JP7667964B2 - Electrode catalyst and method for producing same - Google Patents

Description

The present invention relates to an electrode catalyst and a method for producing the same.

Hydrogen emits zero _CO2 when burned, and is expected to be a clean energy source to replace fossil fuels. In particular, the method of producing hydrogen by electrolysis of water uses renewable energy such as solar, wind, and hydroelectric power, so it does not emit any _CO2 and is highly anticipated as a clean method of producing hydrogen.

As an electrode for electrolysis of water, one that has a platinum particle catalyst fixed onto an electrode substrate such as a carbon substrate is known. However, platinum is expensive and the resource is limited, so there is a demand for technology to reduce the amount of platinum used and for the development of alternative catalysts and/or electrodes.

From this perspective, for example, Patent Document 1 and the like propose a new catalyst containing a transition metal (e.g., Co, Ni, Mn, etc.) with a nano-sized fine structure as an electrode for electrolysis of water.

JP 2000-000470 A

However, in recent years, the performance required of electrodes for producing hydrogen through the electrolysis of water has been listed as lower overpotential, a small Tafel slope, and long-term stability, and there is still room for improvement in conventional electrodes in terms of improving these performances.

The present invention has been made in view of the above, and aims to provide an electrode catalyst that has a low overpotential, a small Tafel slope, and long-term stability, and a method for producing the same.

As a result of intensive research into achieving the above object, the inventors discovered that the above object could be achieved by forming a catalyst from a complex compound containing a specific metal element, and thus completed the present invention.

That is, the present invention includes, for example, the subject matter described in the following sections.
Item 1
An electrocatalyst comprising a catalyst on a carbon substrate,
The catalyst is an electrode catalyst comprising a composite compound having one metal element M selected from the group consisting of Zn, Cu, Ni, Mn, Fe, and Cr, V, and Co as constituent elements.
Item 2
2. The electrode catalyst according to item 1, wherein the composite compound contains the metal element M, VO _x (wherein x is a number between 2 and 3), and Co.
Item 3
Item 1 or 2, a method for producing an electrode catalyst,
A method for producing an electrode catalyst, comprising a step of immersing a carbon substrate in a solution containing a source of metal elements M, a source of V, and a source of Co to perform electrodeposition treatment.
Item 4
Item 3. An electrode for producing hydrogen, comprising the electrode catalyst according to item 1 or 2.
Item 5
Item 5. A method for producing hydrogen, comprising a step of electrolysis using the electrode according to item 4.

The electrode catalyst according to the present invention can be used as an electrode for producing hydrogen, and during hydrogen production, it has a low overvoltage, a small Tafel slope, and excellent long-term stability.

1 shows SEM images of the surfaces of the electrode catalysts prepared in Example 1 and each of the comparative examples. FIG. 1A is a linear sweep voltammetry measurement result using the electrode catalysts prepared in Example 1 and each Comparative Example; FIG. 1B is a bar graph showing the overpotential at 10 mA cm ⁻² and the overpotential at 50 mA cm ⁻² measured from the linear sweep voltammetry curve shown in FIG. 1A; and FIG. 1C is a graph showing the Tafel slope calculated from the linear sweep voltammetry curve shown in FIG. 1A shows a multi-current step chronopotentiometry curve of the electrode catalyst obtained in Example 1, and FIG. 1B shows a chronopotentiometry curve of the electrode catalyst obtained in Example 1. FIG. 1A is a graph showing the measurement results of linear sweep voltammetry using the electrode catalysts prepared in Examples 1 to 4, and FIG. 1B is a graph showing the Tafel slope calculated from the linear sweep voltammetry curve shown in FIG.

1. Electrode catalyst The electrode catalyst of the present invention is provided on a carbon substrate, and the catalyst includes a composite compound having one metal element M selected from the group consisting of Zn, Cu, Ni, Mn, Fe, and Cr, V (vanadium), and Co (cobalt). Such an electrode catalyst can be suitably used as an electrode for hydrogen production. Specifically, the electrode catalyst according to the present invention can reduce the overvoltage during hydrogen production, has a small Tafel slope, and is also excellent in long-term stability.

The carbon substrate is a substrate for supporting a composite compound, and the type is not particularly limited, and examples thereof include a wide variety of known carbon substrates. Specific examples of carbon substrates include carbon paper, carbon fiber paper, and carbon rods.

The carbon substrate can be obtained, for example, by a known manufacturing method, or can be obtained from a commercial product. The shape and size of the electrode substrate are not particularly limited and can be appropriately selected depending on the purpose of use and the required performance. For example, the shape of the carbon substrate can be fibrous, sheet, plate, rod, mesh, etc.

The composite compound is formed on the carbon substrate. As described above, the composite compound contains the metal element M, V (vanadium), and Co (cobalt).

The metal element M is one selected from the group consisting of Zn, Cu, Ni, Mn, Fe, and Cr, and among them, it is particularly preferable that the metal element M is Zn (zinc). In this case, the electrode catalyst can particularly reduce the overvoltage during hydrogen production, can particularly reduce the Tafel slope, and has particularly excellent long-term stability.

The form of the composite compound is not particularly limited as long as it contains the metal element M, V, and Co. In terms of being able to further reduce the overvoltage during hydrogen production, the composite compound preferably contains the metal element M, VO _x (wherein x is a number between 2 and 3), and Co, and more preferably is an alloy of the metal element M, VO _x , and Co. In such an alloy, the metal elements M and Co are zero-valent.

In the composite compound, the content ratios of the metal elements M, V, and Co are not particularly limited. For example, the content ratio of Co is preferably 80 to 99 mol%, more preferably 85 to 98 mol%, and even more preferably 90 to 97 mol%, relative to the total amount of the composite compound. The content ratio of V is preferably 0.5 to 10 mol%, more preferably 1 to 7.5 mol%, and even more preferably 1.5 to 5 mol%, relative to the total amount of the composite compound. The content ratio of the metal element M is preferably 0.5 to 10 mol%, more preferably 1 to 7.5 mol%, and even more preferably 1.5 to 5 mol%, relative to the total amount of the composite compound.

In the electrode catalyst of the present invention, the catalyst formed on the carbon substrate may contain elements or compounds other than the complex compound, as long as the effect of the present invention is not impaired. The catalyst preferably contains 80% by mass or more of the complex compound, more preferably 90% by mass or more, and even more preferably 95% by mass or more. The catalyst may be formed only from the complex compound.

The electrode catalyst of the present invention, in which the catalyst formed on the carbon substrate contains the above-mentioned composite compound, can lower the overvoltage during hydrogen production, can reduce the Tafel slope, and can also reduce long-term stability.

In the electrode catalyst of the present invention, the shape of the catalyst is not particularly limited. For example, the catalyst is preferably in the form of a thin film. In other words, the catalyst is preferably formed as a thin film on a carbon substrate. The thickness of such a thin film is not particularly limited and can be, for example, 0.1 to 100 μm, and is particularly preferably in the form of a nanosheet. When the catalyst is formed in the form of a nanosheet, its thickness is 10 to 2000 nm, preferably 100 to 1000 nm, and more preferably 200 to 500 nm. The catalyst can cover a part or the whole of the carbon substrate. When the carbon substrate is in the form of fibers, the catalyst can be formed so as to cover the fibers.

In the electrode catalyst of the present invention, when the catalyst is formed in a thin film, the thin film can have a porous structure. In addition, the thin film can have not only a single layer but also a laminated structure.

In particular, since the electrode catalyst of the present invention contains a composite compound doped with a metal element M, the metal element M is more likely to be uniformly distributed in the catalyst and the growth of a porous structure is more likely to be promoted, resulting in excellent catalytic performance. Although not necessarily wishing to limit the interpretation, it is presumed that in the composite compound, in addition to the strong interaction between Co and the vanadium oxide (VO _x ) cluster, the crystal structure, electronic structure and coordination environment are further adjusted on an atomic scale by the doped metal element M, and as a result, the catalyst containing the composite compound can exhibit excellent performance.

The most preferred composite compound in the electrode catalyst of the present invention is a composite compound in which a VO _x -Co composite compound is doped with Zn (zinc), where Zn forms an alloy with the VO _x -Co composite compound.

The electrode catalyst of the present invention may be formed only from a carbon substrate and a catalyst, or may be combined with other materials as long as the effect of the present invention is not impaired. For example, the electrode catalyst may be formed directly on the carbon substrate (without any other layer, etc.). In the electrode catalyst, it is preferable that no layer is formed on the catalyst.

The electrode catalyst of the present invention is therefore suitable for use in electrodes for various electrolysis, and in particular, when used as an electrode for water electrolysis, it is capable of providing excellent hydrogen generation efficiency, making it suitable for use in electrodes for hydrogen generation.

2. Manufacturing method of electrode catalyst The electrode catalyst of the present invention can be obtained, for example, by a manufacturing method including a step of immersing a carbon substrate in a solution containing the metal element M source, a V source (vanadium source), and a Co (cobalt source) source to perform electrodeposition treatment. Hereinafter, such a step will be referred to as "Step 1." The metal element M source, V source, and Co source used in Step 1 are raw materials of the composite compound in the electrode catalyst of the present invention.

The carbon substrate used in step 1 is the same as the carbon substrate in the electrode catalyst of the present invention.

In the metal element M source, the metal element M is the same as the metal element M in the composite compound. Therefore, in the metal element M source, the metal element M is one selected from the group consisting of Zn, Cu, Ni, Mn, Fe, and Cr, and among them, it is particularly preferable that the metal element M is Zn (zinc).

The source of the metal element M can be, for example, the metal element M alone or a compound containing the metal element M, with a compound containing the metal element M being preferred.

The type of compound containing the metal element M is not particularly limited. For example, a wide variety of compounds containing the metal element M can be used, including inorganic acid salts of the metal element M, organic acid salts of the metal element M, hydroxides of the metal element M, and halides of the metal element M.

A wide variety of known compounds can be used as the inorganic acid salt of the metal element M, and examples thereof include one or more selected from the group consisting of nitrates, hydrochlorides, sulfates, carbonates, hydrogencarbonates, phosphates, and hydrogenphosphates of the metal element M. In terms of facilitating the production of the electrode catalyst, the inorganic acid salt of the metal element M is preferably a sulfate of the metal element M (e.g., _ZnSO4 ).

A wide variety of known compounds can be used as the organic acid salt of metal element M, and examples of such compounds include one or more selected from the group consisting of acetates, oxalates, formates, and succinates of metal element M.

The source of metal element M used in step 1 may be a single type, or two or more types may be used in combination. The compound containing metal element M may be obtained by a known manufacturing method, or a commercially available compound containing metal element M may be used.

The V source (vanadium source) used in step 1 is not particularly limited as long as it contains V (vanadium), and examples include V alone or a compound containing V, with a compound containing V being preferred.

The type of compound containing V is not particularly limited. For example, a wide variety of compounds containing V can be used, including inorganic acid salts of V, compounds containing an oxoanion of V (metal acid salts), organic acid salts of V, hydroxides of V, and halides of V.

A wide variety of known compounds can be used as the inorganic acid salt of V, and examples of such salts include one or more selected from the group consisting of nitrates, hydrochlorides, sulfates, carbonates, hydrogencarbonates, phosphates, and hydrogenphosphates of V.

Examples of compounds containing an oxoanion of V include an orthoacid salt of V and a metaacid salt of V. Specific examples include vanadates, such as ammonium vanadate (V) (NH ₄ VO ₃ ).

A wide variety of known compounds can be used as the organic acid salt of V, and examples of such compounds include one or more selected from the group consisting of acetate, oxalate, formate, and succinate salts of V.

The V source used in step 1 may be a single type, or two or more types may be used in combination. The V-containing compound may be obtained by a known production method, or a commercially available V-containing compound may be used.

The Co source (cobalt source) used in step 1 is not particularly limited as long as it contains Co (cobalt), and examples include simple Co or a compound containing Co, with a compound containing Co being preferred.

The type of the Co-containing compound is not particularly limited. For example, a wide variety of Co-containing compounds can be used, including inorganic acid salts of Co, organic acid salts of Co, hydroxides of Co, and halides of Co.

As the inorganic acid salt of Co, a wide variety of known compounds can be used, and examples thereof include one or more selected from the group consisting of Co nitrates, hydrochlorides, sulfates, carbonates, hydrogencarbonates, phosphates, hydrogenphosphates, etc. In terms of facilitating the production of the electrode catalyst, the inorganic acid salt of Co is preferably a Co sulfate (e.g., CoSO ₄ ).

A wide variety of known compounds can be used as the organic acid salt of Co, and examples of such compounds include one or more selected from the group consisting of acetate, oxalate, formate, and succinate of Co.

The Co source used in step 1 may be a single type, or two or more types may be used in combination. The Co-containing compound may be obtained by a known manufacturing method, or a commercially available Co-containing compound may be used.

In step 1, a solution containing the metal element M source, the V source, and the Co source is used. The method for preparing this solution is not particularly limited, and for example, the solution can be prepared by mixing the metal element M source, the V source, and the Co source with a solvent in a predetermined ratio. The solvent is not particularly limited, and examples thereof include water, and may also be a mixed solvent of water and a lower alcohol compound.

The concentrations of the raw materials in the solution are not particularly limited. From the viewpoint of excellent solubility and reactivity of the raw materials, it is preferable to use a solvent so that the concentrations of the metal element M source, V source, and Co source are each 1 mM to 1 M. More specifically, the concentration of the metal element M source in the solution is preferably 1 to 100 mM, and more preferably 3 to 50 mM. The concentration of the V source in the solution is preferably 1 to 100 mM, and more preferably 3 to 50 mM. The concentration of the Co source in the solution is preferably 50 to 1000 mM, and more preferably 100 to 600 mM.

In the solution, the content ratios of the metal elements M, V, and Co are not particularly limited. For example, the content ratio of Co is preferably 80 to 99 mol%, more preferably 85 to 98 mol%, and even more preferably 90 to 97 mol% relative to the total amount of the metal elements M, V, and Co in the solution. Furthermore, the content ratio of V is preferably 0.5 to 10 mol%, more preferably 1 to 7.5 mol%, and even more preferably 1.5 to 5 mol% relative to the total amount of the complex compound. Furthermore, the content ratio of the metal element M is preferably 0.5 to 10 mol%, more preferably 1 to 7.5 mol%, and even more preferably 1.5 to 5 mol% relative to the total amount of the complex compound.

The solution may contain additives such as a pH adjuster as appropriate. When the solution contains a pH adjuster, the pH of the solution is stabilized, which makes it easier to suppress hydrolysis of the Co source (e.g., cobalt sulfate), etc., and the electrodeposition process can be performed more stably. The type of pH adjuster is not particularly limited, and a wide variety of known pH adjusters, such as H ₃ BO ₄ , can be used.

In step 1, the method of electrodeposition is not particularly limited, and any known electrodeposition method can be widely used. For example, the electrodeposition can be performed by immersing the carbon substrate in the solution.

Electrodeposition can be performed by various electrodeposition methods. Examples of electrodeposition methods include the constant current method (GM), constant voltage method (PM), cyclic voltammetry method (CV), and pulse electrodeposition method. The pulse electrodeposition method is an electrodeposition method that can control the electrodeposition speed of metal ions, and examples of the pulse electrodeposition method include the pulse voltage method (PPM) in which a high-end voltage and a low-end voltage are applied at regular intervals, the pulse current method (PGM) in which a high-end current and a low-end current are applied at regular intervals, and the unipolar pulse voltage method (UPED) in which the application of a high-end voltage and an open circuit state are repeated at regular intervals.

The conditions for the electrodeposition process are not particularly limited. For example, the applied voltage can be -2 to 2 V (preferably 1.5 to 2 V), and the electrodeposition time can be 100 to 2000 seconds (preferably 300 to 1800 seconds). The temperature of the solution used for the electrodeposition process is not particularly limited, and can be, for example, about 0 to 50°C, preferably 20 to 30°C.

The electrodeposition process can be performed using a carbon substrate as a cathode (working electrode). In the electrodeposition process, in addition to the cathode, a counter electrode, a reference electrode, an electrolysis device, a power source, control software, and the like can be used. The types of these are not particularly limited, and known electrodes can be used depending on the purpose. For example, a silver/silver chloride electrode (Ag/AgCl electrode), a mercury/mercury chloride electrode (Hg/HgCl ₂ electrode), a standard hydrogen electrode, and the like can be used as the reference electrode. A platinum wire can be used as the counter electrode.

By the electrodeposition process in step 1, the composite compound is formed on the carbon substrate, and the electrode catalyst of the present invention is obtained.

The manufacturing method of the present invention may include a configuration other than step 1, or may include only step 1. In other words, the manufacturing method of the present invention can obtain the desired electrode catalyst without including a step such as a calcination step after the electrodeposition process. Therefore, the manufacturing method of the present invention can obtain an electrode catalyst with excellent catalytic performance while using simpler steps than conventional methods.

3. Hydrogen Production Method The hydrogen production method of the present invention includes a step of performing an electrolysis process using the above-mentioned electrode catalyst of the present invention. Alternatively, the hydrogen production method of the present invention includes a step of performing an electrolysis process using the electrode catalyst obtained by the above-mentioned method of producing an electrode catalyst of the present invention.

The hydrogen production method of the present invention can use an electrode catalyst, for example, as a cathode.

On the other hand, in the hydrogen production method of the present invention, an electrode that is generally used as an anode in the electrolysis of water can be used as the anode. For example, an electrode made of carbon, platinum, gold, or other precious metals can be used as the cathode.

In the hydrogen production method of the present invention, the aqueous solution used in electrolysis can be an aqueous solution containing components generally used in the electrolysis of water. The aqueous solution can also contain halogens such as iodine and bromine, sulfate ions, etc. When an aqueous solution containing iodine is used, iodate ions are generated at the anode. The aqueous solution can be in the acidic, neutral, or alkaline range. For example, in the alkaline range, aqueous solutions of KOH, NaOH, etc. can be used, in the acidic range, aqueous solutions of hydrochloric acid, sulfuric acid, etc. can be used, and in the neutral range, PBS (phosphate buffered saline), etc. can be used.

A specific example of a method for producing hydrogen is to _use the electrode catalyst of the present invention as a cathode, a platinum plate as an anode, and KOH, _H2SO4 or PBS aqueous solution as an electrolyte, and apply a voltage. This allows hydrogen to be produced at the cathode. In addition, the rate of hydrogen production can be increased by increasing the applied voltage.

Hydrogen produced by this method can be preferably used as fuel for fuel cells, hydrogen engines, etc.

In the hydrogen production method of the present invention, the electrode catalyst is used as an electrode, so that an increase in overvoltage is unlikely to occur and hydrogen can be produced efficiently.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1
As the carbon substrate, carbon paper (2 x 2 cm) was ultrasonically cleaned in a concentrated nitric acid solution for 1 hour, washed with ethanol and deionized water, and then dried in a vacuum drying oven for 12 hours. Electrodeposition was performed in the solution by an electrochemical oxidation (anodic oxidation) process using a three-electrode system in which the carbon substrate was used as the working electrode, a Pt wire was used as the counter electrode, and Ag/AgCl was used as the reference electrode. The solution was prepared by mixing 50 mL of a 0.5 M CoSO ₄ aqueous solution, 50 mL of a 10 mM ZnSO ₄ aqueous solution, 50 mL of a 10 mM NH ₄ VO ₃ aqueous solution, and 50 mL of a 0.5 M H ₃ BO ₃ aqueous solution. The electrodeposition conditions were -1.7 V (vs. RHE) at room temperature (25 ° C.) for 1200 seconds. By this electrodeposition process, a composite compound was formed on the carbon substrate, and the target electrode catalyst was obtained. The obtained electrode catalyst was named "Zn-VO _x -Co" or "Zn-VO _x -Co-10". From the synthesis conditions and the charge ratio, it was possible to infer that the obtained Zn-VO _x -Co was an alloy of Zn, VO _x and Co, where x was 2 or more and 3 or less.

Example 2
Except for changing the concentration of the _ZnSO4 aqueous solution to 5 mM, an electrode catalyst was obtained in the same manner as in Example 1. The obtained electrode catalyst was named "Zn-VO _x -Co-5".

Example 3
Except for changing the concentration of the _ZnSO4 aqueous solution to 8 mM, an electrode catalyst was obtained in the same manner as in Example 1. The obtained electrode catalyst was named "Zn-VO _x -Co-8".

Example 4
Except for changing the concentration of the _ZnSO4 aqueous solution to 12 mM, an electrode catalyst was obtained in the same manner as in Example 1. The obtained electrode catalyst was named "Zn-VO _x -Co-12".

(Comparative Example 1)
An electrode catalyst having Co supported on a carbon substrate was prepared.

(Comparative Example 2)
An electrode catalyst having a carbon substrate supported thereon Zn--Co was prepared.

(Comparative Example 3)
An electrode catalyst having a carbon substrate supported thereon VO _x -Co was prepared.

(Comparative Example 4)
An electrode catalyst having Zn- _VOx supported on a carbon substrate was prepared.

Figure 1 shows SEM (scanning electron microscope) images of the electrode catalyst surface. Specifically, (a) in Figure 1 is Comparative Example 1, (b) is Comparative Example 2, (c) is Comparative Example 3, and (d), (e), and (f) are SEM images of the electrode catalyst surface obtained in Example 1, particularly the catalyst surface formed on the carbon substrate.

1, the electrode catalyst (Co) of Comparative Example 1 had a uniform nanosheet structure, as did the electrode catalyst (Zn--Co) of Comparative Example 2 (see FIGS. 1(a) and 1(b)). It was found that the electrode catalyst (VO _x -Co) of Comparative Example 3 was a two-dimensional nanosheet (FIG. 1(c)).

In contrast, the electrode catalyst (Zn-VO _x -Co) obtained in Example 1 was found to have a uniform two-dimensional ultrathin structure with nanosheets that had grown large (see Figures 2(d), (e) and (f)). It was confirmed that such ultrathin nanosheets had a multilayer structure formed by overlapping flakes with a major axis of about 1 to 3 μm. Therefore, the electrode catalyst obtained in Example 1 had a large active surface area and was able to provide more exposed active sites, promoting ion migration in the electrolyte and improving catalytic performance.

Figure 2(a) shows the measurement results of linear sweep voltammetry (scan rate 2 mV/s, electrolyte 1 M KOH aqueous solution) using the electrode catalysts prepared in Example 1 and each comparative example. The linear sweep voltammetry curves were obtained by a hydrogen evolution (HER) test using a platinum plate as the cathode and an Ag/AgCl electrode as the reference electrode. The measurement device used to obtain the linear sweep voltammetry curves was a US VersaSTAT4 potentiostat galvanostat electrochemical workstation with a standard three-electrode cell.

FIG. 2(b) is a bar graph showing the overpotential at 10 mA cm ⁻² (bar graph on the right side of the figure) and the overpotential at 50 mA cm ⁻² (bar graph on the left side of the figure) measured from the linear sweep voltammetry curve shown in (a), and (c) is a graph showing the Tafel slope calculated from the linear sweep voltammetry curve shown in (a).

Table 1 summarizes the results obtained in Fig. 2. In the table, η ₁₀ and η ₅₀ indicate the overpotentials (mV) at 10 mAcm ^-2 and 50 mAcm ^-2, respectively.

The Zn-VO _x -Co electrocatalyst obtained in Example 1 has a lower overpotential than the electrocatalyst prepared in Comparative Example, and is also found to have a minimal Tafel slope, indicating superior activity, which suggests that the HER kinetics follows the Volmer-Heyrovsky mechanism.

Figure 3 (a) shows the multi-current step chronopotentiometry curve of the electrode catalyst obtained in Example 1, and (b) shows the chronopotentiometry curve of the same electrode catalyst. From these results, it was found that the electrode catalyst obtained in Example 1 has excellent long-term stability and mechanical robustness.

Figure 4 (a) shows the measurement results of linear sweep voltammetry using the electrode catalysts prepared in Examples 1 to 4, and (b) is a graph showing the Tafel slope calculated from the linear sweep voltammetry curve shown in (a) (the measurement method is the same as in Figure 2). These results show that the composite compounds exhibit excellent catalytic activity over a wide range of elemental compositions.

Claims (5)

An electrocatalyst comprising a catalyst on a carbon substrate,
The catalyst is an electrode catalyst containing a composite compound having Zn , V, and Co as constituent elements. The electrocatalyst according to claim 1 , wherein the composite compound comprises Zn , VO _x (wherein x is a number between 2 and 3), and Co. A method for producing the electrode catalyst according to claim 1 or 2, comprising the steps of:
A method for producing an electrode catalyst, comprising: a step of immersing a carbon substrate in a solution containing a Zn source, a V source, and a Co source to perform an electrodeposition treatment. An electrode for producing hydrogen, comprising the electrode catalyst according to claim 1 or 2. A method for producing hydrogen, comprising a step of performing electrolysis using the electrode according to claim 4.