical reaction system.
Description
Technical Field
The present invention relates to the field of electrochemistry; more particularly, the present invention relates to a water oxidation electrocatalyst and a preparation method thereof, a water oxidation electrode and a preparation method thereof.
Background
The anode water oxidation reaction is involved in the electrolytic hydrogen production and electrolytic carbon dioxide reduction processes, so the water oxidation reaction plays a very important role in the electrochemical process, however, the biggest problem of the water oxidation reaction is that the activity of the electrocatalyst is low, and the cost of the catalyst is high. Therefore, it is one of the current research hotspots to find a cheap, highly active and corrosion-resistant water oxidation electrocatalyst and to develop a simple, convenient and fast water oxidation electrocatalyst synthesis process.
The existing synthesis method generally takes a long time, and various improved schemes are proposed so as to quickly synthesize the water oxidation electrocatalyst. However, in general, these rapid synthesis methods have some limitations, for example, (1) the time required is still long and cannot be prepared within seconds; (2) the whole process needs multi-step reaction, only one step consumes short time, and the whole process still consumes long time; (3) the synthetic process requires costly or environmentally unfriendly reagents.
Disclosure of Invention
The invention mainly aims to provide a water oxidation electrocatalyst and a preparation method thereof, and aims to solve the problems of low activity, complex preparation process, long time requirement and the like of a water oxidation agent in the prior art.
The invention also aims to provide a water oxidation electrode and a preparation method thereof, so as to solve the problems of low activity and the like of the existing water oxidation electrode.
In order to solve the technical problems, the invention adopts the technical scheme that:
a water oxidation electrocatalyst is a self-supporting water oxidation electrocatalyst synthesized by electrochemical reaction of an electrochemical reaction system; the water oxidation electrocatalyst is a composite metal hydroxide deposited on the surface of a metal substrate; wherein one metal element contained in the composite metal hydroxide is derived from a metal substrate electrode of the electrochemical reaction system or the metal substrate connected with the electrode and is obtained through electrochemical oxidation, and the other metal element is derived from a metal salt electrolyte in the electrochemical reaction system.
In some embodiments, the water oxidizing electrocatalyst is a double metal hydroxide; in the double metal hydroxide, the amount of metal element substances derived from the metal base material is 10-30%; the amount of the other metal element substance is 70-90%.
In some embodiments, the water oxidation electrocatalyst is nickel iron hydroxide deposited on the surface of an iron sheet, wherein iron is obtained by oxidizing an iron sheet substrate, and nickel is obtained by a nickel salt electrolyte; the water oxidation electrocatalyst comprises three elements of iron, nickel and oxygen, wherein the iron element exists in a trivalent form, the nickel element exists in a divalent form, and the oxygen element exists in a hydroxyl group.
In some embodiments, catalytic activity is maintained for at least 300 hours; the water oxidation electrocatalyst is spherical nanoparticles composed of nanosheets deposited on the surface of a metal substrate.
The invention also provides a water oxidation electrode, which comprises a metal substrate and a water oxidation electrocatalyst deposited on the surface of the metal substrate; the water oxidation electrocatalyst is the water oxidation electrocatalyst.
In some embodiments, the water oxidation electrode reaches 10 mA/cm in catalyzing an electrochemical water oxidation reaction2The overpotential of the geometric current density is 230-240 mV; the water oxidation electrode is used as an anode in an electrolytic hydrogen production or electrolytic carbon dioxide reduction system.
The present invention also provides a method for preparing a water oxidation electrocatalyst, comprising:
step 1 preparing an electrochemical reaction system: taking a metal salt solution as an electrolyte to be contained in an electrolytic cell, and manufacturing a two-electrode synthesis system or a three-electrode synthesis system;
step 3, immersing the metal base materials into electrolyte and connecting the metal base materials with an electrode in an electrochemical reaction system or using the metal base materials as the electrode, setting a pulse voltage program to carry out synthetic reaction for a preset time, and forming a self-supporting water oxidation electrocatalyst on the surface of each metal base material;
wherein, for a two-electrode synthesis system: placing the metal base materials into the electrolytic cell in the step 1, connecting part of the metal sheets with the working electrode, connecting part of the metal sheets with the counter electrode and the reference electrode, setting a pulse voltage program to synthesize, and forming a self-supporting water oxidation electrocatalyst on the surface of each metal base material;
for the three-electrode synthesis system: the metal substrate is used as a working electrode.
Further, in the step 1, the electrolyte is a sulfate aqueous solution;
in the step 3, the "setting pulse voltage program" specifically includes:
in the two-electrode synthesis system, a voltage U1, 0V < U1, a duration t1 and a duration t1> 0s are applied between two electrodes, then the voltage between the two electrodes is changed into U2, U2< 0V and a duration t2> 0s, and the cycle is one cycle, and a plurality of cycles can be adopted during synthesis;
in a three-electrode synthesis system, one water oxidation electrode is prepared at one time, a metal base material is used as a working electrode, a graphite carbon rod is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode; applying a voltage U1 between the metal substrate working electrode and the reference electrode for a time period t1, t1> 0s, and then changing the voltage between the metal substrate electrode and the reference electrode to U2 for a time period t2> 0s, which is a cycle, wherein one or more cycles are used in the synthesis, wherein U1< 0.65V < U2 or U2< 0.65V < U1
In the step 3, the reaction time for synthesizing the pulse voltage program is set to be 10-20 s, and the self-supporting water oxidation electrocatalyst is obtained.
Further, in the step 1, the electrolyte is a nickel sulfate aqueous solution, and the finally synthesized water oxidation electrocatalyst is a nickel-containing double metal hydroxide material;
in the step 3, a pulse voltage program is set for synthesis reaction, and the water oxidation electrocatalyst is obtained within 10 s;
in the step 3, "setting a pulse voltage program", in one cycle of the two-electrode synthesis system: u1= + 2.4V for t1= 5s, U2= -2.4V for t2=5 s;
the concentration of the sulfate solution was 0.1M.
The present invention also provides a method of preparing a water oxidation electrode, comprising:
step 1 preparing an electrochemical reaction system: taking a metal salt solution as an electrolyte to be contained in an electrolytic cell, and manufacturing a two-electrode synthesis system or a three-electrode synthesis system;
step 3, immersing the metal base materials into electrolyte and connecting the metal base materials with an electrode in an electrochemical reaction system or using the metal base materials as the electrode, setting a pulse voltage program to carry out synthetic reaction for a preset time, and forming a self-supporting water oxidation electrocatalyst on the surface of each metal base material so as to obtain the water oxidation electrode;
wherein, for a two-electrode synthesis system: placing the metal base materials into the electrolytic cell in the step 1, connecting part of the metal sheets with the working electrode, connecting part of the metal sheets with the counter electrode and the reference electrode, setting a pulse voltage program to synthesize, and forming a self-supporting water oxidation electrocatalyst on the surface of each metal base material; for the three-electrode synthesis system: the metal substrate is used as a working electrode.
The technical scheme at least has the following beneficial effects:
the invention provides an ultra-fast self-supporting high-efficiency bimetallic hydroxide water oxidation electrocatalyst and a water oxidation electrode, which can shorten the synthesis time to be within 10 s. The water oxidation electrode of the invention has greatly improved activity.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the surface topography of the IronWE10s (or iron-based water oxidation electrode) of a water oxidation electrocatalyst sample prepared in accordance with an embodiment of the present invention.
FIG. 2 is a scanning electron microscope photograph of the surface morphology of IronCE10s (or iron-based water oxidation electrode) of a water oxidation electrocatalyst sample prepared in accordance with an embodiment of the present invention.
Fig. 3 is a detection diagram of the element composition and the valence state of the water oxidation electrocatalyst prepared by an X-ray photoelectron spectroscopy (XPS) test according to the embodiment of the present invention, wherein fig. 3(a), fig. 3(b), and fig. 3(c) are the valence state diagrams of the Fe element, the Ni element, and the O element, respectively.
Fig. 4 is an activity test curve of an iron-based water oxidation electrode (iron-based water oxidation electrode) prepared in an example of the present invention electrocatalytic water oxidation reaction in an alkaline electrolyte.
Fig. 5 is a stability test curve of electrochemical water oxidation reaction of water oxidation electrocatalyst sample IronWE10s (or iron-based water oxidation electrode) prepared in example of the present invention in alkaline electrolyte, and the test time is 300 hours.
Fig. 6 is a stability test curve of electrochemical water oxidation reaction of water oxidation catalyst sample IronCE10s (or iron-based water oxidation electrode) in alkaline electrolyte, and the test time is 300 hours.
Fig. 7 is an extended synthesis system for preparing a water oxidation electrocatalyst and an iron-based anode according to an embodiment of the present invention.
FIG. 8 is an activity test curve for 10 water oxidation electrodes synthesized by the extended synthesis system of FIG. 7, corresponding to FIGS. 8(a) -8 (j);
FIG. 9 is a graph of the pulse voltage and current versus time for the synthesis of a water oxidation electrocatalyst made according to an embodiment of the present invention.
FIG. 10 is a surface topography of a water oxidation electrode prepared by a three electrode system pulsing method in accordance with an embodiment of the present invention.
Detailed Description
The embodiment of the invention relates to a water oxidation electrocatalyst, a water oxidation electrode and a preparation method thereof. Specifically, the water-oxidizing electrocatalyst of the present invention is a self-supporting composite metal (oxy) hydroxide, more specifically, nickel iron hydroxide deposited on the surface of iron sheets. The specific structure of the water oxidation electrocatalyst prepared by the invention is amorphous ferronickel hydroxide, and the structure shows excellent water oxidation catalytic activity in alkaline electrolyte and has stable catalytic activity.
Referring to the scanning electron microscope images of the surface morphology of the water oxidation electrocatalyst shown in fig. 1-2, the surface morphology of the catalyst prepared in the two-electrode synthesis system was electrified for synthesis reaction for 10 seconds, and the substrate was an iron sheet electrode. FIG. 1 is a photograph taken by scanning electron microscopy of the surface morphology of the catalyst prepared in a two-electrode system within 10 seconds of synthesis time (iron plate electrode connected to the working electrode, named IronWE10 s); as can be seen from FIG. 1, after 10 seconds of the synthesis reaction, a layer of water oxidation electrocatalyst is synthesized on the surface of the iron sheet electrode, and is used as the water oxidation electrode together with the iron sheet substrate, and the surface of the iron sheet connected with the working electrode forms a spherical nano-particle containing a large number of nano-sheets. FIG. 2 is a photograph taken by scanning electron microscopy of the catalyst surface topography (iron plate electrode attached to counter/reference electrode, designated IronCE10 s) prepared in a two-electrode system over a synthesis time of 10 seconds; as can be seen from fig. 2, a layer of water oxidation electrocatalyst, which is mainly composed of nanosheets, is synthesized on the surface of the iron sheet electrode after 10 seconds of the synthesis reaction.
Referring to a scanning electron microscope image of the surface morphology of the water oxidation electrocatalyst shown in fig. 10, the surface morphology of the catalyst prepared in the three-electrode synthesis system is electrified to perform a synthesis reaction for 100 seconds, the substrate is an iron sheet electrode and serves as a working electrode, and the obtained iron sheet electrode has a large number of nano-sheet-shaped water oxidation electrocatalysts on the surface and serves as a water oxidation electrode together with the iron sheet substrate.
With further reference to fig. 3, the elemental composition and valence state of the surface of the iron plate electrode (water oxidation electrode) prepared according to the present invention were tested by X-ray photoelectron spectroscopy. The sample IronCE10s is a self-supporting composite metal (oxygen) hydroxide formed on the surface of an iron sheet electrode connected with a counter electrode and a reference electrode in a two-electrode synthesis system; sample IronWE10s was a two-electrode synthesis system in which self-supporting composite metal (oxy) hydroxide was formed on the surface of the iron sheet electrode connected to the working electrode. The surfaces of the two iron sheet electrode samples IronCE10s and IronWE10s are both mainly composed of three elements of iron, nickel and oxygen, wherein the iron element exists in a trivalent form, and the nickel element exists in a divalent form. The results of FIG. 3(a) show that the water-oxidizing electrocatalyst on the surface of the iron plate electrode sample contains trivalent iron elements; the results of FIG. 3(b) show that the divalent nickel element is contained in the water-oxidizing electrocatalyst on the surface of the iron sheet electrode sample; the results of FIG. 3(c) show that the water-oxidizing electrocatalyst on the surface of the iron plate electrode sample contains oxygen elements and exists as hydroxyl groups. The results of X-ray photoelectron spectroscopy (XPS) tests on the water-oxidized electrocatalyst samples prepared by the three-electrode synthesis system are the same as those in fig. 3, and the surface of the iron sheet electrode mainly consists of three elements, namely iron, nickel and oxygen, wherein the iron element exists in a trivalent form and the nickel element exists in a divalent form.
The invention adopts a three-electrode synthesis system, can prepare one electrode of the water oxidation electrocatalyst at one time, and can prepare the electrode in the three-electrode systemIron sheet as working electrode, graphite carbon rod as counter electrode, saturated calomel electrode as reference electrode, 0.1M NiSO4The solution serves as an electrolyte solution. Applying voltage U1 between the working electrode and the reference electrode for time t1 and t1>0s, then the voltage between the iron plate electrode and the reference electrode is changed to U2 for a time duration of t2>0s, this is one cycle, and multiple cycles can be used in the synthesis, where U1<0.65 V<U2 or U2<0.65 V<U1。
Specifically, a water oxidation electrocatalyst (water oxidation electrode) is prepared through a three-electrode system, voltage-1V is applied between an iron sheet working electrode and a reference electrode for 5s, then the voltage between the iron sheet electrode and the reference electrode is changed to-0.4V for 5s, 10 cycles can be repeated, the surface of the obtained iron sheet electrode has a structure formed by a large number of nano sheets (refer to fig. 10), and through x-ray photoelectron spectroscopy analysis, the catalyst mainly contains three elements of iron, nickel and oxygen, wherein the iron element exists in a trivalent form, the nickel element exists in a divalent form, and the oxygen element exists in a hydroxyl group. The electrode can reach 10 mA/cm in the electrochemical water oxidation reaction catalyzed by 1M KOH electrolyte2The overpotential of the current density is 249.7 mV, and the activity is higher.
If a two-electrode synthesis system is adopted, two electrodes of the water oxidation electrocatalyst can be synthesized once, and both the two electrodes have higher activity and reach 10 mA/cm in the catalytic electrochemical water oxidation reaction2The overpotential of the current density was 240.7. + -. 6.8 mV and 239.5. + -. 3.4 mV, respectively. The efficiency is improved by synthesizing two electrodes at a time. In addition, the two-electrode synthesis system adopted by the invention can be used for preparing 10 water oxidation electrodes (refer to fig. 6) by connecting a plurality of groups of iron sheets in parallel, for example, 5 groups of iron sheets (10) in parallel, and only 10 seconds are needed by one-time pulse synthesis, so that the two-electrode synthesis system can be further expanded to prepare more water oxidation electrodes in a short time.
In the specific embodiment, when two iron sheet electrodes are prepared at one time in a synthesis system, the water oxidation electrocatalyst on the surface of one iron sheet electrode sample contains 20% of iron element and 80% of nickel element; the water oxidation electrocatalyst on the surface of the other iron sheet electrode sample contains 22% of iron element and 78% of nickel element. In some embodiments, when a plurality of iron sheet electrodes are prepared at one time, the water oxidation electrocatalyst on the surface of the electrode sample contains 10-30% of iron element; 70-90% of nickel element, O element exists in the form of (OH), and the total charge is balanced.
The method for preparing the water oxidation electrocatalyst is an electrochemical pulse activation method, improves the synthesis speed of the water oxidation electrocatalyst, and simultaneously improves the water oxidation performance of the electrocatalyst. The method adopts metal salt as electrolyte, two iron sheets as electrodes (in a two-electrode synthesis system), and pulse voltage is applied between the two iron sheets to rapidly synthesize an active substance double-metal hydroxide structure of the water oxidation electrocatalyst, and the structure shows excellent water oxidation catalytic activity in alkaline electrolyte and has stable catalytic activity.
The invention relates to a water oxidation electrocatalyst, which is prepared by using pulse current, and the active substance is a self-supporting water oxidation electrocatalyst of metal (oxygen) hydroxide, and the preparation method (in a two-electrode synthesis system) comprises the following steps:
dissolving soluble metal salt in deionized water, stirring at room temperature to obtain a uniform solution serving as an electrolyte, and preparing the electrolyte into an electrolytic cell of a two-electrode synthesis system;
and 3, placing the even number of metal sheets in the step 2 into an electrolytic cell containing the solution in the step 1, connecting half of the metal sheets with a working electrode, connecting the other half of the metal sheets with a counter electrode and a reference electrode, setting a pulse voltage program, and obtaining the self-supporting water oxidation electrocatalyst within a very short time (10-20 s).
The electrolyte of step 1 may be only one metal salt (mono-metal salt), preferably sulfate, and the final synthetic self-supporting water oxidation electrocatalyst is a double metal hydroxide material, wherein one metal element is from the electrolyte of the mono-metal salt and the other metal element is from the metal oxidation of the conductive substrate connected to the electrodes of the electrolytic cell. In this embodiment, the electrolyte used has a single component, and the concentration may be 0.1M.
In an embodiment, the electrolyte of step 1 may use only one sulfate, such as nickel sulfate, and the final synthetic self-supported water oxidation electrocatalyst is a nickel-containing double metal hydroxide material, wherein the nickel element is derived from the electrolyte and the other metal element is derived from the metal oxidation of the conductive substrate. In this example, the electrolyte used was a single component, only nickel sulfate, and the concentration was 0.1M.
Preferably, in the step 2, the metal sheet is an iron sheet, so as to form an iron sheet electrode. When the electrolyte only adopts nickel sulfate, the self-supporting water oxidation electrocatalyst is finally synthesized into a ferronickel double-metal hydroxide material, wherein nickel is obtained from the electrolyte, and iron is obtained from the oxidation of an iron sheet electrode which is a conductive base material.
In the step 3, the "setting pulse voltage program" specifically includes: a voltage U1 (0V < U1) was applied between the two electrodes for a time t1 (t 1>0 s), and then the voltage between the two electrodes was changed to U2 (U2 < 0V), for a time t2> 0s, which is one cycle, and multiple cycles could be performed during synthesis. The screened, comparatively optimized two-electrode system composite clock pulse voltage program is as follows: u1= + 2.4V for t1= 5s, U2= -2.4V for t2= 5s, this is one cycle, and the condition that the synthesis time is shortest is preferably 10 s. In addition, the present invention tested more cycles of pulsing, including 6 cycles (60 s), 36 cycles (360 s), and increased number of cycles of pulsing voltage, the activity of the prepared water oxidation electrode was close to that of the 10s prepared sample. Therefore, the synthesis conditions of 10s are relatively optimized by taking the catalyst activity and the synthesis time into consideration.
The activity test is carried out on the water oxidation electrocatalyst prepared by the method, and specifically:
when the water oxidation electrocatalyst obtained in the step 3 is placed in 1.0M KOH alkaline electrolyte for testing, excellent electrocatalytic water oxidation activity can be observed, and the catalytic activity is maintained for at least 300 hours. Referring to FIGS. 4-6 and 8, FIG. 4 is a drawing of a waferThe prepared iron-based water oxidation electrode electrocatalysis water oxidation reaction activity curve in alkaline electrolyte; as shown in fig. 4, when the voltage is more than 1.45V, the current density of water oxidation is rapidly increased, and at the same voltage, the current density of the sample IronCE ce10s is higher, indicating that the activity of IronCE ce10s is better. FIG. 5 shows the stability of the electrochemical water oxidation reaction of the prepared iron-based water oxidation electrode IronWE10s in an alkaline electrolyte, and the test time is 300 hours; FIG. 5 shows that the current density at 100 mA/cm2At a current density of (a), the water oxidation activity of IronWE10s was maintained for at least 300 hours. FIG. 6 is a graph showing the stability of the electrochemical water oxidation reaction of the prepared iron-based water oxidation electrode IronCE10s in an alkaline electrolyte, for a test period of 300 hours; FIG. 6 shows that the current density at 100 mA/cm2The water oxidation activity of the iron-based water oxidation electrode IronCE10s was maintained for at least 300 hours at the current density of (a).
The self-supporting composite metal (oxy) hydroxide is synthesized on the surface of the water oxidation electrode prepared by the invention, and the water oxidation electrode is applied to an anode in electrolytic water and is used as the anode in the processes of hydrogen production by electrolysis and reduction of carbon dioxide by electrolysis.
When the activity is tested, a three-electrode system is adopted, the prepared iron-based water oxidation electrode is used as a working electrode, the mercury/mercury oxide electrode is used as a reference electrode, the graphite rod is used as a counter electrode, and the activity of electrochemical water oxidation can be tested in a 1M KOH solution.
Example one
Cutting the polished iron sheet into size of 0.5 × 5 cm, sealing the middle region of the iron sheet with hot melt adhesive, and reserving 0.2 cm at one end of the iron sheet2For immersion in the electrolyte. The electrolyte adopts an aqueous solution of nickel sulfate. Two identical iron sheets are immersed in the electrolyte, one of which is connected to the working electrode clamp of the electrochemical workstation and the other of which is connected to the counter electrode + reference electrode clamp of the electrochemical workstation. A pulse voltage of 2.4V was applied between the two iron pieces, first at + 2.4V for 5 seconds, then switched to-2.4V for another 5 seconds. Then taking out the two electrodes, immersing the two electrodes into ultrapure water to wash off the electrolyte on the surface, and absorbing water by using filter paper or dust-free paper. The two electrodes are named IronWE10s and IronCE10s, respectively. To obtainThe electrochemical water oxidation activity of the iron-based water oxidation electrode was tested in a 1M KOH solution using a standard three-electrode system, and the results of the testing are described with reference to fig. 4-6, and the specific conclusions are described in the above examples.
Example two
In addition to the above-mentioned possibility of preparing two water oxidation electrodes at a time, the invention can also be extended to the synthesis of a plurality of electrodes by connecting a plurality of pairs of iron sheets in parallel, wherein half of the number of iron sheets are connected to the working electrode clamps of the electrochemical workstation and the other half of the number of iron sheets are connected to the counter electrode + reference electrode clamps of the electrochemical workstation. The method of the present invention can also synthesize 2 pairs of water oxidation electrodes (4), 5 pairs of water oxidation electrodes (10) (as shown in fig. 7), and further reduce the synthesis time to 2.5 s per electrode and 1 s per electrode. FIG. 7 shows the connection of 5 pairs (10) of iron sheet electrodes in an extended synthesis system. Fig. 8 shows that 10 water oxidation electrocatalyst electrodes were synthesized at one time (10 s) in the synthesis system, and the activity of each electrode was tested and substantially approximated to that of the water oxidation electrocatalyst electrode synthesized in the two-electrode system (see fig. 4).
The invention has the following characteristics:
(1) compared with the existing synthesis method of powder metal (oxy) hydroxide, the metal iron sheet used in the invention is used for preparing the self-supporting water oxidation electrocatalyst, thus avoiding the use of a binder and improving the conductivity and stability;
(2) compared with the existing synthesis method of the self-supporting composite metal (oxygen) hydroxide, the electrochemical pulse activation method used in the invention improves the preparation speed, can realize ultrashort synthesis time, and simultaneously improves the electrocatalytic water oxidation performance;
(3) compared with the existing synthesis method of the electrochemical activation self-supporting composite metal (oxy) hydroxide, the two-electrode system used by the invention can prepare even times of quantity of water oxidation electrocatalyst electrodes at one time, and at least two catalyst electrodes at one time;
(4) the construction and the expansion of the two-electrode system can realize the preparation of the water oxidation electrocatalyst in batches.
While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
Claims (10)
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